摘要:

ANNUAL REPORTSON THEPROGRESS O F CHEMISTRYANNUAL REPOBTSP. PHILLIPS BEDSON, M. A., D.Sc.A. C. CHAPMAN, F.I.C. .J. B. COHEN, Ph.D., B.Sc.H. J. H. FENTON, M.A., Sc.D., F.R.S.A. FLNDLAY, M.A., D.Sc., Ph.D.ON THEW. D. HALLIBURTO?;, M.D., F. R.S.J. T. HEWITT, M.A., D.Sc., Ph.D.A. HUTCHINSON, M.A., Ph. D.W. J. POPE, F.R.S., F.I.C.F. SODDY, M.A.PROGRESS OF CHEMISTRYF O E 1906ISSUED BY THE CHEMICAL SOCIETY.$ornmittee of $ublicrrtion :H. E. ARMSTRONO, Ph.D., LT,.D.,E. C. C. BALY.A. W. CROSSLEY, I).Sc., Ph.D.BERNARD DYER, D.Sc.M. 0. FORSTER, D.Sc., Ph.D., F.R.S.F. K. S.R. MELDOLA, F.R.S.E. J. MILLS, D.Sc., LL.D., F.R.S.Sir W. RAMSAY, K.C.B., LLD., F.R.S.A. SCOTT, D.Sc., F.R.S.W. A. TIIBEN, D.Sc., F.R.S.JOHN WADE, D.Sc.@I bitar :J.C. CAIR, D.Sc.S u b - &bitor :A. J. GREENAWAY.assistrtnt Siwb-@bitas :C. H. DESCH, D.Sc., Ph;D.V O l . 111.LONDON:GURNEY & JACKSON, 10, PATERNOSTEK ROW, E.C.1907RICHARD C L A P .*ND S O N S , hMITE;D,BREAD STREET HILL, E.C., A N DBUNQAY, SUFFOLKCONTENTS.PAGEGENERAL AND PHYSICAL CHENIESTRY. By ALEXANDER FINDLAY,INORGANIC CHEMISTRY. By P. PHILLIPS BEDSON, M.A., D.Sc. . 30ORGANIC CHEMISTRY-ALIPHATIC DIVISION. By H. J. H. PENTON,ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. By JULIUS B.ORGANIC CHEMISTRY - HETEROCYCLIC DIVISION. By JOHNSTEREOCHEMJSTRT. By WILLIAM JACKSON POPE, F.R.S., F.I.C. . 185ANALYTICAL CHEMISTRY. By ALFKED CHASTON CHAPMAN, F.I.C. . 199PHYSIOLOGICAL CHEMISTRY. By W. D. HALLIBCRTON, M.D., F.R.S.227By JOHN AUGUSTUS VOELCKER, M.A., Ph.D., B.Sc., F.I.C. . . 256MINERALOGICAL CHEMISTRY. By ARTHUR HUTCHIKSON, M. A., Ph.D. 294RADIOACTIVITY. By FREDERICK SODDY, M.A. . . . . . 333M.A., D.Sc., fh.D. . . . . . . . . . 1MA., Sc.D., F.R.S. . . . . . . . . . 7 1COHEN, Ph.D., B.Sc. . . . . . . . . . . 114THEODORE HEWI'rT, 11I.A.; D Sc., Ph.D. . . . . . . 150AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGYTABLE OF ABBREVIATIONS EMPLOYED IN THEREFERENCES.ABBREVIATED TITLE.Agr. Eqm. Slat. Univ.Wisconsi7b . . .Amer. Chem. J. . . .Amel’. J. Physiol. . .Arner. J. Sci. . . .Analyst . . . .Annalen .Ann. Physik . . .Ann. Chim. anal. . .Aim. Chim. Phys. . .Ann. sci. Univ. Jassy .Anzeiger K. Acad. Wiss.Wien. . . . .Apoth. Zeit.. . .Arch. Exp. Path. Pham. .Arch. Hygiene . . .Arch. Pharrn.. . . .Arch. Sci. phys. wat. . .Atti R. Accad. Sci. Toriao .Atti R. Accad. Lincei .Beitr. chern. Physiol. Path.Ber. . . . . .Ber. Detit. pharin. GPS. .Bied. Centr. . I .Bio-Cbm J. . . .Biochem. Zeit. . . .Brit. Med. J. . .Bull. Acad. roy.’Bely. ,Bull. Acad. Sci. Cracozu .BuU. Assoc. Chim. Sitcr.Bull. Coll. Agr. T6ky6 .Bull. SOC. Chim,. . .Bull. Soc. c h i m Belg. .Bull. SOC. franc. Min. .Centr. Bakt. Par. . ,Dist.JOURXAL.Agricultural Experimental Station, University ofAmerican Chemical Journal.American Journal of Physiology.American Journal of Science.The Analyst.Justus Liebig’s Annalen der Chemie.Annalen der Physik.Annales de Chimie analytique appliqde ?i l’Iudustrie,Annales de Chimie et rle Physique.Annales scientifiqnes de 1’ Universitd de Jassy.Anzeiger der Kaiserliche Akademie der Wisseii-Apotheker Zeitung.Archiv fiir experimentelle Pathologie and Pharma-Archiv fiir Hygiene.Archiv der Pharmazie.Archives des Sciences physiques et naturelles.Atti dellir Reale Accademia delle Scienze di Torino.Atti della Reale Accademia dei Lincei.Beitrage fiir chemische Physiologie und Pathologie.Berichte der Deutschen chemischen Geseilschaft.Berichta der Deutschen ljharmazeutischen GesellschaftBiedermann’s Centralblatt fur Agrikulturchemie undThe Biochemical Journal.Biochemische Zeit schrift.British Medical Journal.Acaddmie royale de Belgique-Bulletin de la ClasseBulletin international de l’dcadhie des Sciences deBulletin de 1’Association des Chimistes de Sucrdrie etBulletin of the College of Agriculture, Imperial Uni-Bulletin de la Sociht6 chimique de Paris.Bulletin de la SoriBtQ chimique de Relgique.Bulletin de la SocidtB franpaise de MinBralogie.Cen tralblatt fur Bakteriologie, Parasi ten kunde undWisconsin.k l’Agricnlture, A la Pharmacie e t A la Biologie.schaften in Wien.kologie.(Berlin).rationellen Landwirtschafts-Beti-ieb.des Sciences.Cracovie.de Distillerie.versity, Tbkyb.Infek tionskrankheitenviii TABLE OF ABBREVlATIONS EMPLOYED IN THE REFERENCES.ABBREVIATED TITLE.Centr. Min.. . .Chem. Centr. . . .Chem. News . .Chent. Rev. Fett ‘Ham Ind.Chem. Weekblad. .Chem. Zeit. . ,Compt.rend. . .Fold. Kozlony . .Gazzetta . . .Geol. Mag.. . .Jahrb. Min. . .Jahrb. Min. Bei1.-Bd.Jahrb. Ratlioakt. Elek.J. Agric. slci. . .J. Amw. Chem. Soc. .J. Biol. Chent. . .J. Chim.phys. . .J. Fed. Inst. Brewing.J. Franklin Inst. .J. Hygiene. . .J. LarLdw. . . .J. Path. Bact. . .J. Pharm. Chim. .J. Physical Chem. .J. Physiol. . . .J. pr. Chenz. . .J . Roy. Agric. SOC. .J. Russ. Phys. Chem. Soc. .J. Sanit. Inst. . .J. SOC. Chem. Ind. .Landw. Versuchs-Stat.Menz. R. Aecad. LimeiMilchzu. Zenlr. . .Min. Mag. . . .Monatsh. . . .Mon. Sci. . . .PfEiiger’s Archiv. .Pharm. Centr. -H. .Pharm. Weekblad .Pharm. Zeit. . .Phil. Mag. . .Phil. Trans. . .Phys. Zeit. . .Proc. Antsr. Phpiol. Soc.Proc.Cantb. Phil. SOC.Proc. Physiol. s’oc. . .Proc. K. AJcad. Wetensch.Proc. Roy. SOC. . . .Rec. trav. chim. . . .Amsterdam.JOURNAL.Centralblatt fur Minerdogie, Geologie und Palrteonto-Chemisches Centralblatt.Chemical News.Chemische Revue iiber die Fett- und Harz-lndustrie.Chemisch Weekblad.Chemiker Zeitung.Comptes rendus hebdomadaires des S6ances deFcildtani Kiizlony.Gazzetta chimica italiana.Geological Magazine.Neues Jahrbnch fiir Mineralogie, Geologie und Pnl-aeon tologie.Neues Jahrbuch fiir Mineralogie, Geologie und Pnl-aeontologie. Beilage-Band.Jahrbuch fur Radioaktivitat und Elektrooik.Journal of Agricultural Science.Journal of the American Chemical Society.Journal of Biological Chemistiy.Journal de Chimie physique.Journal ol’ the Federated Institutes of Brewing.Journal of the Franklin Institute.Journal of Hygiene.Journal fur Landwirtschaft.Journal of Pathology and Bacteriology.Journal de Pharmacie et de Chimie.Journal of Physical Chemistry.Journal of Physiology.Journal fur praktische Chemie.Journal of the Royal Agricultural Society.Journal of the Physical and Chemical Society ofJournal of the Sanitary Institute.Journal of the Society of Chemical IndustryDie landwirtschaftlichen Versuchs-Stationen.Memoires della Reale Accademia dei Lincei.iMilchwirtschaftlic11es Zentralblatt.Mineralogical Magazine and Journal of the Mineral-qical Society.Monntshefte fur Chemie und verwandte Theile andererWissenschaften.Monitenr Scientifique.Archiv fur die gesammte Physiologie des MenscheiiPharmazeutische Centralhalle.Pharmaceutisch Weekblad.Pharmazoutische Zeitung (Berlin).Philosophical’Magazine (The London, Edinburgh andPhilosophical Transactions of the Royal Society ofPhysikalische Zeitschrift.Proceedings of the American Physiological Society.Proceedings of the Cambridge Philosophical Society.Proceedings of the Physiological Society.Koninklijke Akademie van Wetenschappen te Amster-Proceedings of the Royal Society.Receuil des travanx chimiques des Pays-Bas et de lalqgie.1’Acaddmie des Scienses.Russia.und der Thiere.Dublin).London.dam.Proceedings (English Version).BelgiqueTABLE OF ABBREVIATIONS EMPLOYED IN THE REFERENCES. ixABBREVIATED TITLE.Rev. Metallurgie ..Sitzungsber. K. Akad. Wiss.Trans. . . . .Trans. Faraday Soc. . .Trans. Roy. Dubl. SOC. ,Tram. Roy. SOC. Canadu .Trans. Buy. SOC. Edin. .T?,ans. Roy. Xoc. S. APLS-Tsnh. Min. Mitt. . .U.S. A . Dqt. Agric. Bull. .Wien. Xitzungsber. . .Woch. €hau. . . .Zeit anal. Chem. . .Zeit. angcw. Chenz. . .Zeit. anorg. Chetn. .Zeit. EZektrochem. . .Zeit. Farb. Text. Ind. .%it. Kryst Min. . .Zeit. Nahr. Genussm. .Berlin.trnliaZeit. physikal. Chem. .Zeit. physiol. Chenz. . .Zeit. Ver. deut. Zuckerind.Zeit. Zuckerind. BQhm. .JOURNAL.Revue de Metallurgie.Sitzungsberichte der Koniglich Preussischen Akademieder Wissenschaften zu Berlin.Transactions of the Chemical Society.Transactions of the Faraday Society.Transact ions of the Royal Dublin Society.Transactions of the Royal Society of Canada.Transactions of the Royal Society of Edinburgh.Transactions of the Royal Society of S. Australia.Tschermak’s Mineralogische Mitteilungen.Bulletins of the Department of Agriculture, U. S. A.Sitzungsberichte der Kaiserlich Akademie clcr Wissen-schaften zu Wien.Wochenschrift fur Brauerei.Zeitschrift fur analytische Chemie.Zeitschrift fiir angewandte Chemie.Zeitschrift fur anorganische Chemie.Zeitschrift fur Elektrochemie.Zeitschrift fiir Farben- nnd Textil-Industrie.Zeitschrift fiir Krystallographie und Mineralogie.Zeitschrift fiir Untersuchung der Nahrungs- undZeitschrift fiir physikalische Chemie, StochiometrieHoppe-Seyler’s Zeitschrift fur physiologische Chemie.Zeitschrift des Vereins der deutschen Zucker-Industrie.Zeitschrift fiir Zuckerindustrie in Bohmen .Genussmittel.und Verwandtschaftslehre

ISSN:0365-6217    

DOI:10.1039/AR90603FP001

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

INORGANIC CHEMISTRY.THE work done during the year in this department of chemistry is notdissimilar to that recorded in previous years; it reveals evidence ofactivity in a great number of directions, and from the circumstances ofthe case places on record the results of the examination of a greatvariety of materials. The revision of atomic weights and the refiningof earlier observatioiis continue still to attract workers prepared t ouse to the utmost advantage the facilities in the niariipulation of gases,liquids, and solids, which are the accumulated heritage from theresearches of the past century. The study of the rare elements, moreespecially of the rare earths, has contributed its quota t,o the year’swork, still to leave the position of some elements in doubt and dispute.The construction of fusion diagrams largely employed in the investiga-tion of alloys has been applied to the examination of the possibilitiesOF combination in the case of other solid elementary bodies.The controversy as to the cause of the rusting of iron would appear to beclosed by the investigations of Moody, who shows that carbon dioxideplays the important part in this chemical change. It is permissible toregard the discovery of a new gaseous oxide of carbon, referred to in alater section of this Report, as an addition to the facts of inorganicchemistry. The complex metalammonia compounds and the isomerismexhibited by these substances have, a t the hands of Werner and others,received further extension and elucidation, and formed the subject ofa special lecture given by Werner to the Berlin Chemical Society.Revision of Atomic Weigl~ts.Gray and Gnye2 have, from a discussion of the results of thedifferent determinations of the atomic weight of nitrogen, inde-pendently concluded that 14.010 may be accepted as the atomic weightof this element.Ann.Report, 1906, 35 ; also Trans., 1906, 89, 1173.BcT., 1906, 39, 1470, aiid A Y C ~ . Sci. ~ J L ~ J s . nut., 1905, [iv], 20, 351, aiid GupeiIIld I ) u ~ c l l a , Ci)l/Zpt. ?*end., 1905, 141, 826INORGANIC CHEMISTRT. 31Guye and Ter-Gazarian 1 have drawn attention t o a source of errorin fixing the atomic weight of silver in the potassium chloridewhich is always t o be found even in the most carefully purifiedpotassium chlorate, the amount varying from 0*022-0*029 per cent.Applying to Stas's results, a correction based upon this observationeffects a reduction in the atomic weigh€ of silver, to which the authorsassign the value 107.89 (0= 16).Baxter 2 has redetermined the atomic weight of bromine, the meanof eighteen determinations of the ratio Ag : AgBr giving a value of'79.953 for the atomic weight of bromine.From the conversion ofsilver bromide into silver chloride the value 79,952 for bromine isdeduced (C1= 35.473). The mean of all Baxter's determinations gives79.953, which is in agreement with Stas's determination, whereasScott's results are somewhat lower. I n this connexion, the determina-tion of the density of chlorine gas may be mentioned.Treadwell andChristie 3 give as the mean of two sets of determinations, representingfive observations, the value 2.4885 (air = l), a value approximating tothat found by Moissan and Binet du Jassoneix, namely, 2.490.Baxter, in association with others, has published the results of theredetermination of the atomic weights of rnnngane~e,~ ~ o b a l t , ~ andcadmium.6 The analysis of manganese bromide and chloride givesMn = 54.96, of cobalt chloride and bromide Co = 59, and of cadmiumbromide gives 112.467 for the atomic weight of cadmium. A morerecent determination of the atomic weight of cobalt from the analysisof the chloride gives a mean value of 58*995.7The analysis of Strontium bromide according to Richards8 gives anatomic weight of 87.663 for strontium, and, if C1= 35.473 be accepted,from the chloride the value 87.661 is deduced; this result is in satis-factory agreement with that derived from the bromide, whereas if theolder atomic weight of chlorine is employed the agreement is not sogood.The author concludes that the mean of these two sets ofdeterminations, namely, 87.662, may be accepted as the atomic weight(0= 16).The alternate oxidation and reduction of pure copper according toMurmann gives for the atomic weight of this element values varyingfrom 63-573-64.153 (0 = 16) ; this variation, it is suggested, arisesfrom the absorption of air by the porous copper, The atomic weightis estimated to be 63.53 with a n error of & -03.Compt. rend., 1906, 143, 411.Ibid., 1905, 47, 446.Rsxter and Coffin, ibid., 1380.Richards, ibid., 1005, 47, 145.'L Zcit.anorg. Chcm., 1906, 50, 389.4 Baxter and Hines, J. Amcr. C'ltenz. Soc., 1906, 28, 1360.7 Baxter and Coffin, Zcit. nnorg. C h e m . , 1906, 51, 171.Baxtw, Hines, and Freveit, ibid.: 770.Moaatsh., 1906, 27, 35132 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Gutbier,l in conjunction with Birckenbach and Mehler, has by threedifferent methods obtained values for the atomic weight of bismuth,the mean of which is 208.074.The determination of the electrochemical equivalent oE iodine madeby Gallo2 gives as a mean of twenty-four estimations the atomicweight 126.89 when silver is 107.93.A new determination of the atomic weight of potassium is recordedby Richards and Stahler,3 who employed for this purpose speciallypurified potassium nitrate, which they subsequently converted into thechloride.The ratios KC1 : AgCl and KC1 : Ag were deterrnined in thesame manner as the ratios NaCl : AgCl and NaCl : Ag (see Kekort, 1905,34). The results of eight experiments with three samples of potassiumchloride gave for the mtio KC1 : AgCl an average of 0.5201 18 : 1.With five different samples of potassium chloride the average of nineexperimental determinations of the ratio KC1 : Ag gave 0.691072 : 1.Taking the atomic weight of silver as 10'7.93 and t h a t of chlorine as35.473, the above results lend to 39,114 as the atomic weight ofpotassium.Brill,4 experimenting with the micro-balance, has shown thatKriiss's method of determining the atomic weights of the rare earthsdepending on the conversion of the acid sulphates into sulphates is notaccurate, the temperature employed being too low.This conversion iscomplete at 450°, and at 700" a decomposition begins resulting inthe formation of basic sulphates which is completed at 900". Thebasic sulphates are completely transformed into the oxides a t 1380".The basic sulphates, M20,*80,, of ytterbium, yttrium, erbium, lan-thanum, and samarium have been prepared by this method. Judgedby the temperature a t which these basic sulphates begin to decompose,the basicity OF the oxides of these elements increases in the followingorder : Yb, Er, Y, Sm, and La. Upon the results of this investigationBrill bases a method for the determination of the atomic weights of theelements of these rare earths.Feit and Przibylla5 show that apractical method of determining the atomic weights of these eIementsis to dissolve a known weight of the oxide in AT/2 sulphuric acidand titrate back with N/10 caust icso da solut ion,using niethyl-orangeas indicator. I n this way the following values for the atomic weightshave been obtained : La = 139.17, Pr = 140.62, Nd = 144.6, Sm = 150.56,Xu = 152.66, Gd = 157.47, Yb = 173.52, Yt = 89.40. With the exceptionof europium and yttrium, the results are in good agreement with themost trustworthy of previous determinations.Zeit. Elektrochena., 1905, 11, 831.Alti R. Aecnd. Lincei, 1906, [v], 15, i, 24.Ber., 1906, 39, 3611.Ibid., 1906, 50, 249.Zeit.nnory. Chem., 1905, 47, 464INORGANIC CHEMISTRY. 33The conversion of dysprosium sulphate, [Dy2(S0,),,8H20] into theoxide (Dy,O,) has been employed by Urbain and Demenitroux todetermine the atomic weight of the element. When the earth isprepared by the fractional crystallisation of the nitrate, the atomicweight found in this way is 162.52, whereas with the earth preparedby the fractional crystallisation of the ethyl sulphates the value162.54 was obtained.1 Hinrichsen and Sahlbom 2 have determinedthe atomic weight of tantalum by converting the metal into thepentoxide, which gives the value 181.0, somewhat lower than theatomic weight assigned t o the metal by Marignac, whose method theauthors consider to be faulty.Rare Earths.Matignon and Cazes find that samarium chloride (SmC1,) is reducedto a lower chloride SmCl,, when heated at high temperatures inhydrogen or ammonia, or with aluminium powder.This chlorideis a dark brown, crystalline powder, and is insoluble in carbondisulphide, benzene, chloroform, and the other organic solventswhich dissolve the anhydrous chlorides of the rare metals. I t isdecomposed by water, forming samarium oxide (Sm203) and an oxy-chloride (SmOC1) ; hydrogen is also liberated. The chlorides ofpraseodymium and neodymium are not reduced ; it is suggestedthat this difference may be employed i n the separation of tlieseelements. Samarium iodide4 is reduced to samarious iodide byheating in a current of hydrogen.The dehydration of the hydrated chlorides of yttrium and ytterbium,YtCl,,GH,O and YbCl,,6H20, has been studied by Matignon,5 and thephysical properties of the anhydrous clilorides so obtained described.The following compounds of neodymium have been isolated :NdC13,H20 ; NdC1,,6H20 ; NdCL3,3EtOH ; NdC13,3C,NH, ; NdOCl ;NdBr, and NdI,, also NdH,(SO,), and Nd202(S04).6 Matignon andTrannoy 7 describe a series of seven compounds, formed by the inter-action of gaseous or liquid ammonia and anhydrous neodymiumchloride ; the temperatures of dissociation and heats of formationof these compounds have been determined.The determination ofthe heats of formation of the sulphates of lanthanum, praseodymium,neodymium, and samarium, made by the dissolution of the oxidesin dilute sulphuric acid, shows the basic function of these oxidesComnpt.rend., 1906, 143, 598, and 142, 785.Ber., 1906, 39, 2600.Matigiion and Cazes, Ann. CJLim. Phyls., 1906, [viii], 8, 417.6 Ann. Chim. Phys., 1906, [viii], 8, 433 and 440.7 Compt. rend., 1906, 142, 1042 ; see also Anti. Report, 1905, 37.Compt. rem~d., 1906, 142, 183.Ibid., 243.VOL. 111. 36 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.to decrease with increase in atomic weight.l For the preparation ofpure cerium compounds the following method is recommended byOrloff .2 The mixed sulphates are treated with ammonium oxalate ; theprecipitate formed consists of the oxalates of lanthanum, neodymium,praseodymium, yttrium, and some cerium, and from the filtrates con-taining the oxalates of thorium and cerium the latter slowlyprecipitates, whereas the former remains in solution.This separationis materially assisted by the addition of sodium sulphite to thesolution,A silicide of thorium, ThSi,, is formed by the interaction of thedouble fluoride of thorium and potassium and potassium silicofluorideand aluminium heated in a n electric furnace a t 1800". This samecompound is produced by heating thoria with silicon in an electricfurnace, or by heating aluminium, silicon, and thorium together a t1000°.3 The compound ThAl,4 is formed by the direct union of theelements when heated together in a vacuum, or by reducing potasFiumthorium fluoride o r thoria with aluminium in an electric furnace. I nappearance this alloy resembles aluminium; it is attacked by thehalogens and mineral acids, but not by alkali solutions, whereas it isviolently acted on by fused alkalis or carbonates of the alkali metals.preparit-tions of terbium compounds, concludes that terbium is a well-definedelement ; according to Urbain? this element forms a sulphate of thecomposition Te2(S0,),,8H20, and has an atomic weight 159.22 (0 = 16).The evidence in support of the existence of the element victorium isstill a matter of discussion, as is evidenced by the publications ofCrookes,s Urbain,g and Marc.loIn conclusion, mention should be made of Urbain's rZsum5 of hisresearches in this field of investigation made since 1S99.11Attempts to prepare metallic thorium both by the action of sodiumon the chloride and by electrolytic processes have not proved success-ful ; the product mas always found to contain some oxide (Moissan andHonigschmid).12Eberhard,5 from a spectroscopic investigation of Urbain'sThe Argon Group.The examination of the gaseous contents of forty-three thermalsprings has revealed the general presence in these gases of argon andChem Zeit., 1906, 30, 733,Hoi:igschmid, ibid., 280.Ann.h'eport, 1906, 57.Matignon, Compt. Tend., 1906, 142, 276.Xitzungsbcr. K. Acad. Jiss. Beriin, 1906, 384.3 Hijuigschmid, Comyt. rewl., 1906, 142, 157.7 Compt. rend., 1906, 142, 957.9 Cornpt. relid., 1905, 14i, 954.l1 J. Chiin. PJbys., 1906, 4, 31, 105.12 Aniz. Chim. Phys., 1906, [viii], 8, 182.Chem. News, 1906, 43, 143.lo Ber., 1906, 39, 1392INORGANIC CBEMISTRI-.35helium, the proportion of which varies with the amount of nitrogenand indirectly with the amount of carbon dioxide. I n the water ofMaziBres, the new gases formed 6.35 per cent. of the nitrogen1(Moureu).Olszewski,2 working with helium obtained from t h ~ r i a n i t e , ~ has notbeen able t o liquefy this gas, even when it is cooled by frozen hydrogenand submitted to a pressure of 180 atmospheres which was suddenlyreduced to 1 atmosphere; in this way the temperature was loweredto - 271.3'. The boiling point of helium is therefore estimated to beThe density of the vapours of zinc, cadmium, mercury, sulphur,selenium, and arsenic has been determined in atmospheres of argonand of helium, and compared with the values obtained when atmo-spheres of nitrogen and of hydrogen are employed.From the resultsof these observations, Ternent Cooke * concludes that these elementsexhibit a tendency to unite with argon and helium. Scheerer (1844),in his analysis of malacone, a silicate of zirconium, entirely over-looked the small proportion of uranium which Kitchin and Winter-son 6nd to be present in this mineral ; further, these authors show thatwhen this mineral is fused with potassium hydrogen sulphate a gas con-taining both argon and helium is given off,below - 271'.Adopting the method used in previous reports, the results of inves-tigations published during the year will be discussed under the head-ings of the several groups in the periodic system of the elements.Group I A .For the electrolytic preparation of lithium, Ruff and Johannsen 0recommend a mixture of bromide and chloride containing 13 per cent.of the latter ; this mixture melts at 520'.A carbon anode and an ironcathode are employed and an E.M.F. of 10 volts and current of 100amperes. Weyberg7 has ob-tained lithium aluminosilicates by fusing kaolin with lithium com-pounds. With the chloride and carbonate, the compound Li, AI,Si,O,,is formed, with the sulphate Li,Al,Si,O,, whilst with the bromide7Li2A12Si208, 2LiBr is produced. The hydroxides of lithium, rubidium,and cesium have been examined by Forcrand ; each forms a mono-hydrate ; the lithium compound, Li(OH)H,O, separates from its solu-tions in well-defined crystals which lose H,O when heated, formingThe metal so obtained melts at 180'.Compt.rend., 1906, 142, 1155.Ann. Beport, 1905, 38.Trans., 1906, 89, 1568.cent?.. Jfi??,., 1905, 646.Bull. Acad. Sci. Cracow, 1905, 40i.Zeit. physikal. Chem., 1906, 55, 537.Zeit. Elektrochem., 1906, 12, 186.Compf. rend., 1906, 142, 1252.0 36 ANNUAL REPORTS Oh: THE PROGRESS OF CHEMISTRY.the hydroxide melting at 445'. The hydrated rubidium and cssiumhydroxides, when dehydrated in silver crucibles, form peroxides whichattack the silver. From solutions of lithium hydroxide and chromiumtrioxide in water at 30°, the substances separating in the solid stateare [Li(OH),H,O 3, Li,Cr04,2H20, Li2Cr207,2H,0, and CrO,. Thesolubility of the chromates of ammonium, potassium, sodium, andlithium increases in the order named, whilst for the dichromatesthe order is potassium, ammonium, lithium, and s0dium.l Lebeau,2experimenting on the carbonates of the alkali metals heated in acurrent of carbon dioxide in an electric furnace, finds these carbon-ates to be non-volatile between 780' and 1 200°, save in the case of czesiumcarbonate, which dissociates somewhat at 720°, a temperature muchbelow that a t which it volatilises.are, accord-ing to Ruff and Geisel,4 mixtures of metal with solutions of the metalin ammonia.These solutions decompose on keeping, with the evolutionof hydrogen and the formation of metallic amides. Ruff and Geiselalso show that the hydrides of the alkali metals are decomposed byliquid ammonia with the liberation of hydrogen and the production ofamides. The oxidation of the solution of rubidium in ammonia yieldsa di- and tetra-oxide (Rb,O, and Rb,O,), but no sesquioxide isformed as in the case with cmium (Rer~gade),~ The peroxide ofcaesium (Cs,O,) is formed when the metal is heated a t 300--350' in astream of oxygen.6The production of caustic soda by the decomposition of sodiumsilicofluoride with lime is the subject of a patent by Reich,' who findst h i t the reaction is more complete when the amount of lime is doublethat required by the following equation :The metalammonium compounds described by JoannisNa,SiF6 + 4Ca0 = Na20 + 3CaF, + CaSiO,.The residue left after the removal of the alkali on dissolution inhydrochloric acid gives a solution of hydrogen silicofluoride which maybe recovered as potassium silicofluoride.From solutions of sodiumsulphate in sulphuric acid, two acid sulphates, namely, Na,H(SO,), andNa,H(SO,),H,O, have been obtaineda8 The investigation of the fusioncurves of mixtures of the haloids of potassium and sodium provesthese salts to form isomorphous mixture^.^ According t o van't HoffSchreineinakers, Chenz. Weekblnd.: 1905, 2, 633 ; see also Zeit, p h y s i k d Chem.,Bull, SOC. chim., 1906, [iii], 35, 5.Afin. Chim. Phys., 1906, [viii], 7, 5. Ber., 1906, 39, 828.Compt. rend., 1906, 142, 1533 ; see also Ann. Report, 1905, 43.D'Ans, Ber., 1906, 39, 1534.KurnakofT and Schemtscl~usch~y, Chem. Ccnkr., 1906, i, 526.1906, 55, 71.Kengade, ibid., 1149.' D.12.-P. 161795INORGANIC CHEMISTRY. 31and Bar~chall,~ glaserite is not a compound of the sulphates ofpotassium and sodium, but an isomorphous mixture of these sulphates.A study of the solid phases between iodine, an iodide, and polyiodideshows in the case of the alkali metals the tendency to form higherpolyiodides to increase in the following order (LiNa), K, Rb, Cs, whichis the order of decreasing solubilities of the platinichlorides (Abeggand Hamburger).2When potassium is heated in a nickel dish, a black mass results,from which nickelous nickelite, (Ni0,Ni0,,2H20), has been obtained.The corresronding cobaltous cobaltite (Co0,Cc02,2H20) is formed bythe action of potassium peroxide on cobaltous oxide.3A simple process f c z the continuous production of potassium chlorateby the electrolysis of a solution of potassium chloride containing somepotassium chromate and hydrochloric acid is described by A.Wallach.4Wohler and Kasarnowski5 consider the blue colour exhibited bysome specimens of natural rock salt may be due to organic matter, assuch specimens when heated in a current of oxygen mere found to losatheir colour and yield carbon dioxide and water. The coloratioLsproduced by heating halides with the metals probably arise frominclusion of tbe particles of the metals, or possibly from the productionof sub-halides. The former explanation is supported by the ultra-microscopic examination of coloured specimens of rock salt made bySiedentopf .6The investigations of the sulphides of rubidium and casium by Biltzand Wilke-Dorfurh show the monosulphides Rb2S,4H20 and Cs2S,4H,0to be colourless, crystalline compounds, as are also the sulphydrates.From solutions of the monosulphides and sulphur the tetrasulphidesRb,S,,2H20 and Cs,S, have been obtained, the former in yellowcrystals, the latter in reddish-yellow prisms.The pentasulphides(see Annual Report, 1905), when heated in a stream of hydrogen, losesulphur and from the residue by dissolution in water the disul-phides, Rb,S,,H,O, Cs,S2,H20, are obtained in colourless crystalsWhen the pentasulphides are heated in a current of nitrogen the tri-sulphides Rb,S,,€€,O and Cs,S,,H,O are obtained.* The sulphides ofrubidium are less hygroscopic than those of cmium, and Cs,S, is morereadily volatile than Rb,S2.Paal and Kuhng record the formation of organosols and gels ofsodium chloride and of sodium bromide by the addition of light petrol-1 Zeit.physiknl. Chem., 1906, 56, 212. Zeit. anorg. Chem., 1906, 50, 403.Hofmann and Hiendlmaier, Ber., 1906, 39, 3184.Zeit. Elektrociiew., 1906, 12, 667 ; see also Coppacloro, Gaxzetta, 1906, 36,ti Zeit. anorg. Chem., 1905, 47, 353.Chem. Cent?.., 1906, i, 388. 7 Zeit. nnorg. Chem., 1906, 48, 297,Ibid., 1906, 50, 67. 9 Ber., 1906, 39, 2839 and 2863.ii, 32138 ANNUAL REI'ORTS ON THE PROGRESS OF CHEMISTRY.eum to the condensation product of ethyl chloroacetate or bromo-aoetate with ethyl sodiomalonate. When freshly prepared the precipi-tates are soluble in benzene, but become insoluble after drying in avacuum.The gsls so produced contain 58 per cent. or more of sodiumchloride.According to Mathewson1 sodium forms a series of definite com-pounds with lead, cadmium, bismuth, and antimony,Group I B.The freezing point of pure copper is 1085" ; it is depressed by cuprousoxide, the eutectic mixture solidifies at 1065' and contains, accordingt o Dejean,2 4.7 per cent. of cuprous oxide which Heyn considers toohigh, and fixes the amount a t 3.5 per cent. The maximum depressionproduced by aluminium is 1039O, corresponding to S*6 per cent, of themetal. Moissan4 has succeeded in distilling copper in an electricfurnace; the ingot left in the crucible on cooling exhibits thephenomenon of '' spitting," and is covered by a layer of graphite.Copper chloride heated in a vacuum with calcium turnings gives anorange-yellow, brittle alloy containing 18.3-1 8.8 per cent of copper.5The chief product of the action of ammonia on heated ouprous oxide isthe nitride Cu,N, ;which is converted into cuprous chloride andammonia by hydrochloric aaid ; it is attacked by nitric and sulphuricacids.6 Cuprosilicon, prepared by h a t i n g a mixture of these elements,consists in the main of the compound Cu,Si and contains some freesilicon ip a form soluble in hydrofluoric acid 7 (Annual Report, 1904,45).The influence of small quantities of phosphorus, arsenic, anti-mony, bismuth, and lead on the structure of copper has been examinedby Hiorns.8 Heyn and Bauer 9 find that copper and cuprous sulphideare not perfectly miscible in the fused state, and that selenium andtellurium produce an alteration in the microstructure of coppersimilar t o that produced by sulphur. The presence of these elementscan be readily distinguished by treating copper turnings with asolution of potassium cyanide.On the addition of cadmium acetate dis-solved in acetic acid, cuprous sulphide gives a yellow precipitate, whereasthe selenide gives an orange ; the telluride gives a coloration similar tothat of permanganate on treatment with potassium cyanide. TheseZeit. anorg. C'hem., 1906, 50, 171. RG'L'. de dlc?tnlZzwgie, 1906, 3, 233.Conzpt. wnd., 1905, 141, 853. 3 Ibid., 345.5 Hackspill, Cmtpt. rend., 1906, 142, 89.7 Lebenu, Compt. rend., 1905, 141, 889 ; 1906, 142, 154 ; and Vigouroux, ibid.Guntz and Bassett, BdZ.SOC. chim, 1906, [iii], 35, 201.1906, 142, 37.,T. SOC. Chem. Ind., 1906, 25, 616. L, MetnlZurgie, 1906, 3, 73INORGANIC CHEMISTRY. 39authors also state that sulphur dioxide does not attack copper a t900-1100', save in presence of a reducing agent ; and a t this tempera-ture the action of cuprous sulphide on cuprous oxide,cu,s + 2cu,o = so, + 3cu2,is complete.From the freezing-point curves of mixtures of cuprous sulphide andferrous sulphide Rontgenl infers the existence of the following com-pounds : 5Cu2S,2FeS, Cu,S,FeS, and 2Cu2S,FeS. The presence ofmetallic copper in copper mattes may arise from the change ofCu,SFeS into Cu and FeS,.The action of strong sulphuric acid on copper is maintained bySluiter2 to be best explained by the reduction theory, since thesesubstances heated together a t 130' with nitrobenzene yield aniline,whereas with sulphuric acid containing 12 per cent.of sulphnr trioxideno aniline is formed. On the other hand, van Deventer3 considersneither explanation satisfactory, but suggests that water plays a part inthe reaction, which he formulates as follows :CU + H,O = CUO + H, ; CUO + H2S04 = CUSO, + H,O ; H, + SO4 =2H,O + so,.The alloys of copper and phosphorus have been investigated byHeyn and Bauer ;* these alloys are harder than the corresponding tinalloye, and a compound, Cu,P, apparently exists. By employing higherpressures than the atmospheric pressure Friedrich has produced alloysof copper and arsenic containing as much a s 44 per cent.of the latterelement, The existence of several definite compounds are indicated bythe melting-point curves of mixtures of these elements. Guillet 6 haspublished an account of the examination of ' special brasses,' namely,copper and zinc alloys to which a third metal is added; whilst Pfeiffer 7concludes that copper does not alloy with iron o r with iron and carbonalloys.The production of colloidal copper oxide and of colloidal copper isdescribed by Paal and Leuze.8von Wartenberg's observations on the relative density of thevapour of silver a t 2000' show the molecule to be mono-atomic, andthat the metal volatilises a t 1950'. The reduction of silver chlorideby metallic calcium results in the formation of alloys containing from6.3 t o 16 per cent.of calcium ; these alloys are grey, brittle, crystal-Metnlliwgie, 1906, 3, 4'79.Ibid., 1906, 3, 515.MetaZ/urgic, 190t5, 2, 4 i i .7 ilfctrclluryie, 1906, 3, 281.9 Ibid., 1906, 39, 381.Chenz. Weekhlad., 1906, 3, 63.Rer. lie Xitrcllicrgic, 1906, 3, 243.Ber., 1506, 39, 1545 and 1550.Mitt. TC. Materid-prtifump Amt., 1906, 24, 9340 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.line solids, oxidised by the air and attacking water a t the ordinarytemperature.1That the electrolysis of a solution of silver nitrate gives a depositof a black powder on the anode has been observed both by Watson2and Barbieri.3 The first of these authors shows this substance to beAg,XO,,, which is decomposed by boiling water, forming silver peroxide,thus :Ag7NOI1 = AgNO, + 3Ag,02 + O,,and by ammonia with the formation of the oxide Ag,O,, from theinteraction of silver peroxide and ammonia :6Ag,O, + 2NH, = 3Ag40, + 3H,O + N,.Barbieri also records the observation that a layer of black oxide isformed on the anode when a solution of potassium hydrogen carbonateis electrolysed with silver electrodes ; this deposit gradually dissolvest o form a brown solution, which readily oxidises ferrous and cobaltoussalts.According to Lewie,4 silver suboxide is not formed by the decom-position of silver oxide Ag,O, a t 5 0 2 O , 5 2 5 O , or 445'.The investigation of the action of silver nitrate on disodium hydrogenorthophosphate shows this reaction to take place in several stages ; thesilver phosphate contains only 76 per cent.of silver, whereas Ag,PO,requires 77.32 per cent. Further, the solution always contains somephosphoric acid not precipit,ated by silver nitrate.5The freezing-point curves of mixtures of silver with sulphur,selenium, or tellurium give no evidence of the existence of compoundsother than Ag.,S, Ag,Se, or Ag2Te.6 The melting-point curves ofmixtures of silver and silver sulphide have been examined by Friedrichand Leroux,' who find that a t 906" these substances separate into twolayers, and from the eutectic mixture a t 806' almost pure silver sul-phide separates out. These authors from their investigation of thealloys of silver and arsenic fail to find any evidence in support of theexistence of the compound Ag,As ; by the reduction of silver arsenatewith potassium cyanide at low temperatures they have obtained alloyscontaining 87*3-89*5" per cent, of arsenicsSilver and zinc appear to form compounds of the formulae Ag,Zo2,AgZn, Ag,Zn,, and Ag,Zn, ; 9 with magnesium, silver forms alloyswhich are harder than either constituent ; those rich in magnesiumCompt.rend., 1906, 142, 89.Alti R. Accad. Liwei, 1906, [v], 15; i, 500.J. Anaer. Chcm. SOC., 1906, 28, 139.Laiig and Kaufmann, ibid., 1905, 27, 1515.Pdlabon, Compt. rend., 1906, 143, 294.Trans., 1906, 89, 578.Metdluryie, 1906, 3, 361. * Ibid., 192. 9 Petrenko, Zeit. anorg. Chem., 1906, 48, 347INORGANIC CHEMISTRY. 41are yellow, are readily oxidised, and decompose water more easily thanmagnes1um.lSilver forms alloys with thallium, bismuth, and antimony ; with thelast only does it form a chemical compound, namely, Ag3Sb.2I n counexion with their determination of the melting point of goldmentioned in last' year's Report, Jaquerod and Perrot3 give thefollowing values for the coefficient of expansion of gases a t tempera-tures ranging from 0" to 1067-4O: air 0.0036644, CO 0.0036638,0, 0.0036652, and CO, 0.0036756 and 04036713, that of nitrogenbeing 0 003664.Ammonia unites with aurous iodide, forming AuT,6NH3, which at28" dissociates into AuI,NH, and ammonia, and when heated formsammonia., iodine, and gold; by water it is converted into ammoniumiodide and gold.Aurous bromide forms AuBr,SNH,, readily passinginto AuBr,NH3 ; whereas aurous chloride forms AuC1,2NH3, which,losing ammonia, gives AuC1,3NH3; this compound is stable at 180",but above this temperature is resolved into ammonium chloride andgold.4Gold and zinc when alloyed appear to form the compoundsAuZn, Au3Zn,, AuZns, and with cadmium gold forms Au4Cd, andAuCd3,5 whilst with antimony it forms the compound AuSb,, but nodefinite compound is obtained with bismuth.6 For the production of goldhydrosols the use of oil of turpentine (or pinene) or oil of rosemary isrecommended by Vanino and Hart1,7 the colours produced dependingon the temperature and concentration of the solutions.Neumann 8 has examined carefully the conditions required for theelectrolytic precipitation of gold from cyanide solutions, using a lead oran iron cathode.The gold may also be deposited from these solutionsusing a carbon cathode, from which the gold may be stripped byusing the gilded carbon as anode.Group I1 A .The analysis of a sample of electrolytic calcium from the Bitterfeldworks shows it to contain some calcium carbide, iron, silica, andmanganese, the Iast-named element being possibly derived from thesteel tool used to break the calcium ( L a r ~ e n ) . ~ According to Doermer,localcium when strongly heated evolves hydrogen, which is reabsorbedSchemtschuschny, Zeit. nnorg. Chent., 1906, 49, 400.Petrenko, ibid., 50, 133.Meyer, Compt. rend., 1906, 143, 280.Vogel, Zeit. anorg. Chem., 1906, 48, 319 and 333.Vogel, ibid., 1906, 50, 145.7 Bcr., 1906, 39, 1696.Zeit. Ekktrochem., 1906, 12, 569.3 Arch. Xci. I'hys. Nat., 1905, [v], 20, 506.9 Chem. Cen.fr., 1905, ii, 1466.lo Ber., 1906, 39, 21142 ANNUAL REPONTS ON THE PROGRESS OF CHEMISTRY.at a lower temperature; when the metal is struck on an anvil ex-plosions not infrequently occur. The dissolution of metallic calciumin molten cast-iron is attended by considerable development of heat, andsome calcium carbide is formed. Whilst calcium reduces ferric oxide itdoes not combine with the iron produced; alloys of calcium with copper,aluminium, and magnesium are described by Stockem.l By the action ofcalcium on fused lead chloride alloys of lead arid calcium are formed.2Calcium hydride is manufactured by heating electrolytic calcium con-tained in horizontal retorts in a current of hydrogen ; the crude productcontains 90 per cent.of the hydride, and may be used as a source ofhydrogen ; when decomposed by water one kilo. yields one cubic metreof the gas.3 Hoffmeister regards the colourless gas left after treatmentof commercial acetylene with acetone and ammoniacal cuprous chlorideas a gaseous hydride of calcinm, for on burning in air it forms limeand water; with oxygen i t forms a n extremely explosive mixture.Attempts to prepare sub-salts of calcium by fusion of the metal withthe chloride, iodide, or fluoride yield products which contain lime andcalcium hydride, the latter resulting from the hydrogen produced bythe action of the metal on the traces of water present, Commercialcalcium peroxide is shown by von Foregger and Philipp 6 to consist ofcalcium peroxide and calcium hydroxide, and to contain about 60per cent.of the peroxide; when treated with water it forms calciumhydroxide and hydrogen peroxide. Calcium peroxide forms twohydrates, namely, Ca0,,8H20 and Ca0,,2H,O ; the dry peroxide can beheated a t 200’ without change and is non-explosive. With respect t oavailable oxygen it stands midway between neutral and acid calciumpermanganate. The peroxides of strontium, magnesium, and zinc aredecomposed a t a lower temperature t h m the calcium compound.Tarugi’s conception of the constitution of bleaching powder, referredto in the Report for 1905, p. 69, is refuted by Ditz,7 whilstTiesenholt 8 considers the view that, bleaching powder is a mixture ofcalcium hypochlorite and calcium chloride to be supported by the ob-servation that mixtures of calcium hypochlorite or lithium hypo-chlorite and calcium chloride are decomposed with the liberation ofchlorine by moisture or carbon dioxide.Further, when bleachingpowder is triturated with carbon tetrachloride it separates into twopowders differing in their densities and chlorine content. The evolu-tion of chlorine from aqueous solutions of bleaching powder is at-I JletnZlz6~gic, 1906, 3, 147 ; also Quasebert, ibid., 28.2 Hnckspill, Cbntpt. rend., 1906, 143, 227.3 Guntz and Bassett, jun., Bull. SOC. chi?%, 1906, [iii], 35, 404.6 J . SOC. Chem. Ind., 1906, 25, 298.8 J, Rim.Phys. Chem. Soc., 1905, 37, 834,Jaubert, ibid., 142, 788. Zeit. aizorg. Chem., 1906, 48, 137.Zeif. ni7,ptu. Chem,, 1905, 18, 1690INORGANIC CHEMISTlLY. 43tributed t o the hypochlorous acid formed by the hydrolysis ofcalcium h ypochlorite, and the fact that calcium chloride more readilythan other metallic chlorides brings about the following decomposition,Ca(OCl), + CaCI, + 2H,O 2Ca(OK), + 2C12,is considered to depend on the peculiar properties of its compounds withwater of crystallisation.Ammonium syogenite, Ca(NH,),(SO,),,H,O, formed by addingcalcium sulphate to a saturated solution of ammonium sulphate, isstable a t 25" ; observations on the solubility of gypsum in ammoniumsulphate 2 and in magnesium sulphate 3 solutions are recorded.By heating strontium hydride in a vacuum a t 1000°, Guntz andRoederer have obtained strontium as a silver-white metal, whichtarnishes in the air and melts about $00'.It is attacked by waterand alcohol; with carbon dioxide at a red heat it forms the carbonateand carbide. The authors have determined the heat of formation ofSrCl,,Aq and of SrO, and obtain results some 11 Cals. higher than thevalues given by Thomsen. The electrolysis of an aqueous solution ofstrontium chloride using a mercury cathode yields two amalgams, oneliquid and the other crystalline, of the composition SrHgll ; the latter,when heated, gives Sr,Hg, and SrHg6, and on distillation an amalgamdistils over, so that metallic strontium cannot be obtained in thisway. 5The so-called strontium-ammonium decomposes slowly in R vacuiimat 20°, leaving a residue of Sr(NH,),; by the action of carbonmonoxide strontium-ammonium is converted into Sr(C0)2, whichbecomes bright yellow when exposed to the air, and when heatedforms strontia, strontium carbonate and carbon.Oxygen convert8strontium-ammonium into strontia and the peroxide, whilst withnitric oxide i t forms the hyponitrite. Hydrogen, nitrogen, andstrontia.mide are formed by the action of ammonia on the metalat 200°, and at 800" a mixture of nitride and hydride is produced6Barium suboxide is formed by heating the oxide with magnesium ina vacuum at 1100O ; when heated together in the proportion of 3Ba0to Mg an alloy distils over, but if aluminium is substituted formagnesium the distillate consists of metallic barium.7 Bauer * hasobtained a hydrated hydroxide of the formula Ba(OH),,3K,O; strontiumand calcium hydroxides do not form similar compounds.The be-haviour of barium carbonate at high temperatures has been investi-D'Ans, Ber., 1906, 39, 3326.Bell and Taber, J. yhysiknl. C'Jcm., 2906, 10, 119.Cameron and Bell, zbid., 210.Guntz and Roederer, BzdZ. SOC. c h h . , 1906, [iii], 35, 494.Roederer, ibid., 1906, iii, 35, 715.Zeit. anorg. Chem., 1905, 47, 401.Coiiipl. r e d . , 1906, 142, 400.7 Guntz, Compt. rend., 1906, 143, 35944 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.gated independently by Finkelstein and Boeke ; both ficd LeChatelier's statement as to the fusion of barium carbonate to beerroneous ; this compound does not melt at 1350°, but fuses partlywhen heated at 1380' in a st,ream of carbon dioxide, By prolongedheating a t 1120' a basic carbonate is formed which dissolves barytaand a t higher temperatures barium carbonate. Boeke finds thatcalcite is formed from aragonite a t 470°, and that calcium carbonatedoes not melt even when heated to 1400-1500' in an atmcsphere ofcarbon dioxide under pressure.The action of the alkali bromides orbarium Carbonate is observed by Taponier3 to increase nith time,concentrat ion, and temperature, and the following represents the ordarof decreasing activity : ammonium, sodium, and potassium bromides(Amzucd Report, 1905, 45). The solubility of barium sulphate inhydrogen Feroxide solution has been established by Gawalomski.4Neuberg and Neimann record some very interesting observations onthe production of gelatinous modifications of salts of the alkalineearths ; gelatinous barium sulphate, for example, is produced bytreating the solution of barium oxide in methyl alcohol with dilutesnlphuric acid.This jelly can be dried in a vacuum without change,but when boiled with water it becomes crystalline. Gelatinous bariumcarbonate is formed by the action of carbon dioxide in the methyl-alcoholic solution of the oxide, and this, if treated with more carbondioxide, forms a white powder, BaC03,H20, which is soluble in water.A gelatinous sulphide, BaS,H,O, and gelatinous forms of other com-pounds are described. Vanino,6 continuing the study of phosphorescentsulphides referred to in last year's Report, finds that the sulphides ofcalcium and zinc do not emit Recqucrel rays, and further, that whilstcalcium sulphide loses its phosphorescence when suspended in water, itis not so affected by suspension in ether, acetone, ethyl, or amylalcohol.The phosphorescence of these sulphides is shown by Joriseenand Ringer 7 to depend on the presence of traces of salts of bismuthcadmium, and manganese, also of potassium and sodium chlorides, asthe pure sulphides themselves are non-phosphorescent.Glucinum hydroxide, heated alone or with water, or aqueous solutionsof ammonia or alkali carbonate, o r with alkali hydroxides, is graduallyconverted into a form sparingly soluble or insoluble in alkalis orBer., 1906, 39, 1585. Zeit.anorg. Chena., 1906, 50, 244.3 Bull. Soc. chim., 1906, [iii], 35, 280.r, Bioehem. Zeit., 1906, I, 166.7 Chem. Centr., 1906, i, 644.4 Chem. Centr., 1906, ii, 7.J. pr. Chcm., 1906, [ii], 73, 446 ; also Ann. Rerort, 1905, 45INORGANIC CHEmSTRY. 45acids.l The conditions determining the existence of the hexa-, tetra-and di-hydrates of glucinum sulphate, and their solubilities, have beeninvestigated by Levi-Malvano.2 Davis 3 shows that from the solutionof magnesium carbonate in carbon dioxide and water crystals of thecomposition MgCO,,SH,O? separate out when the pressure of thecarbon dioxide is reduced.OH*Mg CO,H, 2 H,O,and its production explained by the equation,This trihydrate is regarded asMg(CO,H), + 3H20 = OH*Mg*C03H,2H,0 + H2C03.When boiled with water,' the trihydrate gives a mixture ofmagnesium hydroxide and the hgdroxycarbonate, formed thus :OH*Mg*C03H,2H20 = OH*Mg*CO,H + 2H,O,OH*Mg*C03H + H,O = Mg(OH), + H,O + CO,.The addition of caustic soda to a solution of the bicarbonate doesnot produce a precipitate until boiled, because in the first instance thedouble salt, Mg(CO,Na), (Deville, 1851, and Repolds, Trans., 1898,73, 262), is formed, which on boiling is decomposed, forming a mixtureof OH*Mg*C03H,2H,0, OH*Mg*CO,H and Mg(OH),, which constitutesmagnesia alba.The first stage in the production of magnesia alba is,therefore, the formation of the double sodium magnesium carbonate,thus :2Na2C03 + MgSO, = Mg(CO,Na), + Na2S0,.The microscopic examination of magnesia alba shows it to be hetero-geneous, as the above explanation would imply.Zinc oxide heated in an electric furnace begins to volatilise a t 11 00'and doesiso rapidly at 1700", the volatilised product exhibits well-defined crystalline structure.Cadmium oxide volatilises appreciablyat 800" and readily at 1000" (Doeltz and Graumann).4Precipihated zinc carbonate precipitates iron, aluminium, anduranium completely from cold solutions of ferric chloride, aluminiumnitrate, and uranyl nitrate ; but chromium is only partially precipitatedfrom chromium nitrate solutions in the cold, and completely onboiling. Precipitated cadmium carbonate gives complete precipita-tions with solutions of ferric chloride and nitrate only?When cadmium is burnt a t a low temperature, the product containssome peroxide (CdO.JGA modification of mercurous chloride, Meyer 7 states, is producedby the reduction of mercuric chloride by lithium sulphite, whichAtti 11.Accad. Lincci, 1905, [v], 14, ii, 502. D.R.-P. 165488.Iiohn, Zeit. unorg. Chew, 1906, 50, 315.3 J. Xoc. Chem. I7ad., 1906, 25, 788.ti Manchot, Ber., 1906, 39, 170.Metallwgie, 1906, 3, 212 and 372.Zeit. niiorg. Chem., 1905, 47, 39946 ANHUAL REPORTS ON THE PROGRESS OF CHEMISTRY.gives the ordinary calomel, in the filtrate from it the new formseparates out in lustrous scales. From the study of the solutions ofmercuric iodide in nitrobenzene, m- and p-nitrotoluene, and cc-nitro-naphthalene, it appears that the yellow modification only exists inthese solutions.1By the interaction of solutions of mercuric chloride and borax twooxychlorides of mercury are formed, one crystallising in brown needlesand the second in lustrous, golden scales.2 By the action of iodine onmercurous sulphate, mercurous iodide, mercuric sulphat'e, and freesulphuric acid are formed.The action with mercuric sulphate doesnot take place so readily; in presence of water in excess the productconsists of mercuric iodide and iodate ; in presence of alcohol, sulphurtrioxide is formed in addition and the alcohol is oxidised toacetaldehyde.3Foote and Levy have investigated the double salts which thechlorides of potassium, rubidium, and sodium form with mercuric~ h l o r i d e .~ Duboin has extended-his investigation j of the compoundsformed by mercuric iodide and the iodides of other metals, and hasdescribed the compounds containing the iodides of calcium, strontium,barium, zinc, cadmium, magnesium, and manganese.6A number of investigations have been published during the yeardealing with ;the alloys containing metals of this group. Sodiumdissolves in magnesium to the extent of 2 per cent., forming an alloymelting a t 638--650°, and magnesium dissolves in sodium to theextent of 1.6 per cent., forming a mixture which has the melting point ofsodium. Zinc and sodium are only partially miscible ; they form a com-pound which is either NaZnll or NaZn12.7 Magnesium appears to formdefinite crystalline compounds of the formulze CdMg, Zn2Alg, Bi,Mg,,and Sb,Mg,.8 The statement of Monkemeyer that the compound ZnSbmelts at 561" is not confirmed by Schemtschuschny,1° who finds thatthe compound breaks up a t 5 3 7 O into Zn,Sb, and Sb, which, on cooling,form a stable system of ZnSb and Sb.Cadmium and copper formthe compounds Cu,Cd and Cu2Cd3.11 The freezing-point curves ofzinc and arsenic do not afford definite information as to whether theseelements f orm compounds or solid solutions.12. The alkali andalkali earth metals, according to McPhail Smith,l3 dissolve in mercuryAtti R. Accad. Jineei, 1906, [v], 15, ii, 192.Zeit. anorg. Chem., 1906, 49, 336.Amer. Chenz. J., 1906, 35, 236.Comnpt. rend., 1906, 142, 40, 395, 573, 887, 1338, and 143, 313.!I Abstr., 1905, ii, 171.3 Briickner, Monatsh., 1906, 27, 341.Ann.Report, 1905, 46.7 Mathewson, Zeit. anorg. Chem., 1906, 48, 191.8 Grube, ibid., 49, 72.lo Chem. Centr., 1906, i, 536.l2 Friedrich aiid Leroux, Metallz~rgie, 1906, 3, 472.l1 SalIinien, Zeit. anorg. Chem., 1906, 49, 301.Amer. Chenz. J., 1906, 36, 124lNORGANIC CHEMISTRY. 41in the form of solutions of compounds of tho formula MHg,,, whilstzinc, cadmium, bismuth, lead, and tin dissolve in mercury and do notform amalgams. The influence of small amounts of lead and ofcadmium on the properties of zinc has been studied by N0vak.lGroup I11 A .The mono-, di-, and penta-borates of potassium, Sodium, andammonium are described by Atterberg,2 also barium monoborate andsesquiborate, 2Ba0,3B20,,7H,0 ; and Dukelski,3 from an investiga-tion of the equilibrium at 30° in the systems (1) caustic potash, boricacid, and water, (2) caustic soda, boric acid, and water, concludes thatsolid borates OF the following composition exist : K20,B20,,2QH,0 ;K,0,2B20,,4H20, K,0,5B,03,8H20, Na20,B203,4H20,Na209B203,8H207Na20,2B20, 10H,O, and Na,0,5B20,, 1 OH,O.Zinc and magnesiumperborates are produced by the action of boric acid and sodiumperoxide or of sodium perborate on zinc or magnesium salts; the zinccompound contains 9.5 per cent. of active oxygen, whilst the mag-nesium compound contains 11.9 per cent.4 Boron sulphide, B,S,, isformed by passing hydrogen sulphide over powdered f erroboron heatedat 300-400°, and condensing the product in a U-tube surrounded byiceas Ouvrard has prepared the chloroborates and bromoborates ofstrontium and barium similar to the calcium compounds mentioned inlast year's Beport (p.46).Silver ultramarine is formed by the action of silver nitrate andwater on ultramarine at 1 10-180° ; attempts t o prepare ultramarinecontaining organic radicles such as ethylene, napht hyl, and triphenyl-methyl have been unsuccessful.7 The blue cdour observed by Knapp inhis investigations of boron glass is due, as pointed out by Hoffmann,8 tothe production of a boron-ultramarine by the action of sulphur on thesulphides present in the materials employed. Blue compounds areformed by heating mixtures of boron trioxide and borax in hydrogensulphide or carbon disulphide.Group 111 B.A crystalline basic aluminium sulphate of the composition,4 0 3 , 2 so,,is manufactured by heating an excess of alumina with sulphuric acidZeit.anorg, Chmz., 1905, 47, 421.Ibicl., 1906,50, 38.Hoffmann, Zeit. nngew. @hem., 1906, 19, 1362.G'ompt. rend., 1906, 142, 281.ChabrG and Levallois, ibid., 1906, 143, 222,Zeit. a?zqew. Chem., 1906, 19, 1089.l b i d . , 1906, 48, 367.D.R.-P. 165278 a i d 16527948 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.(s. g. 1.475) ; the solution after treatment with calcium carbonate orlime is evaporated under reduced pressure.1 Although silicon andaluminium do not combine when heated together, yet in presence ofthe oxide or salt of another metal, compounds of silicon, aluminium, andthe metal, so-called silico-aluminides, are formed. Several such silico-aluminides are described by Vigouroux ; 2 they are metal-like, crystal-line, hard and brittle substances; the majority resist the action ofacids, except hydrofluoric acid, and are not attacked by solutions of thealkali hydroxides.J.Meyer draws attention t o sources of inaccuracy in the determina-tion of the atomic weight of indium in the volatility of the oxide athigh temperatures, and the incomplete decomposition of the nitrateeven a t llOOO.By treatment of an alkaline solution of n thallous salt withhydrogen peroxide a t low temperatures a dark brown, flocculentthallic oxide is formed, and at 80-100' it is produced as a black,heavy, sandy powder.4 The increase in weight observed when thallicoxide is heated over a bunsen burner arises from the formation of amixture of normal and thallous sulphates, produced by the action ofsulphur dioxide derived from the burning gas.5 Thomas6 has de-termined the heats of solution of the tetrahydrates of thallic chlorideand t h rllic bromide, also of the chlorobromides, T1C12Br,4H20 andT1ClBr2,4H20.Thallous chloride unites with chlorine a t the tempera-ture of liquid chlorine to form T12Cl,, and a t the ordinary temperatureTl,CI, is produced.The aluminium alloys which Pkcheux' has shown t o decomposewaters also precipitate cjpper from solutions of copper sulphate.Thallium is only partially miscible with copper at 954"; these metalsform neither chemical compounds nor mixed crystals.Thalliumbehaves in a somewhat similar manner with aluminium ; withantimony it is miscible in all proportions.1° Aluminium and tin donot combine chemically with one another; neither do aluminium andbismuth ; further, the two latter metals are only slightly soluble in oneano t her.llGroup I V A .A discovery of considerable interest and importance is that of anew gaseous oxide of carbon, which Diels and Wolf have found1 Spence, D.R.-P. 167.119.3 &it. anorg. Chem., 1905, 47, 281.7 Ibid., 575.9 Doerinckel, Zeit. anorg. Chew., 1908, 48, 185,Cowapt. rend., 1905, 141, 951.Rabe, ibid., 1906, 48, 427.Compt. rend., 1906, 142, 838.Ann. Report, 1905, 46.11 Gwyer, ibid., 49, 311.l b i d . , 50, 158.Williams, ibid., 50, 127INORGANIC CHEMISTRY.49amongst the products of the decomposition of ethyl mslonate byphosphorus pentoxide at 3 O O O . l Its composition is represented by theformula C,O,; i t is combustible, burning with a blue, smoky flame toform carbon dioxide ; by its reaction with water, ammonia, and hydro-chloric acid, malonic acid, malonamide, and malonyl chloride areformed. To the name, carbon suboxide, proposed by its discoverers,lBerthelot 2 objects, as that name has been already appropriated forcompounds discovered by Brodie in 1873, and examined by Berthelothimself. The constitutional formula 0:C:C:C:O has been assignedto this substance, but Michael3 considers it t o be the lactone ofC /Y P-hydroxypropiolic acid, for which the formula C 0 is suggested.\/The production of lamp black and graphite by the explosive decom-position of acetylene under a pressure of six atmospheres is describedby Frank,4 who points out that the carbon resulting from the explosionof a mixture of acetylene and carbon monoxide or dioxide is entirelyfree from oily matters associated with the carbon obtained fromacetylene alone.The carbon so produced is of higher electrical con-ductivity than ordinary charcoal, and forms a dense black pigment ofhigh covering power. Calcium carbide heated in a current of carbonmonoxide or dioxide yields graphite and lime ; strontium and bariumcarbides behave similarly. Commercial calcium carbide containsgraphite, representing carbon which has been dissolved by the fusedcarbide and separates out as graphite on cooling ; the proportion of dis-solved carbon depends on the intensity of the current used in the manu-facture of the ~ a r b i d e .~ Manville 6 has shown that the temperatures offorniatibn of carbon monoxide and dioxide by the direct union of theelements are influenced by the form of the carbon and the velocity ofthe stream of oxygen. When a given form of carbon has beenrepeatedly heated in a vacuum and cooled, the temperature at which itreacts with oxygen is materially changed.Pring and H ~ t t o n , ~ investigating the action of carbon and hydrogenon one another at temperatures ranging from 10003 to 2800", findthat methane is produced at all temperatures, and that the pro-duction of acetylene begins at 1870' and continues up to 2800'.I nthese experiments the carbon rods were heated electrically and thetemperatures estimated by the Wanner pyrometer. The reduction ofBer., 1906, 39, 689.Ber., 1906, 39, 1915.U a h , Conzpt. mzd., 1906, 143, 49.l'rans., 1906, 89, 1591.Compt. rend., 1906, 142, 533.Zeit. anyew. Chem., 1905, 18, 1733.IDitl., 1906, 142, 1190 xiid 1523.VOL. I". 50 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.water vapour by carbon monoxide, according to Gautier,l takes placea t 1200-1250", and equilibrium is established when the volume ofhydrogen is double that of the carbon monoxide, thus :3CO + 2H,O = 2C0, + 2H, + CO.The reductionof carbon dioxide proceeds a t 1300°, and the conditions of equilibriumare represented by the following equation :I n this reaction traces of formic acid are produced.CO, -I- 3H, = CO + H,O + 2H,.These observations explain the presence in volcdnic gases of carbonmonoxide and dioxide, of water and hydrogen, also of formic acid. Ithas been observed by Farup2 that carbon dioxide and water vapourreact with equal velocity 011 carbon at 850°, whereas oxygen attains thesame rate of reaction at 450'.When the diamond is heated in aporcelain tube in a current of carbon monoxide there is no reaction a t1000°, but a t 1250' carbon is deposited on the porcelain but not on thediamond ; thus the catalytic action of the porcelain is greater than thatof the diamond.A carbide of boron, BGC, is formed when petroleum coke and borontrioxide are heated together in an electric furnace; the carbide, BC,previously described by Muhlhiiuser, is probably a mixture of thecarbide B,C and grayhite.3By heating titanium containing some 2 per cent.of carbon in anelectric furnace with a current of 1000 amperes at 55 volts, Moissan4succeeded in distilling the metal. The distillate consists of minutecrystals and contains some nitride. Iron, chromium, manganese, andtungsten can be distilled in the electric furnace, and from theseexperiments Moissan estimates the temperature oE the sun to benearer 2000-3000° than 6950°, as estimated by W i l ~ o n . ~ Chloroformvapour passed over titanium dioxide heated in a hard glass tube givesthe tetrachloride ; the action is a complex one ; titanium, titaniumdichloride and tricbloride are formed, also a colourless, gaseoushydride, TiH,.Tin tetrachloride but not silicon chloride can beobtained in a similar way.6 Titanium silicide, TiSi,, and the corre-sponding zirconium compound are formed by heating together powderedaluminium, sulphur, fine sand, and either titanic acid or potassiumtitanofluoride, or the corresponding zirconium compounds ; the mixtureis covered with a layer of magnesium powder, and the action startedby a Goldschmidt pastile.7 Valuable observations on the autoxidationConzpt. rend., 1906, 142, 1382.J. Arner. Chetn. XOC., 1906, 28, 605.P ~ o c . Boy. SOC., 1902, 69, 312.Hb'nigschmid, Compt. rend., 1906, 143, 224.Zeit. anorg. Chem., 1906, 50, 276.Compt. rend., 1906, 142, 673.Renz, Ber., 1906, 39, 249INORGANIC CHEMISTRY.51of tervalent titanium compounds have been made by Manchot andKichter.l Titznium trioxide shaken up with caustic potash andoxygen absorbs more than an equivalent of oxygen ; hydrogen peroxideis formed first, and this converts the trioxide into titanium dioxide, orpossibly into pertitanic acid. When baryta is substituted for causticpotash the hydrogen peroxide formed is retained as such.Group I V B.The temperature of formation of crystalline carborundum appears toto be 1950°, and a t 2220' it is decomposed into carbon and silicon.2Amongst the products formed by heating lime and coke together inan electric furnace a silicide of iron, FeSi, and also one of the composi-tion FeSi,, have been obtained ; the iron was derived from the coke.3When solutions of sodium disilicate (Nn,Si,O,) are decomposed byhydrochloric acid so as to form solutions containing 1 per cent.ofsilica, the silicic acid so produced exists in two modifications, an U-and p-form; the former is not precipitated by egg-albumin, and isconverted into the latter by heat. Solutions of silicates of the typesR,SiO,, R,SiO,, and R2Si205 all yield solutions containing the a-silicicacid; solutions of water-glass yield the p-form in addition. Themolecular weight of the a-modification is estimated at 155, whilstaccording to Sabandeff the p-modification has a molecular weight of49000.4 Observations on the melting points of silicates and of the rateof reaction in fused silicates have been published by Doelter ; 5 fusedcomplex silicates form viscous masses from which crystallisation takesplace very slowly; consequently the first to separate out from such afused mass are the simpler silicates.The electrolysis of an aqueous solution of stannous chloride con-taining some hydrochloric acid with two tin anodes on either side of arevolving copper cathode gives a deposit of spongy tin.6 The freezing-point curves of mixtures of t i n and sulphur and of tin and seleniumshow that sulphur and selenium behave alike towards tin, which appearsto form with sulphur SnS, Sn2S3, and SnS,, whilst in the case of telluriumthere is only one break in the curve, which corresponds to the pro-duction of a compound, SnTeS7 The solutions of orthostannic acid insulphuric acid give with like solutions of calcium sulphate cubicalcrystals of the composition Sn(S0,),CaS0,,3H,0.S Similar compoundsRer., 1906, 39, 320 and 488,Tucker and Lampen, J. Amer.Chem, SOC., 1906, 28, 853,Vanzetti, Gazzetla, 1906, 36, i, 498.Mylius and Groschuff, Ber., 1906, 39, 116.Zeit. Elektrochem., 1906, 12, 413, and Moncctsh., 1906, 27, 4%.Tommasi, Compt. Tend., 1906, 142, 86. Pklabon, ibid,, 1906, 142, 1147,* Weinland and Kuhl, Ber., 1906, 39, 2951.E 52 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.are formed with the sulphates of strontium, barium, and lead ; they areregarded as derivatives of a compound, Sn[(SO,H),(OH),]M”, corre -sponding to the orthostannates of Bellucci and Parravano (see AnnualReporis, 1904 and 1905).By using a revolving cathode and low current density, lead can bedeposited as an adherent metallic film from solutions of the acetate.lA yellow and red modification of lead monoxide are described byLead peroxide is formed by the action of chlorine on amixture of magnesia and lead sulphate suspended in water ; the crudeproduct is treated with caustic soda and then with nitric acid.3 Crystal-line lead chromate (crocoite) is gradually deposited on exposing to air asolution of lead chromate in caustic soda ; an alkaline solution of leadmolybdate gives under similar conditions crystals of ~ u l f e n i t e .~ I nthe investigation of the freezing-point curves of mixtures of leadoxide and lead chloride the formation of PbCl,,PbO (matlockite),PbCl2,2Pb0 (mendipite), and of PbC12,4Pb0 is observed ; it has alsobeen noted that mixtures containing less than 88 per cent. of leadoxide may be fused in platinum vessels without attacking the p l a t i n ~ m .~The freezing-point curves of mixtures of galena and lead and themicrographical examination of the fused mixtures afford no evidenceof the existence of Pb,S or Pb,S;G further, in a similar way, leadsulphide and iron sulphide when fused together are shown not tocombine with one another.7 Alloys of lead and arsenic containing upt o 34.4 per cent, of arsenic have been prepared by Friedrich ; s theinvestigation of these alloys affords no evidence of the existence ofthe compounds described by Descamps 9 and Spring.Io Bock l1 has sug-gested that in the Pattinson process for the concentration of silver inlead, the iron of the vessels in which the metals are melted plays animportant part in promoting a separation of the metals.This sug-gestion is shown by Friedrich 12to be unfounded, as the separationis as perfect in porcelain as in iron vessels.Group V A .Erdmann l3 describes an apparatus for the condensation of largequantities of nitrogen, which can now be obtained comaercially pure ;Snowdon, J. Plqsical Chenz., 1906, 10, 500.Zeit. anorg. Chem., 1906, 50, 265.Cesliro, Bull. Acad. Roy. Belg., 1935, 327.Zeit. anorg. Chein., 1906, 49, 365.Friedrich and Leroux, Metallzwgie, 1905, 2, 536.Abstr., 1878, 705.l1 Chem. Zeit., 1905, 29, 1149.l 3 Ber., 1906, 39, 1207.3 Cheni.Centr., 1906, ii, 465.7 Weidmann, ibid., 1906, 3, 660. 8 Ibid., 41.10 I b i d , , 1883, 650.12 JfetnllrrTgic 1906, 3, 396INORGANIC CHEMISTRY. 53dry oxygen is liquefied by cooling with Iiqiiid nitrogen, but not whencooled with liquid air. Ozone dissolves in liquid nitrogen, forming ablue solution. The production of oxidised products of nitrogen hasengaged the attention of many workers. Schmidt and Bockerl findthat when ammonia and air or oxygen are passed over platinum orplatinised asbestos heated to redness, some 75 per cent. of theammonia is oxidised to nitric oxide, which is subsequently convertedinto nitrogen trioxide. The products OF the electrolysis of ammoniain presence of caustic soda are influenced by the nature of the anodeemployed : with platinum electrodes, sodium nitrate, a little nitrite,nitrogen and oxygen are formed; when the anode is either of copper,nickel, iron, or cobalt, sodium nitrite, nitrogen, and oxygen are aloneproduced.2 The formation of nitrite has also been observed to takeplace when a solution of ammonia is electrolysed in presence of acopper salt and an alkali.3'I'he production of alkali nitrites by passing a mixture of air oroxygen and ammonia over heated metallic oxides is the subject of apatented process.With ferric oxide at 700' a continuous current ofnitrous gas is obtained, which is converted into sodium nitrite byabsorption in caustic soda.4 I n discussing the fixation of atmosphericnitrogen, Guye5 points out that, whilst the yield of nitric oxide israised by employing high temperatures, difficulties arise from thedecomposition of this gas at such temperatures.The best effect isobtained when the gases are rapidly swept out of the region of the arc,or where a device is employed by which the arcs are rapidly lighted andinterrupted several times a second, or again by causing the arc to playin different regions of the gases. The gases as they pass out oE thevessels in which they have been submitted to the action of the electricarc contain from 1 to 2 per cent. by volume of nitric oxide, and oncooling to 500' or 600°, nitrogen peroxide and trioxide are formedwhich are absorbed by water. Under the influence of the silentelectric discharge the nitrogen and oxygen of the air in presence ofwater or an alkali combine, forming nitric acid or nitrates, thus :2N, + 50, + 2H20 + Aq = 4HN0, (dil.).Neither nitrous acid nor ammonia is formed; the reaction isindependent of the relative proportions of the two gases, and proceedsuntil the whole of the oxygen is used up (Berthelot).6 The oxidationof nitrogen by the passage of silent electric discharge through air hasalso been investigated by Warburg and Leithauser.7Bcr., 1906, 39, 1366.Miiller and Spitzer, Zeit.Elektrochem., 2905, 11, 917.J. SOC. Chenz. Ind., 1906, 25, 567.Ann. Phpsik., 1906, [iv], 20, 743.Tranbc and Biltz, Ber., 1906, 39, 166. D.R.-P. 168272.Conzpt. rmd., 1906, 142,136754 ANNUAL REPORYS ON THE PROGRESS OP CHEMISTRY.Kuriloff 1 concludes that the compounds of ammonia with metalliccompounds are of three classes : (i) those of constant compositioa, inwhich the proportion of ammonia to the nietallic compound is simple;(ii) those in which the composition is not constant, containing avariable amount of ammonia to one molecule of the metalliccompound; (iii) colloidal class, in which thore is no relationshipbetween the ammonia and the metallic salts.The second class areanalogous to hydrates, and the third class to hydrogels.Raschig 2 describes tt potassium hydroxylamineisodisulphonate(SO,K*NH*O*SO,K), obtained from acid solutions of potassium hydr-oxylaminetrisulphonate, this compound is regarded as a derivative ofthe amide of Caro’s acid, namely, H,N*O*SO,H. Ruff and Stiduber 3 givea full account of their investigation of nitrosyl fluoride referred to inlast year’s Repovt.The chlorides of tin, antimony, and molybdenumreact with nitrogen sulphide dissolved in chloroform, the additivecompounds, SnC1,,2N4S,, SbC15,N4S4, and MoC15,N4S4, being formed ;whereas the chlorides of titanium and tungsten are first reduced andthen the reduced chlorides combine with the sulphide to formTi,CI,,N,S, and WC14,N,S,.4 The action of liquid ammonia on solidnitrogen peroxide is one of great violence, but when moderated bypassing ammonia gas over nitrogen peroxide a t - 20°, the products ofthe interaction are nitrogen, nitric oxide, water, ammonium nitrate, anda trace of nitrite, Nitrogen peroxide reacts slowly with ammoniumchloride in the cold, but a t lOOOin sealed tubes the action is complete andresults in the production of chlorine, nitrogen, nitrogen monoxide andtrioxide, nitrosyl chloride, water, and nitric acid ; ammonium nitrateand sulphate are also attacked by nitrogen p e r ~ x i d e . ~ I n connexionwith the removal of nitrous acid from concentrated nitric orsulphuric acids, Silberrad and Smart find that carbamide, leadperoxide, oxamide, methylamine nitrate, or aminoguanidine nitratereact but slowly with nitrous acid i n presence of these acids, whereasthe action of hydrazine sulphate is very violent.DelBpine7 drawsattention to the possible error involved in the use of platinum wireor foil in the Kjeldahl process arising from the decomposition ofammonium sulphate, due to the following reactions :4H,SO, + Pt = Pt(S04), + 2S0, + 4H20SPt(S0,) + 2(NH,),S04 --- 2N, + 3Pt + 8H2S0,.The formation of nitric acid by the interaction of silver sulphate,ammonium persulpbate, and dilute sulphuric acid is recorded by Kempf .*Ann.CJ~ivz. Phys., 1906, [viii], 7, 568.Zeit. anorg. Chem., 1905, 47, 190, 192.J. SOC. Chem. Ind., 1906, 25, 156.Ber., 1906, 38, 3963.Bey., 1906, 39, 245.Trans., 1906, 89, 1575.Conipt, rend., 1905, 141, 886.rj Besson and Rosset, Comnpt. repid., 1906, 142, 653INORGANIC CHEMISTRY. 55Group V R .A convenient method of preparing phosphoric di-iodide is describedby Doughty.1 The conclusions drawn by Giran2 as to the existenceof various sulphides of phosphorus, based upon the behaviour oncooling of mixtures of these elements, are adversely criticised byBouIouch,S who maintains that the trisulphide does not exist. Stock,*in conjunction with others, has made a study of the action of liquidammonia on phosphorus pentasulphide (see Report, 1905), aninvestigation which has resulted jn the isolation of a numberof phosphorus compounds.The additive product, P2S,,7NH,, is amixture of ammonium iminotrithiophosphate, P(SNH,),:NH, andammonium nitrilodithiophosphabe, P( SNH,),iN. From the former,other salts of iminothiophosphoric acid, for example, SH*P(SNH,),:NH,have been prepared, and by the action of water on it ammonium thio-phosphate, PO(SNH4),,K20, is obtained. When heated at 180° in avacuum, the ammonium iminothiophosphate gives thiophosphoricnitrile, NiP:S, which has also been produced by heating ammouiumnitrilodithiophosphate at 300' in a vacuum.Many other derivativesof these compounds are described in the papers referred to.Phosphorus chloronitride, PCI,N, is the product of the interactionof phosphorus pentachloride and ammonium chloride ; i t is insolublein water, but soluble in light petroleum and several organic solvents,and is dissolved by phosphorus oxychloride, sulphur dioxide, ornitrogen peroxide. A cryoscopic determination gives a molecularweight corresponding to the formula (PCI,N),.5 From the measure-ments of the electrical conductivity, Parravano and Alarini 6 attributeto sodium hypophosphate the formula Na,H,P,O,, whilst Rosenheim,Stadler, and Jacobsohn 7 from their determinations deduced the mole-cular formula NaHPO,.From a mixture of a phosphate and sugaron treatment with siilphuric acid, the phosphorus can be completelyvaporised by heat.8 Hydrogen phosphide is evolved from electrolyticferrosilicon by treatment with water; the fatal cases of poisoningwhich have occurred on boats carrying ferrosilicon and the explosionsin cargoes of this material in Liverpool in 1904 are to be attributedto the hydrogen phosphide formed in this way from ferrosilicon.9The examination of the different methods for producing arsenic andsulphur compounds shows that only realgar and orpiment are produced,and that the pentasulphidc, As2SS, is not forrned.l0 Arsenic penta-J. A m e y . Cham. Soc., 1905, 21, 1444.Ibid., 1045, n~id 143, 41.C ' o ? ~ p f .r e d . , 1906, 142, 398..I &r., 1906, 39, 1967.Bey., 1906, 39, 2857.r, Bessoii a i d Rosset, Cmnpt. md., 1906, 143, 37.fi Atti X. Accad. Lincei, [v], 15, ii, 203.lo Borodowski, Chenz. Cclttr., 1906, ii, 297.Ibztl., 1906, 39, 2625. Zcit. ATnJw. Genzcsmn., 1906, 12, 13256 ANNUAL KEPOKTS ON THE PROGRESS OF CHEMISTRY.fluoride (AsFJ is formed by the action of bromine and antimonypentafluoride on arsenic trifluoride. It is a colourless gas forminga yellow liquid a t - 50' and a white solid at - 80'; when dry, it doesnot attack glass, and when heated with silicon, arsenic and siliconfluoride 1 are produced.A black and a yellow modification of antimony are produced by theaction of oxygen on liquid antimony hydride a t -40' and -90'respectively.2 The selenide (Sb,Se,) and telluride (Sb,Te,) areformed by fusion of antimony with selenium or tellurium ; thesecompounds form liquids when fused with either constituent, a propertyby which cryoscopic constant for antimony has been determined.3ChrBtien 4 maintains that other selenides are formed,and gives 628' asthe melting point of antimony.Antimony sulphate, Sb,(SO,),, with water yields the basic salt,(SbO),SO, ; with alcohol, the compound Sb2O3,2S0, is formed.Withalkali sulphates, double salts of the formula Sb,(SO,),,M',SO, areformed ; the dissolution of antimony or antimony sulphide in sulphuricacid is greatly facilitated by the addition of an alkali sulphate.5 ThisIsst observation is applied in a patented process for the preparation ofantimony oxide from antimony sulphide.6The double compounds BiCl,,BKCI and BiBra,2KBr, also.BiBr,, 2 H Br, 4H,O,are described by hloy and F r e b a ~ l t .~ Gutbier and Bunz,8 investigat-ing the so-called peroxides of bismuth, show that the product formedby the oxidation of bismuth oxide by chlorine in presence of analkali is not a uniform material, nor is that which is formed by theoxidation with alkaline potassium ferricyanide as described by Hauserand Vanino (see Report, 1904) ; further, there is no evidence that theseproducts possess acidic properties.By the electrolytic reduction of vanadyl sulphate, vanadium hydrogensulphate, Vd,(SO,),,H2SO,,12H,O, is formed ; it gives double sulphateswith those of rubidium and amm~nium.~ Rutter lo finds that vanadicacid cnn be reduced electrolytically to vanadous sulphate by using amercury cathode, and when a platinised platinum cathode is used thevanadic acid is reduced to a vanadic salt.Vanadous salts reducesilver bromide to metallic silver, and vanadic salts are oxidised bysilver sulphate, a reaction assisted by copper sulphate, which is, how-l Ruff, Graf, and Heller, Ber., 1906, 39, 67.Stock and Siebert, ibid., 1905, 38, 3837.Pdabon, Conapt. Tend., 1906, 142, 207. Ibid., 1906, 142, 1339 and 1412.Metzl, Zeit. ~tnorg. Chenz., 1906, 48, 140. D.E.-P., 161776.Bdl. SOC. cJiinL., 1906, iii, 35, 346.Zeit. n n o ~ g . Chewz., 1906, 45, 162, 294 ; 49, 432 ; a i d 50, 210.Stihler and VTirthwein, Ber., 1905, 38, 3978.lo .%it.h'lektrochena., 1906, 12, 230lNORGANIC CHEMISTRY. 57ever, not reduced to metallic copper. The production of ammoniumvanadate and sodium uranate from Utah sand, containing carnotite,is described by Ohly.1Double salts of columbium oxychloride and oxybromide of the typesCbOCl,,RCl and CbOC13,2RC1 are formed either by adding the halidesto solutions of columbic acid in hydrochloric or hydrobromic acids, orby adding the halides dissolved in alcohol with hydrogen chloride orbromide t o alcoholic soiutions of the oxychloride o r oxybromide ofcolumbium. Caesium, rubidium, quinoline, and pyridine compoundshave been prepared.?G~ozcp V I A .Many workers have busied themselves with the study of theproblems connected with the conversion of oxygen into ozone, Thus,Fischer and Braehmar have succeeded in demonstrating the formationof ozone and of nitrogen trioxide in the burning of hydrogen, carbonmonoxide, acetylene, sulphur, and charcoal below or a t the surface ofliquid air.Ozone is also formed when platinum heated electrically toa white heat is submerged under liquid air or oxygen. Further, i t hasbeen observed that the production of ozone is favoured by rapid heat-ing followed by rapid cooling, whereas the formation of nitric oxidetakes place more readily when these conditions are reversed.* As to theinfluence of the form of the electrode on the yield of ozone, Warburgand Leithiuser find that for small concentrations (4 grams of ozoneper cubic metre) a highly positively charged sphere is the best, and forhigh concentrations (9 grams per cubic metre) a negatively chargedsphere.Moisture reduces the yield of ozone, whereas a rise intemperature up to 80’ has but little effect on the yield from oxygen,but produces a considerable reduction in the yield of ozone fromair. Chassy 6 has observed that with a given discharge reduction ofpressure lowers the yield of ozone; observations on this subject arealso recorded by Cermak.7 The formation of ozone in the electrolysisof solutions of hydrofluoric acid and of potassium fluoride describedby PrideauxS is easily explained in the light of the properties offluorine.The amount of ozone found by Lespieau9 in the air above theglaciers of Mont Blanc is 4.5 milligrams per 100 kilograms, and isshown to be independent of the altitude.A redetermination of the density of ice made from water speciallyWeiiiland and Storz, Bw., 1906, 39, 3056.Ibid., 2857.C’lzem.Cknlr., 1906, ii, 166.Bw., 1906, 39, 940.F, Ann. Physik., iv, 1906, 20, 734 and 751.Chem. Ccntr., 1906, ii, 585.BulZ. SOC. chim., 1906, [iii], 35, 616.ti Compt. mizd. , 1906, 143, 220.Trans. F’nradny S’oc., 1906, 2, 3458 ANNUAL REPORTS ON TlIE PROGRESS OF CHEMISTRY.freed from gases by boiling gives the value 0.91752, whereas Bunsenfound it t o be 0.9176.1Doring 2 finds that chromium, prepared by the alumino-thermalmethod, containing some 97 per cent. of this element is less readilyattacked by the halogen hydracids than those preparations containinga smaller proportion.Chromium can be electrolytically depositedfrom violet solutions of chroma alum, but not from the green solu-tions.s The deposition of the metal from chromic salts is not neces-sarily preceded by the reduction to a chromous salt. hasextended his investigations of the sulphates of chromium referred toin last year’s Report, and describes a green compound,which is formed by reducing with sulphur dioxide n mixture of 2molecular quantities of chromic acid and 3 molecular quantities ofsulphuric acid dissolved in its own weight of water. A green chloro-sulphate, CrCISO4(5H20),3H,O, and a violet compound,are described by Weinland and Krebs; the latter compound reactswith silver nitrate solutions, whilst the former does not.Bjerrum,Gdoes not agree with the conclusions of Weinland and Krebsas to the constitution of the chlorosulphates of chromium, forwhich in a later communication these authors have adopted differ-ent f o r m u l ~ . ~ It is only possible to refer to the researches ofWerner and his pupils on the complex chromium compounds; thespace at disposal in a Report of this kind does not suffice to dojustice t o the results of these important investigations,* nor t oPfeiffer’s 9 discussion of the isomerism exhibited by complexchromium compounds. That solutions of chromium trioxide containH2Cr,07 and H2Cr0, is supported by ebullioscopic and cryoscopicmeasurements, but no such evidence is forthcoming from electricalconductivity deterrninations.1° From experiments on the oxidisingaction of chromic acid and tho results of the study of the action ofdilute solutions of this substance on potassium iodide and hydro-chloric acid, Seubert and Carstens11 conclude that, as solutions ofchromic acid contain Cr,O,” and CrO,” ions, also undissociated CrO,, itmay be assumed that the reaction is represented as follows : CrO,+H’ + I’ = CrO,I*OH, the complex CrO,I*OH reacting with hydriodicacid to form iodine, water, and a chromic salt.ColsonCr,(OH)2(SO,H),,1 OH@,[CrSO,(6H,0),2H,O]Cl,Lednc, Compt.wmL, 1906, 142, 149.:: Zeit. Elektrochem., 1906, 12, 329.Zeit. anorg. Chem, 1906, 48, 251.7 Zeit. anorg. Chenz.,~,1906, 49, 157.Aznalen, 1906, 346, 28.J. pr. Chcm., 1906, [ii], 73, 393.Compt.?end., 1906, 142, 402.Bcr., 1906, 39, 1547.Ber., 1906, 39, 329, 1823, 2656.lo Costa, Gaxzetta, 1906, 36, i, 535.l1 Zeit. anorg. Chern., 1906, 50, 53INORGANIC CHEMlSTRY. 59Alloys of molybdenum and boron are formed by the reduction ofmolybdenum dioxide heated with boron in magnesia crucibles. Thealloys are non-crystalline, the hardness increasing with the percentageof boron ; the highest proportion of boron found in these alloys being 46per cent. These substances are not attacked by hydrochloric or hydro-fluoric acids or alkalis, but are dissolved by dilute sulphuric andnitric acids, and are acted on by fluorine and chlorine at a red heat.1By heating together molybdenum and manganese at 1500O alloys areformed, and alloys richer i n molybdenum are produced by reducingthe mixed oxides with aluminium pomder.2 These alloys are silverwhite, non-magnetic, hard, brittle solids, consisting of mixtures ofmanganese with one or other of the compounds MnzMo, MnMo, orMnMo2.Sodium silicomolybdate is formed by heating a mixture ofsodium silicate and molybdic acid in the proportion1.2 Moo, : SiO, : 2 Na20,with a little water in sealed tubes a t 150'. From the sodium salt nseries of metallic silicomolybdates have been prepared, which areusually isomorphous with the corresponding silicotungstntes. Thecrystals of potassium silicomolybdates and silicotungstates are optic-ally active; dextro- and hvo-crystals have been obtained; the solu-tions are optically inactive.3It has also been observed by Copaux that the acidSi0,,12Rfo03,2H,0,31H20,and the lithium salt,, SiO,,l2Mo0,,2Li,0,29H,O, form mixed crystals,and, further, that the acid, after the loss of 7H,O, forms mixedcrystals with the barium salt, SiO,,l 2Mo03,2Ba0,22H,0.Theauthor concludes that isomorphism is dependent upon crystalline formrather than chemical composition.The following compounds of iron and molybdenum, Fe,Mo, Fe3M04,FeMo, and FeMo,, have been isolated by Vigouroux from the productof the reduction of the mixed oxides by the Goldschmidt method, alsoby heating a mixture of the finely-divided metals in B stream ofhydrogen.Group VI B.I n the formation of polythionic acids by the interaction of sulphurdioxide and hydrogen sulphide, a hydrate of sulphur, S,,H,O, is formed,and not a new allotropic form of sulphur, as suggested by Debus in 1888(Spring).6 Sulphur heated in sealed tubes at 150-180' with aqueoussolutions of cupric chloride reduces i t to cuprous chloride, and underAi*i*ivant, Coinpt.T e n d . , 1906, 143, 285.Chem. Centr., 1906, i, 1673.Ibitl., 464.Cowpt. mid., 1906, 142, 889 and 928.3 Copaiix, Anu. chinz. phys., 190G, [viii], 7 , 118.fj Xec. t m v . chim., 1906, 25, 25360 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRYsimilar conditions reduces potassium dichromate to chromium sesqui-0xide.lThe variations in the vapour pressures of mixtures of sulphurchloride (S,CI2) and of chlorine, and of the boiling points also,confirm the existence of the dichloride SCl,, a conclusion supportedalso by dilatometric measurements., Briickner 3 finds that whenanhydrous metallic sulphates are heated with sulphur in glass tubesthrough which the vapour of sulphur is passed, complex reactions takeplace, which in the cam of the sulphates of the alkali metals and ofthe alkaline earth metals result in the production of sulphur dioxide,and a mixture of sulphide and thiosulphate of the metal.Magnesium,aluminium, and glucinum sulphate do not react with sulphur at a redheat; chromium sulphate gives a black Cr,S, not attacked by hydro-chloric acid ; the sulphates of other metals yield sulphides and sulphurdioxide.Lunge 4 defends his theory of the lead-chamber process for the manu-facture of sulphuric acid against the criticisms of Raschig, and main-tains that the production of nitrous oxide and nitrogen by the actionof sulphuric acid on nitrogen peroxide does not take place; further,that nitrogen trioxide is not an intermediate step in the conversion ofnitric oxide to nitrogen peroxide.The following equations representthe changes taking place in the production of sulphuric acid.I. SO, + NO, + H20 = SO,NH, (sulphonitronic acid).The sulphonitronic wid is decomposed by oxygen or nitrogen per-oxide, forming nitrosylsulphuric acid (S0,NH).11. BSO,NH, + 0 = H,O + 2S0,NH.111. 2S05NH2 + NO, = H20 + 2S0,NH + NO.The nitrosylsulphuric acid is then decomposed, thus :IV. 2S0,NH + H20 = H,SO, + NO + NO,.V. ZS05NH + SO, + 2H,O = H,SO, + ZSO,NH,.The nitric oxide is finally oxidised to nitrogen tetroxide.Examining the question of the loss of nitrogen in the lead-chamberprocess, Inglis5 finds that the reduction to nitrous oxide is veryslight, and the chief source of loss of nitrogen compounds is theinsufficient absorption in the Gay-Lussac tower.Selenium is found inthe manufacture of sulphuric acid from pyrites containing this elementin the elementary form, as selenious acid and as the compound SeSO,,which dissolving in sulphuric acid imparts a green colour to the acid.Zeit. Yhysik., 1905, 54, 55,Zed. anorg. Clwn., 1906, 19, 807, 857, and 881.AZti 22. Accad. Limei, 1906, [v], 15, i, 703.Alo.i.zntsh., 1006, 27, 49.J. Xoc. Chem. Ind., 1906, 25, 149INORGANIC CHEMISTRY. 61Ten grams of selenium per ton of pyrites is suficient to show itself inthe process; the red sludge collecting in the Glover tower contains2-4 per cent.of selenium. Littmannl concludes that the mainquantity of selenium escaping from the pyrites exists as a labilevolatile compound of a low stage of oxidation, possibly SeO, which isreadily reduced to selenium or oxidised t o selenium dioxide. Seleniumcan be readily detected in sulphuric acid by adding a crystal ofpotassium iodide t o the diluted acid and removing the excess of iodineby sodium thiosulphate ; selenium remains suspended in the solution,imparting to it a red coloration, changing to a lemon-yellow.The most favourable conditions for the electrolytic production ofthiosulphates from sulphite solutions have been investigated byVoghera,g who finds that the cathodic fluid should contain poly-sulphides rather than sulphides, the anode should be platinisedplatinum, the anodic solution a concentrated sulphite, faintly alkaline,and further a low anodic density should be maintained.concludes that Caro's permonosulphuric acid is H,SO,, not PriceOH R2S209, and is represented by the constitutional formulat h a t of perdisulpliuric acid being SO,<o o>SO,.OH HOThe statement that the reaction H,S + ZnC1, ZnS + 2HC1 may bedisplaced towards the right or the left by alteration of the externalconditions has been examined by bringing the solutions into contactwith hydrogen sulphide under a pressure of 14-16 atmospheres.Solutions of several metallic salts which under ordinary conditionsgive no precipitate gave precipitates when under pressure ; whereaswhen the pressure is reduced by cooling the mixtures in solid carbondioxide and ether, in no case did the precipitate dissolve, thus demon-strating that the reaction is not displaced to the left.4Gautier 5 finds that metallic sulphides are atkicked by steam at teni-peratures varying from incipient redness to a white heat; sulphurdioxide, hydrogen, sulphur, and in some cases the metals themselvesare formed.Hydrogen sulphide saturated with ste-tm when passedthrough red-hot tubes gives sulphur dioxide, sulphuric acid, andcolloidal sulphur. The presence of sulphur dioxide i n volcanic gases isregarded by Gautier as due to the action of steam on metallic sulphides.The same authority has also studied the action of hydrdgen sulphide onseveral oxides at high temperatures, showing that ferric oxide yields ironsulphide, alumina an oxysulphide, A1,0,, AI,S,, and silica a compound,Zeit.ungew. Clwn., 1906, 19, 1039.Uruiii and Padoa, Atti R. Accnd. Liilte:i, 1905, [v], 14, ii, 525.Compt. reml., 1906, 142, 1465 and 143, 7.Atti R. Accnd. Littcei, 1906, [v], 15, i, 363. ' TI'UIZS., 1906, 89, 5368 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.SiO,,SiS,, whilst carbon dioxide and hydrogen sulphide passed togetherthrough a white-hot porcelain tube yield steam, hydrogen, carbonmonoxide, sulphur, and carbonyl sulphide. The explanation of thepresence of carbonyl sulphide in volcanic gases and in sulphur springsis to be found in this reaction.For the isolation of selenium from sulphuric acid chamber residuesthe treatment with concentrated sulphuric acid at 50-60°, oxida-tion with solid potassium permanganate, and reduction with sulphurdioxide has been patented by Koch;1 by heating amorphousselenium a metallic, crystalline, grey variety is formed, which exists asa labile and stable modification ; both conduct electricity.2 The reduc-tion of selenious and selenic acids to selenium by organic compoundssuch as formic and oxalic acids, formaldehyde, benzaldehy de, dextrose,and others, has been observed by Oechsner de Coninck and C h a ~ v e n e t .~Oechsner de Coninck has also determined the solubility of seleniumdioxide i n several solvents ; when treated with concentrated sulphuricacid, i t yields SeSO,, hydrogen selenide and some amorphous selenium.Phosphorus pentachloride converts the dioxide into selenium tetra-chloride (SeCl,), whilst phosphorus trichloride gives brown amorphousselenium ; both hydrazine and hydroxylsmine hydrochloride reduceselenium dioxide, the former giving a black amorphous variety andthe latter a red modification, The aqueous solution of the dioxide onexposure to light gives a deposit of selenium, insoluble in carbon di-sulphide.Colloidal solutions of selenium and of sulphur can be obtained byelectrolysing water with a cathode consisting of selenium or sulphurfused on to platinum foil ; the selenium solution is fiery red, that ofsulphur milky-~hite.~ With cathodes of this kind Le Blanc findsthat in the electrolysis of solutions of caustic potash, polysulphides andpolyselenides are formed, but these elements do not dissolve whenemplojed as anodes.Tellurium, however, dissolves both as cathodeand anode, in the first case to form polytellurides, and in the second itdissolves as Te"", the "ions " reacting to form TeO," ions. At thecathode Te" ions and a t the anode Te"" ions, in solutions theequilibrium between these ions is 3Te t 2Te" +Te"". The crystal-lography of the compounds TeBr,Ph2 and SeBr,Ph2, also of therubidium hydrogen selenate and tellurate, shows selenium and telluriumto be isomorphous, a conclusion supported by the study of the solidify-' D.R.-P. 167457.Marc, Ber., 1906, 39, 697 ; also Zeit.anorg. Chent., 1906, 50, 446.Compt. rend., 1906, 142, 571.3 Bull. Acnd. Xoy. Belg., 1906, 67 and 601.5 Miiller and Nowakowski, Ppr., 1905, 38, 3779.ti Zeit. Elektrocheiiz., 1905, 11, 813, and 1906, 12, 619INORGANIC CHEMISTRY. 63ing points of mixtures of these elements in vapging proportions(Pellini).'G~oup 1'11 A.Beyond what has already been referred to in the discussion of the othergroups, there remains to mention Doerinckel's study of the freezing-point curves of mixtures of manganese and silicon, which indicate theexistence of the compounds Mn,Si, MnSi, and MnSi,, conclusionswhich confirm the observations of Lebeau based on the results of theaction of different solvents on alloys of manganese and silicon.Group V l I B.Fluorine dissolves in liquid chlorine, but reacts with chlorine water,producing hydrofluoric and hypochlorous acids (Lebea~).~ D e ~ s s e n , ~continuing the examination of the properties of hydrofluoric acid,referred to in last year's 12epoi.t (p.SU), finds the constant boilingsolution of this compound in water has a boiling point of 111' a t750 mm. and contains 43.2 per cent. of hydrogen fluoride.Attention is drawn by Fabinyi and Forster5 to differences in colour,solubility in water, and reactivity with hydrogen of chlorine pre-pared by allowing sulphuric acid to drop on to a mixture of potassiumdichromate and salt, and of chlorine obtained by adding salt to amixture of potassium dichromate and sulphuric acid. This difference,especially the greater activity of chlorine prepared by the secondmethod, it is suggested, may be explained by assuming the chlorineatoms to be constituted of a different slumber of electrons.Thefunction of the catalyst in the Deacon process for the manufacture ofchlorine appears to be in part catalytic and in some degree chemical,and dependent on the formation of unstable hydrates by the catalyst.GLiquid chlorine can be usefully employed in the preparation of iodinetrichloride by causing it t o react on iodine or metallic iodides; withbromine it forms both the mono- and tri-chloride, according to theproportions employed, Sulphur is not acted on by liquid chlorine, butthe di- and tetra-chlorides of selenium are formed by its action onselenium ; arsenic is converted into the trichloride, but antimony andbismuth are not attacked.Liquid chlorine, further, converts thallousinto thallic chloride, but is without action on carbon disulphide, leadand manganese chlorides, or potassium permanganate. 7From an elaborate and thorough investigation of the interaction ofAtti a. Accccd. Lincei, 1906, [v], 15, i, 629 and 'ill ; ii, 46.Zed. anorg. Chem., 1906, 50, 117.Zeit. nnorg. Chem., 1906, 49, 297.Levi and Voghers, Gnzxetta, 1906, 36, i, 513 ; Ann. Report, 1905, 59.Compt. rend., 1906, 143, 425.Chem. C'entr., 1906, i, 636.7 Thomas and Dopuis, Compt. r e d . , 1906, 143, 28264 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.chlorine and hydrogen Burgess and Chapman 1 conclude that there isno evidence of a photochemical induction with moist chlorine andhydrogen, in the absence of impurities which are capable of destruc-tion under the conditions of experiment.The photochemical inductionnoted by other experimenters is attributed by the authors to thepresence of traces of ammonia or of compounds yielding ammonia. Itis also maintained that there is no sufficient evidence to justify theview that the action of these elements is contributed to by the forma-tion of condensation nuclei. The action of light in causing the unionof chlorine and hydrogen appears to be due to the light absorbed by thechlorine becoming degraded into hest, and in this degradation a formof chemically active energy is produced. A method for the preparationof hydrogen chloride and bromide has been patented by Hoppe ; 2 thismethod depends on the hydrolysis of certain metallic chlorides result-ing in the formation of the hydracid and a basic salt of the metal,which is then converted into the corresponding halide by suspendingit in water and treating it with a mixture of hydrogen and thehalogen (chlorine or bromine) ; thus from the basic zinc chloride thenormal chloride is regenerated in accordance with the equation :2ZnClOH + H, + C1, = 2ZnC1, + 2H,O.Bray has published several papers dealing with the oxyhalagencompounds, and especially with the reactions of chlorine peroxide andchlorous acid.From the study of the oxidation of a n iodide bypotassium permanganate, hypochlorous acid, ozone, hydrogen peroxide,iodic acid, potassium persulphate,4 and arsenic acid, it is concludedthat in all cases of oxidising agents containing oxygen the first productis hypoiodous acid or a hypoiodite, and probably similar compounds areformed in the oxidation of other halogens.The cryoscopic examina-tion of aqueous solutions of chlorine peroxide indicate that thissubstance forms a hydrate, C10,,8H20( +, H20), analogous to chlorinehydrate; like chlorine, it forms n compound with water and carbontetrachloride. I n the reduction of chlorine peroxide a chlorite is aprimary product ; the reaction may be represented thus :2C10, + H,O + C1’ = 2 HCIO, + CIO’,the chlorous acid further decomposing into chloric acid and hydro-chloric acid, also into chlorine and chlorine peroxide, thus :4HC10, = +Cl2 + 3C10, + 2H,O.Tmns., 1906, 89, 1899.D.R.-P. 166598.3 Zeit. physiknl. Chern., 1906, 58, 463, 569, and 731 ; also Zeit. nnoyg. Chem,See also Merk, Cl~zem. Cent?-., 1906, i, 397. 1906, 48, 217INORGANIC CHEMISTRY. 65The study of the reactions of chlorine peroxide shows that in thedark with water it forms chloric acid and hydrochloric acid :6C102 + 3H20 = 5HC10, + HC1.This action is assisted by the presence of chlorine ions and bymetallic platinum, but not by chlorate ions. I n alkaline solutions Bmixture of chlorate and chlorite is formed. Chloric acid and hydro-chloric acid,l when the concentration of chlorine ions is small, reactas follows :C10,’ + C1’ + 2H = C10, + iC1, + H20,whereas with relatively concentrated hydrochloric acid the reactionproceeds thus :HC10, + 5HC1= 3C1, + 3H20.The action of chlorine peroxide on iodides in solutions of alkalihydrogen carbonates saturated with carbon dioxide is :(1) c10, + 1’ = C10,’ + I ;in neutral solutions the following change takes place :3c10, + 51’ = 210, + 31 + 3C1’,whereas in acid solutions the reaction is represented by the equation :C10, + 51‘ + 4H’ = 51 + Cl’ + 2H,O.In all cases the first action results in the production of hypoiodousions, which reacting with iodine and hydrogen ions give free iodineand water, thus :10’ + I’ +2H’ = I, + H20.I n presence of a large proportion of acid, then, reaction (1) is followedby the action of chlorous acid on iodine ions, forming iodic acid andhydrochloric acid :3HC10, + 21’ r= 210,’ + 3HC1.The oxidation of iodine to iodate takes place in the followingreactions :C10, + I + H,O = HIO, + HC15HC10, + 41 + 2H20 = 4HI0, + 5HC1.Brornous acid2 is formed when bromine is added to saturatedsolution of silver nitrate; the formation is probably dependent onthe following reactions : .Br, -I- AgNO, + H,O = AgBr + HNO, + HBrOHBrO + Brp + SAgNO, + H,O = 2AgBr + 2HN0, + HBr02.1 See also Luther and MacDougall, Zeit.physikal. C‘hewi., 1906, 55, 477 ’ Richards, J. SOC. Chem. Ind., 1906, 25, 4.VOL. 1x1. 66 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.For the preparation of aqueous solutions of hydriodic acid, Bodrouxrecommends n convenient method, depending on the action of bariumperoxide on iodine, then removing the excess of iodine by sulphurdioxide, and a t the same time converting the barium into the sulphate,the filtrate from which contains the hydriodic acid, and can be concen-trated in the usual may.The volatility of iron is established by Moissan,2 who has succeededin distilling this and several other metals by heating them in anelectric furnace, and in this manner obtaining crystalline distillates.The metals nearly allied to iron decrease in volatility in the followingorder : manganese, nickel, chromium, iron, uranium, molybdenum, andtungsten.Further, Moissan also finds that the metals indium,osmium, palladium, platinum, rhodium, and ruthenium, when heated incarbon crucibles in an electric arc produced by 500-700 amperes at110 volts, are all fused and boil, giving distillates consisting ofspherules or microscopic crystals, Palladium melts more readily thanplatinum, whilst of these metals osmium is the most difficult todistil.3 In the last Report mention was made of the researches ofDunstan, Jowett, and Goulding on the rusting of iron, of whichphenomenon Moody gives the following explanation. The rusting isdue to the influence of carbon dioxide; neither water nor oxygen freefrom this gas has the slightest effect.A trace of carbon dioxidesuffices to start the action, and freshly formed rust always containssome ferrous carbonate, which is readily attacked by oxygen.Hydrogen peroxide when pure and free from acid has no action onmetallic iron. These conclusions are supported by satisfactory ex-perimental evidence.Treitschke and Tammann record the result oftheir study of the freezing-point curves of mixtures of iron and sulphur ;the microphotographical examination of such mixtures shows thatthe injurious effects of sulphur on iron arise, in mixtures containingabove 2 per cent. of sulphur, from the presence of the fusible sulphidelayered between the particles of iron; the brittleness produced by0.02 per cent. of sulphur is dependent on the properties of themixed crystals, rich in iron. Vigouroux6 has prepared silicides ofiron, cobalt, and nickel by the action at high temperatures of silicontetrachloride on these metals. The compounds so obtained have theformuls Fe,Si, Co,Si, Ni,Si, and Ni,Si; iron silicide is magnetic, theConzpt.rend., 1906, 142, 274. Ibid., 425. Ibid., 189.Tram., 1906, 89, 720. Zeit. anorg. C'henz., 1906, 49, 320.Compt. rend., 1905, 141, 828 ; 1906, 142, 635 and 1270INORGANIC CHEMISTRY. 67otlms are non-magnetic. The interaction of iron and silicon, and ofnickel and silicon, has also been investigated by means of the freezing-point curves of fused mixtures of these elements. Quertler andTammannl conclude from these results that iron and silicon formcompounds of the formulae FcSi and Fe,Si, and that nickel and siliconform five compounds, namely, Ni,Si, Ni,Si, Ni,Si,, Nisi, and Ni,Si,.A ferric hydrogen sulphate, FeH(S0,),,4H20, is produced as a whitecrystalline solid by evaporating a solution of ferric sulphate insulphuric acid., Rubidium and caesinm iron-selenium alums areformed by dissolving ferric hydroxide in selenic acid and treating thesolution with rubidium or cmium carbonate. The formula of therubidium salt is Rb,Fe,(Se04)4,24H~20 ; they both form violet crystalsbelonging to the regular system.3 Crystals of ferric hydroxide,Fe20,,2H,0, and of the oxide Fe203, are formed by acting oncrystalline ferric sulphate with caustic soda ; the crystals arts pseudo-morphous with ferric sulphate.4Several researches are recorded dealing with the commercial alloysof iron ; Hiorns has investigated the influence of varying quantities ofsilicon, phosphorus, manganese, o r sulphur on the formation ofcrystals of cementite, ferrite, or graphite in cast iron.Fettweis 6finds, experimenting with iron phosphide, that increase in theproportion of phosphorus diminishes tho proportion of carbondissolved by iron.Itoozeboom’s theory is shown by Wust * not toapply to iron-carbon alloys containing a large proportion of carbon.When the freezing point of iron has been depressed to 1130’ by theaddition of carbon, further increase in the proportion of carbon hasno effect, and graphite does not separate out from the liquid solution.Microscopic examination of the alloys shows cementite to be formed firston solidification ; it is not stable below 1000°, is metastable below 700’,and does not break up on prolonged heating. The final conditionis ferrite and graphite. The influence of foreign elements on theseparation of graphite from cast iron has been studied by adding aweighed amount of the element to a molten cast iron of known carboncontent, and determining the proportion of graphite to total carbon inthe alloy so produced.Thus tin is found to reduce the solubility ofcarbon and increase the separation of graphite ; iron can, in presenceof an excess of carbon, dissolve 16 per cent. of tin. ulphur reducesthe solubility of carbon in iron, but does not promote its conversionZeit, anorg. Chenz., 1905, 4’7, 163, and 1906, 49, 93.Komar, Chem. .&if., 1906, 30, 15.J. ChmL. SOC. I7d, 1906, 25, 50.3 Roiicngliolo, Gnxzettn, 1905, 35, ii, 553.7 Zeit. physiknl. Chew.., 1900, 34, 437.Ber., 1906, 39, 2270.(j i~fctnlla~rgie, 1906, 3, 60.a Mdalliwgie, 1906, 3, 1.F 68 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.into graphite ; in fact, it neutralises the influence of silicon promotingthe separation of graphite.I n a silicon-free iron, phosphorus in amountsbelow 2.5 per cent. has no effect on the carbon, but above this amountit causes the separation of graphite. I n the presence of 0.9 per cent.of silicon the separation of graphite is produced by 3 per cent. ofphosphorus (Wii&t).l The reduction of mixtures of ferric oxide andtungsten dioxide with aluminium yields homogeneous alloys, fromwhich by treatment with hydrochloric acid the ferrotungsten Fe,W,can be obtained (Vigouroux).2 Steels of lom-carbon content can bealloyed with copper, forming homogeneous alloys which contain amaximum of 32 per cent.of copper, whereas with steels of high-carboncontent alloys containing a maximum of 16 per cent. are formed. Thephysical and mechanical properties of a series of these copper steelshave been examined byNickel and antimony alloy readily, and appear to form four com-pounds, of the following compositions, NiSb, Ni,Sb,, Ni,Sb,, andNi,Sb. The first is the colour of copper, and is hard and brittle ;Ni,Sb, is grey, and although harder than the former is not so brittle.Some of these alloys are magnetic (Loss~w).~The composition of Fischer’s salt (potassium cobaltinitrite) isshown by Riiy to be K6C02(N0,),,,3H20, and its decomposition byheat to be represented by the following equation :CO,(NO,)~,~KE(NO,,~H~O = Co20, + 6N0 + 3EN0, + 3KN0, + 3H20.Continuing his investigations of double chromates, mentioned in lastyear’s Report, Groger has succeeded in preparing from potassiumchromate and cobalt chloride a potassium cobaltous chromate,K,CrO,,CoCrO,, 2H20,which crystallises in dark brown needles, and is hydrolysed by water,forming potassium chromate and a basic cobalt chromate, Thecorresponding sodium and ammonium compounds could not, by reasonof their ready hydrolysis, be obtained. The investigation of the salts ofcobaltammine is still continued by Werner, who with Bindschedler7 showsthat trichlorotriamminecobalt, CoCl,(NH,),, is the first, and trixquo-triamminecobalt chloride, [Co(OH,),(NH,),]CI,, is the last of a series,of which the intermediate members have the compositionand [CoCl(OH,),(NH,),]CI,, and are formed by the action of causticsoda on dichloroaquotriamminecobalt chloride. By the action ofCCOC’ ,(OH,) ( NH,),IClMetallurgie, 1906, 3, 169.Z’mns., 1906, 89, 551.Comnpt. rend., 1906, 142, 1197.Zed. nnorg. Qhcm., 1906, 49, 58.o: Zcit. anorg. Chcrn., 1906, 49, 196.8 B i d . , 1421 ; 143, 346 atid 377.i B e y . , 1906, 39, 2673INORGANIC CHEMISTRY. 69acetic acid and hydrochloric acid on trinitratotriamminecobalt,lthe triaquotriamminecobalt chloride [Co(OH,),(NH,),]CI, is formed.The blackish-brown solution produced by the action of carbonmonoxide on dilute aqueous solutions of palladous chloride (from0.005 t o 0.05 per cent. of palladium) contains colloidal palladium(Donau).2An alloy of platinum and iridium containing 10 per cent. of iridiumis dissolved slowly by hot concentrated sulphuric acid ; the solutionboiled with ammonium sulphate gives a precipitate of spongyplatinum, the filtrate from which has yielded a number of iridiumcompound^.^The observations of Quennessen* show that oxygen takes part inthe dissolution of platinum by sulphuric acid, as there is little or noaction when these are heated together in a vacuum. A doublesulphate of potassium and iridium of the composition Ir(SO,K),,H,Ois obtained in bluish-green crystals by the action of sulphuric acidon potassium iridochloride. The solutions give coloured precipi-tates with many metallic salt solutions (Dele~ine).~Magnus’s green salt is formed by the addition of potassium platinouschloride to platodiammine chloride, Pt(NH3)4C12 ; if potassiumplatinichloride is entirely absent then a red isomeride of thegreen salt is formed; to this the formula P t < ( ~ ~ ~ ] ~ ~ : : > p t isassigned, whilst the green salt is represented by the formulaHydrazine and hydroxylamine platinocyanides are formed by theinteraction of the sulphates of these bases and barium platinocyanide ;they are remarkably fluorescent and exhibit different colours witha1 tered hydration .7Werper and Dinklage 8 describe potassium nitrilobromo-osmonate(OsNBr4)K,2H,0; i t is formed by the action of hydrobromic acid onpotassium osmiamate; and is obtained in dark red prisms, thetreatment of the mother liquors of which with ammonium bromidegives dark brown prisms of the composition [OsNBr,](NH4),,H,0.Rubidium and caesium hydrogen nitrilobromo-osmonat es are alsodescribed.A series of alloys of platinum and silver containing from 10 t o 60Jorgensen, Bey., 1882, 15, 1900.3 Jfonatsh., 1906, 27, 71.DelBpine, Compt. rend., 1906, 142, 631. Ibid., 1841.Ibid., 1525.Jorgensen and Siireosen, Zeit. ccnorg. Chent., 1906, 48, 441.7 Levy and Sisson, Tmns., 1906, 89, 125. BeT., 1906, 39, 49970 ANNUAL REPOKTS ON THE PROGRESS OF CHEMISTRY.per cent. of the former. metal has been prepared by Tbompqon andMiller.1 The action of nitric acid on these alloys is irregular, andit is evident that nitric acid cannot be employed t o effect a separationof gold or iridium from platinum when alloyed with silver.P. PHILLIPS BEDSON.J. Awter. Chcrn. Soc., 1906, 28, 1115

ISSN:0365-6217    

DOI:10.1039/AR9060300030

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

ORGANIC CHEMISTRY-ALIPHATIC DIVISION,ALTHOUGH it cannot be said that, during the past year, any verystriking or exceptional discovery has been made in the chemistry ofthe aliphatic compoiinds, yet a vast amount of important work hasbeen done in this department, and the rosclts obtained certainlymark a steady advance in nearly every direction.From the nature o€ the subject it will be readily understood that;a report dealing with experiments which cover so wide an area mustnecessarily take the form of a series of separate, and oftBen isolated,accounts; any attempt at a continuous method of treatment is, ofcourse, out of the question.The subjects have been considered as far as possible in the usualorder of the various organic families or types, but a strict classifica-tion under these heads is, in many instances, undesirable.Hydrocarbons and Combustion.A new octane, namely, hexamethylethane, (CH,),C*C(CH,),, has beenobtained by Henry1 as a by-product in the preparation of pinacolylalcohol by Grignard's reaction, and also from bromopentamethyl-ethane by the action of magnesium methyl bromide (see page 82).It is a crystalline solid which melts at 103O.Clarke and Shreve found that, during the reduction of methyliso-butylpinacone with hydrogen iodide a small quantity of a hydro-carbon is formed which proves to be a new dodecane, namely, dimethyldi-isobutylethane, (CH,),CH*CH,~CH(CH,)*CH(CH,)~CH;CH(CH,),.It has been shown by Lebeau3 that hydrocarbons of the aliphaticseries may be obtained from their halogen derivatives by means ofthe metalammoniums ; methane, for example, is produced from methylchloride and sodammonium.Chablay has extended these observa-tions, and shows that ethylene may similarly be obtained fromethylene dichloride ; propylene, $-butylene, isobutylene, andtrimethylene result in the same way from their respective bromides.The dichlorides of methylene, ethylidene, and propylidene, on the otherhand, yield the paraffins, methane, ethane, and propane respectively. TheCornpt. rzizd., 1906, 142, 1075.3 Compt. I W L ~ . , 1005, 140, 1042." Anzer. Chenz. J., 1906, 35, 513.Loc. cit., 1906, 142, 937 2 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.same author finds that unsaturated primary alcohols of the aliphaticseries react with metalammoniums to give corresponding unsaturatedhydrocarbons, propylene, for example, being obtained, in quantitativeyield, from ally1 alcohol.A method of preparing olefines is suggested by Mailhe2 whichconsists in decomposing the monohalogen-substituted ptraffins by meansof reduced nickel, cobalt, or copper.The products, halogen-acid andolefine, are afterwards separated by means of caustic alkali. Drychlorides of bivalent metals behave similarly as catalytic agents inbringing about this decomposition ; chlorides of univalent metalsappear to be inactive. From these results the author assumes the forma-tion of intermediate compounds, C,H,,:( MCI)CI, in the former case.The simple hexatriene, CH,:CH*CH:CH*CH:CH,, was obtained byvan Romburgh an? Dxssen (1905) by the action of heat on the di-formslte of s-divinylglycol. Smedley 3 has lately carried out a seriesof investigations with the object of preparing hexstrienes fromaa-dichloropropylene and its homologues ; it is found that when thelatter compound is heated with metallic sodium in petroleum at about80' a small quantity of diallyl is produced, whereas it had been statedby previous observers that these two substances do not interact.Therois produced also a small quantity of a liquid which boils at 80' whichis probably identical with the hexatriene above mentioned.It was shown by Walker in 1893 that sodium o-ethylcamphorate, on electrolysis, yields the ester of an unsaturated acid,subsequently proved to b? an ap-compound (isolauronolic acid).Campboric acid being a derivative of glutaric acid, it follows thatduring electrolysis of the abwe-named salt a methyl group movesfrom one carbon atom and becomes attached to an adjacent one.Potassium glutarate also on electrolysis yields, not trimethylene, butpropylene, the result indicating that here again the migration of anatom of hydrogen must have occur.red.4 It became, therefore, amatter of interest to ascertain the behaviour of P/3-.dimethylglutaricacid since, in this case, such a transference of the hydrogen atom isimpossible, and if an open chain hydrocarbon is produced it must resultfrom the transference of a hydrocarbon group as a whole.Walkerand Wood find that the result in this case is unsymmetrical methyl-et hy let hylene :CH2* C0,Na 7%- FH,*CH,CH, *Y.CH, -+ CH,*Y*CH, -+ E*CH, .CH,*CO,Na CH2- CH2Compt.rend., 1906, 143, 123. Chem. Zeit., 1906, 30, 37.:* Proc., 1906, 22, 158.4 Vanzetti, Atli. R. Accnd. Lineti, 1904 [v], 13, ii, 112.Trnns., 1906, 89, 598ORGANIC CHEMISTRP-ALIPHATIC DIVISION. 73There is therefore a fundamental rearrangement of the carbonnucleus, a four-carbon chain resulting from one of three carbon atoms.H. Jackson and D. Northall-Laurie have studied the change whichtakes place when acetylene is subjected to electrical discharges of highfrequency. It is found that a semi-solid brown substance is producedwhich sets to a hard and very insoluble solid on exposure to air. Ifcare is taken to avoid secondary reactions the composition of theproduct is the same as that of acetylene.This substance, which isapparently a polymeride of acetylene, readily absorbs oxygen up toabout 8 per cent. When heated out of contact with air it yields avolatile oil together with a sinall quantity of methane and hydrogen.The same authors2 have also studied the behaviour of methyl alcoholand of acetaldehyde when their vapours are subjected to high-frequency discharges. They find that, with discharges of very shortduration, methyl alcohol yields carbon monoxide and hydrogen, whilstacetaldehyde gives methane and carbon monoxide together with someacetylene and water. Both these changes are reversible, the lattermore readily than the former. The authors have continued theexperiments, which were initiated by one of them some time ago, on anumber of saturated and unsaturated compounds, and they concludethat in the case of paraffiin derivatives :he general tendency is forunsaturated compounds to give polymeric varieties under the influenceof the discharges, whilst saturated compounds under similar con-ditions yield substances of simpler structure.Experiments on the direct union of carbon and hydrogen have hithertobeen carried out either at temperatures of 1100-1300" or at thetemperature of the electric arc between carbon electrodes in hydrogen.Pring and Hutton 3 have recently made a series of observations on thecourse of the reaction at temperatures from 10003 up to about 2800'.Their results indicate that the proportion of methane formed is muchsmaller than was t o be expected from the results of some formerobservers and that the yield is still lower if the carbon rods have beenpreviously purified by heating to a high temperature in chlorine.Theformation of acetylene is just perceptible at 1700O asd becomes pro-gressively greater with increase of temperature up to about 2500'.Bone and Drugman4 have made extensive experiments on thepropagation of a flame, under ordinary conditions, through mixtures oftypical hydrocarbons with amounts of oxygen insufficient for com-plete combustion; from their results they infer that there is noessential difference between the mechanism of combustion above andbelow the ignition point, both phenomena involving the initial forma-tion of hydroxylated molecules.These conclusions are based chieflyProc., 1906, 22, 155.Tram., 1906, 89, 1591,LOG. cit., 156.LOC. cit., 66074 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY,on the fact that there is a remarkable contrast between thebehaviour of olefines and paraffins when exploded with a proportion ofoxygen represented by the relation C,H,+x/20,, and also on thephenomena associated with the inflammation of a mixture of an olefinewith much less oxygen than is represented in this expression. TheBame authors and Andrew have further investigated the behaviourof mixtures of oxygen with ethane and with ethylene, in the propor-tions C,H,+O, and 3C2H,+20,, in such a manner that some dis-crimination could be made between the various products of combustionaccording as they arise at an earlier or later stage in the flame.Theresults indicate that there is probably no essential difference between‘‘ detonation ” and ‘‘ inflammation ” so far as the result of the initialencounters between individual molecules of hydrocarbon and oxygen isconcerned.The same authors2 have made experiments with the object ofascertaining whether the presence of water vapour has an influence onthe combustion of a hydrocarbon which is at all comparable with thatexerted in the cases of carbon monoxide and of hydrogen. Ethyleneand acetylene were selected for experiment, since it had been previouslyshown that no steam is produced in the initial stages of their slowcombustion. The results were compared when the dried and the un-dried hydrocarbons were heated, under similar conditions, with oxygen,and the authors conclude that the rigid exclusion of moisture, bymeans of the best known methods of desiccation, has little if anyinfluence on the rate of oxidation of a hydrocarbon.Action of Ozone.Drugman3 has made a further study on the oxidation of hydro-carbons by ozone a t low temperatures, and his results show that thereis a radical difference between the behaviour of saturated and un-saturated hydrocarbons. I n the case of saturated hydrocarbons,gradual hydroxylation of one carbon atom takes place ; the alcohol isfirst formed and is then quickly oxidised to the relatively stablealdehyde and more slowly to the acid.Unsaturated hydrocarbons givefirst an ozonide or peroxide, which readily decomposes, yieldingproducts containing a less number of carbon atoms.Ethylene reactsso violently with ozone, even a t very low temperatures, that the initialproduct could not be isolated; in the moist state, the products of thereaction were formaldehyde, formic acid, and hydrogen dioxide. Thechanges are probably t o be represented as follows :Trans., 1906, 89, 1614. L‘ LOC. cit., 652.Loc. cit., 939ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 75C2H,03 + H,O = 2H*CHO + H202.An extensive series of investigations has been carried out duringthe last few years by Harries and his colleagues on the bchaviour ofozone towards various organic compounds, and a valuable summary ofthe work has recently been published by the auth0r.l I n conductingthese experiments the substance t o be examined is usually dissolved indry chloroform and a current of ozoniaed oxygen, mixed with carbondioxide, is passed into the solution at a low temperature.Under theseconditions the danger of explosion is lessened and volatile products areremoved in the current of gases. Amongst the many interestingresults which have been obtained, the behaviour of unsaturated com-pounds is perhaps the most important. Unsaturated hydrocarbons oralcohols which contain an ethylene linking combine with one moleculeof ozone to give ozonides, which are usualiy thick oils or syrups andare often explosive. They behave like peroxides in their power ofliberating iodine from potassium iodide and in bleaching potassiumpermanganate or indigo.By the action of water they are decomposedwith production of aldehydes, ketones, peroxides of these, or hydrogendioxide, disruption of the carbon chain occurring a t the position of theoriginal double linking. The author represents these ozonides as con-taining quadrivalent oxygen, although it is perhaps doubtful whetherthere is here any advantage in making this assumption. On this viewthe typical decomposition may be represented asone of tlie -resulting aldehydes or ketones appearing as a peroxidewhich may yield hydrogen dioxide by action of water. Unsaturatedcompounds containing a carbonyl group, such as ketones, aldehydes, ormonobasic acids, when acted on by ozone in the way above mentioned,are found to combine with four atoms of oxygen instead of three ; inthe resulting '' ozonide-peroxides " the additional atom of oxygen isattached to the carbonyl group.On decomposition by water, the latteroxygen appearj as hydrogen dioxide, the ozonide grouping splitting upin the manner above indicated. As examples of these typical decomposi-tions one may refer in the first case to ozonides of the typewhich by the action OF water give the ketone peroxide andAxlzalen, 1905, 343, 31176 ANNUAL REPOnTS ON THE PROGRESS OF CHERiIS'ITtY.the aldehyde R*CHO, and secondly to the ozonide of mesityl oxide,lwhich yields acetone peroxide, methylglpoxnl, and hydrogen dioxide.The latter decomposition should, in accordance with the author's laterview, be represented as follows :0 C( CH,),OQ&~H-C(CH~):O:O +H20 = (CH,),C<Z + CHO*CO*CH, + H,O,.These typical actions of ozonides not only afford simple methods ofobtaining various aldehydes, ketones, &c., which have hitherto beenunknown or difficult to prepare, but the results may also be applied, inmany cases, to the determination of constitution.I n the light of theevidence obtained from these researches, the author discusses, forexample, the constitution of dialiyl, crotonic and isocrotonic acids,oleic and elaidic acids, benzene, naphthalene, and many othercompounds.The behaviour of Para-caoutchouc towards ozone has already beenreferred to in the last Report (p. 80) ; the diozonide, C,,H,,O,, whichis formed is decomposed by water with prodnction of *lsvulinaldehydeand its peroxide and lawulic acid.Similar experiments have sincebeen made by Harries2 with the hydrocarbon C,,,H,, from guttapercha; the results obtained are quite analogous, except that theozonide gives, on decomposition, a greater proportion of laevulic acid andless aldehyde. The results indicate that the parent hydrocarbons arethe same but that the ozonides are different. This difference, theauthor considers, may be due to stereoisomerism. Representing thehydrocarbon as 1 : 5-dimethylcyclooctadiene the diozonides will havethe constitutionV-?(CH,)*CH,*CH,*$JH-O"0-CH- CH2--CH2--C( CH,)-O ' >o,in which the ozonide or methyl groups can be situated in the cis- ortrans-position with respect to the plane of the ring. I n order t oaccount for the different bebaviour on decomposition, the splitting olone pair of oxygen double linkings in each of the two ozonide group-ings may be supposed to occur either in the adjacent or in the oppositepairs.It has already been shown by the author that oleic acid in chloroformsolution, whenacted on by ozone, combines with four atoms of oxygen,behaving therefore in the normal manner of a n unsaturated compoundcontaining the carbonyl group.This product has been further studiedby Harries and Thieme.3 When washed with water and sodium hydro-gen carbonate it yields the normal ozonide and t'he aqueous solutionCompare Ann. Report, 1905, 74. Ber., 1905, 38, 3985,LOG. cit., 1906, 39, 2844ORGANIC CHEMISTRY-ALIPHATIC DIVISION.77shows strongly marked reactions of hydrogen dioxide.duct is therefore oleic acid ozonide peroxide,The initial pro-CH3*[CH,]7*CH*CH*[CH2]7*C0,H.\/0 3The normal ozonide may also be obtained by ozonising oleic acid in aceticacid solution, diluting with water, and neutralising with sodium hydro-gen carbonate. Both these products on decomposition with wateryield azelaic acid or its semialdehyde and nonylic acid or aldehyde;hydrogen dioxide is produced in both cases, but in much larger propor-tion from the ozonide peroxide.Molinari and Soncini obtain the normal ozonide by action of ozoneon oleic acid itself, without use of a solvent, and also when an aceticacid solution is employed. Under the conditions of their experiments,therefore, only three atoms of oxygen would appear to be taken up byone molecule of the acid.A question of priority also a.rises here, sincethe last-named authors claim to have commenced the study of theaction of ozone on various oils in 1903. Weyl, however,2 points outthat in 1898 he applied for a patent for obtaining disinfecting substanceswhich were prepared by the action of ozone on acids of the oleic series.A study of the decomposition products of oleic acid ozonide has beenmade by Molinari and Soncini with the object of establishing the con-stitution of oleic acid. They show that by the action of alkalis four acidsare obtained, in addition to a neutral substance which was not identified.These four acids prove to be : (1) azelaic acid, CH,(*[CH,],*CO,H), ; (2)normal nonylic acid, CH,*[CH,],*CO,H; (3) a monobasic acid, C,,H,,O,,CH3*[CH217\C/OH and (*) ft which appears to have the constitutionCH,*[CHJ7/ \CO,H’ ~~ O*SH*[CH,]7*C0,HO*CH-[CH,]7*C0,H* dibasic acid, I 1The formation and decomposition of this normal ozonide leaves nodoubt, in the authors’ opinion, that the double linking in oleic acid isbetween the atoms C, and Clo.An interesting general method of obtaining the dihalogen derivativesof paraffins is afforded by the reaction discovered by Braun,4 whichconsists in the action of phosphorus pentachloride or pentabromide oncyclic imino-compounds.Benzoylpiperidine, for example, when actedon by phosphorus pentachloride, yields aedichloropentane and benzo-nitrile, the latter being easily removed by steam distillation, Braunand Beschke have recently shown that pyrrolidine behaves similarly.1 Ber., 1906, 39, 2735.LOC. eit., 3347. Loc. cit.Ann. Keport, 1904, 71. Ber., 1906, 39, 411978 ANNUdL REPORTS ON THE PROGRESS OF CHEMISTRY.When benzoylpyrrolidine is beated with phosphorus pentachloride, thechanges which take place depend somewhat on the conditions, the pro-ducts being either benzo-6-chlorobutylamide, or dichlorobutane andbenzonitrile : [CH,];N*CO*C,H, -+ [CH,],*N*CCi,*C,H, and[CH,~,*N*CCL,*C,H, = CH2Cl[ CH,],*NH*CO *C,H, orCH,Cl[CH,],*Cl+ NC*C,H,By the same type of reaction Braun and Schmitz have obtained di-chloro- and dibromo- octanes from coniine. Benzoylconiine, when heatedwith phosphorus pentachloride, gives in the first instance the ‘ amide-chloride,’ C,H,,*N(Cl,)C,H,, and this, when quickly distilled, breaks upinto dichloro-octane and benzonitrile, as in the previous example,Nef, in 1897, came to the conclusion that certain halogen-substitutionproducts of the hydrocarbon C2H2 must be regarded, not as acetylenecompounds, but as derivatives of acetylidene, H2C: C, containing bi-valent carbon.At first it appeared probable that compounds of bothtypes might exist, such as the mono- and di-substituted acetylenes,RCiCH, RCiCR,and the isomeric acetylidenes, RHCZC, R2C:C. But thisappears not to be the case, since all the known halogen-substituted hydro-carbons corresponding with these formule, such as Behrend’s di-iodo-acetylene, Sabankeff’s monobromoacetylene, and Wallach‘s monochloro-acetylene, are t o be regarded, according to Nef, as acetylidene deriv-atives, The so-called iodoacetylene of Baeyer is stated to be, in reality,di-iodoacetylidene. The monohalogen-derivatives of alk ylated andarylated acetylenes, however, such as CH,*CiCI and C,H,*CiCX, can beisolated ; they prove to be sweet-smelling and ‘ harmless,’ whereas theacetylidene compounds are highly poisonous, sometimes spontaneouslycombustible, and have a disagreeable odour.Lemoult, in 1903, by the action of alcoholic potash on tribromo-ethylene, obtained a compound which he regarded as dibromoacetylene,but which is probably also an acetylidene compound.It is now shownby Lawrie 2 that the latter substance unites with hydrogen iodide togive an addition compound, C,Br,,HI, which is obtained as a heavyoil.When this product isoxidised by nitric acid it yields dibromo-acetic acid and iodine, and when treated with alcoholic sodium phenoxideit gives unsymmetrical phenyl dibromovinyl ether, Br2C:CH*O*C,H,.That the two bromine atoms are here united to the same carbon atomis shown by the fact that nitric acid converts the compound almostquantitatively into isomeric dinitrophenyl dibromoacetates,CHBr,*CO,*C,H,(NO,),,and these by the action of ammonia yield the isomeric dinitrophenolsand dibromoacetamide.From these and other observations the author concludes that the1 Ber., 1906, 39, 4365. Amer. Chem. J., 1906, 36, 487ORGANIC CHEMISTRY-ALIPHATIC DIVISION.79mono- and di-halogen substituted acetylenes are unknown and that itis extremely improbable that such compounds will be isolated.AZcol~oZs, Aldehydes, and Ketones.Henry * proposes to distinguish tertiary from primary and secondaryalcohols by the actions of acetyl chloride ; this reagent converts primaryand secondary alcohols quantitatively into acetic esters, whilst tertiaryalcohols yield the corresponding chlorides. With fuming hydrochloricacid again, tertiary alcohols, except those of high molecular weight, areat once converted into chlorides even in the cold, whereas primary andsecondary alcohols are not esterified unless the mixture is heated. Theauthor is of opinion that tertiary alcohols are to be regarded asalcohols par exceEZence and that in them the true alcoholic function ismost simply represented, since, in their behaviour, they most nearly re-semble metallic hydroxides. The latter react with ncetyl chloride, forexample, to give a metallic chloride and acetic acid, and the difficulty ofpreparing the sodium derivative of trimethylcarbinol is compared tothe inertness of sodium hydroxide to metallic sodium.According to the French patent (360,180) of Jouas and others, thepreparation of ethyl alcohol from acetylene is effected by passingthe gas into a mercuric salt, which causes the precipitation of mercuryacetylide.On boiling the resulting mixture, acetaldehyde is producedand the mercuric salt regenerated. The aldehyde is afterwards reducedto alcohol by sodium amalgam, or it may be used for the preparationof acetic acid by oxidation.prepare pure methyl or ethyl alcohol by actingon a solution of potassium methyl or ethyl sulphate with rather morethan the calculated quantity of pure sulphuric acid, concentratingthe distillate by fractionation and by means of potash, and finallyremoving the last traces of water with filings of metallic calcium.The alcohols so prepared are quite odourless, and are not colouredwhen heated on a water-bath with an equal volume of sulphuric acid.As examples of some of the recent applications of Grignard'sreaction to the preparation of alcohols, the following may be men-tioned, Reif,4 by acting with magnesium ethyl bromide on croton-aldehyde, obtains the unsaturated alcohol AB-hexene-8-01,and, with magnesium prop91 bromide, in a similar way, As-heptene-Klason and NorlinCHa*CH: C EI*CH(OH)*CH,*CH,,8-01, CaH,*CH(OH)* CgHpBull.Acnd. roy. Bely., 1906, 261.a LOC. cit., 537, and Cbmpt. rend., 1906, 142, 129.:; AT-kiz?. Kena. Min. Geol., 1906, 2, No. 24, 1. Btr,, 1906, 39, 160380 ANNUAL REPORTS ON THE PROGRESS OF CHEMlSTBY'.From ethyl chloroacetate and magnesium ethyl bromide Susskindprepares chloromethyldiethylcarbinol, CH,Cl*C(C,H,),*OH, and Paaland Weidenkaff,2 by the action of magnesium phenyl bromide onethyl glycollate, obtain diphenylethylene glycol,(C,H,),*C(OH) CH,*OH.Fournier ?I states that in preparing alkyl bromides by the action ofhydrogen bromide on primary or secondary saturated alcohols, it isnot necessary, as was supposed, to heat the mixture under pressure.The author prepares a regular current of hydrogen bromide bydropping bromine into toluene in contact with iron wire.The gas ispassed into the heated alcohol at a suitably regulated temperature,the excess of hydrogen bromide is afterwards expelled, and theresulting alkyl bromide distilled off. Operating in that way, a yieldof 70 per cent. is obtained.Wohl and Schweitzer have shown that aliphatic dialdehydes, inthe form of their acetals, may be obtained by the electrolytic method,the changes being quite comparable with those which take place inKolbe's well-known synthesis of hydrocarbons. The double acetal ofsuccinic dialdehyde, for example, results from the electrolysis ofpotassium P-di-ethoxypropionate :Potassium diethoxybutyrate similarly yields the double acetal ofadipic dialdehyde, acraldehyde acetal being also produced.Thedialdehydes themselves are obtained by hydrolysis of the acetals withdilute sulphuric acid. Adipic dialdehyde is in ordinary circum-stances very stable, but when heated with water for five hoiirs at1 1 Oo with continued agitation, it yields cyclopentenealdehyde,CH,-YH,CHO*QQQH-CH,.The latter compound was obtained in 1898 by Baeyer and Liebigwhen attempting the preparation of adipic dialdehyde by the actionof lead peroxide on dihydroxysuberic acid.Haehn5 describes a method of preparing ketones by the action ofcalcium carbide on monobasic fatty acids.The dry acids react in thecold with calcium carbide t o produce acetylene; but a t a highertemperature the ketones are obtained :2R*CO,H = R0CO.R + CO, + H,O.Ber., 1906, 39, 225. Loc. cit., 2062.Ber., 1906, 39, 890. 3 Bull. SOC. chim., 1906, [iii], 35, 621.6 LOC. c i t . , 1702ORGANIC CHEMISTRY-ALl PHATIC DIVISION. 81The water produced then reacts with calcium carbide to produceacetylene and calcium hydroxide or oxide. It might, of course, bethought that the change consists simply in the usual decompositionof the calcium salt, but the author considers that such is notthe case, since the products are not necessarily the same. Calciumisovalerate, for example, on heating yields principally valeraldehyde,whereas isovaleric acid and calcium carbide give principally valerone,with only little valeraldehyde.I n a later communication 1 the author suggests that, in the above-rrientionecl change, the acid anhydride is first produced, and is thencatalytically decomposed by fresh calcium carbide into the ketone andcarbon dioxide.It is shown, for example, that acetic anhydride whenheated with the carbide yields acetone, Ketones are produced in thisreaction of acids with calcium carbide a t a much lower temperaturethan by the dry distillation of calcium salts.With the object of ascertaining whether acetone can behave towardscertain reagents as isopropenyl alcohol, CH,*C(OH):CH,, Taylor hasstudied the action of sodium and of magnesium methyl iodide onacetone. It is shown by the author that the so-called eodium-acetoneis a mixture of caustic soda with R small proportion of isopropyloxide ; this result indicates that acetone does not contain any hydrogendirectly replaceable by sodium under the conditions employed. By theaction of Grignard's reagent, a t the ordinary temperature and up to 1 40°,no methane was liberated.I n these cases therefore acetone shows noindications of the behaviour above suggested.The question is discussed by Rothmund3 whether the compoundswhich acetone forms with alkali sulphites, or bisulphites can existin aqueous solution. It has been shown that in alkaline photo-graphic development by quinol or pyrogallol, a mixture of acetone anda sulphite may replace the alkali; also if a solution of a sulphite,made neutral towards phenolphthalein by addition of an acid, is mixedwith acetone, it becomes alkaline towards that indicator.Theseresults indicate that the change should be represented as (CH,),CO+SO, + H,O = C,H60*HS0, + OH, sulphurous acid being approximatelydibasic towards phenolphthalein, acetone-sulphurous acid monobasic andthe latter being a stronger acid. Electric conductivity and cryoscopicmeasurements favour this view.It has been shown by Couturier and Meunier (1905) that acetonereacts with magnesium amalgam to give a compound which probably-- - -has the constitution Mg< 0*(?(CH3)2, and that this is decomposed by0. C(CHJ2Arch. Pharm., 1906, 244, 234. PTOC., 1906, 22, 173.3 Monntsh., 1905, 26, 3545.VOL. 111. 82 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.water with formation of pinacone hydrate.As a method of preparingpinacone, Holleman 1 modifies this process by acting with magnesiumwire on a solution of mercuric chloride in acetone ; the yield is about35 per cent. of the acetone employed.Henry 2 finds that pinacolin reacts with magnesium methyl bromideand yields pentamethylethanol, CMe3*CMe,*OH, which Butlerofforiginally obtained in 1875 by the action of zinc methide on trimethyl-acetyl chloride. This reaction, and the formation of /3-cyano-yy-dimethylbutan-/3-01, CMe,*CMe(OH).CN, by the action of hydrogencyanide on pinacolin, are brought forward as further proofs of theketonic nature of pinacolin.The same author 3 shows that succinic pinacone,OH*CMe,*CH,*CH2*UMe,*OH,is produced by the action of magnesium methyl bromide on ethyl 1m.u-late, COMe*CH,*CH,*CO,Et.Zelinsky in 1902 obtained a compound,which is doubtless identical with this, by action of magnesium methylbromide on acetonylacetone, COMe*CH,*CH,*COMe; the melting pointsgiven by these two authors differ, however, considerably. Thebehaviour of succinic pinacone as a tertiary alcohol is illustrated byits behaviour towards fuming hydrochloric acid or acetyl chloride ;these reagents convert it into the corresponding dichlorodimethyl-hexane, CMe,Cl*CH,*CH,*CMe,Cl.Bouveault and Locquin4 have published a summary of their in-teresting work on the action of sodium on esters of the aliphatic seriesand several new results have also been added.It was shown byBouveault and Blanc in 1903 that esters may be reduced to thealcohol corresponding to ths acid from which the ester is derived byaction of sodium in alcoholic solution. Amy1 acetate, for example,yields ethyl alcohol, methyl butyrate, m-butyl alcohol, and methyloctoate gives m-octyl alcohol. The action may even be applied toesters of unsaturated acids, oleyl alcohol, for instance, being obtainedfrom ethyl oleate.When the dry ester is added slowly to metallic sodium in dry ether,the sodium becomes, after a time, converted into a yellow powder, andthis product when decomposed by water yields a ketone-alcohol of thetype R*CO*CH(OH)*R ; for these compounds the authors suggest thegeneral name “acyloins.” The changes are considered by the authorsto take place as follows :R(ONa)C:C(ONa)R + 2EtONa + 4H,O =ZR*CO,Et + 4Na = R(ONa)C:C(ONa)R + 2EtONa and4NaOH + 2EtOH + R(OH)C:C(OH)R,Bcc.trccz.. chim., 1906, 143, 20.Bull. SOC. cJii)n., 1906, [iii], 35, 629, 636, 637, 641, 643, G46.Compt. m i d . , 1906, 143, 20.8 L O C . c i f . , 496ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 83the latter compound then irnniediately undergoing tautomeric changet o R*CO*CH(OH)*R. A large number of these acyloins have beenprepared and examined by the authors; the formation of the firstmember -methylacetol-has been proved to take place in this generalreaction, but the method is not suitedfor its preparation, owing to thesolubility in water and instability of the substance. When theacyloins are reduced, by means of sodium and alcohol, the productconsists of a mixture of two stereoisomeric modifications of a sym-metric disecondary glycol, R(OH)CH*CH(OH)R, and a secondaryalcohol, CH,R*CRH( OH).These products are readily converted intoketones, R*CO-CH,R, by heating with dilute sulphuric acid and byoxidation respectively, so that a general method is afforded of con-verting acyloins almost quantitatively into ketones of this type.On oxidation the acyloins yield a-diketones ; the usual oxidisingagents are not, however, suitable for this purpose, but the authorsfind 1 that the catalytic method of Sabatier and Seriderens gives goodresults.Diphenylketene, (C6H,),C:C0, was obtained by Staudinger in 1905by the action of zinc on diphenylchloroacetyl chloride.The sameauthor and Klever have now prepared the corresponding dimethylderivative, (CH,),C:CO, by acting with zinc on bromoisobutyrylbromide in ether or ethyl acetate solution. The pure substance is amobile liquid, which is stable a t - ZOO, but readily polymerises at t b eordinary temperature, giving a white substance which appears t o bethe diketone, [(CH,),C:C0I2. With water it gives isobutyric acid,and with aniline and phenylhydrazine it produces the anilide andphenylhydrazide respectively of isobutyric acid, Oxygen converts itinto a white explosive powder, which is perhaps a peroxide,Synthesis and Condensation of Fovnaucklehyde.The much-disputed question as t o the reduction of carbonic acid,directly or indirectly, t o formaldehyde is still receiving much atten-tion.With the object of throwing further light on this question and onthe nature of carbon dioxide assimilation, MT.Lob 4 has made an ex-tensive study of the behavionr of various g;rseous mixtures when theseare submitted to the influence of the silent discharge.5Amongst the many interesting results which were obtained, the fol-lowing may be mentioned.B d l , Xoc. chim., 1906, [iii], 35, 650.Lzer., 1906, 39, 968.Zeit. Elckti*oc?ie?n., 1905, 11, 745, mid 1906, 12, 282.C o i n p ~ c Collie, Aiiii. IL’cpo~l, 1905, 71.a A m . fiepoyt, 1905, 7084 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.It is shown that a mixture of carbon dioxide and water-vapour can,under the influence of the silent discharge, yield formaldehyde, thechanges probably being :(1) 2C0, = 2CO + 0,, (2) CO + H,O =CO, + H,, and (3) CO + H, = H*CHO.The author regards this as the first experimental proof which hasbeen given of the production of formaldehyde as a direct reactionproduct of carbon dioxide.The yield of formaldehyde is increased ifthe oxygen is removed from the sphere of action by means o€ reducingsubstances such as salicylaldehyde, pyrogallol, or chlorophyll. Muchlarger quantities of formaldehyde were obtained when a mixture ofmoist carbon monoxide and hydrogen was employed, and in this casethe author was able to make the important additional observation thatglycollaldehyde is formed as well. It is possible that the glycoll-aldehyde results from the condensation of formaldehyde.' But on thewhole it appears more probable that the initial product is an unstablereactive compound, H,CO, which may perhaps be a tautomeric labi,leform of formaldehyde, such as H-+-OH.It is further shown that methane results, in small quantity, when amixture of carbon monoxide and excess of hydrogen is similarlytreated. Losanitsch and Jovitschitsch have already observed that,under siinilar conditions, a mixture of methane and carbon monoxidegives rise to acetaldehyde, aud although the direct hydrogenisation ofacetaldehyde to ethyl alcohol, under the influence of the silent dis-charge, has not yet been accomplished, the change may fairly beassumed as a step in the natural assimilation process, Finally, it isshown that a mixture of ethyl alcohol, water, and carbon dioxide,when subjected to the action of the discharge, gives, after evapora-tion, a sugar which, from the character of its osazone, appears tobe p-acrose. The latter arises, doubtless, from the condensation ofglycollaldehyde.It will be observed t h a t the final change hererepresent's the converse of that in alcoholic fermentation,BC,H,*OH + 2C0, = C6HI2O6.Glycollaldehyde is obtained when carbon monoxide is substituted forthe dioxide, and also from a mixture of. acetaldehyde and carbonmonoxide. From a general consideration of the results obtained, theauthor is of opinion that the natural synthesis of sugars from carbondioxide may arise in two different directions. The initial unstableproduct above referred to results from the change CO,+H,O=H,CO + 0,.This product may on the one hand undergo polymerisa-Coiiipare Yechmann, Ber., 1897, 30, 2459. LOC. cit., 135ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 55tion into glycollaldehyde and higher sugars; if the velocity of con-densation is great as compared with the tautomeric change toformaldehyde, the latter may not actually be formed at all. On theother hand, the initial product may break up in various directions,giving rise to carbon monoxide, hydrogen, methane, &c., and. from theseacetaldehyde and ethyl alcohol, and finally sugars, may result in tliemanner above indicated.For the qualitative recognition of formaldehyde in the experimentshere described the author employs the reaction of Pilhashy, whichdepends on the yellowish-green colour which is given on addition ofa few drops of phenylhydrazine, a drop of concentrated sulphuric acid,and heating.Glycollaldehyde was identified by its phenylosazone,oxidation to glycollic acid, condensation to tetrose and hexose, andalso by the nitropheny1osazone.lRuss 2 shows that carbon monoxide and hydrogen are produced whenformaldehyde vapour is subjected to the action of the silent dischargeat 150'.Bach, it will be remembered, in 1893 stated that by passing a streamof carbon dioxide through solutions of uranyl acetate which wereexposed to direct sunlight he obtained a violet precipitate which whenexposed became yellow, and was transformed into a mixture of uranousand uranic hydroxides, together with a trace of ft brownish substancewhich he considered t o be uranium peroxide.He proposed to explainthis result by assuming that formaldehyde and percarbonic acid arefirst formed, and that the uranium percarbonate which results thenundergoes decomposition into uranium peroxide and carbon dioxide.I n a later experiment he substituted a salt of dimethylaniline for theuranium acet .tte, and considered that the production of formaldehydewas confirmed by the formation of tetramethyldiaminophenylmethane(Trillat's test). Euler in 1904 repeated these experiments, and statedthat a similar precipitate is obtained from the uranyl acetate solutionwhen a current of hydrogen or nitrogen is substituted for carbondioxide, and also that in the experiment with dimethylaniline noreaction is obtained if the reagent is carefully purified.The currentof gas, in the experiments with uranium,"appears only to be instru-mental i n removing oxygen.state that they have confirmed Bach's (earlier)results, but that the decomposition is extremely small even after threeweeks' exposure. They also made similar experiments with liquefiedcarbon dioxide and uranium acetate solution in sealed tubes. I n thiscase they obtained formic acid and a violet precipitate apparently con-Bach3 has since confirmed this view,Usher and Priestley1 Wohl and Neuberg, Rw., 1900, 33, 3107.2 Zeit. Elektrochewi., 1906, 12, 412.4 Proc. Aoy. SOC., 1906, 77, 369, and 78, 318.Be?.., 1906, 39, 167286 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.taining uranium peroxide, but no formaldehyde.Since there areobvious objections to using an organic substance as sensitiser, theyrepeated the experiments, substituting uranyl sulphate for the acetate.The results obtained in this case were similar ; no formaldehyde wasdetected, but after evaporation of the solution and separation of theformic acid a brown syrup was obtained, which had a bitter taste andreduced Fehling’s solution. A similar product was obtained by allowinga solution of formaldehyde to stand for some time in presence of uranichydroxide. The authors consider that this product resembles Butleroff’smethylenitan ; it does not, however, react with pheny1hydrazine.lFrom these results, and from other observations, the authors con-clude that formaldehyde is produced as a transitory intermediate pro-duct.The action of chlorophyll as serisitiser was also investigated :glass plates which had bean coated with gelatine and painted with asolution of chlorophyll in light petroleum, or other solvent, were placedin a bell-jar containing moist carbon dioxide, and exposed to light. Thechlorophyll became bleached, and the gelatin aft,erwards gave a pinkcolour with Schiff’s reagent. An aqueous solution of this exposedgelatin gave, on distillation, indications of formaldehyde by the testsmentioned below. The remaining observations deal principally withthe problem of carbon assimilation i n green plants, and will be con-sidered elsewhere.With reference to the disputed question as to theactual detection of free formaldehyde in the living plant, the authorsconsider that it is useless to look for the aldehyde in healthy assimi-lating leaves, since it there undergoes immediate condensation underthe influence OF protoplasm. Bat after killing the protoplasm, anddestroying enzymes, by immersion in boiling water, leaves which wereexposed to sunlight in water saturated with carbon dioxide gave, whensubjected to steam distillation, a solution containing formaldehyde.For the identification of formaldehyde in these experiments theauthors rely principally on the methylene-aniline test, and also on theformation of hexamethylenetetramine, which they identify by treat-ment with bromine,z but details of this are not given.I n connexion with the foregoing statements it would be well torefer to the criticisms of Euler 3 on the very similar experiments ofPolacci, who in 1899 stated that he obtained a distillate containingformaldehyde from leaves which had been exposed to sunlight andextracted with water.H.and A. Euler have continued their studies on the behaviourof formaldehyde towards various bases.* As previously stated,5Compare Loew, J. pr. Chem., 1888, 37, 205 ; and Fischer, Be?.., 1886, 21, 991.Legler, Bcr., 1885, 18, 3343, and Horton, ibid., 1888, 21, 1999.Ber., 1904, 37, 3412.Aim. Report, 1905, 74.LOC. cit., 1906, 39, 36 and 39ORGANIC CHEMISTRY-ALlPHATIC DIVMION 57the action takes place in two directions, the condensation tosugars and the production of formates and methyl alcohoI.It wasshown that the power of different bases in bringing about the con-densation does not stand in any simple relation to the rate a t whichformates are produced. Sugar condensation does not appear to beginuntil a part of the aldehyde has been changed to formate and methylalcohol ; on the other hand, the concentration at which sugar formationcommences is not influenced by the amount of formate present.Reasons are given for considering that the production of formate ispreceded by the formation of a metallic “salt ” of formaldehyde,or ‘‘ formolate ” as the authors term it. From cryoscopic determina-tions with mixtures of soda and formaldehyde it is calculated that thedissociation constant of formaldehyde, behaving as an acid, isI n making estimates of the nature and quantity of the sugars pro-duced by condensation it is evident, as the authors point out, thatstrong alkalis are objectionable as condensing agents, since they tend todestroy or modify the products in question.Advantage is thereforetaken of the observation that the condensation of formaldehyde may bebrought about by means of calcium carbonate; although the action ofthis reagent is slow, it has the advantage that the change is effected inpractically a neutral solution, and the formate production appears totake place to a less extent.By heating a litre of 2 per cent. formaldehyde with 10 grams ofcalcium carbonate for several hours, precipitating the calcium salts withalcohol and ether and distilling the remaining solution, a syrup was leftfrom which, by the action of phenylhydrazine acetate, a yield of osazonew t ~ s obtained corresponding to 60-80 per cent. of the formaldehydeemployed.The crude mixture of osazones so obtained yielded, afterpurification with benzene, a definite yellow crystalline product whichmelted at 166O and had the composition of a pentosuxone. The existenceof a, pentose in the crude condensation product from formaldehyde wasindicated in one of the analyses given by Fischer in 1888. Neubergalso, in 1902, obtained a phenyl methyl osazone from crude formosewhich melted a t 1 3’i0 and corresponded in composition to a pentosazone ;this was considered by the author to be derived from a keto-pentose.The pentose obtained in the present case might be either arabinose orribose ; the latter appears, however, to be excluded by the fact that onreduction of the original syrup with sodium amalgam no adonite couldbe obtained.By oxidation of the syrup with bromine, or nitric a.cid, aconsiderable quantity of trihydroxybutyric acid was produced ; fromthese results, anci from the behaviour of the syrup with resorcinol andwith phenylmethylhydrazine, the authors conclude that the principalcondensation product of formaldehyde, under the above-mentioned con-1.4 x 10-1488 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.ditions, is i-arabinoketose. From the part of the crude osazone whichis more soluble in benzene a Aexosazone melting at 140-142O wasobtained.If the condensation is interrupted when about half the formaldehydehas disappeared, and the unaltered formaldehyde is then removed bymeans of pdihydrazinodipheny1,l the remaining solution gives, withphenylhydruzine acetate, a resinous oil from which, by treatment witha mixture of pyridine and light petroleum, a crystalline osazone melt-ing at lSOo was obtained.This product corresponds in compositionand properties to the osazone of glycollaldehyde. I n the process of puri-fying this osazone by means of pyridine and light petroleum, a sub-stance was deposited from the solution, after some weeks, in the form ofcolourless scales melting at about 162'; the composition of this pro-duct corresponds with that of the hitherto unknown glycollaldehydehydrazone.I n addition to the above-named substances, the presence ofdihydroxyacetone was indicated by means of phenylmethylhydrazine ;glyceraldehyde appeared t o be absent.I n reference to the experiments which are here described,Loew points out that in 1888 he succeeded in bringing about the con-densation of formaldehyde by means of metallic tin containing somelead, SO that the change here occurred in a wholly neutral solution.Heconsiders that tho result obtained by Euler with calcium carbonate wasdue to the initial production of some calcium formate, since he hasalready shown that the acetates of calcium, lead, or magnesium can act,although slowly, as condensing agents in this way.That formaldehyde may arise as a degradation-product of sugar isconfirmed by the recent experiments of Trillat.3 When sucrose isheated to loo", or higher temperatures, formaldehyde is produced, thequantities obtained varying from 0.2 to 5.7 per cent.The larger amountsare obtained if the sugar is heated in contact with copper foil, Thepresence of air is not necessary, although the yield is smaller when airis excluded. Benzaldehyde, acetone, methyl alcohol, acetic acid, acet-aldehyde, and phenol derivatives are also produced. Formaldehyde isfound not only in the evolved gases, but also in the residual caramel, afact which perhaps accounts for the antiseptic properties of caramel. Itwould appear that a portion of the formaldehyde polymerises and formsprodiicts analogous t o methylenitan, and caramel itself may perhaps bethe result of such changes.The caramel-like properties of the productsobtained by heating formaldehyde with alkalis are well known.Neuberg, Ber., 1899, 32, 1961. Loa. cit., 1906, 39, 1592.3 Zcit. Vcr. Iliibcnozck-lnd., 1906, 95 ; and Compt. rend., 1906, 142, 454ORGANIC CHEMISTRY-ALIPHATLC DIVISION. 89Carbohydrates.Apiose is the name given by Vongerichten (1900) to a new pentosewhich is contained, as a disaccharide with a-glucose, in the glucosideapiin found in parsley seeds. The same author and Mullerl now showthat the sugar exists also in the green parts of parsley as well as in theseeds. This pentose, when oxidised with bromine or nitric acid, yieldsthe monobasic apionic acid, and, when further oxidised with nitric acida dibasic acid is produced which is isomeric with trihydroxyglu taricacid ; the relationships of the latter indicate that it is hydroxymethyl-tartaric acid :[ CH,OH] , : C (OH) CH (OH) C HO-+[ C H,OH] : C: ( 0 H) C H( 0 H) C0,HJVith phenyl benzyl hydrazine apiose yields a colourless crystallinehydrazone, from which the sugar may be recovered unchanged by meansof formaldehyde.Rhodeose is a methylpentose discovered by Votocek in 1900, and isobtained by hydrolysirig convolvulin with dilute sulphuric acid ; theglucose which is also present can be removed by fermentation, sincerhodeose is non-fermentable.This sugar has been further studied byVotoEek and Bulir.2 It is shown that on reduction by means of sodiumamalgam it yields a corresponding polyhydric alcohol-rhodeitol-which was obtained in white crystalline plates.This substance is notoxidised by the sorbose bacterium, and it therefore follows thatits configuration must be represented by the formulaOH B OH*CH2- $I - F-[CH*OH],*CH,,H OHor its image.3 A similar configuration must apply to rhodeose. Whenrhodeose and its optical antipode fucose are mixed in equal proportionsand reduced by sodium amalgam the racemic form of the polyhydricalcohol (1.-rhodeitol or T-f ucitol) is obtained.The trisaccharide melezitose, or melezitriose, has hitherto beenregarded as containing three dextrose residues, yielding, it was thought,three molecules of this sugar on hydrolysis. Tanret4 now shows thatwhen heated with 20 per cent.acetic acid melezitose yields a mixture ofdextrose and turanose; C12Hz20,,. The latter can be obtained, afterremoval of the dextrose by fermentation, in the form of hygroscopic,non-crystalline granules containing alcohol, which may be purified byBw., 1906, 39, 235. Zeit. Zzsckerind. Bohm, 1906, 30, 333.3 Compare Bertrand, A m . Report, 1904, 64. Compt. rend., 1906, 142, 142490 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.heating to 100’. Turanose is readily hydrolysed by mineral acids, andyields a mixture of equal parts of dextrose and lmwlose.According to Ofner,] phenylethylhydrazine reacts with glucose inneutral solution to give the hydrazone, but iu acetic acid solution ityields the corresponding osazone ; the change takes place more readilythan with phenylmethylhydrazine, and the yield is about 60 per cent.Fructose gives about the same yield.This behaviour of glucose affordsa further proof that unsymmetrica 1 secondary hydrazines are able togive rise to osazones with aldoses as well as with ketoses.2Blaquenne found that reducing sugars, when treated in a uniform waywith phenylhydrazine, showed considerable differences both in the yieldof osazone and in the time required for precipitation; upon thesedifferences nlulliken has since based a scheme for the identification ofcertain pure sugars. Sherman and Williams have now made furtherexperiments in this direction, especially with regard to the influence ofdilution and of the presence of other sugar$.I n the case of glucoseand fructose the time required for precipitation varies with the con-centration, and is nearly constant for a given dilution, but withfructose the time is about one-third of that required with glucose.Prom invert sugnr the osazone is precipitated almost as quickly as fromfructose. I n solutions containing about 0.1 per cent. of glucose theprecipitation is considerably accelerated by the presence of 1 per cent.,or more, of sucrose, but only slightly by 5 per cent. of raffinose. Thepresence of maltose or of lactose exerts a retarding influence on theprecipitation of glucosazone.It would appear that no direct method has hitherto been devised forthe addition of hydrocarbon residues to the carbon chain in pentoses orhexoses, and with this object in view Paal and Hornstein 4 havestudied the behaviour of Grignard’s reagent towards derivatives ofglucose such as the penta-acetate and the bromoacetyl derivatives.Thelatter compounds, however, show but little tendency to react, probablybecause the aldehydic oxygen of the original glucose is now (‘ ether-linked.” But it appeared that the desired result might be attained byemploying the lactones of the corresponding monobasic acids producedby oxidation of the aldose sugars ; Houben (1904) has, in fact, alreadyshown that tertiary alcohols are obtained by action of Grignard’sreagent on lactones. The lnctone of d-gluconic acid is not itself suitablefor this purpose, since it is not soluble in ether or other solvent appro-priate to Grignard’s reaction, but by acting on d-gluconic acid withacetic anhydride a product is obtained which dissolves easily in amixture of ether and benzene.This product, probably a tetra-aceto-lactone, was not isolated in a pure condition, but was acted on byMonntsh., 1906, 27, 75. Coniliare Ann. &port, 1904, 65.Ber., 1906, 39, 1361. 3 J. Amer. Chcni. SOC., 1906, 28, 630ORGANlC CHEMISTRY-ALIPHATIC DIVISION. 91magnesium phenyl bromide in excess. After decomposition of theresulting products with dilute sulphuric acid the authors obtained, inaddition to diphenylmethylcarbinol, a substance which crystallised inwhite needles ; this product is shown to be a hexahydroxydiphenyl-hexane or diphenylhexitol. From the mode of formation it wouldappear that the configuration of the latter substance is to be repre-sented by the formula,OH H OH OHI I I IOH*CPh,*C -I: -C-C* CH,*OH,I I I I H O H H Hassuming, of course, as is probable, that no steric rearrangement hasoccurred in the above-rn-entioned changes.The new compound is there-fore to be regarded as 1 : 1-diphenyl-d-sorbitol.I n a later communication1 the authors state that they have isolatedthe lactone of tetra-acetyl-d-gluconic acid as a gummy mass. Theyhare also somewhat modified the details in the preparation of diphenyl-d-sorbitol so as to improve the yield.Paal and Weidenkaff have since made a similar synthesis from thelactone of tetra-acetylgalactonic acid, and have obtained in this wayanother diphenylhexitol. Since the steric configuration of this pro-duct is somewhat uncertain, the authors provisionally name it1 : 1 - diphenyl-d-gdactohexitol.LIditol,H OH H OHI I I I OH*CH,*C--C-C--C*CH,*OH,I I I I OH H OH Hwas obtained as a syrup by Fischer and Fay in 1895 from xylose bytreatment with hydrocyanic acid and reduction of the resultingI-idonic acid or its lactone with sodium amalgam.Bertrand andLanzenberg 3 have now succeeded, by a modification of this method, inobtaining the pure substance in a crystalline state.A paper of considerable interest has been published by Schade4 inwhich an acl,ount is given of a series of investigations on the behaviourof sugar solutions towards alkalis. From the results obtained theauthor was led to believe that it was possible, in a purely chemicalway, and without the use of enzymes, to transform dextrose orlzevulose quantitatively into ethyl alcohol and carbon dioxide.It hasbeen previously shown by Framm, in 1896, that the yellow or browncolouring which is usually observed during the action of alkalis on-I Zeit. ph.ysika1. Chem., 1906, 57, 1,Ber., 1906, 39, 2823. LOC. cit., 2827.8 Compt. rend., 1906, 143, 29192 ANNUAL REPORTS ON THE PROGRESS O F CHEMISlRY.sugar solutions may be prevented altogether if a current of air ispassed through the mixture. Schade finds that a similar result maybe obtained by operating under reduced pressure or by the addition ofhydrogen dioxide. The final products obtained when the first methodsare employed appeared t o be formic acid and acetaldehyde, the latterbeing indicated in the distillate. When hydrogen dioxide was addedthe products were formic acid and acetic acid. The yellow or browncolouring appeared therefore t o be due to aldehyde-resin, resulting fromthe decomposition of acetaldehyde; if the latter was removed, asvapour or by oxidation, the solution remained clear.This view seemedto be supported by the observation that the colouring could alsobe prevented by the addition of substances which combine with acet-aldehyde, such as ammonia, bisulphites, or cyanides. Estimation of theformic acid and acetaldehyde (the latter as acetic acid in the hydrogendioxide experiment) appeared to indicate that the reaction of alkalison dextrose or lsvulose is to be represented quantitatively by therelationC,H,,06 = 2H*CO,H + 2CH,*CHO.The question then suggested itself whether i t might not be possible tobring about a further reaction betweer, these products in such amanner as to transform them into ethyl alcohol and carbon dioxide.Deville and Debray in 1874 showed that formic acid under thecatalytic influence of rhodium-black is resolved into carbon dioxide andhydrogen ; the latter then, ‘‘ in the nascent state,” might react withacetaldehyde, converting it into ethyl alcohol.This idea was successfullycarried into effect by the author. A 5 per cent. solution of sodiumformate, made faintly acid with acetic acid, was warmed to 60° in con-tact with a small quantity of rhodium-black (colloidal rhodium, pre-pared by Bredig’s method, was found to be ineffective), and thecalculated quantity of acetaldehyde, in the form of vapour, was passedgradually into the mixture; in this way a yield of 60-70 per cent.ofethyl alcohol was obtained after three hours. From these results t.heauthor concluded that the resolution of sugar into alcohol and carbondioxide is a spontaneous process which is accelerated by catalysts. Manyanalogies are pointed out between these purely chemical operations andordinary fermentation. The final products are reached in the one caseby the agency of two different catnlysts, namely, hydroxyl ions andrhodium ; in the other case by zymase. I n both cases the reactionvelocity is proportional to the mass of the catalyst or of the enzyme;the changes take place in absence of oxygen and are influenced by thepresence of minute traces of foreign substances, by concentration ofthe solution and by the accumulation of the reaction-products.As inyeast fermentation there appears to be, in the purely chemical processORGANIC CHEMISTRY-ALIPHATIC DIVISION. 98an '' optimum " temperature which, in the latter case, lies between40° and 80'.It is disappointing to learn from a subsequent communication byBuchner, Meisenheimer and Schade 1 t h a t , on repeating certain ofSchade's experiments, they have obtained entirely different results, andthat the conclusions arrived at by this author can no longer be main-tained. The volatile aldehydic substance which was regarded as acet-aldehyde appears to have been furfuraldehyde, and is only produced insmall quantity.The yield of formic acid is greater than that abovestated, and, in addition, there is formed trihydroxybutyric acid, glpcollicacid, and probably a mixture of hexonic acids, &c. The authors considerthat formic acid is not a primary product in this decomposition, but thatglyceraldehyde is first formed; this under normal conditions would betransformed into methylglyoxal and so into lactic acid; but in thepresent case it might split up into three molecules of formaldehyde,which would then be oxidised by the hydrogen dioxide as shown byBlank and Finkenbeiner.2 The yellow or brown colouring abovereferred to is caused, the authors consider, by some non-volatile andeasily oxidisable hydroxyaldehyde, possibly glyceraldehyde.Purdie and Young3 find that when methylrhamnoside is completelymethylated by means of silver oxide and methyl iodide it yieldstrimethylrhamnoside, which, on hydrolysis, gives trime thylrhamnose.Dimethylrhamnose is similarly obtained from acetonerhamnoside.Yimethyl- and trimethyl-rhamnose display the ordinary properties ofreducing sugars and give crystalline phenylhydrazones.Trimethyl arabinose is obtained in a similar way from Fischer'sa-meth~larabinoside.~Irvine and Moody 5 shorn that when solutions of the equilibriummixture of tetramethyl glucose in ordinary organic solvents are cooledfrom + 20' to - 20°, the specific rotations undergo very little alteration,and, on again heating to the initial temperature, the original valuesare exactly obtained.When, however, an alkyl iodide is used assolvent the specific rotation at first slightly increases and then rapidlydiminishes, as the solution is cooled: On reheating to 20° distinctdownward mutarotation mas observed before the initial value wasreached. The same regularities were shown by solutions of molecularproportions of the sugar and alkyl halide or hydrogen chloride in carbontetrachloride. The authors consider that these results point to theformation of oxonium compounds of the sugar with alkyl halides, andthe a-form of the aldose appears t o be more reactive than the/3-isomeride. Tetramethyl a-methylglucoside also behaves abnormallyBer., 1906, 39, 4217.Truns., 1906, 89, 1194.LOG.cit.,1898, 31, 2979.Purdie and Rose, loc. cit., 1204.LOC. cit., 157894 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.when cooled in ethyl iodide solution, but the P-isomeride shows noindication oE combining with the solvent.Amongst other papers which have been published in connexion withthe chemistry of sugars, attention should be drawn to the work ofGaldwell1 on the siicroclastic action of acids, in which the author dis-cusses the important question of '' weight-normal ') versus '' volume-normal " solutions ; also a paper by Rosaxioff,2 which contains acriticism of Fisaher's d and l classification of stereoisomerides andsuggests a revised nomenclature which will include also the poly-hexor?es, These papers will be more appropriately referred to in thesections on physical chemistry and stereochemistry.The highest product of the acetylation of cellulose was a t one timeconsidered t o be a tetra-acetate, C,H,O(OAc),.The existence of sucha derivative would not be in accord with the constitutional formulaproposed- by A. G. Green, which in other respects gives a very completeindication of the chemical relationships of cellulose.3 This authorand A. G. Perkin have reinvestigated this supposed tetra-acetate,and have determined the acetyl groups by three different methods,and -they come to the conclusion that the compound in question isbeyond doubt a triacetyl derivative. They admit that higher acetylatedproducts may be obtained if condensing agents such as zinc chlorideor sulphuric acid axe present, but these, they consider, are derivativesof the hydration products of cellulose and not of cellulose itself.Withregard to Green's constitutional formula, it is pointed out that it isonly intended to represent cellulose in its simplest o r unpolymerisedform, in which, for instance, it may be present in a n ammoniacalcupric solution. The cellulose of fibres may be regarded either as aphysical aggregate of these simple molecules or as a chemical polymeridemade up of a number of C, complexes, of the structure suggested,united together by means of their oxygen atoms.Cross and Bevan, as pointed out in the Annual Report of last year(page S9), regard the matter from a different standpoint, and theirviews are expressed a t length in their recently published 12esearclbe.s onCellulose, II., 1900-1905.Thesolnble acetates were prepared by various different methods, such asthose of Cross and Bevan, Lederer and Bayer, and in all cases thesame product was obtained, namely, the triacetate, C,H70,(0Ac),.The author considers, however, that it is questionable whether atriacetate of normal cellulose exists, and that the products obtainedare rather to be regarded as acetates of a series of hydrocelluloses ofJ.A m r . Chein. Soc., 1906, 28, 114.Trans., 1906, 89, 811.The cellulose acetates have also been examined by H. Ost.5Proe. Eoy. Soc., 1906, 78, 272.See Anii. Xeport, 1904, 69.Zczt. mcyeiti. C'hem., 1906, 19, 99ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 95various degrees of degradation.He estimates the acetyl groups inthese compounds by hydrolysis with dilute sulphuric acid and distilla-tion of the resulting acetic acid with steam, and considers that thesupposed existence of the tetra-acetate is accounted for by the highresults obtained when the saponification is effected by alcoholic potash,a process which may give rise to the production of acids a t the expenseof part of the cellulose.Glucosides.I n order to establish the structural formulze of glucosides, it hasbeen the custom in the majority of cases to rely only upon a studyof the products obtained on hydrolysis ; in comparatively few instanceshas the evidence obtained in this way been supplemented by a directsynthetical preparation of the glucoside itself.I n order to obtainevidence bearing upon the linking of the sugar residue, Irvine andRose show that it is necessary to prepare derivatives of the glucosideand to study the hydrolysis of the compounds so obtained. Alkylatedglucosides are well adapted for such work owing to the stability ofthe alkyloxy-groups, the occurrence of secondary changes duringhydrolysis being in this way largely precluded. It has previously beenshown by Purdie and Irvine (1903) that when the crystalline tetra-methyl glucose, prepared from either the a- or P-tetramethyl gluco-side, is oxidised, it is converted into tetramethylgluconolactone, thisresult indicating that the parent glucosides possess the y-oxidic link-ing.Similar reactions have now been applied with the object ofestablishing the complete structural formula of a natural glucoside,salicin being selected as a typical example. Previous investigationshave proved salicin to be saligenin /3-glucoside, and its syntheticalformation from helicin proves that the two parts of the molecule areunited through the phenolic hydroxyl group. The authors have nowobtained a pentamethyl salicin by the usual method of alkylation withmethyl iodide and silver oxide; it is a colourless crystalline compound,practically insoluble in water, but readily soluble in organic solvents.The hydrolysis of this compound presented, however, considerabledifficulty, and the following synthetical method was therefore devisedit1 order to prove the y-oxidic linking.Saligenin and tetramethylglucose mere condensed t o saligenin tetramethyl glucoside by heatingwith hydrochloric acid in benzene. The remaining hydroxyl groupwas now alkylated by the silver oxide method, and a compound wasthus obtained, which proved to be identical in every way with thepentamethyl salicin prepared, as described above, from the naturalg 1 11c osi cl e .Trans., 1906, 89, 81496 ANNUAL REFORTS ON THE PROGRESS OF CHEMISTRP.Neilson 1 finds that the hydrolysis of salicin and amygdalin can bebrought about by the catalytic influence of platinum black. I n thecase of salicin, the hydrolysis could be conducted under conditionsexactly comparable with those of enzyme action, but with amygdalinit was necessary to use open flasks since the hydrocyanic acid producedin the reaction had a strong inhibitive influence on the catalysis.According t o Loew and AsbY2 platinum black has the power of con-verting maleic acid into fumaric acid ; and Neilson states that starchniay be hydrolysed by platinum black.A substance is contained in the cell sap of the leaf epidermis ofvarious plants which gives a blue colour with iodine.The colour dis-appears on warming, but returns on cooling, as in the case of starch ;it is not, however, confined to well-marked grains, but extends m i -formly throughout the cell as a fine blue precipitate. The substancewhich gives this reaction, often called '' soluble starch " by botanists,has now been isolated by Barger,4 and proves to be a glucoside.Itcrystallises in microscopic needles, has the composition C21H2t012,2H20,and is optically active. The name saponarin is adopted for this newglucoside in reference to the source (5'aponaria o$icinc&s) from whichit was prepared, leaving open the question of its probable identity withthe " soluble starch " of other plants.When hydrolysed with acids it gives rise to glucose and vitexin, acolouring matter which was obtained by A. G. Perkin (1898) from aNew Zealand dye-wood.Auother colouring matter is produced at the same time, which appearsto be isomeric with, or closely related to, vitexin; for this the authorsuggests the name saponaretin.[It may be mentioned here that the mych-disputed question as tothe nature of the blue substance produced from starch and iodine hasbeen attacked by Padoa and Savark in a new way.They investigatethe changes in electric conductivity of a solution of iodine in potassiumiodide which are caused by addition of given quantities of starch, andthey conclude that the blue substance is a n additive compound ofiodine, starch, and potassium (or hydrogen) iodide, the starch andiodine being present in the ratio 4C,H,,O, : I.]Further studies of the occurreuce of cyanogenetic glycosides havebeen made by Dunstan, Henry, and AuldYG Guignard,7 H6bert,8 andBert~-and.~Amer. J. Physiol., 1905, 15, 148.Amer. J. Physiol., 1906, 15, 412.Gazxetta, 1906, 36, i, 313.Bull. Coll. Agr. Tckyd, 1906, 1.Trans., 1906, 89, 1210.ti Proc. Eoy.Soe., 1906, 78, 145, 152.7 Compt. rend., 1906, 142, 545 ; 143, 451.1ti Bull. Xoe. ehim., 1906, 35, 919. Conzpt ?.end., 1906, 143, 832ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 97Acids.Thorpe and Higson 1 describe a new method of obtaining succinicacid and its alkyl derivatives which is based upon the condensation ofethyl sodiocyanoacetate with the cyanohydrin of either an aldehyde ora ketone, and subsequent hydrolysis of the resulting ethyl ester. Thegeneral reaction is indicated by the following changes :CO,Et*C(CN)NaH + HO*C(CN)R -+ CO,Et*C(CN)Na*C<CN)R + H20and CO,Et*CH(CN)*CR,(CN) -+ C02Et*CH2*CR2*C02Et.R RFormaldehydecyanohydrin and ethyl sodiocyanoacetate, for example,yield succinic acid, and benzaldehydecyanohydrin, in a similar way,gives phenylsuccinic acid.When, however, the condensation of formaldehydecyanohydrin andthe cyanoacetate is brought about in hot solution, the product is ethyla$-dicyanoglutarate, and from this product glutaric acid is obtained onhydrolysis.The condensation-product CO,Et*CNa(CN)*C(CN)R, which is firstformed in the above reaction is stable in presence of cold water, sothat it is not affected by the small quantity of water produced in thechange. I f this product is then directly acted on by alkyl iodides, thehigher alkyl derivatives of succinic acid can be obtained :CN*CNa(CO,Et)*C(CN)R, + RI -+ CN*CR(CO,Et)*C(CN)R, +NaI -+ C02H*CHR*CR2*C02H.I n this way, for example, acetonecyanohydrin, when condensed withethyl sodiocyanoacetate, gave a product from which, by the action ofmethyl iodide, trimethylsuccinic acid was prepared.It.Meyer and Bock2 have sought for an improved method ofobtaining isosuccinic acid, since the directions usually given for themalonic ester synthesis did not yield a pure product, and thepreparation from a-bromopropionic acid and potassium cyanide wasfound to be unsatisfactory. An attempt to attain the desiredobject by means of Crignard’s reaction-that is .by acting withmagnesium on a-bromopropionic ester in order to obtain the compoundCH,*CH(MgBr)*CO,Et and treating this product with carbon dioxide-gave a negative result. Finally, the authors consider that the bestmethod of preparation consists in first obtaining pure isosuccinamide(from the impure ester) and hydrolysing this by means of sodiumhydroxide.The properties of isosuccinic acid and its salts, cptc., havebeen further studied and its heat of combustion re-determined.Trans., 1906, 89, 1456.VOL. 111.Annalen, 1906, 347, 93.98 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Resnlts of considerable importance have been obtained by Lossenand his colleagues1 in a series of investigations on the halogenderivatives of aliphatic acids. It will only be possible, in the limitedspace here available, to give a brief indication of some of these resultswhich are of more general interest.Chloro- and bromo-acetic acids when boiled with bases yield not onlyglycollic acid but also diglycollic acid, the results depending on thenature and proportion of base. Trichloro- and tribromo-acetic acidswhen similarly treated give chloroform and carbon dioxide, or, underother conditions, a formate, chloride or bromide, and carbonate.a-Bromopropionic acid yields both lactic and acrylic acids, whereas/3-bromopropionic acid gives hydracrylic and acrylic acids ; in the lattercase the proportion of acrylic acid is larger and the change takes placemore rapidly, contrary to what would be expected from Wislicenus’stheory.aa-Dibromopropionic acid gives pyruvic and a- bromoacry lic acidsand the so-called ‘‘ acryl colloid.” The latter, which appears to havethe composition (C3H40&, is probably a polymeride of pyruvicacid.ap-Dibromopropionic acid decomposes more rapidly than the aa-acid,and yields glyceric acid with a-bromohydracrylic acid and a smallquantity of pyruvic acid; according to theory, the aa-acid shoulddecompose more rapidly.Tribromosuccinic acid has hitherto been but little studied ; it wasobtained originally by Petri by the action of bromine on bromomaleicacid.His method of preparation presented, however, certain difficulties,especially as the solution obtained was evaporated at the ordinary tem-perature, an operation which may take some weeks. The authors haveconsiderably improved this method, and find that the acid may beprecipitated by passing hydrogen chloride into the solution. Whenboiled with caustic potash it yields dibromomaleic acid, and a similarresult is obtained when a benzene solution of the acid is heatedfor two hours, the yield then being almost quantitative.This resultagain is opposed to theory, since the formation of dibromofumaric acidwas to be expected :HCO,H*$l*Br CO,H*gaBr - HBr = Br C*CO,H Br C CO,H*BrDibromomaleic acid is also produced when dry ammonia acts on tri-bromosuccinic acid in absolute alcoholic solution ; but if aqueousAnnalen, 1905, 342, 112, 157 ; 1906, 348, 261ORGAKIC CHEMlSTRS-ALIPHATIC DIVISION. 99ammonia is gradually added to an aqueous solution of the acid, theammonium salt of bromofumaric acid results :3C4H30,Br3 + 14NH3 = 3C,H0,Br(NH4), + 6NH4Br + N,.By the action of chlorine water on the normal sodium salt offulnaric or maleic acid, the authors have obtained chloromalic acid,CO,H*CHCl*CH(OH).CO,H; i t was also obtained by the action ofsodium hypochlorite on the acid salt or of hypochlorous acid on thefree acids.Chloromalic acid when subjected to dry distillation, or when heatedwith concentrated hydrochloric acid, yields chloromaleic acid ; onreduction by means of zinc it gives malic acid.When an aqueoussolution of the acid is boiled, aldehyde and tartaric acid are produced :C,H,O,Cl+ H,O = C,H406 + HC1 and C4H,0,C1 = C,H,O + 2C0, + HC1.Bromomnlic acid was similarly prepared, and its behaviour is inalmost every respect analogous to that of the chloro-derivative.An acid of considerable interest is obtained by the action of alkalison chloro- or bromo-malic acid; when either of these acids is treated,a t the ordinary temperature, with caustic soda, the mixture allowed tostand, acidiged and extracted with ether and ethyl acetate, a crystallineproduct is obtained which melts at 203’ and has the compositionC4H405.Analysis of its salts, esters, chlorides, and arnide shows theacid to be dibasic. The absence of alcoholic hydroxyl is shown by thefact that both acetyl chloride and phenylcarbimide are without actionon the dimethyl ester. The authors therefore assign to this acid theconstitution O< CH*CozH I and name it fumarylglycidic acid. ItsCH*CO,H’formation from chloromalic acid is represented thus :C4H505Cl + 3KOH = C,H,O,K, + KCl + 3H,O.An aqueous solution of furnarylglycidic acid, when boiled, givesrise to racemic and i-tartaric acids, aldehyde and carbon dioxide.The authors have also studied the decomposition of bromomaleic andbromofumaric acids, and the preparation and reactions of acetylene-dicarboxylic acid.Experiments bearing on the constitution of fulminic acid by Wohlerand Theodorovits were referred to in the previous Bepoyt (pp. 98-99),from which it appeared t h a t fulminic acid is not formed from mono-carbon compounds by action of nitric acid and mercuric nitrate.Theseresults appeared to speak in favour of the double formula for fulminicacid, but Wohler’s measurements of the molecular weight and equiva-lent conductivities of sodium fulminate pointed to the single formulaHCNO.H 100 ANNUAL REPORTS ON THE PROGRESS O F CEIEMIS'I'RT.Nef, it will be remembered, regards fulminic acid as C:NOH orcarbonyl oxime.Jowitschitsch 1 bas again attacked this question, andconsiders that this formula is improbable for several reasons ; bearing inmind, for example, the reactivity of nitric acid with unsaturated carboncompounds, one would not expect an unsaturated mono-carbon com-pound to be produced, almost quantitatively, by the action of nitric acidon a saturated two-carbon compound. The author is inclined rather to7H:N.OI , which was proposed CH:N*O prefer the glyoxime peroxide formula,by Scholl,, and has therefore synthetically prepared a compound cor-responding to this constitution in order to compare its properties withfulminic acid.Y(C0,Et):N.b I wasC( C0,Et) :N* 0' The peroxide of diisonitrososuccinic ester,first prepared (from the nitrolic acid of ethyl acetoacetate), and this, bythe action of sodium hydroxide under stated conditions, gave rise to 'thesodium salt of glyoxime peroxide, from which the silver salts wereprepared.The di-silver salt closely resembles silver fulminate ; it isexplosive, and yields h) droxylamine by the action of hydrochloric acid,but differs from silver fulminate in being easily soluble in nitric acid andless explosive. By the action of hydrochloric acid on a nitric acidsolution of the silver salt, the free glyoxime peroxide was obtained insmall quantity as a yellow, acid liquid.Esters.Ethyl nitrogentricarboxylate, N( CO,Et),, was prepared by Diels in1903 by heating a mixture of ethyl chlorocarbonate and ethylcarbamate with sodium. Attempts to saponify this ester with alkaliswere not successful, since under these conditions i t splits up into ethylalcohol, carbon dioxide, and ethyl iminodicarboxy late, NH( CO,Et),.I n this case, therefore, both carbethoxy-groups remain attached tonitrogen, It is now shown by this author and Wolf 3 that a differentdecomposition occurs when the ester is acted on by dry ferric chloride,the products then being ethyl carbonate and ethyl carbimide-carboxyla t e :N(CO,Et), = CO(OEt), + O:C:N*CO,Et.Since the separation of these two substances is dificult, the authorssought a method of decomposition which would yield the latter freefrom inconvenient by-products, and they found that this object couldbe attained by heating the txicarboxylic ester with phosphoric oxide.LOG.cit., 1906, 39, 1686.1 ZL7L?LLLleIL, 1906, 347, 233. L'w., 1890, 23, 3505ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 101I n this case the by-products are ethylene, carbon dioxide, andwater :N(CO,Et), = 2C2H4 + CO, + H20 + 0:C: N*CO,Et.The foregoing observation led the authors to investigate the action ofphosphoric oxide on other esters with the view of ascertaining whetherreactions of a similar type could be effected, and with malonic esterthey have obtained results of considerable interest.lEthyl malonate was slowly distilled, at a pressure of 12 mm., over alarge excess of phosphoric oxide, distributed in glass wool and heatedto ahout 300O; the evolved gases were passed first through a well-cooled tube to remove any unaltered ester, and then into a vesselsurrounded by liquid air.The products obtained were ethylene, alittle carbon dioxide, and a substance having a very pungent odour,which proves to be a colourless liquid boiling at 7". By allowing themixture to boil at the ordinary temperature, the ethylene and carbondioxide are removed, and the new product is then vaporised and collectedin a tube cooled to - 60'. It is a very mobile, refractive liquidhaving an odour resembling that of acraldehyde or mustard oil. It burnswith a smoky blue flame. When treated with cold water it yields malonicacid, and with dry hydrogen chloride, ammonia, and aniline it givesrise to malonyl chloride, malonamide, and malonanilide respectively ;it behaves, therefore, as an anhydride of malonic acid.Analysis bycombustion with copper oxide and by explosion with oxygen, andmolecular weight determination by Hofmann's vapour-density method,show that the compound has the formula C,02. The authors considerthat its formation is represented by the change :CH,(CO,Et), = 2C,H4 + 2H,O + C,O,.The name carbon suboxide is proposed, and the constitution is repre-sented as 0:C:C:C:O.The liquid oxide slowly decomposes at the ordinary temperature,being converted after a time into a dark red solid which dissolves inwater giving an eosin-red solution ; the composition of this product isapproximately the same as that of the original liquid. The decom-position is very rapid at 37" and is instantaneous at looo, and underthese conditions carbon monoxide escapes ; the solid product whichthen remains contains less oxygen and is partly soluble in water, givinga brown solution.Berthelot 2 takes exception to the name carbon suboxide, since thereappear to be a t least three oxides, previously known, to which thename is appropriate.(1) Brodie's oxide, C,O,, obtained by subjectingcarbon monoxide to prolonged electric discharges ; this might beregarded as an anhydride of tartaric acid. (2) Berthelot's oxide,Ber., 1906, 39, 689. Ann. Chim. Phys., 1906, 8, 173102 ANNUAL REPOlI'1'8 ON THE PROGRESS OF CHEMISTRY.C,O,, which is formed by heating Brodie's oxide to 300--4OOO; informula this would correspond t o an anhydride of dihydroxyphthalicacid. (3) An oxide richer in carbon which results from the action ofheat on (2).Berthelot also mentions that in 1891 he gave reasons forsuspecting the existence of a volatile lower oxide of carbon, but thatowing to the inefficiency of the methods of refrigeration known at thattime it was not possible to condense the product.Michael considers that the constitution assigned to this new oxideby Diels and Wolf is improbable, since in parallel cases the changeusually follows an unsymmetric course .when the elimination of wateroccurs with possibility of ring formation, Acetonylacetone, forexample, yields not an acetylene derivative, but dimethylfuran.For this and other reasons he suggests that the compound should beregarded as the lactone of j3-hydroxypropiolic acid, and explains itsformation thus :C*OEt CH2C<C02Et C0,Et -+ -+ c<>o.co coAnhydrides of diethylmalonic acid have been obtained by Einhornand von Diesbach,3 but they prove to be multimolecular. By treatingdiethylmalonyl chloride with a dilute aqueous solution of pyridine, ayellow amorphous powder is obtained which is dissolved by potassiumhydroxide in the cold,:giving the salt of diethylmalonic acid.Ammoniaconverts it into diethylmalonic acid, diethylmalonamide, and diethyl-malonamic acid. Analysis and molecular weight determination by thecryoscopic method (in ethylene dibromide) show the formula to be[C(C,H,),<~~>O] . When this compound is heated in some in-12 -different solvent, such as benzene, it decomposes, giving carbondioxide, diethylacetic anhydride, and a crystalline malonic anhydridewhich behaves towards reagents in the same manner as the originalcompound, but which has the molecular formula (C7Hlo03)4.The methyl ester of dicarboxyaconitic acid,C(CO,Rle),:C(CO,Me)* CH(CO,Me),,which was first isolated by Anschutz in 1903, has been further studiedby this author and Deachauer.3 It is shown that this ester, whenreduced by means of zinc and acetic acid, gives a quantitative yield ofmethyl dicarboxytricarballyate,CH(C02Me)2* CH(C02Me)*CH(C02Me),.The sodium derivative of dicarboxyaconitic methyl ester reacts withmethyl iodide, giving the corresponding methyl derivative ; this, whenAnnalen, 1906, 347, 1.Ber., 1906, 39, 1915.LOC. cit., 1222ORGANIC CHEMISTRY-ALIPHATIC DIVISION.103reduced ascarbsllylich ydrolysedbefore, yields the methyl ester of dicarboxymethyltri-acid, CH(C02Me)2*CH(C02Me)*CMe(C02Me)2, and whenwith sodium hydroxide, methylaconitic acid,C02H* CH: C( C0,H) * CHMe*CO,H.Considerable discussion has taken place with regard to the view putforward by Lewkowitsch in 1900 that the saponification of fats takesplace in stages. Balbiano, for example, in 1902-1903 opposed thishypothesis, and considered the change to be of the type C,H,(OR),+3MOH = C,H,(OH), + 3MR. I n support of this opinion he stated thatif the saponification of glyceryl tribenzoate is interrupted before theaction is complete, the products are only glycerol, benzoic acid, andunaltered tribonzoin, no mono- or di-benzoin being found.Fanto 1expressed a similar opinion, and was unable to detect the presence oflower glycerides; the reaction, that is, appeared practically to bequadrimolecular. Marcusson also 2 comes to similar conclusions, andconsiders that the high acetyl numbers which Lewkowitsch found, andwhich he himself observes only under certain conditions, are to beexplained by the changes experienced by the fatty acids, such asoxydation or anhydride formation. Lewkowitsch, h ~ w e v e r , ~ effectivelyreplies to these criticisms.Kremann has thrown important light upon this question by makingmeasurements of the reaction velocity in the saponification of glyceryltriacetate and glycoldiacetate. According to Balbiano’s view, thefirst-named reaction should be quadrimoleculsr and the secondtermolecular.The values which he obtained, however, were approxi-mately constant when calculated f o r a bimolecular reaction ; if theyare calculated on the assumption that the reaction is ter- or quadri-molecular, the numbers increase as the action proceeds. These resultsappear, therefore, to favour the hypothesis that the change takes placein stages. The rates of saponification of the different acetyl groupsdiffer so little, in the author’s opinion, that the effect is analogous tothe saponification of the ester of a monohydric alcohol by an equivalentquantity of alkali.Abel,4 reasoning from a kinetic standpoint, proposes to explain thefact that the changes mentioned appear to be reactions of the secondorder by assuming that the rates of saponification of glyceryl mono-, di-,and tri-acetates are in the ratio of 3 : 2 : 1, and those of glycol mono-and di-acetates in the ratio 2 : 1.The hydrolysis of esters under the influence of lipase has alreadyMonnlsh., 1904, 25, 919.LOC.eit., 4095.Ber., 1906, 39, 3466.4 Zeit. Elektrochem., 1906, 12, 681 ; and Zeit. physikal, Chem., 1906, 56, 558104 AMNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.been the subject of considerable investigation by Kastle and Loeven-hart, Armstrong, Nicloux, and others. The enzyme undoubtedlydisplays a selective power in promoting by preference the hydrolysisof esters of the higher fatty acids, such as those present in the nrturalfats. The first-named authors (1900) succeeded in effecting the hydro-lysis even of the lowest members, but they concluded that the higherthe molecular weight of the acid, the more readily is its ethyi esterhydrolysed by lipase.Armstrong and Ormsrod 1 have made a furtherinquiry into the nature of the change, with the object of throwinglight on this selective action. Their results lead them to the pro-visional hypothesis that the hydrolysis oE the ester by lipase involvesthe direct association of the enzyme with the carboxyl centre, and thatsuch association may be prevented by the hydration of this centre.Esters, therefore, which are more attractive of water will be lessreadily hydrolysed, and this view is in accordance with the fact thatthe solubilities of ethyl ester3 diminish as the series is ascended.Theinfluence of hydroxyl replacement is well illustrated by the authors’results obtained with the ethyl esters of siiccinic, malic, and tartaricacids, the amounts of hydrolysis after twenty-four hours being in theratio of 20.4 : 15 : 1.8 respectively.Kastle 2 states that the alkyl groups-methyl, ethyl, butyl, isobutyl,allyl, and benzyl-have almost the same effect on the hydrolysis ofester6 by (liver) lipase, but that the presence of acyl groups in thehomologous series has considerable influence. I n the case of methylpropionate the introduction of iodine, in the @position, tends rather toaccelerate than to retard the action, and cyanogen (for example, incyanoacetic ester) has a retarding influence.The hydrolysis of nitric esters of glycerol and of cellulose is alwaysa complicated process, owing to the fact that the nitric acid becomesreduced and the alcohol oxidised.Further studies on this subject havebeen made by Silberrad and and they show that the hydrolysisof ‘ nitrocellulose ’ gives rise to nitric and nitrous acids, ethyl nitrate,ethyl nitrite, alcohol, ammonia, and the following acids : formic, aceticbutyric, dihydroxybutyric, oxalic, tartaric, isosaccharinic, andhydroxypyruvic. Carbohydrates and other compounds are alsoproduced. The abnormality of the hydrolysis both of ‘ nitrocelluloses ’and of ‘ nitroglycerine ’ is also confirmed by the fact that the amount ofalkali consumed on saponification is . much higher than that requiredby theory for the normal change, and further that the velocity ofsaponification, instead of decreasing norm:tllg with the progress of thechange, continues to have about the same value until a large proportionJ Proc, Roy.Soc., 1906, 78, 376. Chem. Cetttr., 1906, i, 1536,Trans,, 1906, 89, 1182 and 1759ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 105of the alkali is used up. Intermediate products are probably formed,and these are gradually acted on by the alkali, so that the saponifica-tion measured during the later stages is not that of the ‘ nitrocellulose ’alone, but is in part a hydrolysis of decomposition products. Nocellulose, or glycerol, is regenerated during these hydrolytic operatioqalthough it can be shown that these substances can resist the action ofnitric acid of the concentration present in the experiments.A moreactive condition of the nitric acid at the moment of its liberation istherefore suggested.I n order to explain the formation of nitrite on the saponification ofnitric esters, Nef (1899) assumed that, in addition to the normal reaction,dissociation takes place in the alkyl group with formation of anethylene and an ethylidene grouping, and that the latter is oxidised t oaldehyde by the nitric acid, nitrous acid resulting. Vignon andMaquenne (1891), on the other hand, assumed the formation of anisomeric nitrate, R-CH(OH)O*NO. Klason and Carlson 1 now con-sider that a more probable explanation is afforded by assuming theperoxide formula for the alkyl nitrate, OR*O*NO; the changes onsaponification might then be represented as OR*O*NO + KOH =KO*O*NO + ROH and OR*O*NO + KOH = KO*NO + OR*OH. Theformation of an alkyl peroxide in this way appears probable from theauthors’ experiments, in which nitric esters were saponified in presenceof phenyl hydrosulphide, in which cases it is shown that a certainamount of phenyl disulphide is formed.Hydrogen dioxide and otherperoxides are known to react with phenyl hydrosulphide with formationof phenyl disulphide, and the authors suggest that the change atpresent under consideration may take place in the following way:RO-O*NO + KOH = RO*OH + KOoNO and RO-OH + BR-SH = ROH +R’,S, + H20. ‘ Nitroglycerine,’ ‘ nitrocellulose,’ and ethyl nitrate,when saponified under these conditions, all gave rise to some phenyl di-aulphide.According to Twitchell,2 sulphophenyl- and sulphonaphthyl-stearicacids may act as catalysts in the hydrolysis of fats, A 1 per cent,solution of the latter acid, for example, effects a nearly completeseparation of the glycerol from a fzit in the course of eight or tenhours.shows that when ‘ nitrocelluloses ’ are boiled with a1 kalis inpresence of hydrogen dioxide, the whole of the nitrogen is obtained asnitrate and nitrite.On acidification the nitrite is oxidised by thehydrogen dioxide to nitrate, and the total nitrogen can then beestimated in this state by the “ nitron ” reagent.BuschBer,, 1906, 39, 2752. J. Amer. Chertb. Soc., 1906, 28, 196,a .Be?-., 1906, 39, 1401106 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.van Romburgh,l by acting on glycerol with excess of anhydrousoxalic acid, obtains a product containing 90 per cent.of triformin;diformin yields a similar result when acted on by anhydrous formicacid. When this product is cooled sufficiently, crystals of triforminseparate. The pure substance crystallises in needles which melt at18'. It is slowly hydrolysed by cold water and more rapidly by warmwater.flitrogen Compounds,Metallic copper, as is well known, is not dissolved by aqueousammonia alone; in presence of oxygen, however, the metal is rapidlyoxidised and dissolved. A t the same time, as shown by Schonbeinand by Tuttle, a considerable portion of the ammonia is oxidised tonitrous acid. Extending this observation to organic bases in place ofammonia, Traube and Schonewald2 have found that ethylamine isoxidised to acetaldehyde and methylamine t o formaldehyde.I n thesecases the copper is converted t o hydroxide, but the ammonia is notoxidised. It is probable that the aldehydes are primarily obtained asaldehyde-ammonias, since the latter do not appear to be acted on byoxygen in presence of metallic copper. When the sodium derivativeof glycine is similarly treated the products are nitrous acid andprobably glyoxylic acid.Burmann 3 describes a convenient method of preparing methylamine.Commercial methyl sulphate is acted on by 10 per cent. aqueousammonia and the mixture is afterwards distilled with 30 per cent.caustic soda ; the ammonia and methylamine are collected in hydro-chloric acid and the resulting hydrochlorides separated by fractionalcrystal lisation.The preparation of acetamide by the usual method of distillingammonium acetate gives a comparatively poor yield, since, according toFrangois,* the initial products are ammonia and ammonium hydrogenacetate, the latter then breaking up into acetamide, water, and aceticacid.By starting with ammonium hydrogen acetate, a yield of 45per cent. of acetamide may be obtained.For the preparation of amides from esters H. Meyer recommendsdigestion of the ester with concentrated aqueous ammonia as the bestmethod, since the action of gaseous or liquefied ammonia may lead tothe formation of mixed products. The action of alcoholic ammoniaon esters is a reversible process, and if excess of alcohol is present theformation of ester may be the principal reaction even at temperaturesbelow 100'.1 Proc.K. Akad. Wetensch. Amsterdam, 1906, 9, 109.4 J. Pharm. Chim., 1906, [vi], 23, 230.Ber., 1906, 39, 178. Bull SOC. chim., 1906, [iii], 35, 801.Monatsh., 1906, 27, 31ORGANIC CHERIISTRY-ALIPHBTIC DIVISION. 10'7The methyl esters are much more quickly and completely convertedinto amides by the action of aqueous ammonia than the higherhomologues. On the other hand, the change takes place more readilyas the acidic radicle is stronger ; trichloroacetic ester, for example,readily givas the amide in this way, whereas trimethylacetic esterdoes not.Attention was called in the previous Report (1905, 75) to the form-ation, by Windaus and Knoop, of methylglyoxaline, or methyliminazole,CH3'8g$WH, from dextrose by the action of ammonia in presenceof zinc hydroxide.It was assumed that glyceraldehyde is first formedand that this then passes into methylglyoxal, which in its turn isacted on by ammonia and formaldehyde to give methylglyoxaline.This view is favoured by the fact that a better yield is obtained iEformaldehyde is added to the dextrose and zinc hydroxide-ammonia.Since methylglyoxaline occurs in some natural alkaloids it is evident thatthe synthesis here described may have an important bearing in plantphysio1ogy.l Windaus has now extended these observations by thesubstitution of acetaldehyde for formaldehyde i n the above-mentionedsynthesis and has in this way obtained 1 : 4-dimetbyliminazole.Thechange is probably represented as follows :>C*CH, + 3H,O. CH,-$*NHCHON NH3 + OCEPCH, =CH,*YOCHO NH,I n absence of acetaldehyde only the mono-methyl base is produced ;this appears to indicate that under the conditions here employedacetaldehyde is not formed by the action of hydroxyl ions on dextrosein presence of ammonia.3I n order t o establish the constitution of this base advantage wastaken of Wallach's observation that the substitued iminazoles inwhich the replacing radicle is attached to nitrogen are transformed,when led through a red-hot tube, into the l-substituted compounds.Thus 5-methylglyoxaline yields the l-methyl compound under theseconditions. Now the 1 : 4(or 5)-dimethylglyoxaline has alreadybeen obtained by Jowett and Potter.* By passing this through astrongly heated glass tube and purifying the resulting compound bymeans of its silver salt, the author obtained a product identical inevery way with the 1 : 4-dimethyliminazole prepared from dextroseand acetaldehyde.The preparation and synthesis of amino-acids is still receiving con-siderable attention owing to the importance of these compounds from aCompare Meldola, Trans., 1906, 89, 764.Compare Schade, p.91, this volume.Bar., 1906, 39, 3886.Trans., 1903, 8108 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.biological standpoint. A complete summary of this subject, bringingthe results up t o the end of last year, will be found in an addressgiven by Fischer to the German Chemical Society.1Of all the known general methods of preparing amino-acids, thesimplest appears to consist in the treatment of the a-halogen fatty acidwith ammonia.For the purpose of obtaining these halogen derivatives,Fischer and Schmitz2 recommend the bromination of t h e alkylinalonic acids. This method gives a yield of the bromomalonic acidderivative, which is almost qiiantitative, and the latter on heatingreadily breaks up into the required bromo-fatty acid and carbon dioxide,especially under diminished pressure. I n this way the authors prepareda-bromoisohexoic acid from isobutylmalonic acid and y-phenyl-a-bromo-butyric acid from y-phenylethylmalonic acid.The preparation of amino-acids, through the amino-nitriles, fromaldehydes or ketones, may be carried out, as first pointed out byLjiibavin in 1882, by the direct action of ammonium cyanide instead ofby the successive treatment with ammonia and hydrogen cyanide ; inthis way Gulewitsch (1900) obtained a large yield of a-aminoisobutyricacid from acetone.The same author and Wasmus 3 make a furtherstudy of the most favourable conditions and show that the reaction isof general application for all ketones of the series :The method has the advantage that iminonitriles and oxynitriles arenot produced. Whereas the aminonitriles hitherto described areunstable oils which cannot be distilled, many of those obtained bythe present authors could be distilled unchanged, under reducedpressure, and were stable when kept.Zelinsky and Stadnikoff,4 for this preparation, prefer to act on thealdehyde or ketone with potassium cyanide and ammonium chloride, inequal molecular proportion, in aqueous or aqueous -alcoholic solution.They represent the change as taking place in the following way :(1) KCN + H20 Z KOH + HCN, (2) R*CHO -t HCN = R*CH(OK).CN,(3) NH4C1 + KOH = KCl + H,O + NH,, and (4) R.CH(OH).CN +NH, = R*cH(NH,).CN + H20.For the preparation of amino-acids, the resulting aminonitriles arehydrolysed by means of hydrochloric acid.Paal and Weidenkaff 5 have continued their investigations, whichwere referred to in the previous Report (p.69), on the behaviour ofGrignard's reagent towards amino-acids ; the investigation was under-taken with the object of obtaining products which might serve for thecharacterisation of these acids, glycine being first studied. TheCnH,,, 1'CO*CnH,n+ 1.1 Bcr,, 1906, 39, 552.2, LOG. cit., 351. 3 LOG. cit., 1181.LOC. cit., 1722. LOC. ciL, 810ORGAN 1 C C HEM ISTRY - ALI PH ATIC DIVISIOK. 109authors now show that the ethyl ester of diethylaminoacetic acid withmagnesium ethyl iodide gives rise to diethylaminomethyldiethyl-carbinol, OH*C(C2H5),*CH2*N(C2H5)2. This compound, like the productpreviously described, dissolves easily in Trganic solvents, but issparingly soluble in water.is similarly obtained from ethyldiethylaminoacetate and magnesiumphenyl bromide.Extending these observations to aminodicarboxylic acids, the sameauthors 1 find that the ethyl ester of inactive aspartic acid reacts withmagnesium phenyl bromide to give r-/3-amino-aa66-tetraphenyl-butane-as-diol :C02Et*CH(NH,)*CH2*C02Et --+0H*C(C6H5)2*CH(NH2)*CH,*C(C,H,)2*OH.It is a crystalline substance and is very sparingly soluble in water, butdissolves easily in alcohol, ether, benzene, &c.Siegfried, in 1905, found that on mixing solutions of glycine andbarium hydroxide in equivalent quantities and passing carbon dioxideinto the mixture, no precipitation of barium carbonate takes place andthe clear solution only begins to cloud after standing for some time.Other amino-acids, such as alanine, leucine, aspartic acid, andglutaminic acid, behave in a similar way, and it is shown that thesolutions obtained contain salts of corresponding substituted carbamicacids, CO,H*R'*N H*C02H.Glycine, for example, forms '( carbamino-CH2*NH*7Oacetic acid," the calcium salt of which has the formula I CO-OCa-0It would appear that other amphoteric substances, such as peptonesand albumoses, can, in presence of bases, form loose compounds withcarbon dioxide which are probably of analogous constitution. Even inabsence of bases these amino-compounds are capable, to a certainextent, of fixing carbon dioxide.Leuchs2 has now prepared the anhydride, and salts, of carbamino-acetic acid (glycinecarboxylic acid) in an entirely different manner, asfollows : carbethoxyglycine is readily converted into its correspondingacid chloride by means of thionyl chloride; on warming this acidchloride for some time a t 80" ethyl chloride splits off, leaving theThe corresponding compound,OH*C(C,H,)2'CH2*N(C2H,)27anhydride, TH-">O.A better yield is obtained if the carbo- CH,*COmethoxyglycyl chloride is employed. This anhydride dissolves, givingan acid solution in ice-cold water, but at about 15' carbon dioxide isevolved and pure glycine is left in solution. If the ice-cold aqueoussolution of the anhydride is mixed with the calculated quantity ofBer., 1906, 39, 4344. LOG. cit., 857110 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.baryta-water, a crystalline barium salt is obtained which is found tobe identical with the product prepared by Siegfried’s method abovementioned.When the anhydride is rubbed with twice its weight of water a t theordinary temperature it evolves carbon dioxide and is converted into awhite, nearly insoluble powder, which appears to be a glycine anhydride(C2H30N),.This product differs from diketopiperazine and isprobably identical with the substance previously obtained by Balbianoand Trasciatti in 1900 by heating glycine with glycerol, and by Curtiusfrom the ‘‘ biuret base.”has extended this observation to a study of thebehaviour of malonic ester chloride under similar treatment. Whenthis compound was heated a t 125-130’for an hour, hydrogen chloridewas evolved, but ethyl chloride was not produced ; on continuing thereaction, a brownish, horny substance separated, which, after purificationby ether, yielded a citron-yellow, crystalline compound having theformula C,,H,,O,.The author considers that the change which takesplace consists in the condensation of three molecules of the ester-chloride, with elimination of hydrogen chloride, to phloroglucinol-tricarboxylic ester, and this, by loss of alcohol, yields the compound inquestion, which may beThe same authorO-O--ICO,Et/\CO or CO,Et/\CO,EtOH1 (OH \/ OH1 (OHC0,Et co-- \/The synthesis of serine was accomplished in 1902 in two differentways by Fischer and Leuchs and by Erlenmeyer, jun., respectively.The first-named authors treated glycollaldehyde, prepared fromdihydroxymaleic acid, with hydrogen cyanide and ammonia, andobtained in this way the nitrile of a-amino-P-hydroxypropionic acid ;this on hydrolysis gave the corresponding acid, or serine.Erlen-meyer’s method consisted in the condensation of the esters of hippuricand formic acids to hydroxymethylenehippuric ester ; this on reduc-tion gives rise to benzoylserine, which yields ssrine on saponification.Neither of these methods serves well as a method of preparing thesubstance, and an advantageous new synthesis has now been effectedby Leuchs and Geiger 3 in which the starting point is commercial chloro-acetal. By action of sodium ethoxide on chloroacetal at 12O-l6O0,ethoxyacetal, CH,(OC,H,)*CH(OC,H,),, is obtained, and this byheating with dilute acids yields ethoxyacetaldehyde, CH,(OC,H,)* CHO.Coinpare Ann. Ryort, 1904, 77. * Zoc. cit., 2641.a Ber., 1906, 39, 2644ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 111The crude product so obtained is then treated with ammonia and withhydrogen cyanide, in which way the aminonitrile,CH,(C)C,H,)*CH(NH2)'CN,is produced, and this by action of concentrated hydrochloric acid yieldsthe corresponding acid, namely, P-ethoxy-a-alanine,C H, ( 0C2E5) CH (N H,) C0,H.For the object in view, i t is unnecessary to isolate this product, andthe reaction mixture, after separation of ammonium chloride andevaporation, is now acted on with concentrated hydrobromic acid toreplace the ethoxy-group by hydroxyl :CH,(OC,H,) CH(NH,) CO,H + HBr =CH,(OH)*CH(NH,)*CO,H + C,H,Br.The yield of serine obtained in this way is about 40 per cent.of thatrequired by theory from the ethoxyacetal employed.Although serine has hitherto been obtained only in the racemicform, there is reason to believe that, like other amino-acids, itexists in protein substances in the optically active form, and thatracemisation takes place on hydrolysis.It becomes, therefore, a matterof interest to attempt the resolution of ordinary racemic serine, andthis has now been successfully accomplished by Fischer and Jacobs.'For the purpose of resolving racernic leucine, Fischer, in 1899,prepared the benzoyl derivative and combined this with ciichonine,but later it has been found by this author and Warburg2 that a moresuitable method consists in obtaining the formyl derivative andseparating this into its components as brucine salt. Neither of thesemethods appeared to be successful in the case of serine, but it wasfound that the resolution can easily be effected by forming the p-nitro-benzoyl compound and converting this into quinine and brucine salts,The amino-acid was first acted on by p-nitrobenzoyl chloride in presenceof potassium hydroxide, and the resulting crystalline, sparingly soluble21-nitrobenzoyl d-E-compound was heated with quinine in alcoholic solu-tion, when, on cooling, the d-quinine salt separated out in colourlessneedles. Hydrolysis of this salt with sodium hydroxide yielded thefree d-nitrobenzoyl derivative, from which d-serine was obtained bydecomposition with hydrobromic acid. It is a crystalline dextro-rotatory substance, and is more easily soluble than the racemic serine.The quinine salt of p-nitrobenzoyl-Z-serine which remains in themother liquor after the above separation can be obtained on evapora-tion; it is not pure, however, and still contains about 10 per cent. ofthe dl-compound. For further purification it is converted into thebrucine salt and separated as before. By converting Z-serine intoits methyl ester and allowing this to stand for some hours at 25', theBey., 1906, 39, 2942. LOC. c i t . , 1905, 38, 3997112 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRP.anhydride, C,H,,O,N,, is obtained. This product is a crystalline,strongly lsvorotatory substance, and appears to be identical with asubstance which the author has obtained by the hydrolytic decom-position of silk fibroin. From t h i s observation i t would appearprobable that natural serine is the I-compound.F. Ehrlichl states that racemic amino-acids are readily attacked byyeast in solutions containing a relatively large proportion of sugar,and that good yields of Z-alanine, d-leucine, and I-a-aminoisovalericacid were prepared in this way from the corresponding racemic com-pounds. The yeast appears t o attack both optical isomerides, but, ingeneral, one is attacked more rapidly Shan the other.Polypeptides.The refiearches of Fischer and his colleagues on the chemistry of thepolypeptides continue to make a rapid advance. A useful summaryof the subject, which includes the results obtained up to the end of1905, will be found in Fischer’s lecture to the German ChemicalSociety on amino-acids, polypeptides, and proteins, to which referencehas already been made. Since that time a large number of highlyimportant results have been obtained, but, in the limited space hereavailable, it would serve no useful purpose to attempt any abstract ofthis highly detailed and descriptive work2As an example of the progress which has been made in the synthesisof peptides containing long chains of amino-acid residues, it may bementioned, in passing, that Fischer has succeeded in building up adodecapeptide, containing one leucine and eleven glycine residues.By acting on bromoisohexoyldiglycylglycyl chloride,C,Hg*CHBr* CO(NH* CH2* CO);NH*CH2~COCl,with diglycylglycine, NH,*CH2*CO-[NH-CH2*CO]*NH*CH2*C02H, andtreating the resulting bromo-compound with ammonia, the hepta-peptide leucylpen tagly cy lglycine,C,H,*CH( NH2)*CO(NE*CH,eCO),*NH*CH2-C02H,was obtained. If a similar series of operations is performed with thesubstitution of triglycylglycine for diglycy lglycine, the result is anoctapeptide ; or, if pentaglycylglycine is employed, a decapeptide.Finally, by proceeding in a similar way with bromoisohexoyltetra-glycylglycine chloride and pentaglycylglycine, the dodecapeptide,leucy ldecaglycylglycine,C,H,* CH( NH,)*(NH*CH,* CO),,*NH*CH,*CO,H,was prepared.nearly colourless mass, and ha8 no definite melting point.I n the dry state i t has the appearance of a loose,I n alkaline%%it. Yer. deut. Zuciccrind, 1906, 840. ’ Ih., 1905, 38, 4173 ; 1906, 39, 453, 530, 752, 2315, 2893, 3981ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 113solution it gives a strong biuret reaction, and its solution in diluteaqueous ammonia is precipitated by a saturated solution of ammoniumsulphate; in most of its properties, in fact, it shows a close resem-blance to the natural proteins.A considerable number of polypeptides containing optically activeamino-acid residues have been synthesised and studied ; amongst these,I-leucylglycine, which was obtained from d-a-hromoisohexoylglycineC,H,*CH*KH*$!O which isand ammonia,’ yields the anhydrideproved to be identical with a product which Fiscber and Abderhaldenobtained from elastin by hydrolysis with sulphuric acid.2~‘o-NH- CH;H. J. H. FENTON.1 Compare Walden, Ber., 1897, 30, 3146. Loe. eit., 2318.VOL. 111.

ISSN:0365-6217    

DOI:10.1039/AR9060300071

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION.Reagents and Reuctions.SODAMIDE, which was used by Claisen (AnnuaE Report, 1905, 108) as acondensing agent, has been employed by Semmlerl for breaking downa cyclic ketone wherein a methyl carbon complex adjoins the ketonegroup :*C *C\Q(CH,), + 4 - \(?H(CH,),*NHNa'NHNa. C P 0Thus, fenchone gives the amide of dihydrofencholenic acid ( b ) , whichdiffers from Mahla's acid (a). The following, according to Semmler,represents the relation of fenchone to the acid :CH CH CHFenchon e , Dihydrofencholcnic acid.Sachs2 and his collaborators in a preliminary paper describe theuse of sodamide for preparing aromatic amines from sulphonic acids.A number of naphtholsulphonic acids have been converted into amino-naphthols by fusion of the sodium salt of the sulphonic acid withsodamide,The 1 : 5-, 1 : 8-, and 2 : 7-naphtholsulphonic acids give good yields ofthe corresponding aminonaphthols, whilst the 2 : 6- and 2 : 8-acids form1 : 6-aminonaphthol. As P-naphthol is converted directly into the1 : 6-amino-compounds, the above isomeric change appears to result fromthe rupture of the sulphonic group and the intermediate production ofP-naphthol from the two P-naphthol sulphonic acids :CloH,*ONn + NaNH, = CloK,(ONa)*NHNa i- 33,.The nitro- and halogen derivatives of benzene give poor yields ofBer., 1906, 39, 2577. Ibid., 3006ORGANIC CHEMISTRY-HOMOCYCLIC DIVJSION.115amino-derivatives ; benzene- and naphthalene-sulphonic acids furnish30-50 per cent. of the amino-compounds.A curious result was obtained by fusing together a mixture ofnaphthalene, phenol, and sodamide, when a-naphthylamine and1 : 5-naphthylenediamine were obtained.Sodium bisulphite, which Bucherer has already utilised in variousingenious synthetic processes,1 has now been applied by the same ob-server2 to the preparation of w-sulphonic acids and o-cyanides of aromaticamines. The reaction in question consists in acting on the amine with analdehyde bisulphite and heating the product with potassium cyanide :R*NH, + HO*CHR1*SO,Na = R*NH*CHR,*SO,Na + H20.R*NH*CHR,*SO,Na + KCN = R*NH*cHR,.CN + KNaSO,.Thus, formaldehyde bisulphite and aniline yield sodium methyl-aniline-w-sulphonat e, N HPh*CH,*SO,Na, and w-cyanomet h ylan iline,NHPh.CH,.CN.The importance of this reaction in its connexionwith the indigotin synthesis may be realised from the fact that o-cyano-methylaniline and w-cyanomethylanthranilic acid can be readily obtainedand transformed in to the corresponding acids.The preparation of a-amino-acids, described by Zelinsky andStadnikoff ,3 by the combined action of potassium cyanide, ammoniumchloride, and water on aldehydes, although apparently not new (theprocess was actually patented by Bucherer in 1904), is sufficientlyinteresting t o be reproduced. The changes are explained by thefollowing series of equations :1. KCN + H20 = HCN + KOH.2. R-CHO + HCN = R*CH(OH).CN.3. NH,Cl + KOH = NH, + KC1 + H20.4. PLCH(OH).CN + NH, = R*cH(NH,).CN + H20.Seyewetz and 1610ch4 have employed sodium hyposulphite in presenceof sodium phosphate as reducing agent for nitro-compounds, andobtained the sodium sulphonamates of the base.Nitrobenzene givesan equal weight of the sulphonamate, whilst the yield from nitro-toluene is even better :C,H,*NO, -t Na2H204 + H20 = C,H,*NH*SO,Na + NaHSO,.The action of thiocarbimides on ethylene-aniline and -t,oluidine hasbeen studied by Davis,5 with interesting results. The general characterof the products is represented by the following formulte :$lH9-NR*CS N HR, FH2*NR:CS*NHRC H ~ ~ N H R CH,=NR-CS*NHM,’Ann. &epo?l, 1904, 86.Cow@. rend., 1906, 142, 2052.Be?., 1906, 39, 986, 2796. Ibid., 1722.Trans., 1906, 89, 713,J 116 ANNUAL REPOKTS ON THE PROGRESS OF CHEMISTRY.the union with one or two molecules of thiocarbimide being determinedby the nature of the two reacting substances.The use of copper referred to in a former Report has been furtherextended by Ullmann and Maag 2 to the preparation of y-phenylene-dianthranilic acid, C,H,( NH* C,H,*C0,H)2, from p-dibromobenzene andanthranilic acid dissolved in amyl alcohol in presence of cuprouschloride and finely-divided copper, .which are heated together to140-150".Tbe product is readily condensed to quinacridone,A similar method is described by Goldberg3 for convertinganthranilic into phenylanthranilic acid, &c. Ullm-inn and Stein 4 havealso used copper as a catalytic agent for preparing phenyl et.hers fromphenols arid aromatic bromo-compounds. Bromobenzene and guaiacol,or o-bromoanisole and phenol, with potassium hydroxide and a trace ofcopper, yield o-methoxydiphenyl ether.Francis has shown that benzoyl nitrate, C,H,*CO*O*NO,, obtainedby the action of silver nitrate on benzoyl chloride, may be employedas a useful nitrating agent.Ponzio 6 finds that sodium hypochlorite converts aromatic aldoximesinto diarylglyoxime peroxides of the formula,R*CH:N,O,:CH*R.Minunni and Ciusa 7 use amyl nitrate for the same purpose.On theother hand, the chief product of the action of nitrogen peroxide onbenzaldoxime, which Scholl described as diphenylglyoxime peroxide,is in reality dinitrophenylrnetbarle, C',H,*CH:N,O,. Other aromaticaldoximes give similar products.sA new method of esterification is described by Raikow and T i s c h k o ~ , ~who use syrupy phosphoric acid for effecting the union of alcohol andacid.Gattermanri 10 gives a long and interesting review of the variousmethods which he has introduced into the preparation of aromaticaldehydes.Some of these have already boen described, and include(1) the carbon monoxide method, (2) the hydrogen cyanide methodin presence of cuprous or aluminium chloride. The use of organo-magnesium compounds in conjunction with (3) formic ester and (4)Ann. Beport, 1905, 102.Ibid., 1691. Ibid., 622. Ibid., 3798.Atti 12. Accccd. Sci. To~ino, 1906, 41, 415 ; J. yr. Chcm., 1906, 73, 797.7 Atti K . Accccd. Lincei, 1905, [v], 14 ; ii, 518 ; also Fraiizen and Zimniciniann,. li A t t i 1C. Accad. Lincei, 1906, [v], 15, 118.!' C'hcwi.Zc:t., 1905, 29, 1268.Ber., 1906, 39, 1693.J. pr. C'hc71~. lbO6, 73, 253.lo A?Lnale?i, 1906, 347, 347ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 117ethoxymethyleneaniline is quite new, and the reactions take phceaccording to the following equations :1. CH,*C,H, + ClCHO = CH,'C!6H4*CH0 + HCI.2. CH3*O*C,H, + C1CR:NH = CH,*O*C,H,*CH:NH + HCl.CH,*O*C,H,*CH:NH + H20 = CH,*O*C,H,*CHO + NH3.3. RMgBr + C02H-C,H, = R*CHO + C,H,-OMgBr.4. RMgBr + C,H,O*CH:N*C,H, = R*CH:N*C,H, + C,H,*OMgBr.R*CH:N*C,H, + H20 = R*CHO + C,H,*NH2Lapworth 1 has continued his researches on the addition of hydrogencyanide to unsaturated hydrocarbons (Annual Report, 1904, 104), andhas prepared cyanodihydrocarvone, which on hydrolysis yields twostereoisomeric carboxylic acids exhibiting dynamic isomerism :Cyanodihydrocarvone.Grignard's Reaction.-This protean synthetic reagent still engagesthe attention of chemists; but although many papers have appearedon the subject in the past year, few novel applications have beenbrought to light.Reference may be made to the following: Kohlerand his collaborators have continued their investigations on theaction of alkyl and nryl magnesium bromides on unsaturated com-pounds, and find that the phenyl esters of cinnamic and a-phenyl-cinnamic acid with magnesium phenyl bromide yield, among a varietyof other products, triphenylpropiophenone and tetraphenylpentsnone :CHPh,. CHPh COPh CO(CH,.CHP~I~)~.Triphcnylpropiophenone. Tetraphenylpentnnone.With a/3-unsaturated cyanides,3 additive compounds are formed.Thus, magnesium ethyl bromide and a-phenylcinnamonitrile give twostereoisomeric derivatives according to the equation CHPh:CPh.CN +Et*MgBr + H,O = CHPhEt*cHPh.CN + MgBr*OH.With magnesium phenyl bromide two products are obtained, namely,an unsaturated ketone and a saturated nitrile :C HPh:CPh*CPh:O CHPh,* CHPh* CN.An interesting method for obtaining esters of alcohols and phenols,which depends on Grignard's reagent, is the subject of a patent byH ~ u b e n .~ It consists in treating the anhydride or acid chloride withthe magnesium alkyl halide and the alcohol or phenol. The alcohol isTrans., 1906, 89, 945.Amer. Chcm. J., 1906, 35, 386.'L Kohler and Heritage, Amel.. C'hem. J., 1905, 34, 568.Ber., 1906, 39, 1736.118 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.converted into the halide magnesium alcoholate, which then reacts withthe anhydride :For unsaturated alcohols, magnesium benzyl, methyl, or ethylchloride were found necessary.In this way esters of linalool,terpineol, thymol, borneol, &c., were obtained.It is well known that magnesium alkyl and argl halides unite withcarbon dioxide to form acids.1 Honben2 has shown that carbondioxide can be replaced by carbon disulphide in quite an analogousfashion, forming what the author terms cccrbithionic acids :R*MgX+CS, -+ R*CS,*MgX -+- R*CS,H.They are yellow, red, or violet oils, which are unstable in the freeThey have no tendency to state and have strongly acid properties.form anhydrides, but easily pass into thioacyl disulphides,R*CS* S,*SC *R.To a similar class of reactions belongs the union of sulphur dioxidewith magnesium alkyl halides, which has been investigated by Wuytsand Cosyns,s and also by Houben and Doescher, and independently byBorsche and Lange.Houben found that magnesium piny1 chloride, C,oH,7*MgCl, andsulphur dioxide yield dihydropinenesulphinic acid ; with sulphur dis-solved in toluene, thioborneol and bornyl disulphide.On fraction-ating the latter, it decomposed into thioborneol and thiocamphor.Bornyl sulphide, (ClOHl7),S, was prepared by oxidising thioborneol.Borsche and Lange5 obtained thioborneol and the disulphide by thereduction of the sulphonic bromide and subsequent distillation.Wuyts and Cosyns had previously obtained the same thioborneol bythe action of sulphur on magnesium phenyl chloride.A reaction notvery dissimilar from the above is described by Smiles and Le Rossignol,6in which sulphinic acids are formed by the action of sulphur dioxideon aromatic compounds in presence of aluminium chloride.Meyer and Togel7 have shown that Grignard’s reagent may beapplied t o the synthesis of ketonic esters by the action of magnesiumon a mixture of the acid chloride or bromide and a halogenated ester.Thus, magnesium bromoacetic ester and benzyl bromide gave benzoyl-acetic ester, whilst a-bromopropionic ester yielded P-benzoylpropionicester.1 Grignard, Ann. Chi~n. Phys., 1901, [vii], 24, 435 ; Houben, Ber., 190% 35,3 Bull.SOC. Chim., 1903, [iii], 29, 689.Ber., 1906, 39, 2346.7 Annalen, 1906, 347, 55.2519, 3695 ; 1903, 36, 2897 ; 1905, 38, 3796. a Ber., 1906, 39, 3219.4 Wuyts, Ber., 1903, 36, 869.Proc., 1906, 22, 158ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 219Gomberg and Cone 1 have used the reagent for obtaining tetraphenyl-methane and some of its homologues from triphenylmethyl chloride :(C,H,),CCl+ C,H,*MgCl = (C,H,),U + ILIgCl,.Redwtion.-The study of electrolytic reduction of aromatic acidsreferred t o in a previous Report2 has been continued by Mettler.3He uses lead electrodes and an alcoholic sulphuric acid solution of thesubstance at 20-30°, with a current strength of 6-12 amperes per100 sq. cm. of surface, I n the majority of cases the correspondingalcohols were obtained.Whilst isophthalic acid gave the dialcohol,phthalic and terephthalic acids were converted into dihydro-acids, theformer yielding the A3:,-, and the latter the A2:5-acid. Electrolyticreduction has also been applied to camphoric imide by Tafel andB ~ b l i t z , ~ who obtained two isomeric U- and P-camphidones to whichthey assign the following farmuls :CH,-CH-C oa-Carnphidone. B-Camphidone.and also to camphorcarboxylic acid by Bredt,, who obtained borneol-carboxylic acid.Brand,G who has applied the electrolytic method to aromatic poly-nitro-compounds, obtained nitrohydroxylamino- and nitro-azoxy-com-pounds ; o-nitroacetanilide 7 in alkaline solution gave o-azoacetanilidetogether with traces of the azoxy-compound, in mineral acid solution,o-phenylenediamine and in acetic acid solution 2-methylbenziminazole.o- Ni troace tanilide.2-Methybenzimiiiazole.Among other reducing agents which have been studied in conjunc-tion with polynitro-compounds is hydroxylamine in alkaline solution,which has been introduced by Meisenheimer. The results obtained. byMeisenheimer and Patzig with o- and p-dinitro-compounds indicatethe formation of diaci-dinitrodihydrobenzene. For example, o- andp-dinitrobenzene react in the following way :C,H,(NO,), + 2NH,*OH + 2KOH = C,H,(,NO,K), + 4H,o + N, ;the products on acidifying pass into the nitronitroso-compounds.Ann. Report, 1905, 106.Ibid., 1905, 38, 3806.ti Bcr., 1905, 38, 4006.Ber., 1906, 39, 2526, 2533.Ber., 1906, 39, 1461.3 Ber., 1906, 39, 2933.5 Annnlert, 1906, 348, 199.7 Brand and Stohr, Ber., 1906, 39, 4058120 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The nt-dinitrobenzene behaves quite differently, and yields am-dinitro-m-phenylenediainine as the result of a long series of changesdescribed by the authors in the original memoir.finds sodium hyposulphite to be an active reducingagent for azo-, nitro-, and nitroazo-compounds ; also for quinones anddiketones like benzil, the latter being converted into hydrobenzoin.An interesting case of reduction is described by Willstatter andGoldmann,2 in which the amino-derivatives of benzophenone on reduc-tion with tin and hydrochloric acid undergo condensation into ethylenederivatives.p-Dimethylaminobenzophenone, for example, yields tetra-methyldiaminotetraphenylethylene :Grandmougin2Me,N(>Ph :O -+- Ne,N<_)CPh:CPh/-\NMe,.\-/A very important case of reduction is one described by Semmler,s inwhich he shows that y-, 3-, and r-glycols can be readily obtained fromthe corresponding lactones by redaction with sodium in alcoholicsolution.Ozidcction.--Harries 4 ha5 continued his study of the action of ozoneon organic compounds. He shows that unsaturated alcohols as wellas unsaturated hydrocarbons combine with a molecule of ozone andform ozonides. On the other hand, unsaturated ketones, aldehydes,and monobasic acids take up four atoms of oxygen, one moleculeof ozone attacbing itself to the double link C:C and the fourth atomof oxygen to the carbonyl group C:O.The structure of the lattergroup of ozonides and their decomposition by water may be illustratedin the case of the ozonide of mesityl oxide :0 Q + H,O=CMe,<b + COMe-CHO + H202. '' 0 CH. CMe :O:OThe acetone peroxide which is formed subsequently breaks up bythe action of another molecule of water into acetone and hydrogenperoxide. The author sums up the action of ozone under two heads :the molecule of ozone either attaches itself as 0, and forms an ozonide,or it breaks up and yields a labile peroxide. The ozonide method hasbeen utilised for obtttining a variety of rare preparations, such aslevulinaldehyde, as well as for ascertaining structure.I n this uonnexion the formation of a triozonide of benzene (I) and atetraozonide of diphenyl (11) is cited in opposition to the centricformula for benzene.Naphthrtlepe (III), on the other hand, givesa diozonide, and indicates therefore a diihrence in the structure of thetwo nuclei :Ber., 1906, 39, 3561, 3929. Ibid., 3765. Ibid., 2851.Annalen, 1906, 343, 311ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 121J.I n a later paper 1 Harries and Neresheimer point out that theunsaturated hydroaromatic compounds are sharply distinguished fromthe open chain compounds and members of the aibomatic series by theirstability in presence of water. Tetrahydrobenzeneozonide, to take oneexample, is obtained as a white jelly-like mass, which becomespowdery on washing with ether, and is only decomposed on long boil-ing with water, when i t is transformed into n-adipic acid and a smallamount of the corresponding aldehyde.The oxidation of phenols and amines by means of silver oxide,2which has led to such interesting results in the hands of Will-stPtter and his co-workers, has been the subject of furtherIn the present case benzidine, dihydroxystilbene, and the a zophenolshave been selected for investigation.It has already been stated thatbenxidine in indifferent solvents yields an oxidation product. This hasnow been synthesised and identified, not as diphenylquinonedi-imine(An7iuaE Repoi-t, 1905, 128), but as cliaminpazodiphenyl :The formation takes place apparently through dipbenoquinonedi-imine, which then polymerises, the process being marked by variouscolour changes.p-Azophenol is oxidised by silver oxide or leadperoxide in ethereal solution to quinoneazine :O=(-\=N.N-/-\-*\-/ -\-/- -Quinoneazine.It has a deep orange-red colour. On reduction it changes into a newmodification of p-azophenol, which the author regards as a geometricalisomeride of the original compound. 0- and m-Azophenol are notoxidised by silver oxide, nor is p-azoaniline, but p-dihydroxystilbeneis converted into stilbenequinone. Kehrmann and Prager have usedferric chloride in aqueous solution for oxidising aminophenols, andobtained quinoneimines. For example, 2 : 4-diaminophenol yields2-amino-1 : 4-benzoquinoneimine which was precipitated as dichromateand picrate, but was not isolated :HN=-(-\=o\-/NH,.2-Amino-1 :4-benzoquinoneimine.-I IbM2 3437.Ber., 1906, 39, 2846.Ber., 1906, 39, 3474, 3482, 3492.Ann.Beport, 1904, 122; 1905, 127122 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.I n a further study of the structure of the aromatic purpuric acids,Borsche and Gahrtzl have oxidised the products of the action ofpotassium cyanide on polynitrophenols with potassium hypobromite, andobtained a series of nitrocyanophenols.Chlorination.-The researches connected with chlorination andbromination have followed former lines. Crossley and Hills 2 havestudied the action of phosphorus pentachloride on trimethyldihydro-resorcin, which yields 3 : 5-dichloro-1 : 1 : 2-trimethyl-Aa:4-dihydro-benzene ( I ) and, by loss of hydrogen, 3 : 5-dichloro-1 : 2 : 6-trimethyl-benzene (11).(11.)Chattaway by passing chlorine into an alkaline solution of saccharinobtained one or other of two products, determined by the quantity ofalkali present.The changes are indicated as follows :The latter then breaks up in presence of excess of alkali :A research on the chlorination of the substituted oxamides4 basyielded results not very dissimilar from those obtained by the chlorina-tion of the anilides, &c., already reported.A continuation of Zincke’s investigation 5 on the action of bromineand chlorine on phenols 6 is too long to be satisfactorily curtailed, andthe reader is therefore referred to the original papers.An interesting series of additive compounds with the halogens andhalogen acids is described by Hantzsch and Denstorff.7 The seriesis divided into t w o groups named perhuloids, containing bromineand iodine, and hgdrogen perhaloids, containing a certain number ofmolecules of hydrogen bromide and iodide.Among the formerthe best characterised is the tetraiodide of a-diethoxydinaphtha-stilbene and the dibromide of the same compound,OI,Et*C,,H,*CH :CH*C,,H,*OI,Et.Dixanthylene apparently gives products up to the decaiodide.Ber., 1906, 39, 3359.Ibid., 1905, 87, 1882.Annalen, 1906, 343, 75, 100 ; 349, 67 ct seq.Ann. Report, 1904, 95,Trans., 1906, 89, 875.Ibid., 1906, 89, 155.Annulen, 1906, 349, 1ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 123Dibenzylideneacetone gives an additive product mhich containshydrogen iodide and iodine (CI7Hl40),,HI5, and dimethylpyroneforms a compound, (C,H,O,),,HBr,.They are precipitated by mixingsolutions of the constituent substances as dark-coloured, amorphouscompounds, which can also be obtained in the crystalline condition.The union of the halogen and halogen acid is a very feeble one, andappears t o be partly broken by solution in indifferent solvents.Nevertheless, the cryoscopic results point to the actual existence ofthese compounds in solution. A. Werner1 has studied the behaviourof aromatic dibromides (containing bromine in the side chain) towardsalcohols and phenols, and found that an ortho- or para-methoxylgroup greatly enhances the reactivity of the a-bromine atom, so thatby warming with the alcohol or phenol the bromine is replaced.Thus, o-methoxycinnamic dibromide and ethyl alcohol combine asfollows :\-/ '-\CHBr*CHBr*CO,H + 2EtOH = <\CH(OEt)*CHBr*CO,Et -/Anisylideneacetophenone dibromide shows a similar behavipur :O*CH, O*CH,+ HBr + H,O.The difference in reactivity is manifest by comparison with thedibromide of cinnamic acid, which is not affected by alcohol.Diaxotisation.-An interesting case of steric hindrance in connexionwith the diazo-reaction is recorded by Schmidt and Schallj2 who findthat whilst the 4-aminodiphenic acid is readily diazotised, only one ofthe amino-groups in the 6 : 6'-diamino-acid is attacked, whilst the6-aminodiphenic acid cannot be diazotised :CO,H CO,H C0,H CO,HNH2 NH, H,N/-L/-\ /-\ /-'\-/ \-/ \-/ \2Morgan and Micklethwait 3 have attempted to ascertain the structureof the p-diazoimino-compounds described in the AnnuaE Report for lastyear (p.108) by studying the constitution of the diazo-compound frombenzenesulphonyl- 1 : 8-naph thylenediamine. They conclude that theBer., 1906, 39, 27. Ibid., 1905, 38, 3769.3 Trans., 1906, 89, 4 ; Ber., 1906, 39, 2869124 ANNUAL HEPOIt'rS ON THE PROGRESS O F CHEMISTRY.similarity between this and the p-diazoimide, previously obtained, pointst o similarity in structure, which they represent as follows :i n preference to the iminodiazide formula which was suggested a8 apossible alternative. No anhydride formation of this character hasbeen observed with the sulphonyl derivatives of m-diamines.1The study of the action of nitrous acid on the mixed aliphatic andaromatic bases like W- benzenesulphonylaminobenzylamine,H,N .C,H,*CH,*NH*SO,*C,H,,has disclosed the fact that both ortho- and meta-compounds (the lattermuch less readily) yield diazoimides, whereas the para-compounds donot.The diazoimino-formation depends on the presence of hydrogenin the group NH*SO,'C,H,,for if it is ieplaced no anhydride formation occurs.The structure of the compound obtained by the action of nitrousacid on dibenzoylmethane, which was previously described by Wielandand Bloch,2 has now been identified by them 3 as a diazoanhydride, andis probably formed in the following way :C,H,*CO*F]H=~(OH)*C,H, --3 C,H,*CO*F]=Y *C,H, ~NO NO, NO NO,C,H,*CO* Y=y'c6H5.N:N*OA further contribution by Morgan and Clayton4 on the influence ofsubstitution on the formation of diazoamines and aminoazo-compoundsstudied in the ciise of s-dimethyl-4 : 6-diamino-m-xylene,__ CH3H,C/ \NH*CH,, \--/NH*UH,serves to confirm previous observations that dimethylation of bothsymmetrical and unsymmetrical amino-groups of a dipara-substitutedm-diamine greatly retards but does not entirely prevent the intro-duction of a diazo-complex into the aromatic nucleus of a diamine.Trans., 1906, 89, 1289.Ibid., 1906, 39, 1488.Ber., 1904, 37, 1524, 2524.Trans., 1906, 89, 1054125 ORGANIC CHEMISTRY-HOhIOCYCLIC DIVISION.Meldola and Stephens,l in continuation of former work ( A n n u a lReport, 1903, 106) on the removal of nitro- and methyl-groups in thecourse of diazotisation, show that since 4 : 6-dinitro-rn-anisidine,CH,*ON02<1>NH,,NO24 : 6 -Din i tro - nz- ani d i n e .behaves normally, the rupture of the nitro-group depends on theortho and para position of the diazonium group, and on the presenceof a similar group in the adjacent position.A further study of diazotisation by Meldola and Dale2 has shownthat 4-brorno-2-nitro-1 -naphthylamine, when diazotised in sulphuricacid solution, diluted and heated, loses a nitro-group and passes into adiazo-oxide :Br*CloH,<N2*Hso4 -+ Br*C,,H,<T2 or Br*C,oH5<N2.NO2 0 0The action of diazohydrates on oximes is the subject of a researchby Mai and his collaborators,3 in which a series of condensationproducts of one molecule of diazo-compound with two of the oxime hasbeen obtained.A new method is described by Silberritd and Smart4 for obtainingbistriazobenzene, by which in the place of p-phenylenediamine thep-acetyl derivative is diazotised and converted successively into theacetyl-p-amino triazobenzene and p-aminotriazobenzene, and finally intothe perbromide and the bistriazo-compound.A group of aromatic cyanamides are described by P i e r r ~ n , ~ whoobtains them by the action of a neutral diazobenzene salt on a primarycyanamide :C,H,*N,Cl+ CN*NKa*C,H, = C6H,*N2*C,H,*N H-CN + NaC1.They are acid substances, form alkali salts, take up water in acidsolution, passing into carbamides, and break up on reduction intoaromatic amines and p nminocarbamides.Co?&nsatio.rz.Among the products of condenaation which have latterly attractedattention are the so-called fulgenic acids and f u l g i d e s of Stobbe andhis collaborators.The results of their investigations are contained ina series of papers which have appeared since 1904, and to which aTraiis., 1906, 89, 923.Ber., 1906, 39, 876.Proc., 1906, 22, 156.Tram., 1906, 89, 170.Contpt. rewd., 1906, 143, 340126 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.brief reference has already been made in last year's Annual Report.1The subject has attained some importance in view of the presentuncertain nature of the relation existing between colour and structure.The fulgenic acids are derivatives of succinic acid, the fulgide ofits anhydride, and possess the following general structure (R = aryl oralkyl) :R*CH:F* CO,H (R),:C:F*CO,H (R),:C:Y*CO,HR*CH: C*CO,H R*CH:C*CO,H (R),:C:C*CO,HThey are obtained by condensing aldehydes with succinic ester, orwith y-mono-substituted itaconic esters, thus :CH,*CO,RC,H,* CH: F*CO,RC, H C H : C: C 0,R2C,H,*CHO 3-Q H, CO,Ror C,H,*CHO + C,H,*CH:C*CO,R -The tri- and tetra-substituted derivatives are obtained in a similarmanner, using ketone's and aldehydes in place of aldehydes alone.The f ulgenic acids are crystalline substances which are faintlyorange or yellow in colour.The acids are readily converted into theanhydrides or fulgides by fusion or by the action of acetyl chloridein the cold. They are well-crystallised compounds of a red, orange-yellow, yellowish-green, and brown colour, which exhibit metalliclustre and occasionally marked pleochroism.The colour is closelyassociated with the nature of the radicles present. The anhydridesare converted by alkalis into the corresponding faintly-coloured acids,passing in the process through an intermediate coloured stage, Thefulgides are affected by heat and light, some of them when exposed tobright light changing into highly coloured products, and reverting tothe original colour in diffused light. The reversible change becomesless and less marked with each successive transformation, whilstthe orange or yellow colour becomes paler, until a final condition isreached which represents a new isomeric compound. Similar reversiblecolour changes are produced by heat, with the formation of the sameisomeric substances.But the chief interest connected with these compounds lies in thecolour change effected by the presence of different radicles.Thus,the tetramethylfulgide is colourless, the phenyltrimethyl compoundis sulphur-yellow, the phenyl, diphenyl, and dimethyl compoundsare orange-yellow, whilst the tri- and tetra-phenyl derivatives areorange-red and blood-red respectively.2 Similar results have beenexperienced with other substituents, that is to say, the alkylfulgidesA m . Aeport, 1905, 158. Rer., 1905, 38, 3673ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 127are colourless and the aryl derivatives are coloured, the colour deepen-ing with the number of aryl radicles.1 The introduction of a fury1group in place of phenyl intensifies the t i n t still more ; thus diphenyl-furylfulgide is dichromate-red compared with triphenylfulgide, whichis orange-red.2 The o- and m-nitrophenyl groups also produce a deepercolour than the unsubstituted phenyl group, whilst the p-nitro-grouphas the reverse effect and lightens the tint.3 The methoxyl group inthe phenyl radicle also intensifies the c01our.~The reader is referred to the section on colour and structure(p. 143), in which the above results appear to harmonise well withthe views of Hartley and v.Baeyer.An interesting case of condensation is that of ethyl a-chloro-propionate with aldehydes, which has been studied by Darzens.6Glycidic esters of the formula O< CMe*Co’Et I are formed, the yieldbeing greater in the case of aromatic than of the aliphatic members.Moureu and Lazennec 6 have succeeded in preparing acetylenicnitriles of the formula R*CiC*CN from the corresponding esters andainides by distilling the latter with phosphorus pentoxide.Thesesubstances can be used for obtaining /I-alkyloxy and aryl-acrylic nitrilesby condensation with alcohols and phenols :CHRR,C( OR.,): CH-CN.They break up on hydrolysis into a ketone as follows :R,C(OR,):CH*CN + 3H20 = R,CO*CH, + R’,*OH + NH, + CO,.The products of condensation of o-phthalaldehyde with other sub-stances has been studied by Thiele and Falk.7 They find that ring-formation usually follows, except in the case of Perkin’s reaction,which in the case of acetic acid gives o-phenylenediacrylic acid,C,H,( CH:CH*CO,H),, and phenylhydrazine, which yields a di-hydrazone. Acetone forms 2-acetyl-3-hydrindone, and acetophenonethe corresponding benzoylhydrindone :CH(0H)a/\/\\/\/+- I I C*CO*CH,.CHo-Plith&ldehydc. Intermediate product.Aeetylhydrindone.Ber., 1905, 38, 3897.Ibid., 4081 ; 1906, 39, 392.Compt. rend., 1906, 142, 214.B i d . , 4075.Ibid., 761.Ibid., 211, 338, 450.7 Annalen, 1906, 347, 112128 ANNUAL HEPOR'I'S ON THE PROGRESS OF CHEMISTRY.Also o-phenylenediamine condenses to o-benzylenebenziminazole :CH2/ \ A N - /1 I Ic --I * \/- \/\/NPerkin, jun., and Robinson have condensed a-hydrindone and 4 : 5 -dimethoxy-a-hydrindone with salicylaldehyde and p-methoxysalicyl-aldehyde, with the object of elucidating the structure of certainbrazilin and hsematoxylin derivatives,a-Hydrindone and salicylaldehyde undergo condensation as follows :A continuation of the former researches on the condensation ofphenylpropiolyl chloride with sodium acetylacetone by Ruhemann 2has served to confirm the previous formula assigned to the red com-pound ~ b t a i n e d .~ The transformation from the red compound to acolourless derivative by union with phenylhydrazine, semicarbazide,and hydroxylamine indicates, according to the author, an intrn-molecular change of the following character :Betti has shown that /?-naphthol and formaldehyde condense togetherBy replacing ammonia by hydroxylamine he now with arnrn~nia.~obtains a compound to which the following formula is assigned : 5Clough 4 has condensed benzophenone chloride with U- and P-naphtholand obtained di-a-hydroxynaphthyldiphenylmethane,and di-/3-naphthoxydiphenylmethane, (C,H5),C(OC,oHi)2, respectively.following formul2e were obtained :(C6H5)2C(C10K60H)2~With the sodium salts of the two naphthols, compounds of the0Proc., 1906, 22, 160.l'rn7ts., 1906, 89, 682.Gazwttn, 1906, 36, i, 388.Ann. Report, 1905, 147.Ann.Repol-t, 1904, 99.II'ruw., 1906, 89, 771ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 129Isomeric Change.There are few interesting cases of isomeric change to be recordedduring the past year. Klages and Kessler 1 have continued a formerinvestigation 2 on the isomeric change of ethylene oxides, and showthat diphenylethylene oxide by distillation under low prt ssure or byboiling with concentrated bisulphite solution passes into diphenyl-acetaldehyde :(C6H5),C<IH2 ---+ (C,HS),CH*CHO.The same result has been arrived at by Tiffeneau3 by boilingpp-diphenylethylene glycol with 20 per cent.sulphuric acid, whereasthe diphenylglycol iodohydrin (C,H6),C(OH)*CH21 gives desoxy-benzoin.A similar result was obtained mi th a-phenylpropylene-~@-gly col,which gives phenylacetone on boiling with dilute sulphuric acid,C,H,*CH(OH)*CH(OH).CH, --+ C,H,*CH,*CO*CH,,whilst the iodohydrin is transformed by intramolecular change intoatropaldehyde :C,H5* CH(OH)*CH I* CH, -+ C,H5* C( CHO) :CH,.On the other hand, both phenylethyleneglycol and its iodotiyclrin,C,H,*CH(OH)*CH21, give phenylacetaldehyde.I n a further communication on the subject,* Tiffeneau andDorlencourt show that the molecular changes involved in the con-version of hydrobenzoin into diphen ylace talde hy de and similar trans-formations depend on the stability of the hydroxyl in proximity t o thophenyl group ; for in y-ethylpentylene-py-glycol, and aa-diphenyl-propylene-ap-glycol, in which a hydroxyl is vicinal to an alkyl group,ketones are formed and no interchange of radicles occurs,KRC(OW)*CH(OH)mCH, --+ HRC:C(OH)*CH, -+ RRCH*CO*CH,,whilst methyl- and ethyl-hydrobenzoins change as follows :C,€€,*CH(OH)*C(OH)RR’ -+ C,H,*C(OH):CRR’ --+C,H,*CO* CHKR’.Thus, the hydroxyl is stable in juxtaposition to the phenyl group,and where both hydroxyls occupy this position and are thereforestable, a more fundamental change follows and a shifting of radicleaoccurs.A long paper on a similar topic has also been published by Stoermer.5a Cowpt.reszd., 1906, 142, 1537,VOL. 111. 1CBer., 1906, 39, 1753. Am. Report, 1906, 112.lbid., 1906, 143, 126.Bc?.., 1906, 39, 228F130 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The author’s object was to obtain glycol ethers, to convert themby hydrolysis into the corresponding glycols, and then by removalof water into aldehydes. The preparation of the glycol etherswas effected by Grignard’s method from ethyl phenoxy- and ethoxy-acetates. Irhe conversion into aldehydes by boiling with dilutesulphuric acid occurred much more readily with the ethoxy- than withthe phenoxy-derivatives.The author found the phenoxyl could bereplaced by the ethoxyl group by boiling the former compound withalcoholic potassium hydroxide under pressure. For example, dipheny 1-phenoxymethylcarbinol from ethyl phenoxyacetate and magnesiumphenyl bromide on boiling with alcoholic potash gave the corre-sponding ethoxy-compound,OH*CPh2*CH2*OPh -+ OH*CPh2*CH2*OEt,and on decomposition with 20 per cent. sulphuric acid, diphenyl-acetaldehyde, I n this way a series of both aromatic and aliphaticaldehydes was prepared.The above changes are clearly associated with the pinacone-pinacolinconversion referred to in the Asznucd Report of last year,l a processwhich has been submitted t o further investigation by Delacre withoutleading to any definite result.The structure of a- and P-benzo-pinacolins has also been the subject of a fresh investigation byWertheimer 3 and also by Delacre.4 Whilst the former considers bothcompounds to be oxides of the following formuls,QHPh* YGH4CPh2-0 9Delttcre is of opinion that the structiire of neither is fullyestablished.To the same order of phenomena belongs Wallach’s observation ofthe conversion of cyclopentane glycol by heating with dilute sulphuricacid into cyclopentanealdehyde :YH2*CH CH2*CH2 *>C(OH)*CH.OH -+ C H 2 * C H 2 > ~ ~ o ~ ~ ~ . &2eGH2Another interesting case of isomeric change is described by Johnsonand Jamieson.6 They find that the benzoyl derivatives of un-symmetrical *-methyl- and 3-ethyl-thiocarbamides pass, on boilingtheir alcoholic solutions, or by heating them above their meltingpoints, into the stable symmetrical compounds :NBz,*C(SMe):NH --+ NHBz*C(SMe):NEz.Ann.Beport, 1905, 110.Xonntsh., 1906, 26, 1533.5 Anmxlcn, 1906, 347, 316.Bull. Xoc. china., 1906, [iii], 35, 343.Bd1. Acad. Aoy. Belg., 1906, 7.Anaer. Chem. J., 1906, 35, 297ORGANIC CHEMISTRY -HORIOCY CLIC DIVISION. 131The two classes of compounds are easily distinguished by theirbehaviour with alkalis and hydrochloric acid. The former aredecomposed by alkalis into monobenzyl-$-carbarnides and benzoic acid,whereas the latter are dissolved and precipitated by acids unchanged.On boiling with hydrochloric acid they are decomposed into mercaptaasand dibenzoylcarbamides,Titherley and Hicks last year isolated two benzoyl derivativesof salicylamide, the one melting at 144' readily changing into theother melting a t 208'.The relation between the two compounds wasthen expressed by the amide and iminohydroxy-formulae :BzO*C~H,*CO*NH, -+ BzO C,H;C(OH): NH.This view was contested by Aumers. The authors2 now suggestanother interpretation, according to which the more stable compoundmelting a t 208" has the following constitutiou :CO N HBzCGH4COR fand its conversion into the more labile compound on the one hand andinto the N-ester on the other is brought about by a series of reversiblechanges :CO*NH, -+ ,,<CO*YH - CO-NHBzC6H4<()Bz +- 0-C(0H)Ph +-- -+ C6H,<()HFinally, mention should be made of the action of light on benz-aldehydephenylhydrazone, which, according to Chattaway,3 changesinto the isomeric azo-compoundCGH,*CH:N*NH*CGH5 Z C,H,*CH,*N:N*C,H5.Unsatui-ated Compounds.Gomberg and Cone4 return to the discussion of the structure oftriphenylmethyl, to which reference has already been made.') Theydiscard the hexaphenylethane theory, on the ground that both tetra-and penta-phenylethane are entirely stable substances, and there is noreason for assuming that hexaphenylethane should differ in thisrespect from the other two, Tho oxidisability and reactivity withiodine exhibited by triphenylmethyl are opposed to the htability whichone would infer from a union between two nuclei as represented in thequinonoid formulce of Heintschel and Jacobson. If either formula iscoirect, i t should manifest itself by the behmiour of the p-halogen1 TmrLs., 1905, 87, 1207.IhkZ., 1906, 89, 1.318. Proc., 1906, 22, 36.Bcr., 1906, 39, 3274. Ann. Beport, 1905, 117.K 1352 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.derivatives of triphenylmethyl. The formulze of Heintschel andJacobson would represent these substances as follows :[(XC6H4)2C:/=\/'j (XC,H,),C:/=\/ 6\=/\ i d \=/\C( C6H,X),(X = Cl).I n both cases the chlorine atom in the quinone nucleus, indicated bythe asterisk, should be removable by zinc or silver, thereby linkingtogether two molecules of the original compound. The authors havesubmitted this view to a critical experimental examination by study-ing the behaviour of a series of halogen derivatives of triphenylchloro-methane.From the resulbs, which can only be traced here in outline,they consider that the problem is not yet definitely solved. Thecoloured products, which are formed by the removal of the '' carbinol-chlorine " -with molecular silver from the haloid derivatives oftriphenylchloromethane, must possess the same structure as triphenyl-methyl, since they all give peroxides under similar conditions ; but t h i sstructure cannot be represented by (XC,H,),C-that is, as a derivativeof triphenylmethyl-since it assigns the same function to all threephenyl groups. This cannot be the case, as they show that the halogenof one of the phenyl groups is removable, and therefore one phenylgroup possesses a different function from the other two.Theyattribute this to the probable presence of a quinonoid structure ofsome kind, but different from either of those proposed, and considerthe coloured products obtained by the removal of halogen to be relatedto the triphenylmethane dyes.Thiele and Buhnerl have studied the reducing action of thealuminium-mercury couple on certain fulvene derivatives. Theseunsaturated hydrocarbons were first obtained by Marckwald by con-densing aldehydes with indene. They have a yellow colour, arid areregarded as derivatives of the hypothetical hydrocarbon namedfulvene :The authors find that reduction with the couple takea place readilyif there is a phenyl or carboxyl group attached t o the unsaturatedcarbon group outside the ring, and at the same time the yellow colourAwnnlex, 1906,,347, 249 ; 348, 1.Bey., 1895, 28, 1501ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 133vanishes.indene,Thus, yellow benzylideneindene yields colourless benzyl-gH-CGH5 (p,*C,%C C/\/\CH /\/\CH '\/-I I IlCK ---+ 1 I-ICH, \/Benzyliodene. Benzylideneindene.whereas dimethylfulvene is not reducible :Dim ethyl fulven e.The reducibility also appears to depend on the presence of t h e cyclo-pentadiene ring, for whilst bisdiphenylene-ethylene (I) is reducible,tetraphenylethylene (11) is not :/--\ /-\\ / \ // \/-\ /-\\-/ \.-/--\c:/-11.The result thus contradicts H. Wislicenus's rule that the couple isnot adapted to the reduction of aromatic nuclei or double bonds in opencarbon chains.Where reduction occurs with a conjugated double bond the additionof hydrogen usually, although not invariably, follows Thiele's rule.1The authors find further that benzylindene undergoes condensationwith benznldehyde, yielding a yellow hydrocarbon t o which they assignthe formula of benzylbenzylideneindene :This hydrocarbon also takes up hydrogen on reduction, and gives acolourless product of the formula :1 Ann, Beport, 1904, 105134 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.A further interesting outcome of this research is the proof thatbenzylindene obtained by Tbiele, as described above, and Marckmald'sbenzylindene, prepared by direct benzylation of indene, are identical,and that the same is true of the reduction products of benzylanisylidene-indene and anisylbenzylideneindene, the first of which is obtained bycondensing benzylindene with nnisaldehyde, and the second by con-densing anisylindene with benzsldehyde. The identity of these pairsof compounds is explained by the presence of an '' oscilhting doublebond " :CH*C,H,*O*CH, CH2.C,H4*O* CH,I /\A /\AI I I~H,*C,H, I I\/-- \ / - - ~ H - c , H ~An interesting class of new compounds was described last year byStaudingerl under the name of Letenes, having the general formulaR,C:CO.They have since b3en the object of furtherstudy.2 Diphenyl-ketene is obtained by the action of zinc filings on chlorodiphenylacetylchloride,(C6H,),CC1*C0C1 -+ (CGH5),C:C0.Diphenyleneketene is prepared in a similar fashion from chloro-diphenyleneacetyl chloride, and in properties resembles diphenylketene.It is a yellow crystalline compound, which melts a t 90-90.5O anddecomposes in a vacuum at 150'.It is extremely sensitive to water,combining with it and forming diphenylene-acetic acid, and withalcohol forming the corresponding ester. It also combines with anilineto form the anilide, and with phenylhydrazine to form the hydrazide.If the precipitate of zinc chloride and ketene obtained in the course ofits preparation is exposed to the air, a new compound is produced, towhich the author assigns the following formula :The investigations of Posner, referred to in last year's Report,(p. 115) on the behaviour of unsaturated compounds have been~ontinued.~ In the present case the author has studied the union ofhgdroxylamine with cinnamic and p-methylcinnamic acids, and obtainedP-hydroxylaminophenylpropionic acid, C,H,*CH(NH*OH).CH,*CO,H,and the corresponding p-tolyl compound.A number of their deriv-atives are described and their structure discussed. The preparationof a- chlorocinnamic and chloroccllocinnamic acids is described bySudborough and James.4 Both compounds are formed fromIbid., 3515, 3705. 1 BEY., 1905, 38, 1735. Ibid., 1906, 39, 3062.Tram., 1906, 89, 105ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 135up-dichloro-P-phenylpropionic acid by removal of hydrogen chloridewith alkali, and the acids are subsequently separated by crystallisationof the barium salts in a similar fashion to the bromine derivatives.The conditions of interconversion of the allo-acid and its isomeride arediscussed.Derivatives of Hydvocarbons with Condensed Nuclei.Among the multitude of new naphthalene, anthracene, andphenant hrene derivatives which have been produced during the year,mainly in connexion with the colour industry, and to which from wantof space reference cannot be made, the following possess a certaintheoretical interest :Atkinson and Thorpe have succeeded i n synthesising ethyl1 : 3-diaminonaphthalene-2-carboxylato (11) by condensing ethyl sodio-cyanoscetate with benzyl cyanide, and treating the product (I) withstrong sulphuric acid :I.11.Orchardson and Weizmann 2 have prepared chloronaphthacene-quinone and certain other derivatives from hydroxynaphthoylbenzoicacid ;CO O H co C1And Dienel and Lzgodzinski * have independently obtained1 : 4 anthraquinone, using the following method :0 co II /\/\/\I l l /\/\/\/ co1 : 4-Anthraqninone.a-Anthrol (I) is converted by nitrous acid into 2-(11) and 4-(llI)Trans., 1906, 89, 115.Bcr.) 1906, 39, 926. Pt.oe., 1905, 21, 305.Ibicl., 1717136 ANNUAL IlEPORTS ON THE PROGRESS OF CHEMISTRY.nitroso-1-anthrol, from which by reduction and subsequent oxidation1 : 2- and 1 : 4-anthraquinone are formed :I. 11. 111.The important discovery by Vongerichten and Schrotter in 1881, thatmorphine when distilled over zinc dust yields phennnthrene, has givena definite direction to the study of derivatives of this hydrocarbon.Further investigation has shown that morphol-an integral pnrt ofthe morphine molecule-is a dihydroxyphenanthrene :OH O HThe dimethyl ether of this phenol has since been synthesised bySimilarly, thebaine contains the complex Pschorr and Snmuleanu.14-hydroxy-3 : 6-dimethoxyphenanthrene :Me0 OH OM0/ \-/--\\-/ \ / * \-/-Morphenol, another morphine derivative, has now been converted byVongerichten and Dittmer into trihydroxyphenanthrene,OH OH OHwhilst Pschorr and his collaborators 3 have succeeded in building up aseries of hydroxyphenanthrene derivatives.The method is similar t othat used in the preparation of 3 : 4-dirnethoxyphenanthrene, of whichthe following single example must suffice. Condensation is effectedbetween o-nitrovanillin methyl ether, sodium o-tolylacetate, and aceticanhydride.A nitrocinnamic acid derivative is obtained, which, onreduction and diazotisation, gives 3 : 4-dimethoxy-8-methylphenan-threne :1 Ber., 1900, 33, 1810. Ibid., 1906, 39, 1718,Ibid., 3106ORGANIC CHEMISTRY-HOMOCYCLIC DIVTSIOPI’. 137c HII@-ocyclic Cornpounds.Sabntier and Mailhe 1 have successfully applied the well-knownnickel reduction method 2 to the xylenols, and obtained the correspond-ing djmethylcyclohexanols.Perkin, jun., in conjunction with Simonsen,3 has continued hisresearches on the synthesis of bridged rings. The action of sodiummalonic ester on tribromopropane gives rise t o a dibasic ester,C,,HI5O2Br, which loses hydrogen bromide with potassium hydroxide.The product after hydrolysis loses carbon dioxide on heating and istransformed into a monobasic acid, t o which the authors assign one ofthe following formulae :C H, : F H 2 > ~ ~ * ~ ~ , ~ C--- C H = p IC H,-CH CO, H ’A second ester containing bromine, C,,H,O,Br,, which is formed atthe same time, is supposed t o possess the constitution 111, and loseshydrogen bromide with potassium hydroxide, yielding an acid whichprobably has the structure represented by I V :CH2:Y*CH2--F0,HCH:CH*CH111. IT.A similar class of hydrocyclic compounds t o those of formula TVhave been studied by Wallach.4The siibstances are obtained by condensing cyclic ketones withbromoacetic ester and zinc.The ester of the hydroxy-acid thusformed loses water when heated with potassium hydrogen sulphate,and passes into a n unsaturated acid.The latter in turn lose carbonCon@. rend., 1906, 142, 553.Proc., 1905, 21, 256; 1906, 22, 133.Ann. Beport, 1904, 93.4 n?i,aZcrt, 1906, 345, 139 ; 347, 316138 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.dioxide on heating and give methylene hydrocarbons, although theauthor does not commit himself to the vic 7v that the double-link isnecessarily in the side-chain. These unsati xted hydrocarbons formnitrosochlorides and glycols in the usual maj The latter part with amolecule of water in presence of acids and ve saturated aldehydes(see p. 130). The following scheme represen the changes which ar0supposed to occur :F>C(OH)*CH,*CO,H -+ F>C:CH, -+ R KPerkin, jun., and Kay,l by condensing butane-ap8-tricarboxylicacid by heating with sodium, have obtained ethyl cyclopentanone-2 : 4-dicarboxylate and from i t the monocarboxylic acid,I n a similar manner, ethyl pentane-ayc-tricarboxylate yielded ethylcyclohexanone-2 : 4-dicarboxylate :Wedekind and Weisswange2 have studied a new process for pre-paring diketones of the cplobutane series by removing hydrogenchloride from acid chlorides with triethylamine.isoButyryl chlorideyields 1 : 3-diketotetramethylcyclob~i tane,S(CH,),CH*COCl --+ (CH,),C<~~>C(CH,),.Bauer and Breit have obtained cyclobutane derivatives from/3-benzyl-/I-styrylpropiophenone (from magnesium benzyl halide andcinnamylideneacetophenone, C,H,*CH:CH*CH: C€€*CO* C,H,), andsimilar compounds by heating with equal parts of glacial acetic andsulphuric acids :C,H,* CH: QH C,H5-yH*yH,C6H5*CO*CH*CH*CH,*C6E€,* -+ C,H,*Co* c H,*CK*CH,* C,HGrignard's reaction has also been utilised by Freundler * for obtain-Trans., 1906, 89, 1640.i b i d ., 1916.Bcr., 1906, 39, 1631.C m p t . rcntl., 1906, 142, 343ORGANIC CHERIISTRY-HOR'IOCTCLIC DIVISION. 139ing cyclohexylacetone from magnesium hexahydrobenzyl iodide andacetaldehyde :C,HI,*CH,*MgI + CH,-CHO -+ C,H,;CH(C H,)*OMgT: -+CGH,, *CH,*CH(OH)*CH, + 0 -+ C,H,,*CH2.CO*CH,.Also by Wallach 1 for preparing methylsuberone and other heptacyclicderivatives. The stages of the process will be sufficiently indicated bythe following formuls :Aldehydes of cyclohexane have been obtained by Darzens andLef6bure by condensing cyclohexanone with monochloroxcetic ester andsodium ethoxide.The glycid ester is easily hydrolysed, and the free <I>&&...". *CO,Et,acid on distillation in a vacuum converted into hexahydrobenzaldehydeby loss of carbon dioxide.The comparative study by Crossley and Renouf of dihydro-laurolene, dihydroisolaurolene, and 1 : 1-dimethylcycZohexane has ledto the conclusion that dihydroisolaurolene is 1 : I : 2-trimethylcyclo-pentane and not a cyclohexane derivative, as proposed by Zelinskyand Lepeschkin, a conclusion which has been fully attested by Blanc'ssynthesis of isolaurolene (p. 141).CH2*$!(CH3)2 1 FH*CH,.CR,*CH,Di hy droisolaurolene.I n series of interesting papers, Knoevenagel and others* discussthe structure of two compounds obtained by Pinner 5 and by Kerp andMiiller by condensing acetone with itself, and termed xylitones. Theyappear to be derivatives of cyclohexenone, but although the authorshave succeeded in synthesising a similar substance by condensingAnnnnlcn, 1906, 345, 139.See A m .Eeport, 1905, 120.Ibid., 1882, 15, 586.Trans., 1906, 89, 26.BET., 1906, 39, 3441 el scq.6 Annnlen, 1898, 299, 203190 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.phorone with ethyl scetoacetate, the constitution of the xylitones isstill unknown.Terpenes and Camphors.Among the synthetic preparations of members of the terpene andcamphor group' the following may be mentioned. Perkin, jun.,l hassucceeded by methods previously described in obtaining tertiary men-thol and A3-p-menthene from 1 : 4-methylcycZohexanone and magnesiumGopropyl iodide.Kay and Perkin, jun.,2 have also been successful inobtaining the active modification of A3y-menthenol and A3 ' s(9)-p-menthadiene by first resolving the 1-methyl-A3-c~cZohexene-4-carb-oxylic acid into its enantiomorphs. The subsequent stages in thesynthesis have already been described.3A synthesis of menthene is also recorded by Wallach* by con-densing 1 : 4-methylcyclohexanone and ethyl a-bromoisobutyrate withzinc. The acid obtained from the product by hydrolysis loses carbondioxide on heating and passes into i-A4(8)-menthene, and on boilingthe latter with sulphuric acid into i-A-3-menthene.H CH, H CH,\/ \/ICO,Et*C(CH,),/\(CH,),t: OHC0,EtH CH, H CH,\/ \/ICH, CH CH,A further synthesis of and of active A3 ' *@'-menthadiene isdescribed by Semmler and Rimpel.5 The starting point is a-citron-ellal (I), which is converted successively into isopulegole (II), iso-pulegyl chloride (III), and by the action of sodium and alcohol intoAs(9)-mentbene (IV) :CH-CH, CH*CH, CH'CH, CH-CH,H,O/\CH, H,C'/\CH, H , C A C H , H,C/)CH,OHCl ICH, (H0)HCI JCH, ClHCI/UII, H,Cl / \/ .\ P H 2QH2 7" Q* QHC H,: C-CH, CH,: C'CH, CH,: C-CH, CH,: C-CH,1. 11. 111. IV.1 Tram., 1906, 89, 832. ]bidd,, 839. Ann. Report, 1905, 123. * Ber., 1906, 39, 2504. Jbid., 2582ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 141If isopulegyl chloride dissolved in quinoline is dropped into quino-line heated to 200-2 1 Oo, it is transformed into A3 : s(g)-menthadiene.Semmler and McKenzie have also succeeded in obtaining Buchu-camphor (found in the leaves of Bcwosina betulinna) synthetically.Itrepresents the enolic form of p-menthadione-2 : 3 (11). The synthesiswas effected by the aid of hydroxymethylenementhone (I)z, which isoxidised by means of ozone.CH*CH, CH-CH,H ,c/) c : c H ( o H ) H,C/\CO--3 H,d ICOH2C(/C0 \/C'H.C,H, CH*C,H7I. 11.The diketone undergoes isomerisation under the influence of acidsand alkalis to the enolic form, which is identical with the naturalproduct .Among other interesting syntheses is that of isolaurolene and isa=lauronolic acid by Blanc,, and camphoric acid by Perkin, jun., andT h ~ r p e . ~ Blanc's synthesis is effected by distilling aa-dimethyladipicanhydride under pressure, when i t changes into dirnethylcyclopentanone,The latter yields with magnesium methyl iodide and decomposition ofthe product a tertiary alcohol, which on distillation breaks up intowater and isolaurolene :yH,*C(CH,),*CO*Y FH2C(CH3),*C')0 ~H2*C(CH,),'~(0H)*CH,,FH,*C(CH,),*~*CJHaCH,---CH,-CO CH,--- CH, CH,---- CH2CH,-- CHisolanrolene,The starting point for the new syntliesis of cainphoric acid is y-bromotrimet hylcyclopentanecarboxylic acid or its ester. The compound whenshaken with a mixture of potassium cyanide and hydrogen cyanide andthen heated gives an acid, which on boiling with acetic anhydride iaBey., 1906, 89, 1158, See A m , Chini.Phys,, 1904, [viiil, 3, 49,Trans., 1906, 89, 795.ii G'oinpt. reid., 1906, 142, 1084142 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.converted into i-camphoric anhydride, and from this camphoric acid canbe prepared :CH,*$!MeBr CH,. ?Me* C0,HCH,~H*CO,H CH,*CH*CO,HI CMe, -+ I y3-fe2The numerous researches connected with the study of the structureof terpene and camphor derivatives can only be briefly indicated.Harries finds by the ozone method that guttapercha contains the samefundamental hydrocarbon as Para rubber, namely, 1 : 5-dimethylcylo-octa-Al: -diene, for it yields the same decomposition products.2Wallach and Laiitsch3 have made a study of the structure ofisocarvoxime, which is formed when carvoxime hydrochloride or hydro-bromide is treated with alcoholic potash.As the substance is inactive, the choice of formulz lies between thetwo following :OCH, C*CH,HC/\C:NOH HC/\C:NOHH,C!,)CII, HC\\/CH,C:C( CH,), C*CH(C H 3)2I.11.Further, isocarvoxime when heated with dilute sulphuric or oxalicIt is a hydroxycarvacryl- acid is converted into a base cccrvoline.amine,C*CH,HCH\C*N H,H C ~ ) C H IC*C(OH) (CH,),Cltrvoline.and the mechanism of its formation from isocarvoxime (I) through (11)is fully discussed by the author.I n connexion with the terpenes, the study of nerol by v. Soden andTreff 4 should be mentioned. The authors describe a t length its methodof separation, the preparation of numerous derivatives, and itsbehaviour with various reagents. Without discussing these in detail,it may be stated that the authors conclude, from the close similarityexisting between geraniol and nerol, that the constitution of the twois very similar, and the association of nerol with linalool in essentialoils points to an isomeric change in the latter under the influence ofvegetableacids.They assign one of the following formulz to the com-Ber., 1905, 38, 3985.i:?LllnZc?t, 1906, 346, 26U.Am. aeport, 1905, 126.Ber., 1906, 39, 906ORGANIC CHEMlSTRY--HOMOCY CLIC DlVISION. 143pound, but give preference to the second, in which the central doublebond of geraniol is displaced :C,H,*CH,* CH,*CH : F*C,H ,*OH C,H,* CH,*CH,*CH,*;Ci! C,H4* OHI n another paper by Zeitschell on the same subject, the authorcomes to the conclusion that geraniol is stereoisomeric with nerol. Heshows that by the action of acetic anhydride and other reagents linaloolcan be converted not only into geraniol and terpineol, but into nerol,by a process of isomeric change.The two stereoisomerides are furthershown to be directly connected with the isomeric citrals s and b, whichare likewise stereoisomeric :Cfrl[, CH,(CH,),C: CH*CH,* C H ,*$* CH,Citral n = Geranisl.(CH,),C: CH* CH, CH,-;c;'*C H,HC*CHO CHO-CHCitral b =Nerd.(CH,),C:CH*CH,*CH,*;c;'*CH, (CH,),C:CH*CH,* CH,*g* CH,Geraniol. Nerol.The conversion of pinene hydrochloride into borneol and bornylacetate has been effected by Houben, by means of magnesium.Magnesium piny1 chloride, which is formed, is exposed to a current ofoxygen and then decomposed with sulphuric acid or acetic anhydride.I n the former case borneol, in the latter the acetate, is formed :HC*CH,*OH HO* CII,*CHCloHl~.MgC1 + 0 -+ C1,H,7*OMgC1 -+ CloH17*OH + Mg(0H)CI.CloH17~OMgC1 + (CH,CO),O = Cl,H17*O*CO*CH3 + CH,DCOeBIgC1.Tilden and Shepheard 3 find that magnesium methyl iodide convertsa- and p-limonene nitrosochloride into isomeric compounds of the formulaC,,H,,ON,Cl, by removing oxygen from the bisnitrosochloride.Rupe and Liechtenhan4 have obtained from carvone by means ofmagnesium methyl iodide a hydrocarbon, CllH16, and a small quantityof a ketone, CllHl,O, of unknown constitution.A long and importantpaper on derivatives of pinene by Wallach does not admit of usefulabstraction, and the reader must be referred to the originalmemoir.Colour and Structure.I n the two former Repoyts an indication was given of the direction ofresearch on the relation of colour to structure, and a brief referencewas also made to the results which might be anticipated from the workof Hartley and others on absorption spectra.During the past yearBet-., 1906, 39, 1780. IBid., 1700. Trans., 1906, 89, 920,Be?'., 1906, 39, 1119. Annalen, 1906, 346, 220144 ANNUAL BEPORTS ON THE PROGRESS OF CHEMISTHY..the subject has been actively pursued, and many of the views formerlyadvanced have been modified, matured, or moulded into definiteshape.The absorption bands in the ultraviolet portion of the spectrum of alarge number of coloured and colourless compounds have been sub-mitted by Hartley and his collaborators to careful examination andmeasurement, and have led him to the following views on the structureof coloured substances.The formation of a colouring matter from abenzene derivative depends on the introduction of such modificationsof the structure of the molecule as will displace the absorption bandstowards the visible portion of the spectrum; that is, by retarding therate of oscillation. But whilst the colour depends on the peculiar kindof oscillation of the benzene ring, the retardation may be effected byreplacing hydrogen by hydroxyl or amino-groups (Witt's auxochromes)or by the condensation of several benzene nuclei. Thus, the condensa-tion of three benzene nuclei into triphenylmethane is manifestedby the decrease in number of oscillations and increase in theirintensity, whereby the bands are displaced to the edge ol the visiblespectrum. The characteristic six bands OF benzene become fused intoa broad band on the fringe of the ultraviolet.These views have beenaccepted by v. Baeyer, for they appear to harmonise with his latestinvestigation on the relation of colour to structure.'The coloured solutions of o-trianisylcarbinol and o-hydroxytriphenyl.carbinol in acetosulphuric acid are no longer ascribed to the union of theacid with the quinone oxygen which becomes quadrivalent, for the de-composition of the salt by water should give a t least a passing indicn-tion of the formation of the coloured quinone :CH CHt lCPh,I ICPh,But this only occurs where there is R hydroxyl already in the paraposition to the carbinol group.It therefore follokvs that the colour oftriphenylcarbinol salts is not necessarily connected with the quinonestructure of its hydroxy- or halogen derivatives. v. Baeyer consequentlypeturns to his original view, according t o which the cause of colour isdue to the multiplication of benzene nuclei in triphenylcarbinol. Thechromophore includes the whole complex which already possesses thepower of manifesting colour, and only requires a chemical change sucha8 that produced by union w i t h sulpliuric acid to make it evident. I nthe language of Witt, triphenylmethane is the chromophore and theZeit. nngew. Chem,, 1906, 29, 1287ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION.145sulphate group, the auxochrome. The authoi; has prepared varioushydroxy -derivatives of f uchsone which dissolve in alkalis withcharacteristic colours, para with violet, ortho with blue, and metawith blood-red. To these compounds, which may be regarded asanhydrides of a p-hydroxycarbinol, theis given :f ollo wing q uinvnoid structureR C/\(OH)C,H, C,H,0-, m-, aud p-Hydroxyfuchsone.If excess of alkali is added the colour vanishes, and this is explainedby the addition of the elements of water and the formation of ahydroxycarbinol. The addition of acid reproduces the colour, but at arate varying with the position of the hydroxyl group. The p-hydroxy-fuchsone is precipitated at once as the yellow quinone, whereas the o-and m-compounds separate as colourless carbinols, and only slowly losewater and pass into the quinonoid form.Thus, the hydroxytriphenylcarbinols possess in a varying degree thebasic properties of an alkali, and like the latter lose water on unionwith acids.The same views hold in regard to the amino-derivatives,but in this case i t is necessary for colour to be manifested, that notone but the two amino-groups should occupy a para position to thecentral carbon atom. Why this is necessary is not explained, but thefact remains that with only one quinonoid amino-group the compoundis colourless; but here again many of the salts are coloured. In aformer Report a brief outline was given of Hantzsch’s views on therelation between colour and constitution.He assumed that thechange from a colourless to a coloured substance generally denotes a con-current change of structure. This principle has now been applied to thenitrophenols. All true nitrohydrocarbons are colourless ; so are thestructurally immobile derivatives of nitrophenols like the ethers andesters. Thus, the nitro-group itself is destitute of chromophoricproperties. On the other hand, certain nitrophenols aud all their saltaare coloured. This has been usually explained by saying that thechromophoric character of the nitro-group is enhanced by the auxo-chromic hydroxyl. The view is contested by Hantzsch, who bringsevidence to show that there exist two series of ethers, namely, colour-VOL. 111.Ann, &eporI, 1904, 122.146 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.less or true nitrophenol ethers, and coloured quinonoid or uci-nitrophenolethers.They are represented by the general formulze :True nitrophenol ether mi-Ni trophenol etherColourless. Colotired.Every case of colour in the nitrophenol group is explained in thelight of these new facts. Thus, the free nitrophenols which arecoloured consist of a solid solution or equilibrium mixture of the twodynamic isomerides, the colour intensity depending on the proportionof the coloured or mi-constituent present. Picric acid is a case inpoint. The alkali sal ts represent the preponderating mi-form. Onefact requires explanation, The salts of picric acid are much lighter incolour than the mi-picric ethers which have a red colour.Theexplanation is that there are two aeries of ccci-ethers, a light and adark coloured one. The picrates :correspond to the light colouredseries. The change of colour is not only effected by conversion of thenitrophenols into their salts, but by rise of temperature and by solvents.Light petroleum produces a colourless solution, whereas water, withits greater ionising power, produces a certain amount of the colouredaci-structure. Hantzsch, however, does not subscribe to the view thationisation alone produces colour, because the ions of acids which giverise to coloured salts may exist without colour. The existence ofcoloured and colourless nitrophenol ethers which are non-ionisablecompounds is sufficient evidence of the fact.The colour change isessentially n structural or chemical change in the first instance, andionisation is only a secondary phenomenon. Thus the idea ofchromophore and auxochrome as separate and distinct factors in colourproduction does not hold, but the phenomenon of colour is the effectof a chemical interchange which is promoted by their association inthe same compound :Both forms possess a dissociation constant in aqueous solution, butat present there appears no way of determining it. The fact that thealkali salts as well as the free nitrophenols deepen in colour on heatingwhen the uci-form is almost wholly present is ascribed to a changingproportlion of the yellow variety, or to a greater or less dissociation ofthe mi-compound. 0-, m-, and p-Nitrophenols give coloured salts, andtherefore possess a quinonoid structure, although no m-quinonoid ethershave so far been prepared.The many apparently contradictory facts have been so ingeniouslymet by Eantzsch that the theory almost disarms criticism.NotORGANIC CHEMTSTRY-HOMOCYCLIC DCVISlON. 147withstanding, Kauffmann has taken up the defence of the auxochrometheory, and bases it, in the first place, on the change in the position ofthe absorption band produced in benzene by the introduction ofdifferent groups; in the second place, on the existence of colourednitroethers like nitroquinol dimethyl ether, and nitrohydrocarbonslike nitrostilbene. The existence of Hantzsch's colourless ether isascribed by Kauffmann to the weak ausochromic character of theacetonyl and methoxyl groups.Hantzsch in reply points out that theabsorption spectra cannot determine the presence or absence ofauxochromic groups, because no relation has been shown to existbetween them; he throws doubt on the purity of the colouredspecimen of nitroquinol dimethyl ether, and lays aside the question ofthe general structure of coloured substances as outside t,he presentdiscussion, which only embraces those compounds which exhibit asimple change from colourless t o coloured.I n reference to absorption bands, he supports his contention byBaly's observation2 of the similarity of the bands of colourlessp-nitrophenol and its methyl ether, and the great divergence exhibitedby the coloured sodium salt.I n a further paper3 Hantzsch brings evidence to show that thecolour of the salts of colourless phenol aldehydes and their ethers mustbe ascribed to a similar structural change,and the same explanation has been applied to the case of the hydroxy-ketones and hydrovybenzoic acids.A similar principle to that oE Hantzsch has been adopted by Greenand King4 in support of their view of the quinonoid structure of thephthaleins.They bring evidence to prove the existence of colouredquinonoid alkyl esters of the phthdeins such as0: C6H,:C(CGH4* OH)*C,H,*CO,Me,and hence regard the coloured salts of these compounds as possessingan analogous structure, the sodium salt having 'the formula,O*C,H,: C( C,H; OH) *C,H,* C0,Na.The relation of colour to structure is viewed by Bitly and hiscollaborators from a very different standpoint.Hantzsch's ex-planation of colour phenomena is, in a sense, a statical one, depend-ing on a particular structure, which, however, is not necessarily opposedto the views of Hartley, Baly, or v. Biteyer. Bsly's view is essentiallydynamical. The absorption spectra in the ultra-violet of certaincoloured and colourless substances show characteristic bands which areBer., 1906, 39, 1959. ' Uei.., 1906, 39, 3080.Trans., 1906, 89, 518.Ibid., 2365.L 148 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY./\I I\/ascribed by Baly to the presence of mobile groups (usually associatedwith dynamic isomerism) which give to the molecule, by virtue of theirpotential tautomerism, a rapid vibration or oscillation termed isorro-pesis. The theory embraces a variety of diverse phenomena such astautomerism, steric hindrance, structure, and colour. Thus, thetautomerism of acetoacetic ester and similar substances is supposedto be manifested by distinctive ul tra-violet absorption bands whichthey exhibit in solution.The reactivity of the a-diketones and quinones is associated withother prominent absorption bands,2 and the colour of some of themembers of these groups is traced to internal oscillations set up bychange of structure in the ketone groups. This change of structure isascribed to the change of residual affinities of the ketone oxygen atoms.The quinonoid structure is regarded as the statical representation ofsuch an internal oscillation which: affects the visible region of thespectrum. The colour of the nitroanilines and nitrophenols 3 isascribed in the same way to oscillations set up by the change ofthe residual affinities of the nitrogen and oxygen and the t w onitrogen atoms respectively :t- --+0 OH\/I I\/N I\HNp-Nitrophenol in alcoholic solution and its sodium salt are re-presented by :0 0 0 ONa 0 ONa\/I I\/N/I\U HThe free phenol is staticalThe same principle has beenmica1 and coloured.and colourless, the sodium salt dyna-applied to determining the structure ofthe isonitroso-compounds which are colourless in the free state andTmns., 1904, 85, 1039.Baly and Stewart, Trans., 1906, 89, 489, 502.13nly, Edwards, and Stewart, Traits., 1906, 89, 514ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 149coloured in alkaline solution.1 Finally, the diminished persistence ofthe absorption bands in the case of the substituted quinones isadvanced t o explain the diminished reactivity of the quinone groupformerly attributed by Kehrmann to stericIn summing up the theories of the four chemists whose work hasbeen described, it will be seen that those of Hartley and Baly areessentially dynamical. Colour is manifested by molecular vibration ;but whilst I-Iartley is satisfied with formulating the principle thata particular molecular structure gives rise to bands which bydisplacement may become visible as colour, Baly goes further, andpostulates a potential change of structure as being responsible for theoscillations which are set up, thus manifesting in certain cases thephenomenon of colour. v. Baeyer and Hantzsch confine their attentionto structure, without discussing specifically the nature of thosemolecular oscillations which must be in every case its ultimate cause.Whilst Hantzsch limits his investigation to those compounds whichchange readily from a colourless to EL coloured modification, andexplains the process by a definite isomeric change, Baeyer attacks thebroader question of structure and ,colour, and finds the answer inHartley's theory, which has already been discussed.J. 16. COHEN.Raly, Marsleii, a i d Stewart, Tr'rgns., 1906, 89, 966.Stewart and Baly, Tram, 1906, 89, 618

ISSN:0365-6217    

DOI:10.1039/AR9060300114

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION.The work of the past year among heterocyclic compounds exhibitsthe usual variety ; from a theoretical point of view, the chief 'interestattaches to the questions of ring-formation and the salt-forming pro-perties of numerous substances which contain oxygen or sulphur asmembers of ft ring.Whilst there are no startling results to record in the uric acid groupor amongst the naturally occurring organic dyestuffs, two alkaloidgroups (the quinine and morphine groups) have received a great deal ofattention.Ring-formation.B matter which receives constant attention is that of the number ofmembers possible in a closed-chain compound. A second communicationby R. Meyer contains an account of the results obtained on condensingdibasic acids with the isomeric diaminobenzenes.o-Phenylenediaminenormally condenses to give compounds of the general typewhere R" -maybeen isolated.be as large as C8HI6, o-phenylenesebacamide havingSimilar closed-ring amides cannot he produced fromm- and p-phenylenediamines ; the compounds obtained are certainlyisomeric, but contain a free smino-group, and have to be formulatedthus :N H,*c,H,~N<~~>R~~.On the other hand, G . T. Morgan and F. M. G. Rlicklethwait 2 areinclined to assume the existence of para-bridged rings in the case ofthe diazoimides obtained by the action of nitrous acid on monoaryl-sulphonyl-p-diamines. These have been occasionally formulated witha quinonoid structure, but the products obtained from the benzene-sulphonyl derivatives of 1 : 4- and 1 : 8-nayhthylenediamines show suchgreat similarity as t o render any difference in structure very im-1 Annulen, 1906, 347, 17.2 Trans., 1906, 89, 4, 1158 ; and Ber., 1906, 39, 2869OR,GANIC CHEMISTRY-HETEROCYCLIC DIVISION.151probable. The peri-compound cannot possess a quinonoid constitution,and consequently the authors formulate the 1 : 4- and 1 : 8-derivativesin the following manner :N:N*N-SO,*C,H,I /\A A/\ I 1 I I N I l l \/\L-# \/\/-----N*S02*C,H5It may be noted that a similar ring structure is assigned byW. Vaubel and 0. Scheuer t o the diazoamine resulting from theaction of nitrous acid on ben2idine.l This substance reacts with hydro-chloric acid to yield 4-aminodiphenyl-4'-diazonium chloride.Several compounds containing eight-membered rings have beendescribed during the past year ; thus o-phenylenediamine and succin-aldehyde condense readily, forming a substance which has a normalmolecular weight.On this account, C. Harries and H. Krutzfeld assignto the substance the following constitutional formula : 2Another case in which an eight-membered ring is easily produced isseen in L. Knorr's and P. Roth's study of the spontaneous polymerisa-tion of dimethyl-y-chloropropylamine.3 The resulting &-quaternaryammonium chloride,yields isoallyl ether, dimethylallylamine and tetramethyltrimethylene-diamine on distillation with potash. These results induced H. Hiirleinand R. Kneise14 to examine further the quaternary salt obtainedby Gabriel and Stelzner from 1-y-bromopropylpiperidine ; in this case asimilar conclusion is arrived at, namely, that two molecules condense,with formation of an eight-membered ring.On the other hand, J.von Braun 6 finds that the double formula hesuggested for bis-piperidonium bromide is incorrect, and that thesubstance must be represented as(CH,),:NEr:(CH,),.The substance is only attacked with difficulty by ammonia, andthen a compound,Zeit. Fnrb. Tmt. 17d, 1906, 5, 61.Ber., 1906, 3 9 , 1429.Bw., 1906, 3 9 , 3670.3 Ber., 1906,39, 1420 ; compare S. Gabriel and J. Coliiian, Ber., 1906, 39, 2875.Ibid., 1906, 3 9 , 4347. Ibid., 1896, 29, 2389152 ANNUAL REPORTS ON THE PKOGltESS OF CHEMISTRY.results, whilst had the double formula been correct, another compoundwith a twelve-membered ring should have been formed,J.von Braun and C. Muller 1 also find that the production of the eight-membered ring-heptamethyleneimine-by heating heptamethylene-diamine is impossible ; only a polymeride has been isolated in the formof its platinichloride.E. E. Blaise and Houillon2 find that a base of the compositionC,H17N results by the elimination of a molecule of ammonia fromoctamethylenediamine, but instead of containing a nine-membered ring,it is identical with 2-butylpyrrolidine which they have synthesisedfor purposes of comparison from /3-butyrylpropionic acid. Morerecently they have shown that the supposed decamethyleneimine ofKraff t and Phookan is in reality 2-hexylpyrrolidine.Relationship.between Siructuw und Basicity.During the past year several papers have appeared devotingattention to the relationship existing between the structure of cycliccompounds and their strength as bases. G . Dedichen5 finds thatglyoxaline is a much stronger base than the isomeric pyrazole, therespective affinity constants being 1.2 x and 3.0 x 1O-I2. Thesubstitution of methyl for hydrogen increases the basicity in theglyoxaline series, and also in the pyrazole series if i t is hydrogenatoms attached to carbon that are substituted; on the other hand, thebasicity is diminished by substitution with regard to the imino-group.Both the triazoles and the isodihydrotetrazines are found to be veryweak bases, an increase in strength again being observed whenhydrogen attached to carbon is replaced by methyl.G.T. Morgan and E. M. G. Micklethwait6 find that coumarin isslightly basic, and forms salts of abnormal type such as4C,H,02.H2Y tC1,,4H20.6-Aminocoumario, however, gives salts of normal composition (forexample, 2C,H,( NH2)0,,K2PtCl,, but when the amino-group isacetylated, the salts produced are again of the same type as thosefurnishsd by coumarin itself. The paper contains a discussion on thesubject of residual affinity, and the same subject has attractedA. Hantzsch and 0. Den~torfl,~ who have prepared many additionproducts of halogens and per-halogen hydracids with oxygenBer., 1906, 39, 4110.Ihid., 1906, 143, 361.Ber., 1892, 25, 2252 ; see also Krafft, Ber., 1906, 39, 2193.Compt.rend., 1906, 142, 1541.8 Ber., 1906, 39, 1831. Tram., 1906, 89,$363. Annalen, 1906, 349, 1ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION. 153compounds. The fact that dimethylpyrone frequently forms salts inwhich two molecules of the basic oxygen compound are united toone molecule of the acid, for example, (C7H,02),HBr3, raises thequestion as to whether the oxygen really becomes quadrivalent,or if the halogen or per-halogen acid is not rather attached by aNebenvalenx.”But although ethers do not take up alkyl iodides with the readinessexhibited by most tertiary amines, the two classes of compounds showa certain similarity in their behaviour towards dimethyl sulphate.E. Kehrmann and A. Duttenhofer found that this ester and dimethyl-pyrone slowly combine ; after four weeks at the ordinary temperature,and a further eight days with a small addition of dimethyl sulphate,the mass, on solution in water and addition of potassium iodide, yieldsa tertiary oxonium iodide which the authors think is most probably>o<p. CH:CMeCH:CMe represented by the formula CO<Further examples of the residual affinity of furan, pyrrole, andthiophen derivatives are afforded by the work of K.A. Hofmann andH. Arnoldi,Z and F. Wagener and B. toll en^.^The similarity of functions exercised by oxygen, sulphur and theimino-group is exemplified in the coeroxene, coerthiene andcoeramidene compounds examined by H. Decker and his co-workers.*These three substances/\/‘\/\I I I I\/’\/\ /NHderive their name from coerulein, a colouring matter- prepared byA. von Baeger by the action of sulphuric acid on pyrogallolphthalein.5The constitutions of this colouring matter and its leuco-compoundwere eventually shownlby Orndorff and Brewer to be/’\ /\I 1 I 1y > c o \C$COH/\/\/\ /\/\/\H*I I I I HOI I ’ I (OH \/’\/\/ \/\A/\*H O 0 OH HO 0 OHBer., 1906, 39, 1299.Ibid., 339. Ibid., 410.A?Litaleii, 1906, 348, 210. Ber., 1871, 4, 555, 658.6 Amer. Chcm. J., 1900, 23, 425 ; 1901, 26, 96154 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.respectively. These substances, in the nomenclature employed byDecker, are trihydroxycoeroxenone and tetrahydroxycoeroxenol,whilst for other important compounds containing the same nucleus thefollowing names are proposed :Coeroxone-9.Coeroxan. Coeroxenol-9.The coeroxonium salts are obtained by the action o€ fumingsulphuric acid on fluoran and its derivatives. The latter first dissolvewith the formation of yellow salts; water is then eliminated and redcoeroxonium salts are produced.I80,H k04HThe superior stability of the coeroxonium salts as compared withthose of fluoran furnishes a ready method of separation, Thecoeroxonium salts correspond to a carbinol pseudo-base, ethers ofwhich may be prepared as in the acridanol series; these compoundsare formulated in the following manner :Coeroxenol, the reduction product of the coeroxonium salts, isscarcely capable of isolation, but if the reduction is carried out inpresence of acetic anhydride, its acetyl derivative is obtained.Employment of hydriodic acid and phosphorus as reducing agents ordistillation with zinc dust give coeroxene.A quite independent method of synthesising coeroxonium salts haORGANIC CHEMISTRY-HETEROCYCLIC DIVISION.1 55/'\/\P\ -+! I l l\/\/\/'been worked out by 13. Decker and E. Laube ;I this consists in thecondensation of 1-phenoxyanthraquinone with concentrated sulphuricacid :/\I I/\/\/\1 1 I I\/\ A//\ I I/ j C O 1 -+ y c o/\ O C ! A I ! I 1\/\ /\/0kO,H\/0Laube has prepared similar derivatives of the naphthalene series byemploying the a- and P-naphthyl ethers of erythroxyanthr,zquinone.2The sulphur analogues of these compounds have been prepared byH. Decker and A. Wiirsch3 by the condensation of l-phenylthio-anthraquinone with sulphuric acid, whilst the substance for whichDecker proposes the name coeramidonine was first prepared by theFarbenfabriken vorm.F. Bayer 4 from a-anilino-an thraquinone, andshown to possess the structure/\ I II /\/\A -+ /\/\/\.l i t 1 I I I i\A /\/ \/\/'\156 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The last reaction, it will be noted, is the exact analogue of theformation of coeroxonium salts from fluoran.Somewhat similar relationships to those holding between coeroxeneand the coeroxonium salts have been observed in the case of di-naphthylene dioxide.1 Decker finds that this substance dissolves inconcentrated sulphuric acid with a bright yellow colour and violetfluorescence, but on adding an oxidising agent the colour changes toblue from the production of an oxonium salt :Pseudo- Bases.The relationship of quaternary ammonium salts to pseudo-bases hasagain attracted a considerable amount of attention, and the viewsadvocated by Hantzsch and by Decker with regard to acridine derivativeshave received striking confirmation through C.K. Tinkler’s study ofthe absorption spectra of several acridine derivatives.2Acridine methiodide and acridine hydrochloride give practicallyidentical absorption spectra, but when caustic soda is added to anaqueous alcoholic solution of the methiodide, the absorption spectrumassumes a close resemblance to that of dihydroacridine. Similarchanges have been observed with the methylacridine derivatives, andanalogously phenanthridine methiodide and the corresponding hydroxidegive quite different absorption spectra, the spectrum of the latterresembling that of Pictet and Ankersmit’s dihydrophenanthridine.Tinkler further shows that the cyanides obtained from the methiodidesare not true salts, but ratherpseudo-cyanides ; their absorption spectraare almost identical with those of the dihydroacridines and of thepseudo- bases.A very interesting question relating to pseudo-bases in the acridineseries has been examined by C.S ~ h e n k . ~ Suppose acridylpropionicacid to be converted into its methyl ester and this in turn into amethiodide. By the action of alkali, the methyl attached to csrboxylwill be hydrolysed, and the elements of hydriodic acid will be removed.The resulting base may be expected to be ( a ) a lactone, ( b ) an un-saturated acid, or (c) a betaine, as shown by the formulae :Ber., 1906, 39, 3069.Trans., 1906, 89, 856.3 Ber., 1906, 39, 2424ORGANIC CHEMISTRY-HETEROCY CLIC DIVISION. 157CH-CH,* CO,H CH,* CH,* CO/\/\/\I 1/\/\/\I I I I\/\/\/N----OI N*CH3 N-CH,a. 6. C.CH3The experimental result showed that a colourless lactone is precipi-tated from the solution, but this dissolves in water to a certain extentas a betaioe salt exhibiting a yellow colour and strong fluorescence.By the addition of hydrochloric acid to this solution, acridylpropionicacid methochloride is produced.The question of the constitution of the oxazine :md thiazine dyeshas received much attention from Hantzsch and Kehrmann.1Hantzsch considers these dyes to possess a pccvaquinonoid structureand to be quaternary ammonium salts.Kehrmann, on the other hand,considers them to be ovthoquinonoid oxonium or thionium salts ; againstthe latter view, Hantzsch2 brings forward the fact that salts of thetypesArG&>C6H4 and Ar<igpC6H4.(Ar = bivalent aromatic radicle, R = N, X = acid radicle), whichKehrmann regards as the parent substances of Meldola’s blue andmethylene-blue, are the salts of very weak bases and entirely hydro-lysed by an excess of water. Meldola’s blue and methylene-blue are, onthe contrary, quite stable salts, and this difference cannot be explainedsimply by the substitution of amino-groups for hydrogen, for, takinga simple case, o-phenylenediamine is actually a weaker base thanan i 1 in e .A further argument oE Hantzsch’s is’ not so happy; Bernthsenobtained a substance, me thylene-azure,3 by the oxidation of methplene-blue, and in this he supposed the sulphur had been oxidised to asulphone group.Hantzsch, accepting this view, states that according toKehrmann, the chloride of methylene-azure must have the structurewhich would accord better for behaviour with an acid chloride thanwith a salt. This argument is, however, quite valueless, since Kehr-mann has shown that methylene-azure does not contain oxygen, andSee AWL. Ecyort, 1905, 139. Bcr., 1906, 39, 153.Anmden, 1885, 230, 169158 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.further that it results from methylene-blue by removal of one ormore methyl groups ;Kehrmann has further compared the properties of a number ofsubstances in the methylene-blue ~ e r i e s .~ Adopting his nomenclature,these are the chlorides of : (I) dimethylphenazthionium ; (11) nnilino-phenazthionium ; (111) acetylaminophenazthionium ; (1V) amino-phenazthionium ; (V) diacetylthioninc ; (VI) thionine, and (VII)methylene-blue. Of these chlorides, none, according to Kehrmann,is totally hydrolysed in solution; I and I1 are partially hydrolysed,I11 and IV somewhat less, and V, VI, and VII not at all.Hantzsch 4 cannot see that these results in any way nullify his argn-ment; all they do is to render Kehrmann's theory more improbable.To take an extreme case, even supposing a thionium salt of thestability of methylene-blue could be prepared, it would not then beproved that mehh ylene-blue was necessarily a thionium salt, but merelythat it might equally as well possess a thionium as an ammonium con-stitution.Another question which has received considerable attention in thelast few years is respecting the constitution of aposafranone and alliedcompounds.From the inability of isorosindone to react withmagnesium phenyl halides, H. Decker and A. Wiirsch conclude thatthe internal ammonium phenoxide formula is the more probable.this result is fully confirmed by Bernthsen.2Syntheses.A number of new compounds containing well-known heterocyclicgroupings have been prepared during the past year.Pyrrole Group.C.Biilow and C. Sautermeister have further examined the iV-arnino-pyrrole derivative obtained by condensing hydrazine hydrate withethyl diacetylsuccinate ; the amino-group reacts with phenylthio-carbimide to give a thiocarbamide derivative,6 and Biilow withR. Weidlich 7 finds that it is possible to bring both amino-groups intoreaction with ethyl diacetylsuccinate if symmetrical dihydrazides suchas malonylhydrazide, CH,(CO*NHoNH,),, are employed.N-Substituted pyrroles from ethyl diacetylsuccinate and phenetidineare described by L. Rossi,* whilst the condensation of 1 :4-diketoneswith ammonia has been the subject of a study by W. Eorsche andA. The change actually takes place in two stages, an un-.I Ibid., 1365.Ibicl., 2653. Ibid., 647.Ber., 1906, 39, 1403. Ibid., 1804. Ibid.) 914.Ibid., 3372.Bcr., 1906, 39, 3877.* Rend. Accnd. Sci. Fis. Mat. Napoli, 1906, [iii], 12, 299ORGANIC CIIEMISTRY -HETEROCYCLIC DIVISION. 159saturated amino-ketone being first produced ; this then undergoes afurther condensation :The only case hitherto known 6f the isolation of such an inter-mediate product is the ethyl p-amino-Afi-hexene-3-one-y8-dicarboxylateobtained by Knorr and RaFel from ammonia and ethyl diacetyl-succinate. The present authors increase the number of observedcases, and have obtained unsaturated amino-ketones from ethylplienacylacetoacetate and eth j l acetonylbenzoylacetate ; the structureof the compounds is rendered quite certain by the possibility of trans-forming them not only into pyrrole derivatives but also into keto-lactams.CO,E t .C= C-R I \NHC02Et*CH*CO*ki .,---* CH:C/R/CO-CH*CO*RICH:C<gH2 1%NH I 'CR':CHThe hydrogenation of pyrrole to pyrrolidine, using reduced nickela t 180-190" as catalyst, has been studied by M.Padoa;2 andthe opening of the pyrrolidine ring by benzoylation and subsequenttreatment with phosphorus pent achloride o r pentabromide has beenexamined by J. von Braun and E. Beschke.3 According to tho tem-perature a t which the reaction is carried out benzoylpyrrolidinemay be made to yield either benzo-6-chlorobut,ylamide or as-dichloro-butane.shows that the substances obtained by Wislicenusand Sattler5 by the action of sodium ethoxide on mixtures of ethyloxalate and the acetyl derivatives of primary aromatic amines containrings made up of one nitrogen and four carbon atoms.The so-calledxanthoxalanil results from an indogenide condensation of the first-formed product in the following manner :S. RuhemannHz?mopyrrole has received considerable attention from W. I<uster,GEm., 1900, 33, 3801.Her.., 1906, 39, 4119.Bcr., 1891, 24, 1245.2 Atii 12. i l c c i d Lincci, 1906, [v], 15, i, 219.Tmns., 1906, 89, 1236, 1847.Amale?z, 1906, 346, 1160 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.and R. Willstatter describes the substances isolated from the firststeps in the hydrolysis of chlorophyl1;l the interest of both thesepapers is largely physiological.Indole und Indigo.A few new indole derivatives have been prepared.D. J. Grginobtains 3 : 3 : 5-trimethylindolenine by the reaction between p-tolyl-hydrazine and isobutaldehyde a t so low a temperature as 60°,2 andC. Bdis obtains isoindolinones by the reaction of phenylphthalimidewith nascent magnesium alkyl halide^.^0. Carrasco and M. Padoa have examined the formation and decom-position of the indole nucleus by finely-divided nickel; this acts,in presence of hydrogen, as a hydrogenating agent at 200--250°, butat 300-330° it dehydrogenates methyl-o-toluidine to ind01e.~A. Ellinger 5 shows that the substance obtained by F. G. Hopkinsand Cole on oxidising tryptophan 6 with ferric chloride is not really ahitherto unknown hydroxyquinoline, but indole-3-aldehyde which maybe spnthesised from indole, chloroform, and caustic potash, althoughat the same time some 3-chloroquinoline is obtained.CHCHOThe transformation of tryptophan into kynurenic acid in the organ-ism is evidently ol a similar type :I n a later paper, Ellinger and C.Flamand7 prove that the productof the action of chloroform and potash on scatole is /?-chlorolepidine ashad been supposed by Magnanini.8Emil Fischer and C. Kaas have prepared a glycylrnethylind~le,~Amalen, 1906, 350, 1.Compt. rend., 1906, 143, 430. ’ Ber., 1906, 39, 2515.Ber., 1906, 39, 4388.Ibid., 1906, 39, 1276.? Monntsfi., 1906, 27, 731.6 J. Physiol., 1903, 29, 451.8 ]bid., 1884, 17, 246; 1887, 20, 2608.Atti R. Accad. Lineei, 1906, [v], 15, i, 699ORGANIC CHEMISTRY-HETEROCYCLIC DIVISIOH. 161and R.Pschorr and W. Karo have isolated and hydrogenised N-methyl-P-naphthindole.The molecular weight of indigotin in various solvents has been deter-mined by $1. Beckmmn and W. Gabel ; the formation of double mole-cules was only observed in the case of the cryoscopic determinationin a p-toluidine solution.A number of patents have been taken for increasing the yield ofindoxyl and indigotin in synthetic processes. The fusion of phenyl-glycine with alk:t!i is generally unsatisfactory. Meister, Lucius,& Briining add lead and sodium to a mixture of potassium and sodiumhydroxides on fusion with potassium phenylglycine, and claim to raisethe yield of indigotin to 40-50 per cent.3 The Basler ChemischePabrik employ an intimate mixture of potassium and sodium hpdr-oxides a t 210-260", whilst Lt:on Lilienfeld has patented an addition ofslaked lime or magnesia to the fused alkali and subsequent heatingin a current of ammonia at 150-300°."The Badische Anilin- und Soda-Fabrik obtain indigotindiacetic acidfrom anthranilodiacetic acid ; from the former they obtain successivelyisatin-acetic and phenylglycine-o-carboxylic acids.6The chlorination of indigotin forms the subject of two patents of theBadische C O ., ~ and J. Schwarz describes 6 : 6'-dinitro- and diamino-indigotin which he obtains by using 4-nitro-2-aminobenzoic acidinstead of anthranilic acid in the usual indoxyl reactions.3The Badische Anilin- und Soda-Fabrik also obtain indoxyl by a newprocess, in that they fuse hydroxyethylaniline and its derivativeswith alkalis,C,H,*NH*CH,*CH,OH - 2H, = C,H,<CO->CH2 NH ;'and H.Decker and C. Kopp lo have observed the formation of indigotinby the alkaline oxidation of the addition product of quinoline andethyl chloroacetate.The so-called " thioindigo-red " which stands in the same relation-ship to indigotin that thiophen does to pyrrole, and is manufactured byKalle and Co. has been examined by R. Wirther.ll The formation ofthe substance from thiosalicylic acid is described by P. Friedliirider.12Thiosalicylic and chloroacetic acids react quantitatively in presence ofBer., 1906, 39, 3140. 2 IBid., 2611. ' D.R.-P. 163'339. D.l{.-P. 165691. ' D.R.-P. 166447. ' D.R.-P. 1G8292.7 D.R.-P. 160187, 163280.' D.R.-P. 171172.11 FarberzsiturLg, 17, 85.12 Ber., 1906, 39, 1060.16100, 16101, 16907 of 1906.illonatsh., 1905, 26, 1255.lo Bcr., 1906, 39, 72.Compare the following English patents (Kalle & Co.),VOL. 111. 162 ANNUAI REPORTS ON THE PROGRESS OF CHEMISTRY,alkali; the further action of alkali furnishes a sulphur-analogue ofindoxylcarboxylic acid :coThe latter substance is readily oxidised in alkaline solution tothioindigotin, C16HS02S2, which dissolves in chloroform with bluish-redcolour and strong, yellowish-red fluorescence. The solution in con-centrated sulphuric acid has an intense blue colour.Pyvaxole, Pyraxolone, and Indaxole Derivntiues.E. Azzarellol finds that pyrazoline results from the direct additionof diazomethane to ethylene despite the statement of von Pechmannto the contrary.,The formation of ethyl 4 : 5-dihydropyrazole-3 : 4 : 5-tricarboxylateobserved by 0.Silberrad and C. S. Roy, when ethyl diazoacetatespontaneously decomposes, is evidently due to the formation of ethylfumarate or maleate, which then combines with undecomposed diazo-acetic ester.3L. Knorr and A. Kohler find that pyrazole readily gives l-methyl-pyrazole methiodide which yields sym.-dimethylhydrazine on distilla-tion with strong caustic potash solution.*Further pyrazole syntheses have been effected by G. Minunni andG. Lazzarini,s L. Berend and P. Herms,6 and J. B. Tingle andC. J. Robinso~i.~Amongst pyrazolone syntheses, is to be noted the condensation ofphenylhydrazine with ethyl alkylpropiolates by C.Moureu andI. Lazennec,s for example, the same product is produced on condens-ing phenylhydrazine with ethyl amylpropiolate as with ethyl hexoyl-acetate.Mixed azo-compounds containing pyrazolones as components havebeen examined by A. Eibner and 0. Laue9 and C. Bulow andF. Busse ;lo whilst the condensation of phenylmethylpyrazolone withGazzettn, 1906, 36, i, 618.Trans., 1906, 89, 179.Atti 22. Accnd. Liiacci, 1906, [v], 15, i, 19, 136.J. pr. Chem., 1906, [ii], 74, 112.Ber., 1895, 28, 885.Ber., 1906, 39, 3257.Amer. Chem. J., 1906, 36, 223,Ber., 1906, 39, 2022. 8 Compt. rend., 1906, 142, 1534.lo Ber., 1906, 39, 3861ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 163aldehydes has afforded 31. Betti and C.M. Mundici some interestingresults.1Normally one molecule of an aldehyde forms a condensation productwith two molecules of the pyrazolone, but with P-hydroxynaphth-aldehyde, /?-naphthol is eliminated and a substance possessing theconstitutionN*C,H, N*C,,H5/\ /\ M Q0 Q0 M CH,* C-CH*CH:C-C *CH,results.A. Michaelis and A. Zilg find that phosphoryl chloride reacts in adifferent 1 manner with aldehydo- and keto-bispyrazolones as com-pared with simple pyrazolones.2 Whilst the pyrazolones furnishchloropymzoles, the bis-compounds lose water, the aldehydo-compoundsfurnishing products which may be looked on as carbon analogues ofrubazonic acid. A later paper by A. l\lichaelis and H. Schlecht3shows that whereas 5- and 3-pyrazolones react readily with diazoniumchlorides, this property is not shared by antipyrine and thiopyrine,although l-phenyl-3-methyl-4-benzeneazo-5-pyrazolone may be sub-sequently methylated by the employment of dimethylsulphate.A recent paper by Michaelis * contrasts the action of nitrous acid on5- and 3-pyrazolones, the former yield red unstable isonitroso-derivativeswhich easily furnish rubazonic acid ; the green nitroso-derivatives ofthe 3-pyrazolones may be reduced to .aiuino-compounds which givediazonium salts of reinarkable stability.have obtained good yields of 3-hydroxy1 -phenyl-5-pyrazolone by the condensation of phenylhydrazine andethyl maloiiate in presence of sodium >ethoxide ; the compound hasbeen already described by Michaelis.6An interesting indazole synthesis is described by P.Freundler,7 whoshows that benzene-o-azobenzoic acid condenses with phosphor uspentachloride to furnish chloro-3-hydroxy-2-phenylindazole.M. Conrad and A . ZartP. Car&* finds that a similar reaction takes place with o-hydrazo-benzoic acid, a non-chlorinated product resulting (3-hydroxy-o-indazyl-benzoic acid),E. Bamberger and S. Wildi show that azoindazole results in 90 perGaxetta, 1906, 36, i, 178.Ibid., 1964.der., 1906, 39, 2282,7 Comnpt. r e d , 1906, 142, 1153,Ber., 1906, 39, 370.(i Ibid., 1892, 25, 1506.rj Ibicl., 1906, 143, 54.1 A ~ ~ ~ ~ ~ I C ? L , 1906, 350, 288.nr 164 ANKUAL REPORTS ON THE PROGRESS OF CHEMISTRY.cent. yield when aminoindazole is oxidised by a i r in alkalineso1ution.lStructurally related t o indnzole are the compounds produced byG.Ortoleva.2 When iodine is added t o a solution of benzaldehyde-phenylhydrnzone in pyridine solution, the hydriodide of a newbase,is produced. The phenyl attached t o nitrogen can be oxidised to ttcarboxyl group and carbon d i o d e eliminated from the resultingacid.Iminaxoles.A. Windaus has continued his work on the formation of 4-methyl-glyoxaline by the action of ammoniacal zinc hydroxide on dextrose.3The sugar is resolved into formaldehyde and glyceraldehyde, andthe latter isomerising t o methylglyoxal, the two aldehydes reactwith ammonia according to the following equation :CH,*E*NH + 2NH, + CH,O = CHON >CH + 3H20.c€€,*yoCHOConfirmation of this view is afforded by the fact t h a t addition ofacetaldehyde causes the formation of a certain amount of 2 : 4-dimethylgl y oxaline.S.Gabriel 4 has revised the work of Andreasch on the reactionbetween bromine and a-lsctylcarbamide ; the supposed ‘‘ pyruvicureide ” possesses the formula C,H,O,N,, and is probably constitutedthus :NH*y: CH*$Xe*NHCo<NH*CO CO-NH >co.R. Meldola describes a new trinitro-acetylaminophenol(CH,*CO*NH : OH : NO, :NO, :NO2= 1 : 4 : 2 : 5 : 6)produced by the energetic nitration of diacetyl-p-aminophenol.6 Withprimary amines, nitrons acid and water are eliminated and benz-iminazoles of the general formula :NO, NRproducedBw., 1906, 39, 4276.Ber., 1906, 39, 3886.5 Monatsh., 1902, 23, 812.Gnxxsttn, 1906, 36, i, 473.Trans., 1906, 89, 1935.4 A m a h , 1906, 348, 50, and 350, 119ORGANIC CHENISTRY-HETEROCYCLIC DIVJSLON.1G5Other benziminazoles are prepared by Otto Fischer and F. Limnierfrom 4-chloro-1 : 2-phenylenediamine 1 and by R. von Walther 2ndA. Kessler from 4-nitro-2-aminodiphenylamine ; 2 whilst H. Franzenhas prepared an N-aminobenziminazole of the constitution :which only shows the reactions of an as-sec.-hyclrazine in a, very im-perfect manner, many aldehyde reactions being absent.3M. 0. Forster and H. Grossmann have prepared nitrogen halidesfrom can~phoryl-~-carbsmide,~ whilst the first author 5 has also pre-pared diazoamino-derivatives of $-semicarbszino-camphor. Thesesubstances do not exhibit the usual tautomerism of mixed diazoamino-compounds ; their absorption spectra are of considera,ble interest.Triaxoles.The recognition of the so-called (' trimethintriazimid '' of Curtius(which Hantzsch and Silberrad took for dihydrotetrazine) asI-N-amino-3 : 4-triazole is the most interesting fact to be recorded inthis class of compounds.shows that this substance has afree amino-group, in that it condenses with ethyl diacetylsuccizat e toform a compound containing both pyrrole and triazole rings, and theproduction of triazole from this compound by the action of nitrousacid is no longer surprising, neither is the fact that it yields only amonoacetyl derivative. The discussion between StollQ and Ruhemannas to the constitution of the condensation product with benzaldehydeloses its interest ; the substance obtained is simply a hydrazone.R.Stoll4, A. Weindel, and A. Bambnch9 synthesise triazoles byconverting symmetrical diacylhydrazines into imiuo-chlcrides and re-acting on the latter with ammonia and other bases.C. BulowN--NI I I I R*CO*NH*NH*CO*R -+ R*CCl:N*N:CCl*R --3 RC C *Xi\/NR.0. Dirnroth,. E. Frisoni, and J. Marshall condensed phenylazo-irnide with ketones in the hope of effecting a direct triazole synthesis.10J. pr. Che/~z., [ii], 74, 57.]bid., 1906, [ii], 73, 545.Ibid., 222.Ibid., 826. 8 Zbid., 1228.J. pr. C'henz., 1906, [ii], 74, 1, 13.Ibid., 18S, 241.Tmm., 1906, 89, 402.Bcr., 1906, 39, 2618, 4106.lo Bcr., 1906, 39, 3920166 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The reaction followed a different course according ,to the equation2C6H5*COeCH3 + 2CGH5N3 = C,,H,,ON, + CGH,*NH, + H20,The product of the reaction furnishes 4-amino-1 : 5-diphenyl-1 : 2 : 3-triazole on reduction, which can be reconverted into the com-pound C,,H,,0N5 by diazotisation, coupling with ethyl benzoylacetate,and removal of the carbethoxy-group. It is evident that in theoriginal reaction half of the phenylazoimide plays the part of adiazotising agent.0.Dimroth and H. Aickelinl have obtained 5-triazolone frommethyl l-phenyl-5-triazolone-4-carboxylate by introducing two nitro-groups and subsequent complete hydrolysis ; the substance was isolatedas its p-tolueneazo-derivative. Further triazolone derivatives aredescribed by 0. Dimroth and L. Taub2 and T.Curtius and J.Thornps~n.~E. Fromm and K. Schneider4 have studied the action of phenylhydrazine on perthiocyanic acid ; the expected phenylaminodithio-biuret was not isolated, but in its place three compounds of theformule C,H,N,S,C,IX7N,S, and C,II,N,S,. The first two cornpoundscontain rings made up of two carbon and three nitrogen atoms owingto the elimination of hydrogen sulphide and ammonia respectivelyfrom the initially formed phenylamino- (or anilino-) dithiobiuret.C6H5-~--~Hsc csNH= NH,+\/C,H,*r*NH, ( C6H5*N,H;TH((6) SC CS-NH, Or N.H,*CS CSNH\/NHC,H,* r *NH, C6H5*T-#(b) SC CS*NH, = H2S -!- SC C*NH,\/ \/NHorThe first formula ( b ) is preferred, whilst the compound C,H,N,S, islooked on as having one of the two constitutions :7-7 S-S IC,H,*Y-C &NH Or CGH,*NH*N:C C:NH\/NHNH, \ .Bw., 1908, 39, 4390.Ilkt?., 3912. Jbid., 4140.A~ziinlcit, 1906, 348, 174ORGANIC CHENISTRY-HETEROCYCLIC DIVISION. 167A.. Werner and W. Peters 1 have obtained nitrosoazo-compoundsfrom o-chloronitro-compounds and phenylhydrazine ; E. Grandmouginhas obtained similarly constituted substances by the reduction ofo-nitroazo-compounds with sodium hyposulphite ; the reaction in bothcases may be expressed in the iollowing manner :Furan Gvoup.No important syntheses have been effected in this group, but severalcompounds have been studied containing a ring of one oxygen andfour carbon atoms, E. Vongerichten and F. Miiller consider glycosanto beHO* ~lZ*O*$!H--$!H-OHHO*CH--CH*O*CH, *J.Dekker assigns the constitutionHO/\*CO-->o ,,-,,OH OHROI I*C(OH) \-/OH\/H Ot o tannin,4 whilst S. von Kostanecki and V. Lampe consider thatcatechin is most probably to be represented by the formula0HO HO/’\/’\CH,HO/-\-CH(OH)-~ I JCH, * \-/ \/-OHWhilst W. J. Hale, W. D. ~lcNally, and C. J. Pnter have success-fully converted ethyl pyromucate into tertiary alcohols (furyl-dialkylcarbinols) by aid of magnesium alkyl halides, the attempts of S.Courant and S. von KostaneckiT to prepare flavanonos from P-furyl-chromanones have simply resulted in the opening of the furan ring.R. Stoermer and W. Konig have succeeded in isolating 2-amino-coumaran, but all attempts at making l-aminocoumaran have beenunsuccessful, the substance losing ammonia at the moment of itsformation.C~H~<&>CH.NH, = NH, + c~H,<~($>cH.~Ber., 1906, 39, 185. a Ibid., 3931.Ibid., 241. Ibid., 2497.Compare A. G. Perkin, Trans., 1902, 81, 1160.d n z c ~ . Chcm. J., 1906, 35, 68.- Ibid., 4927. 7 Ber., 1906, 39, 4031168 ANNUAL REPOKTS ON THE PROGRESS OF CHEMISTRY.The " fulgides " mentioned in last year's Report have been furtherexamined by H. Stobbe with very interesting results as to the relation-ship between colour and constitution.lJ. von Zamidzki has determined some of the constants of carefullypurified pyridine, and states that its melting point is +4Z0,2 whilstD. Vorliinder gives a method for the purification of commercialpiperidine which contains unsaturated bases.3With regard t o syntheses in the pyridine series, A.E.Tschitschibabin finds that the action of ammonia on aldehydesalways consists of a termolecular condensation according to thegeneral equation3K*CH,*CHO + NH, = H, + 3H,O + CH<~~:C(CH$$N.P. I. Petrenko-Kritschenko and N. Zoneff show that when methylacetonedicarboxylate and benzaldehyde are condensed in the presenceof ammonia, the product is not a tetrahydropyrone deriva.tive aspreviously described, but methyl 2 : 6-diphenylpiperidone-3 : 5-di-carboxylate.5H. Rogerson and J. F. Thorpe have prepared new cit,razinic acidderivatives.G The sodium derivative of ethyl cyanoacetate and ethyloxalacetate give the sodium derivative of ethyl a-cyanoaconitat e.Ethyl a-cyanoaconitate is transformed into ethyl 2 : 6-dihydroxy-pyridine-4 : 5-dicarboxylste by cold concentrated sulphuric acid :flO,EtC cEtO,C*FH QH EtO,C*flH QHCN C0,Et co co\/The preparation of several other pyridine derivatives is described inthis paper.The etherification of y-pyridone with diazomethane and diazoethaneis interesting; A.Peratoner and E. Azzarello find that a mixture of4 nl kyloxy pyridine ant1 N-alkyl pyritlone is produced in both cases.;Zcr., 1906, 39, 292, 761 ; A?Lnfilc)h, 1C06, 349, 333.Chem. Zeit., 1906, 30, 299.J. Buss. PILy.q. C7zem. SOC., 1905, 37, 1229 ; Abstr., 1906, 90, i, 451.Bcr., 1906, 39, 1358.Annalen, 345, 277.2?1.aits., 1906, 89, 631.7 Atti A. Accarl. Limci, 1906, [v], 15, i. 139ORGANIC CHERIISTKY-HETEROCYCLIC 1)IVISION. 169F.Reitzenstein and J . Rothschild find that 1 : 5-dichloro-2 : 4-di-nitrobenzene and pyridine yield a condensation product,which decomposes on boiling with hydrochloric acid, a substance havingthe composition of 3 : 4-dinitro-5-hydrosyphenylpyridiniurn hydroxidebeing pr0duced.l(2 u in o line.Some interesting qninolirie syntheses have been effected in the pastyear. L. J. Simon and C. Mauguin condense benzylidene-p-naphthyl-amine and ethyl oxalacetate t o ethyl phenyldihydronaphthaquinoline-dicarboxylate, which is readily oxidised to the naphbhaquinolinederivative.2H. Hubner 3 has obtained P-phenylcinchoninic acid by the condensa-tion of isstic acid with phenylacetaldoximeThis work, which is a continuation of that of W.Pfitzinger,, hasbeeii further developed by B. Mu1ert.jhlizarin-blue is converted by mild oxidation to a yellow o ~ t h o -quinone, reconverted to the blue by red iiction, and furnishes alizarin-blue arnide with ammonia.6 Whilst p-aminoalizarin condenses withglycerol and sulphuric acid to give alizarin-blue by the ordinarySkraup reaction, P-aminosnthraquinone condenses with two moleonlesof glycerol t o form benzanthronequinoline.7CHAH;CI’ EH C H C C/\/’\/\\\/\/\AI€? FHH C C C CC H COHC czr\/CHIJ. p r . CJWIIL, 1906, [ii], 73, 257.Ber., 1906, 39, 982.J. p r . Chem., 1897, [ii], 56, 283, and 1902, [ii], 66, 263.Bcr., 1906, 39, 1901.Compt. rmd., 1906, 143, 427, 46ti.Farbeiifitbriken Bayer, D. R.-P. 171836.7 R.A.S.F.: D.R.-P. 171939170 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The degradation of the quinoline nucleus by hydrogen and reducednickel at 260-280" has been found to yield 2-methylindole, methylo-toluidine, and o-toluidine (M. Padoa and A. Carughi).lH. Meyer, in an examination of kynurine derivatives, finds that4-chloroquinoline and sodium alkyloxides yield 4-alkyloxyquinolines ;the methyl compound is transformed into the $-methyl ether a t300-310", whilst the ethyl ether undergoes a similar change at3 6 0'.A, Benrath 3 finds that addition of benzaldehyde to quinoline takesplace on exposure t o sunlight, N-benzoyl- 1 : 2 -dihydroquinoline beingproduced. When, however, quinaldine is substituted for the quinoline,2-P-hydroxy-P-phenylethylquinoline results.Generally, the condensa-tion of aldehydes with quinaldine takes place with elimination ofwater, and the colouring properties of the substances formed havebeen examined by E. Noelting and E. Witte.4 These authors find thatthe product from quinaldine and protocatechuic aldehyde,C,H,N*CH: CH*C,H,(OH),is both a basic and a mordant dyestuff. The nearly related quino-naphtlialones obtained by condensation with naphthalic anhydridehave been studied by A. Eibner and M. Loberirig.5W. Kanig 6 considers that the blue diethylcyanine is representedconstitutionally by the formulaI f so, the subst'ance shows some analogy with the pyridine dyesobtained by the same author from furfuraldehyde.7F. Fichter and R. Boehringer * have prepared a substance containingboth quinoline and indole nuclei, two carbon atoms being common toeach group; this they name quindoline.For its preparat,ion, ethylbis-o-nitrobenzylmalonate is boiled with alcoholic caustic soda, ethylAtti R. Accnd. Lincei, 1906, [v], 15, ii, 113.Monatsh., 1906, 27, 255.Bcr., 1906, 39, 2749.J. pr. Chem., 1906, [ii], 73, 100.ti Bw., 1906, 39, 3932.J. p r . Chem., 1906, [ii], 73, 383.Ibid., 2215.7 lbid,, 1905, [ii], 72, 5 5 5 ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION. 171alcohol and carbon dioxide are removed, and the resulting 6is-o-nitro-benzylmethane condenses to dihydroxyquindoline :NThe two hydroxy-groups may be successively removed by the actionof phenylhydrazine, that attached to nitrogen being first eliminated.Quindoline (ni.p. 247-248O) is a base which yields quaternaryammonium compounds, from these pseudo-bases are produced by theaction of alkalis.Acridine.F. Ullmann has, in conjunction with E. Ruhler, H. W. Ernst, W.Denzler and J. Broido, extended the number of acridine syntheses,land C. Baezner, J. Gueorguieff, and A. Gardiol have prepared hydroxyl-ated phenonaphthacridines.2 The compound obtained by Baezner andGardiol 0x1 condensation of o-aminobenzylaniline with 2 : 7-dihydroxy-naphthalene :OH/\/'\/\/I + 0 = C,H,*NH2 + 2H,O +HOI IOHA.CH I I/\/\/\/I l l 1\/\/\/Nexhibits interesting behaviour. On decomposing its quaternaryacridinium salts with ammonia, a dark blue product, insoluble inalkalis, is produced; the authors think this may be an internalanhydride resulting from the removal of water from the ammoniumand phenolic hydroxyl group; the writer of this report would like topoint out the possibility of the substance being quinonoid in structureand derived from the carbinol pseudo-base. The two views may berepresented in the following manner :Zcit. Farb.Text. I n d . , 1905, 4, 521 ; Ber., 1906, 39, 298, 356, 4332..Ber., 1906, 39, 2138, 2623172 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.OH OH 0-/\Me OHI/\Rile AN/\--Me0The latter view receives support from the work of A. E. Dunstanand J. T. Hewitt on the acridinium compounds of chrysanilinel a.ndchrysophenol ; the corresponding pseudo-bases have only a transitoryexistence and yield quinonoid anhydro-bases.Various derivatives of 9-phenylacridine have been prepared duringthe past year by H.Decker, C. S ~ h e n k , ~ and A. Schmid,* as well asby A. E. Dunstan, with R. O'F. Oakley and J. A. Stubbs.GS . Cut t i t t a has obtained 2 - o - n i t r 0-p- t o lu i d in o - 3 : 5 - di ni t r o ben z oicacid by the condensation of 2-chloro-3 : 5-dinitrobenzoic acid witho-nitro-p-toluidine, and has shown that it condenses in presence ofstrong sulphuric acid to 1 : 3 : 6-trinitro-7-methylacridone.7The dinaphthacridines resulting from the action of chlorides of thetype R-CHCl, on a- and P-naphthylamines, separately or mixed, havebeen examined by A. Senier and P. C. Austin,s whilst di-acridine(quinacridine, &c.) derivatives have been prepared by S.von Niemen-towski,g F. Ullmann, and R. Maag,l0 and (3. Baezner.11Diaziizes.But little has to be recorded with respect to o-cliazines ; J. Thieleand 0. Gunther12 have worked out a method for the preparation ofo-phthalaldehyde in quantity, and the former and K. G. Falk l3 havestudied the products formed on condensation with bases. With phenyl-Trans., 1906, 89, 482. Ibid., 1472. Ecr., 1906, 39, 748.Gaxzetta, 1906, 36, i, 325.Ber., 1906, 39, 385. lo Ibid., 1693. Ibzd., 2656.Ibid., 933. Ibid., 977. 6 Ibid., 2402.Tmns., 1906, 89, 1387.r3 Attnalen 1906, 347, 107. l3 Ibid., 112ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION. 173hydrazine hydrochloride a quaternary ammonium chloride is formedwhich yields a pseudo-base on treatment with alkali :It is a very remarkable fact that an eight-membered ring is not pro-duced by the interaction of o-phthalaldehyde and o-phenylenediainine ;o-benz ylenebenziminazole, 7H2-y:76n4, being formed instead.C,H4* C .NAmongst the nz-diazines, many syntheses of barbituric acid and itsderivatives (especially 5 : 5-dialkylbarbituric acids) must be noted,these have formed the subject matter of many patents.The processesusually consist in a condensation of a derivative of malonic acid(ester, acid chloride, amide, or nitrile) with a derivative of carbonicacid, and the greater number of patents have been taken by theFnrbenfabriken vorm. F. Bayer & Co. and E. Merck.Other syntheses of pyrimidine derivatives are due to T. B.Johnson in conjunction with G.A. Menge,l E. V. McCollum,2 C. 0.Johns3 and McCollum, Johns and F. W. HeyL4 Many of thesesyntheses result in the production of cytosine (6-amino-2-oxypurine)derivatives, and may be illustrated by Johnson and McCollum's pre-paration of 5-hydroxycytosine. Ethyl formate and ethyl ethyl-glycollate are condensed by sodium to the metallic derivative of ethylP-hydroxy-a-ehhoxyacrylate, NaO-C H: C( OEt) C0,Et. The lattersubstance reacts with the hydrobromide of $-ethylthiocarbamide tofurnish 6-oxy-5-ethoxy-2-ethylthiolpyrimidine, which heated withhydrochloric acid to 150' is hydrolysed to isobarbituric acid (2 : 5 : 6-trihydroxypurine). This differs from 5-hydroxycytosine in having Ahydroxyl- instead of an amino-group in position 6.consider that purpuric acid and murexideare most probably represented by the respective formulz :R.Mohlau and H. Litterarhilst 0. Kiihling and 0. Kaselitzof N-substituted o-diamines with alloxan and its derivatives.R. Behrend and H. Friedrich1 J. Bid. C h i t . , 1906, 2, 105.4 A.mer. Cl~cm. J., 1906, 36, i36, 149, 160.6 Bey., 1906, 39. 1314.have examined the condensationfind that dialuric acid forms onlyIbid., 305.J. pr. Chesn., 1906, [ii], 73, 449,]bid., 1906, 1, 437.7 Anncdm, 1906, 344, 1174 ANNUAT. REPORTS ON THE PROGRESS OF CITEMISTRT.one series of salts, C,H,O,N,M, and further, that its acetyl andbenzoyl (mono-) derivatives are also monobasic acids.Before passing on to the purine group with its conjugated pyrimidineand glyoxaline rings, we may note that various quinazoline syntheseshave been effected by M.T. Bogert and his co-workers.lPurine Group.0. Isayz gives a synthesis of purine starting with Behrend's5-nitrouraciL3 The substance is converted into 2 : 4-dichloro-5-nitro-pyrimidine by phosphoryl chloride ; in this compound the 4-chlorineatom may be replaced by the amino-groiip by ammonia in the cold.I f the resulting 2-chloro-6-nitro-4-aminopyrimidine is reduced withhydriodic acid and phosphonium iodide, 4 : 5-diaminopyrimidine results,which may then be condensed with formic acid to purine :A new synthesis of guanine is patented by E. Merck,* and othersyntheses in the purine group are described by W. Traube in conjunc-tion with W. Nithack5 and F.Winter.6Emil Fischer and F. Ach7 describe the transformation of caffeineinto paraxanthine, theobromine, and theophylline. Phosphorus penta-chloride reacts with caffeine to replace hydrogen in position S bychlorine, but then successively converts the methyl into chloromethylgroups. On hydrolysis, the chloromethyl groups are eliminated asformaldehyde, and the resulting chloroxanthine derivative may bereduced.G. Denicke8 has obtained several compounds containing five-membered rings by oxidising uric acid in presenee of ammonia.J. K. Wood has quite recently 9 determined the affinity constantsof xanthine and a number of its methyl derivatives. The dissociationconstants of xanthine, heteroxanthine, theobromine, theophylline,paraxanthine, and cnff eine, were determined, regarding the substanceexamined as ( a ) a base, ( b ) an acid. Caffeine, as might be expected,Ber., 1906, 39, 250, J.Amer. Chem. Soc., 1906, 28, 94, 207, 884, 1449.Ber., 1906, 39, 227.Ber., 1906, 39, 423.Tmns., 1906, 89, 1831,Annalen, 1887, 240, 4 ; 1889, 251, 238. ' D.R.-P., 162336.Arch. Phalm., 1906, 2M, 11.Annnlen, 1906, 349, 269ORGANIC CHE1IIISTRT-ITETEROCTCLIC DIVISION. 175exhibits no acid properties ; the relationships exhibited by theobromineand the isomeric paraxanthine are, however, remarkable. One wouldhave expected the former to behave as the stronger acid, having animino-group joined on both sides t o carbonyl ; the reverse is the case,the value of k, being about twenty times as great for paraxanthineas for theobromine.A number of ureides have been examined ; barbituric acid and5-ethylbarbituric acid are both stronger than acetic acid, but5 : 5-diethylbarbituric acid is extremely weak, the value of k., beingbut one-thousandth that of the monoethyl compound.The conclusionis drawn that the hydrogen atoms of the methylene group in barbituricacid are responsible for furnishing hydrogen ions.Pcwadiaxines.Strictly speaking, the a-P’-diketopiperazines are p-diazine derivatives,but on account of their near relationship to +,be polypeptides will notbe treated amongst the heterocyclic c0mpounds.lA new synthesis of aa’-diketopipernzines has been effected byT. B. Johnson and E. V. McCollum.3 Benzenesulphonylaminoaceto-nitrile is condensed with ethyl chloroacetate, the resulting compoundbeing then successively treated with caustic soda and hydrochloricacid :In the phenazine group, P.Barbier and P. Sisley continue theirstudy of s- and as-phenosafranines 3 and two interesting papers in thenaphthaphenazine group have appeared from 0. Fischer in con-junction with E. SchindlerI n the first of these communications it is shown t h a t naphthaphen-mine yields LZ diketo-compound by oxidation with chromic acid ;on fusion of the o-quinone with caustic soda a hydroxycarboxylic acidis produced :and K. Arntz s respectively./\0See Einil Pischer, Xu., 1906, 39, 530, 752, 3981.2 Amer. Chem. J., 1906 35, 54. Bull. Soc. china., 1906, [iii], 35, 858, 1278,Ber., 1906, 39, 2238.Ibid., 3807176 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.I n the second paper, it is shown that the supposed oxime ofisorosindoae is in reality an amino-compound ; the formulz of thesubstance expected (I), and of that actually obtained (IT), are given ;/\N I II.c,*,1 I.Azines derived from quinoline are described by W. Meigen andE. Nottebohm,l and from anthraquinone by the Farbenfabriken vorrn.P. Bayer SL Co.2Triaxines ccnd Tetmxines.A. Hantzsch has examined the behaviour of cyanuric acid as apse~do-acid,~ whilst papers dealing with tetrazines have appearedfrom T. Curtius and J. Thompson,4 and Curtius, A. Darapsky, andE. il!luller.5 These deal with the relationships existing betweenbisdiazo-, pseudo-diazo-, and dihydro-tetrazine compounds ; but in viewof Biilow’s proof of an aminotriazole formula for the so-called‘‘ dihydrotetrazine ” evidently need revision.Biilow: points out thatthe transformations of ‘‘ bisdiazoacetic acid ” are perfectly explicableif formulated as HO,C*C<~H*N~>C*CO,H ; the isomerisation t oaminotriazoledicarboxylic acid only necessitates an addition andsubsequent elimination of a molecule of water, whilst the hydrolysisto two molecules, of oxalic acid and two molecules of hydrnzine isobvious from the formula.The discussion between Ruhemann and Stoll6 has been alreadyreferred to.Pyrone and Allied Cornp~unds.A method for determining the constitution of the hydroxyl-derivatives of pyrone has been devised by A. Peratoner7; thesubstances are alkylated by diazohydrocarbons of the fatty seriesbefore being submitted to fission by baryta.Thus Yeratoner andBer., 1906, 39, 744. * D.R:P. 167255, 170562.Ber., 1906, 39, 139. Ibid., 3398.lbid., 3410, 3776. Ibid., 4106.‘i Gmzeltcl, 1906, 36, [i], 1ORGASIC CHEMISTRY-HETEROCYCLIC DIVISION. 17 7R. Spallinol find that the ethyl ether of pyromecoriic acid yields aformate and ethoxyacetone mit,h baryta,CH-O- -CHCH*CO*C- 0 Etli IIthe ketone being readily isolated as the p-nitrophenylhydrazone.Applying the same method to the hydroxycomenic acid described in1881 by Reibstein,2 and subsequently obtained by the action ofhydrogen peroxide on meconic acid by Collie and T i ~ k l e , ~ Peratonerand V. CastelIana show that it must be 2 : 3-dihydroxypyrone-6-carboxylic acid, since its trimetbyl derivative furnishes acetylcar binolmethyl ether on fission.For the determination of the constitution of comenic acid, themethod of fission will not distinguish between 3-hydroxypyrone-Z-carboxylic acid and 3-hydroxypyrone-6-carboxylic acid.Bnt a com-parison of the dissociation constants of comenic and conianic acids byPeratoner and F. C. Palazzo,5 has shown that the latter is thestronger acid of the two. Ostwald showed that benzoic acid is astronger acid than p-hydroxybenzoic acid, but weaker than salicylicacid, and hence comenic acid is most probably the 3-hydroxy-y pyrone-6-carboxylic acid.Maltol, identical with the larixinic acid of Stenhouse, has now beenreferred to the pyrone group.The formiila-,CH,assigned to this substance by is unsatisfactory as only mono-acyl derivatives can be preparetl. A. Peratoner and A . Tamburello'find that i t yields only a monoinethyl ether with dinzomethane, andtrhis ether undergoes fission with baryta, furnishing formic and aceticacids and acetylcarbinol methyl ether. Such behaviour is consistentwith one of the two following foi*m&e,CH,*C-O- -CHCH,.O*C-CO*CH - I 1 I1 and CH,*C-O- -CHI1 IIH-C* CO*C*O*CH,of which the second is the more probable, inGazzettn, 1906, 36, i, 14. 2Truns., 1902, 81, 1004. 4Ibid., 7. 6Gazzetta, 1906, 36, i, 33.YOL. 111.that maltol differs fromJ. pr. Chenb., [ii], 24, 286.Gnzzexelta, 1906, 36, i, 21.Ber., 1894, 27, 806.178 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.its lower homologue, pyromeconic acid, in not reacting with amylnitrite, diazonium salts, sulphuryl chloride or iodic acid.has acted on the disodium: derivative of dimethyl-pyrone with ethyl iodide, obtaining thereby a mixture of dimethylethyl-pyrone and dimethyldiethylpyrone. But unless absolute alcohol andperfectly dry materials are used, an isomeride of dimethylethylpyroneis produced, to which the formulaA. W.BainE. E. Blaise and H. Gault publish a synthesis of alkylpyrandi-carboxylic acids, starting with the condensation products of aldehydesand ethyl oxalacetate, and R. Fosse has continued his work on theoxonium salts obtained by the oxidation of pyran derivatives. Hefurther finds that xanthydrol condenses with P-diketones and analo-gously constituted compounds t o form derivatives of which ethylxanthy lacetoacetate,O<%E:>CH* CHAc*CO,Et,may be taken as typical.4C.Bulow and his co-workers have prepared several new anhydro-pyranol compounds, whilst S. von Kostanecki has continued his workin the flavonol series and, jointly with V. Lampe and J. Tambor,effected the synthesis of morin.6Concerning other natural dye-stuff s, the appearance of two papersby J. Herzig and J. Pollak7 must be mentioned ; these authors thinkthat brazilin most probably possesses the constitution,0HO/\”\CH,\/\/ 1 I /C(OH)* 0:: CH-CH,-\/The constitution of euxanthone, the product of the hydrolysie, ofIndian-yellow, has been definitely settled by its synthesis. F.Ullmann and L.Panchaud,s condense 2-chloro-6-methoxybenzoic acidand the monomethyl ether of quinol, using copper powder as catalyst ;on treatment of the resulting 3-phenoxy-6-methoxybenzoic acidTrans., 1906, 89, 1224.Conapt. rend., 1906, 143, 239.Ber., 1906, 39, 625.Annalen, 1906 350, 108.Compt. rend., 1906, 142, 452.Ber., 1906, 39, 214, 850, 2027, 3664.3 Bull. SOC. chim., 1906, [iii], 35, 1005 ; Compt. rmd., 1906, 142, 1543.7 Ibid., 265, and Monatsh., 1906, 27, 743ORGANIC! CHE~ISTRP-W~TEROCYCLZC DJT'ISTON. 1'39with strong sulphuric acid, the dimethyl ether of euxanthone isproduced :OMe OMeOMeSeveral papers have appeared on derivatives of fluoran, A. G .Green and P. E. King1 obtaining an oxonium chloride of a methylester of quinolphthalein by treating a solution of the latter with zincchloride in hot methyl alcohol with hydrogen chloride.To thissubstance and the qiiinonoicl ester obtained from phenolphthalein theyascribe the respective formulze,F,,H,*CO,Me F,H,*C'O,MeC CI I I I H O I I IH*A/\/\()H and /\/\/\\/ \/\0\/\//\/? c 1E. Noelting and K. Dzieworiski 2 find that whilst ccporhodamineethyl ester yields ccporhodamine on treatment with an alkali, ncolourless ethylnted carbinol base is produced by employing alcoholicpotash, and alcoholic ammonia produces a colourless imide.0. Silberrad has produced fluorescent substances by the condensa-tion of mellitic and pyromellitic acids with resorcinol, and concludesfrom the examination and analyses of a.number of derivatives thatfluorescence is not necessarily conditioned by tautornerism,Unc I assijed Cyc Zic Compounds.As usiial, a, very large number of papers have appeared dealing withheterocyclic compounds containing nitrogen, oxygen, and sulphur inthe ring; of these, only a few which have especial interest can benoticed.F. Ullmann and A. Stein have obtained o-diphenylene dioxide,0/\/\/\I l l 1\/\/\/0Ber., 1906, 39, 2365 l b i d . , 2744. Tmns., 1906, 89 1787,N 180 ANKUAL REPORTS ON THE PROGRESS OF CHEMISTRY.by elimination of water from o-dihydroxydiphenyl ether, the dimethylether of the latter compound being obtained by heating a mixture ofbromoanisole, guaiacol , and potas3ium hydroxide in presence ofcopper powder.1 Di-2 : 3-naphthylene dioxide has also been examinedby these authors as well as by A.A. NeiL2The corresponding phenothioxiii has been prepared by F. Mauthner,who prepares a nitrocarboxylic acid of this substance by condensationof 4-chloro-3 : 5-dinitrobenzoic acid with thiocatechol. The nitro-groupis subsequently eliminated by reduction and the diazo-reaction, thecarboxylic group by heating.3T. Zincke and K. Siebert have published a very interesting synthesisof anthroxan (anthranil) derivatives ; they find that o-nitrobenz-aldehyde and phenols condense in presence of hydrochloric acid in thefollowing manner :C-.--(--)OHC,H4<gEY -I- C,.H, *OH + HC1 =The substance produced was first isolated by Guyot and Haller,who, however, assigned to it the constitution of a chlorohydroxy-acridone.It.Stolld and K. Thomae 6 find that dibenzoylhydrazide reacts withphosphorus pentachloride, yielding an imide chloride,C,H,*CCl: N-N: CCl C,H,,and a certain amount of 2 : 5-diphenyl-1 : 3 : 4-oxadiazole. The formersubstance reacts with primary amines, yielding 1 : 3 : 4-triazoles ; thereaction has been extended by Stoll6 and his pnpils by employing sub-stituted dibenzoylhydrazides.G. Young and S. I. Crookes7 have methylatecl several thiazoles ofthe type I, obtaining derivatives of type I1 :I. 11.On the other hand, they confirm the results obtained by Prager,swho found that aminodihydrothiazoles (formula 111) furnish methylderivatives of type IV :FHR*:>C*NHR -+ $?HR-S >C*N(CH,)R'.CH, *h CH,.NIIr. IT.Rer., 1906, 39, 622.Ihid., 1905, 38, 1411 ; 1906, 39, 1340.Bull. SOC. chim., 1906 [iii], 31, 350.Truns., 1906, 89, 59.Ibid., 1059.Ibid., 1906, 39, 1930.J. pr. Chsnz., 1906, [ii], 73, 288.8 Ber., 1889, 22, 1142, 2984ORGANIC CHEMISTRY-HETEBOCYCLIC DIVISION. 181von Pechmann stated the rule that when mixed aniidines arealkylated, the alkyl group attaches itself to the more negative nitrogenatom, and the results obtained by Young and Crookes prove that thisis applicable to cyclic as well as open-chain amidines.A lkalo ids.Amongst new alkaloids the anagyrine of G. Goessmann,* andhordenine of El LBger2 are to be recorded. The former, obtainedfrom Anagyris f g t i d a , has been assigned the formula C,5H220N2, butit is possibly a mixture.Hordenine occurs i n malt germs and hasalso been examined by 0. Gaebel; 3 both his results and those ofLhger agree with the formula,OH.C,H;CH2OCH,*NBle, [OH : CH, = 1 : 41.A. Ladenburg announces the complete synthesis of coniine.Whilst natural coniine gives a rotatory value [.ID 15*6O, thesynthetical reputed coniine gave [.ID 18*3', and the slight differencewas ascribed to an admixture of '' isoconiine " in the synthetical base.It now appears that the artificial product is really a stereoisomeride ofconiine into which i t may be transformed by heating for many hoursat 290--300' and subsequent distillation. The base thus obtainedagrees with coniine in boiling at 164-166", and giving the valueA Pictet has published two r i s u d s of the work on the tobaccoalkitloids, whilst M.Freund and H. H. Reitz 6 have examined thebehaviour of cotarnine towards the Grignard reagents. The re-actions observed are reconcilable with the usually received cotarnineformula, but cyanocotarnine appear6 to be a quaternary ammoniumcyanide.The chemistry of the opium alkaloids has engaged a great amountof attention, and the relationship of the alkaloids morphine, codeine,and thebaine may be taken as fully established. The bases inquestion may be written in the following manner :[a],, 15.67'.Uorphine. Codeine.Arch. Phurin., 1906, 244, 20.5 Arch. €'harm., 1906, 244, 435.6 BdZ. SOC. chirn., 19OS,'[iii], 35, 1 ; Arch. YJLQT~IZ., 244, 3 i 5 .6 &fir., 1906, 39, 2239.Conzpt.remi., 1906, 142, 108 ; 143, 234.Bw., 1906, 39, 2486182 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Code,inone. Thebaine.the conversion of thebaine into codeinone elucidating the rela-tionships of the two latter substances. This conversion has beeneffected in two different mays ; Freund obtained an additive productof thebaine with bromine, but this could not be isolated on account ofits spontaneous decomposition into iiiethyl bromide and bromocode-inone, a substance which successively furnishes codeinone and codeineon reduction. L. Knorr and H. Horlein * have, moreover, obtainedsmall quantities of codeinone by the hydrolysis of thebaine withN-sdphuric acid.The position of the ring containing nitrogen is still undecided,Ereund is inclined to make i t part of a bridged ring,s whilst Pschorrhas proposed a '' piperidine " f ~ r r n u l a , ~ which would receive supportif his formula for apornorphine were correct. This last, however,necessitates a formula (IV) for methylmorphimetliine which isincompatible with the results obtained for hydroxycodeine by Knorrand €iorlein,G the latter substance being capable of further- trsnsfor-11.mation to hydroxymethylmorphimet hine. Hydroxycodeine differsfrom codeine in containing a hydroxyl group in place of hydrogenB e y . , 1906, 39, 844. Jbid., 1409,]bid., 1902, 35, 4382.Ibid. 1906, 39, 3124. * Ibid., 32523 Ibid., 1905, 38, 3234 ; 1906, 39, 844ORGAKIC CHEMISTRY-HETEROCYCLIC DIVISION. 183attached to one of the carbon atoms (9 or 10) of the bridge in thephenanthrene nucleus. This hydroxyl is alcoholic and not phenolicin function so that Freund's formula for thebaine is disproved, whilstformula IV for methylmorphimethine, necessitated by Pschorr'smorphine formula, is also rendered untenable.Knorr and Horlein's most recent work deals with the transforma-tion of chlorocodide into pseudocodeine 1 and the preparation of a fi€thmethylmorphime t hine.2Two very important papers on the cinchona alkaloids have ap-peared ; in the first of these W. Koenigs gives a complete account ofthe work which has been carried out on these substances and thendiscusses the constitution of the non-quinolinic half of the molecule.The constitution of meroquinenine, the product of the hydrolysis ofcinchene, is definitely settled, so that the hydrolysis of cincheneto meroquinenine and lepidine may be represented in the followingmanner :The derivation of cinchene from cinchonine seems to have only twoformulze for cinchonine possible,andc'H,--CH--C H~C'H: m2I.and of these, Koenig's proposed the first i n 1900 * and has retainedit in the present paper.P. Rabe5 points out, however, that the latter formula agreesbetter with the properties of cinchotoxine-an isomerisation pro-BPI.., 1906, 39, 4409. ? Thid., 1412.3 Anianlen, 1906 347, 143. J. pr. Clwm., 1900, [ii], 61, 1.5 Anianlen, 1906, 350, 180184 ANNUBL REPORTS ON THE PROGRESS OF CHERIISTRP.duct of cinchonine. Cinchotoxine furnishes an isonitros~-derivativeindicating tha.t the grouping *CH,*U(OH)-N< in cinchonine becomestransformed into *CH,*CO* and *NH*. Further, when this isonitroso-derivative is submitted t o the Beckmann resclion the molecule breaksup, furnishing t h e nitrilo of meroquinenine and cinchoninic acid asproducts of fission. From this result Rabe decides t h a t the secondformula is to be preferred.IJ. T. HEWITT

ISSN:0365-6217    

DOI:10.1039/AR9060300150

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

STEREOCHEIHSTRY.ALL substances exhibiting optical activity in solution which havehitherto been prepared are known t o contain one or more asymmetricatoms and it is customary t o attribute the optical activity to the pre-sence in the molecule of the asymmetric atom. It has, however,gradually become realised that the optical activity is a direct result ofthe enantiomorphous configuration of the molecule and that the latteris determined by the presence of the asymmetric atom ; it is possibleto write numerous constitutional formulae in which asymmetry is notassociated with any component atom but which, interpreted in accordancewith the tetrahedrsl configuration of methane, actually representenantiomorphous molecular configurations. Thus, in the acid of thefollowing constitution,i t must be supposed that the bonds in the hexaniethylene ring all liein one plane, that of the paper, and that the bonds attaching the groupsH and CO,H t o that ethylenic carbon atom not in the ring also lie inthe same plane.The bonds holding the H and CH, groups to thecarbon atom in the para-position to the ethylene group must, however,lie in a plane at right angles to the first and therefore perpendicular tothe paper and consequently the configuration represented must be anenantiomorphous one. No case of this kind mas known until thepresent year, when W. Marckmald and R. Meth prepared an acid towhich they assign the above constitution and resolved it into itsoptically active components by crystallisation with cinchonine ; theythus obtained the dl-4-methylcyclohexylidene-1-acetic acid with a speciticrotatory power of [a],, + 1 6 O .1 Subsequent to this, W. 11. Perkin, jun.,and W. J. Pope2 state that they have prepared an acid to which theyassign the above constitution and have been for some time endeavouringto resolve it ; their acid is different from that of Marckwald and Meth,and for the latter they suggest the following constitution :Bw., 1906, 39, 1171 and 6404. Proc., 1906, 22, 107186 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Marckwald and Meth quote reasons 1 supporting the constitutionwhich they originally assigned to their acid, and conclude that the acidof Perkin and Pope is the one which contains the double bond in theclosed ring. I n the event of Marckwald and Meth's view provingcorrect, their results must be regarded as marking a distinct advance instereochemistry, in that they furnish the first case of a substancepossessing optical activity in consequence of enantiomorphousmolecular configuration not due to the presence of an asymmetricatom.E. Erlenmeyer has continued his previous work on the stereoisomericcinnamic acids, C,H,*CH:CH*CO,H, and finds 3 that from alcoholic solu-tion three different brucine salts of synthetic cinnamic acid can beseparated ; these melt at 1 3 5 O , 11 3O, and 107" respectively.Cinnamicacid from storax is less soluble in alcohol than the former and gives onlythe brucine salt melting at 135' ; this salt is practically inactive whilstthe others are strongly laevorotatory in alcoholic solution.Erlenmeyertherefore suggests that cinnamic acid from storax is only one of the com-ponents of synthetic cinnamic acid, and supports this contention byquoting results obtained by crystallising cinnamic acid from the twosources with d- and Z-isodiphenyloxyethylamine. The further investi-gation of these substances and their crystallographic examination hasled Erlenmeyer and Barkow 4 to conclude that the following six iso-meric cinnamic acids must be regarded as distinct substances : (1)Erlenmeyer, sen.'s, isocinnamic acid, m. p. 37-38' ; (2) allocinnamicacid, m. p. 68"; (3) Liebermann's isocinnamic acid, m. p. 5 9 O ; (4)anorthic cinnamic acid, m. p. 80' ; (5) a-cinnamic acid, m. p. 134-135' ;(6) p-cinnamic acid, m. p.132-1 33'. The isocinnamic acid containedin the most soluble of the brucine salts, which differs slightly in crystal-line form from Liebermann's acid, and the synthetic acid apparently Con-stitute two more isomerides. Erlenmeyer's conclusions have beencriticised very adversely by W. Marckwald and R. Meth; theseauthors show that the salt melting at 11 3' contains alcohol of crystal-lisation and that the salt melting at 135" contains two molecules ofcinnamic acid to each one of brucine. They also point out that on dis-solving equivalent quantities of synthetic and natural cinnamic acidand brucine in alcohol, the solutions have the same rotatory power.They therefore conclude that the experimental evidence does not justifythe conclusions of Erlenmeyer.The view that mineral oil originates from the bacterial decompos-tion of proteins is put forward by C.Neuberg and supported by the1 Ber., 1906, 39, 2035.3 Ber., 1906, 39, 285.5 Ibid., 1177, 1966, and 2598.2 A m . Report, 1905, 168.4 r b i d . , m o .Biochem. Zeit., 1906, 1, 368STEREOCHEMISTRY. 187similarities between the optically active acids of petroleum and thoseobtained by the putrefaction of cheese, gelatin, &c. Vegetable lipasewas found to liberate d-dibromostearic acid and a dextrorotatoryglyceride from dI-dibromostearic triglyceride, showing that unorganisedferments are capable of producing optically active substances from in-active fats.E. Fischerl has contributed in the connected form of a lecture avaluable digest of his chemical investigation of the amino-acids,polypeptides, and proteins, in which the stereochemical relations ofthese substances are fully considered.a-Bromoisohexoic acid has been resolved into its optically activecomponents by E.Fischer and H. Carlj2 the method employed being thecrystallisation of the mixed brucine salts ; the lavorotatory acid yieldsd-leucine ( [ u ] ~ - 14-20') with ammonia. a-Bromo-/I-phenylpropionicacid, C6H5*CH2*CHBr* CO,H, has also been resolved by crystallisationwith brucine and quinine ; the kevorotatory acid gives d-phenyl-alanine, C,H,*CH,*CH(NH,)*CO,H, ([.ID + 31 T8') with ammonia.Fischer also describes convenient methods for preparing d- andE-leucines, and for converting these amino-acids into derivatives ofd-a-bromoisohexoic acid.H e has resolved synthetic a-aminoiso-valeric acid into its optically active components by crystallising itformy1 derivative with brucine ; the compound of the I-acid crystal-lises as the less soluble product. Fischer gives the name valine tothe acid and identifies d-valine with the active aminovaleric acid,(cH,),CH*CH(NH, j*CO,H, separated from lupins, horn, and casein ;d-valine has a bitter taste, whilst the I-isomeride, which has not yetbeen found in nature, possesses a pronounced sweet flavour. Thisdistinction between the taste of two enantiomorphously related iso-merides is similar to that observed in the case of the leucines andasparagines.E. Fischer and W. A. Jacobs have resolved externally compensatedp-nitrobenzoyl-dl-serine, OH*CH2*CH(C0,H)*NH*CO*C,H4*N0,, bycrystallisation with quinine ; the salt of the d-acid separates first andthe E-acid remaining in the mother liquors is conveniently purified bycrystallisation with brucine.The d-and I-serine,OH*CH,*CH(NH,)-CO,H,prepared by hydrolysing the nitrobenzoyl derivatives, differ in taste,the former being thesweeter; the I-serine is identical with the serineisolated from silk. isoserine, NH,* CH,*CH(OH)*CO,H, and diamino-propionic acid have been also resolved by crystallising their benzoylderivatives with optically active bases.C. Neuberg and E. Ascher resolve up-diaminopropionic acid,Ber., 1906, 39, 530. Ibid., 3996. Ibid., 2893.Bid., 2320. Ibid., 2943.Biochem. Zeit., 1906, 1, 380188 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.NH,*CH,*CH(NH,)*CO,H, by crystallisation with d-camphorsul-phonic acid ; the salt of a d-rotatory acid is thus first separated but, asit is donvertible into Z-glyceric acid by the action of nitrous acid,it must be termed Z-ap-diaminopropionic acid.An improvement of Warburg and Fischer’s method 1 of resolvinga-bromopropionic acid, CH,*CHBr *CO,H, has been dsvised byL. Ramberg;, the dZ-acid is frozen out from the acid which has beenpartially resolved by cry stallisation with cinchonine.dl-Aminobenzylidene-/3-naphthol has been resolved by M. Betti 3 bycrystallisation with d-tartaric acid ; the salt, dBdA, separates inalniost theoretical yield as the more sparingly soluble salt,J.C. Irvine4 contributes a simple method for the separation ofi-lactic acid from the dZ-acid by cry stallisation with morphine ; mor-phine Z-lactate crystallises readily from the mixed solution, and fromthe mother liquor the d-isomeride can be conveniently separated as thezinc salt.use Z-menthylcarbamide forthe purpose OF resolving externally compensated hydroxy-compoundsinto their optically active components; the method can be appliedeither by directly combining the carbimide and the hydroxy .com-pound, or by first converting the latter into a chlorocarbonic ester andthen condensing with Z-menthylamine. On applying the method todZ-~-phenyl-u’-4-hydro~yphenylethane, p-HO*C,H;CHMePh, d-a-phenyl-a’-4-hydroxyphenylethane Z-menthylcarbamate,C,,H,,NH*CO,.C,H,.CHMePh,is obtained as the less soluble product and, on hydrolysis with soda,yields the optically active hy droxy-compound.have resolved tetrahydro-l-naphthoicR.H. Pickard and W. 0. LittleburyR. H. Pickard and J. Yatesacid, CGKI<CH(CO,H) CH2-CH2>CH2, ([MID 2 1 *lo), and tetrahydro-2-naphthoic([MI,, 90.5’) into their optically active CH,*YH,CH,*CH*CO,H’ acid, C,H,<components by crystallisation with Z-menthylamine ; in each case thesalt ZBZA separates as the least soluble component. The molecularrotatory powers of the acid ions, stated in brackets above, are muchsmaller than that of the A2 (Or ’)-dihydro-l -naphthoic acid,CH(CO,H)-EH ,CH(C02H) CH,Or C,H, \CH----bH --- 9 C,H,<(TH --- CHnamely, [MI, 374*5”, found by Pickard and Neville.’R.H. Pickard and W. 0. LittleburyS have resolved ac-tetrahydro-Ann. Report, 1905, 174.3 Gazzetla, 1906, 36, ii, 392.Ibicl., 467.7 .7bid., 1905, 87, 1766.Annnlen, 1906, 349, 324.Tmns., 1906, 89, 935.Ibid., 1906, 89, 1252.lj &d., 1101STEREOCHEMISTRY 189by their method which involves con-CH,*F]H,CH,*CH*OH' 2-naphthol, C6H4<densation with I-menthylcarbamide and cry stallisation of the resultingmixture of the products ZBdA and ZRZA p in the present case the formercompound proves to be the less soluble and is readily hydrolysed,yielding the d-ac-tetrahydro-2-naphthol. This substance does notreadily undergo optical inversion, and therefore contrasts in behaviourwith the corresponding amine which Pope and Harvey1 found to bevery easily inverted.A' "-Dihydrophthalic acid was resolved into its active componentsby Proost by crystallisation with strychnine, and A.Neville has nowresolved the isomeric trans-A' : 5 - ~ ~ r n p ~ ~ n d ,CH/\HY YH*CO,G,HC CH*CO,H LI \/CHby crystallisation of its acid strychnine salt. The salt of the I-base withthe I-acid separates from the solution as the least soluble component.The cold aqueous solution of the Z-A-3:5-dihydrophthalic acid does notundergo optical inversion in the cold, b u t at 97" the inversion of thesodium salt proceeds as a unimolecular reaction ; the transformationoccurs, also as a unimolecular reaction, much more rapidly in presenceof excess of soda. From the solution remaining after the transformationthe optically inactive A2 ' 6-dihydrophthalic acid has been isolated,the change proceeding thus :CK C'H/\ /\\/ \/H$J $JH-CO,H NaHO H2V Y-CO,HHC CH*CO,H -+- H,C C*CO,HC H UHA.Neville has also resolved the 2 : 3-dibydro-3-methylindene-2-carb-oxyiic acid, C6~~,<~,HM"SCH*C0,H, into its optically active com-1ponents by crystallisation with I-menthylamine ; the salt ZBdA is themost sparingly soluble, and from this the pure d-acid is obtained.Although the acid contains two asymmetric carbon atoms only one d-and Z-acid were isolated.F. W. Kay and W. H. Perkin, j ~ n . , ~ have resolved syntheticdl- 1 -methyl-A3-cyclohexene-4-carboxylic acid,Trans., 1901, 79, 83. I! Ber., 1894, 27, 3185.Tm?ts., 1906, 89, 1744.4 lbid., 383. 6 B i d . , 839190 ANNUAT, REPORTS ON THE PROGRESS OF CHEMISTRY.by crystallisation with brucine and strychnine ; with the first basethe salt ZBZA is obtained as the less soluble, whilst with strychninethe salt ZBdA crystallises first. Prom these acids, by the aid of theGrignard reaction, the authors have succeeded in obtaining for thefirst time synthetic optically active terpenes and their derivatives.E. Erlenmeyer 5 has resolved dZ-a-brorno-p-phenyl-@-lactic acid,C6H5*CH(OH)*CHBr*C0,H, into its optically components by crystal-lisation with cinchonine and strychnine ; the corresponding chloro-derivative has been resolved by means of strychnine and the iodo-derivative with the aid of cinchonine. E. Erlenmeyer and C.Barkowhave prepared a dZ-P-amino-P-phenyl-a-lactic acid,C,H,*CH(NH,)*CH(OH)*CO,H,isomeric with that already known, by the action of ammonia on sodiumphenyl-lactate ; the lzvo-acid is prepared from sodium phenyl-lactate.CH,*CH,-CH,*CH,*CH(NH,) *CO,H,is excreted in the urine after administering externally Compensatedleucine to rabbits; leucine is in general not excreted in the urineof dogs, although in one case the administration of the inactiveamino-acid resulted in a small quantity of d-leucine being found inthe urine.On administering externally compensated alanine to dogs, A.Schittenhelm and A. Katzenstein findthe amino-acid is conveniently separated by aid of its a-naphthalene-sulphonic derivative.0. Warburg 4 shows that pancreatin hydrolyses leucine ethyl esterasymmetrically, Z-leucine, CH,*CH;CH2*CH,*CH(NH2)*C0,H, beingproduced.finds that by the action of yeast on a solution of sucroseand externally compensated alanine, leucine, or a-nminoisoraleric acid,both components of the amino-acid are attacked, but, in general, atvery different rates ; Z-alanine, d-leucine, or I-a-aminoisovaleric acidcan be readily separated from the product in a 65 to 75 per cent.yield,According to E. Reiss,o d-alanine is more readily utilised in theanimal organism than is its enantiomorphously related isomeride.P. Mayer7 finds that cl-lecithin is converted into dl-lecithin byheating to 100° with methyl alcohol, and that steapsin attacksE. Abderhalden and F. Samuely found that d-leucine,that only Z-alanine is excreted%. EhrlidhBcr., 1906, 39, 788.2 Zeit.physiol. Chenz., 1906, 47, 3-16. :? %&. mp. Pcd7i. 777iw.) 2, 5GO.Zeit. phylsiol. Chem., 1906, 48, 208.f, Biochem. Zeit., 1906,1, 8 ; Zeit. Yer. deut. Zuckwind., 1906, No. 608, 840.6 Beitr. chem. Physiol. Path., 1906, 8, 332. 7 Bioc7~.em. Zeit., 1906, 1, 39STEREOCITERSISl'RY 191dZ-lecithin, leaving Z-lecithin in the solution. 0. Riesser shows thatd-arginine is converted into a mixture of dl-arginine and dl-ornithineby heating with diluted sulphuric acid at 160-180°.A number of optsically active alkyl derivatives of benzene have beenprepared by A. Klages and R. Sautter.2 The fact that these hydro-carbons are formed without optical inversion from their sulphonicacids has led Klages 3 to attempt the resolution of sec.-butylbenzene,CHMeEtPh, by crystallising the sulphonic acid of the externallycompensated hydrocarbon with quinine, cinchonidine, and strychnine ;the attempts were not successful.Pschorr, Roth, and Tannhauser* show that the optically active a-and p-methylmorphimethines and a-etlhylthiocodide crystallise in thesphenoidally hemihedral subdivision of the orthorhombic system andafford examples of the recently discovered occurrence of opticalactivity 5 in the crystalline state of biaxial substances.I n view of the optical activity and other properties of tannin,J.Dekker 6 assigns to it the following constitution which indicatesthe presence of an asymmetric carbon atom in the molecule,?(OH): CH-E- GO*? gH*C(OH): ?*OHC(OH):C(OH)*C--C(OH)*C--CH==C*OH'Haller and March7 have prepared, and determined the specificrotatory powers of, hexahydrobenzyl-, hexahydrobenzylidene-, oen-anthyl-, and oenanthylidene-camphors ; the results confirm the pre-vious conclusion that the specific rotatory power of the unsaturatedderivative is higher than that of the corresponding saturated com-pound.The statement is made by E.Jungfleisch and M, GodchotS thatduring the preparation of d- or Z-lactide by heating the correspond-ing lactic acid, they observe that Z-lactic acid or Z-lactide is muchmore rapidly optically inverted by heat than the correspondingd-isomeride.I n continuation of previous work, J. B. Cohen and I. H. Zortmannhave prepared, and determined the rotation constants of, the 2-menthylesters of the isomeric dibromobenzoic acids,O and J.B. Cohen andH. P. Armes have prepared and examined the Z-menthyl esters of theisomeric chloronitrobenzoic lo and dinitrobenzoicR. H. Pickard and J. Yates12 have examined as a time reactionthe conversion of the sodium or methyl salts of cZ-Az-dihydro-l-acids.Zeit. pJn~s/sioZ. Chcm., 1906, 49, 210.Bey., 1906, 39, 1938 ; compare Ann. f i e p o d , 1905, 178.L'er., 1906, 39, 2497 and 3754.:! Ber., 1906, 39, 2131.8 Ibid., 637.16icl.) 19. Pocklington, Phil. Mag., 1900, 6, 2.T~cms., 1906, 89, 47.7 Compt. rei~cl., 1906,142, 316.lo Jhid.* 454. Ibid., 1479. 12 Ibid., 1484192 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.C(CO,€€):~H in naphthoic acid into the inactive Al-acid, C6HH,<CH2--CH,,presence of a number of basic hydroxides and bases ; the conversionproceeds as a unimolecular reaction and is easily followed polari-metrica1ly.l The hydroxides of the alkaline earths hasten the transfor-mation of the sodium salt more than the alkali hydroxides, and thelatter are rather more active than the tetra-alkylammonium hydroxides ;the relative strengths of the bases in this respect differ somewhatfrom the relative electric conductivities, and this is attributed to theeffect of the base on the electrolytic dissociation of the salt.R. H,Pickard, W. 0. Littlebury, and A. Neville have studied the reactionsbetween I-menthylcarbimide and a number of alcohols as time re-actions; the rotation constants of a number of esters of I-menthyl-carbamic acid have been determined.Further examples of asymmetric syntheses are given by A.M~Kenzie,~ who applies Grignard's reaction for this purpose.Theaction of magnesium propyl, isobutyl, tert.buty1, and a-naphthyliodides or bromides on I-menthyl benzoylformate and of magnesiummethyl, ethyl, iso-butyl, and a-nsphthyl iodides or bromides on I-bornylbenzoylformate leads in each case to an asymmetric synthesis of asubbtituted glycollic acid. I n each case a mixture of the d- and I-sub-stituted glycollic acids resulted on hydrolysis of the product, and inthis mixture one component predominated; the excess of onecomponent over the other was greater in the case of the rnenthyl thanof the bornyl esters.The asymmetric synthesis of phenymethyl-glycollic acid can be effected both by the action of magnesium methyliodide on I-menthyl benzoylformate and by that of magnesium phenylbromide on Lmenthyl pyruvate ; the former method leads to formationof excess of the Z-acid, whilst the latter gives the d-acid in largerquantity. A. McKenzie and H. Wren4 also effect an asymmetricsynthesis of I-lactic acid by the reduction of I-bornyl pyruvate andsubsequent hydrolysis of the p r ~ d u c t . ~have shown that on heating eitherdl- or I-mandelic acid, C,H,*CH( OH)*CO,H, with the equivalentquantity of brucine at 150-160' it becomes converted into d-man-delic acid, that is to say, the mandelic acid subsequently separatedshows a slight dextrorotation. Similarly, on heating dl-mandelicacid with strychnine or nicotine under the same conditions, therecovered acid is dextrorotatory.On heating dl-p-methoxymandelicacid with brucine or strychnine, it becomes dextrorotatory, andW. Marckwald and D. M. PaulAm. Beport, 1905, 174.]bid., 365. Jbitl., 688. Compare Ann. Zeport, 1905, 170.Ber., 1906, 39, 3654.Tyans., 1906, 89, 93STEREOCHEMISTRY. 193after heating P-phenyl-lactic acid with brucine the recovered acid isfound to be slightly I~vorotatory.Winther shows 1 that in the catalytic optical inversion of d-tartaricacid, i-tartaric acid is first produced, the reaction being one of the firstorder and reversible ; the generally accepted view that the dl-tartaricacid produced during the optical inversion of d-tartaric acid is a directproduct of the change is thus incorrect.The dFtzLrtaric acid obtainedis produced from d-tartaric acid, i-tartaric acid being formed as anintermediate product. The effect of alkalis in accelerating the opticalinversion of d-tartaric acid is connected with the presence of hydr-oxylic hydrogen, which becoines replaced by the alkali metal ; thusthe substance CO,Na*CH(ONa)*CH(OH)*CO,Na can be separated fromstrongly alkaline solutions of sodium tartrate and caustic soda. Nocorresponding compound containing potassium could be isolated and inaccordance with this it is observed that caustic potash exercises aslighter catalytic effect on the inversion than soda. He has also found athat the optical inversion of mandelic acid by caustic alkalis proceedsas a unimolecular reaction.finds that P-cholestene dibromitle gives [a], - 39.6'immediately after solution in chloroform but that the solution becomesoptically inactive in a day and after several days gives the specificrotatory power [a],, + 39.4" ; the change occurs more slowly in benzenesolution and the solution on evaporation yields the isomeric a-cholestenedi bromide,R.Torrese4 has shown that the hydrolysis of sucrose is notbrought about by glutaconimide derivatives of types (1) and (a), butthat those derivatives which contain the group (3)J. Mauthnerare alone capable of causing the hydrolysis. The presence of thesingle double linking in (3) is thus essential if the derivative is t obring about the hydrolysis of sucrose; further, if one of the carbonylgroups is replaced by the group CPlille,, the power to hydrolyse sucroseis lost.A convenient method for graphically representing the configurationsof sugar-like substances and their derivatives is given by Rosanoff ;he considers that the stereochemical classification of these and relatedsubstances would be rendered more consistent by regarding d-guloseZeit.phpsilial. Chenz., 1900, 56, 719.Monutsh., 1906, 27, 421.a ]bid., 465.Atti B. Accad. Xci. Torirzo, 1906, 41, 309.6 J. Amer. Chern. Soc., 1906, 28, 114.VOL. 111. 194 ANKUAL REPORTS ON THE PROGRESS OF CHEMISTRY.as belonging to the I-family and not to that of &glucose and by makingcorresponding changes in the nomenclature of other similarly relatedcompounds. He also discusses 1 the question of optical superpositionand states as a new principle that ‘ I the optical rotatory power of anasymmetric carbon atom depends upon the composition, constitution,and configuration of each of the four groups.”T.&I. Lowry 2 has applied his solubility method 3 for determiningthe proportions in which dynamic isomerides are in equilibrium i nsolution, t o the halogen derivatives of camphor, which Kipping hasshown to undergo reversible isomeric change in presenco of alkalis. Hefinds that the solubility of each of these substances which contains thegroup -CHBr*CO- or -CHCl*CO- is increased by approximately one-tenth by the addition of the alkali, but no such increased solubility isobserved with camphor derivatives containing the group -CH,*CO- or-CBr(NO,)*CO-.The extent to which the partial optical inversionoccurs is a result of the isodynamic reversal in sign of the asymmetriccarbon atom in the group -CHBr*CO- or -CHCl*CO-. T. M. Lowryand E. H. Magson4 have applied similar methods to the study of alarge number of sulphonic derivatives of camphor, and have obtainedevidence enabling the above conclusions t o be extended.T. Purdie and C. R. Young5 regard ordinary crystalline rhamnoseas the a-form and Fischer’s crystalline anhydrous rhamnose as the@-form of the sugar; they describe an improved method f o r thepreparation of the latter form, which involves assisting the changea -+ P t o occur.The P-rhamnose is stable a t high temperatures andthe a-€orm a t low temperatures; the former is I-rotatory and thelatter strongly d-rotatory in aqueous solution. A number of methyl-rhamnosides have been prepared and classified as of the a- and p-form.have isolated /3-methylarabinoside cor-responding to Fischer’s a-methylarabinoside from the mother liquorsobtained during the preparation of the latter ; both are unaffected byyeast enzymes or by emulsin. Trimetbyl-a-arabinoside is crystallineand was isolated ; the P-isomeride is apparently a liquid and has alower dextrorotation than the former.J. C. Irvine and A. Bl. Moodie7 have investigated the addition of alkyliodides to alkylated sugars and glucosides, and, from the behaviour oftetramethyl-a- and -P-glucosides and tetramethyl glucose towards suchsubstances, conclude that the observed mutarotation takes the followingcourse when the solutions are cooled and then reheated : (1) a decreasein rotatory power owing t o formation of an oxonium derivative ; (2) anincrease in rotatory power a t the lower temperature owing to theT.Purdie and 3%. E. RoseJ. Amer. Clzem. Xoc., 1906, 28, 524,Ibid., 1904, 85, 1541.Ibid., 1194. (i Ibid,, 1204, Did., 1578.Trans., 1906, 89, 1033.Ibid., 1906, 89, 1042STEREOCHE?UZISTKT. 195uncombined sugar changing in the direction p -+ a ; (3) a rapid risein rotatory power during reheating owing to the dissociation of theoxonium derivative; and (4) a fall in rotatory power a t the highertemperature due to the change a -+ p in the sugar,P.Waldenl has determined the rotation constants of a largenumber of optically active esters and other substances for light ofdifferent wave-lengths under a variety of different conditions ofsolvent, concentration, and temperature. H e concludes that therotatory dispersion is a highly constitutive property, and is in the mainindependent of the temperature and solvent ; homologous substanceshave practically the same rotatory dispersions, but deviations fromthis rule are found in the lower members of a homologous series. Ahigh rotatory power usually accompanies a high rotatory disper-sion, although this is not always true, the two constants being notgenerically related. Most solvents have li?hle influence on therotatory dispersion of a dissolved substance, but some, which differwidely in constitution and optical properties, exert a distinct in-fluence on the rotatory dispersion of the solute.A few solvents,such as chloroform, quinoline, and cinnamaldehyde, sometimes effecta complete change in the rotatory dispersion of the solute; thisalteration is to be traced to chemical change leading to the forma-tion of new optically active complexes. Walden replies to Patterson'scriticism of his previous conclusion^,^ quoting a large amount of freshexperimental data, and adhering to his former statement that adirect relation is observable between the molecular weight and therotatory power of an optically active substance in both concentratedand dilute solutions.C. Winther contributes a quantity of experimental data fromwhich he concludes that a simple relation exists between changes ofrotatorypower on the one hand and the specific volume and molecularweiiht on the other.I n the case of certain substances, such asnicotine and amyl itaconate, the results obtained a t differenttemperatures indicate that the changes in rotatory power are duesolely to changes in the molecular volume or molecular solutionvolume ; the same holds in numerous cases investigated by Franklandand Patterson, in which the rotatory power and molecular volumechange proportionally when the temperature is altered. I n other cases,such as those of menthol, ethyl and propyl tartrates, and diethyldibenzoyltartrate, the changes of rotatory power are functions of thechanges in molecular volume and also in molecular weight.If acertain change in rotatory power, A[a], occurs as the result ofthe quantity, Am,, of single molecules being produced from doubleZeit. pkysiknl. G ' l z m . , 1906, 55, 1. BcT., 1906, 39, 6%.Zeit. physiknl. Chcm., 1906, 55, 257 ; 56, TO,?. 3 Ann. Eepoyt, 1905, 176.0 196 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.molecules in the liquid by a rise of temperature, T, the change inrotatory power should be represented byA[a] = K-Am, + K',*Av = 1ClaAT/T17, + IC2*Av.This expression applies satisfactorily to the substances last mentionedboth in the undissolvecl and dissolved state. The amount of associationoccurring in the solutions may be determined from a knowledge ofthe changes in rotatory power ancl in molecular volume, becauseK* An?, = A[a] - hr2*4v.Cases like those of nicotine and ethyl tartrate, in which A[.]=E A v , are found in camphor and turpentine in the dissolved state.Grossmann and Wieneke from an extensive series of rotatorypower determinations a t different temperatures and concentrationsconclucle that in aqueous solution boric acid and tartaric acid form Rmonoboryl tartaric acid,CO,H* CR(0H) 'CH(0H) CO; BO, the hydrolyticdissociation of which increases with rise of temperature and decreaseof concentration.The sodinm salt of this acid appears to exist insolution arid evidence of the forlaation of a sodium boryl bitartrateis also adduced. Both normal and acid tartrates and malates of pyrirlineexist in aqueous solution.With the aid of the approximately monochromatic light of mave-length4SS.5pp which passes throngh R pale-blue light filter, H.Grossniannhas investigated the optical effect of adding alkaline copper solutionsto solutions of c2-glucose, d-fructose, d-mannitol, rl-rhamnose, sucrose,isosaccharin, asparagine, and tartaric and quinic acids. The effect ofthe alkaline copper solution is in all cases greatly to increase therotatory power, and in the cases of glucose, fructose, sucrose, ancl1-hamnose, the sign of the rotation is reversed. The maximum changesin specific rotatory power due to the addition of copper solution arefrom + 78.0" to - 375" with glucose, - 134.5Oto + 1423' with fructose,+1012" to - 111.3' with sucrose, and +72*Oo t o +1327" withtartaric acid.T.S. Patterson and J. Ksye3 have examined Z-menthyl 2-tartratefor purposes of comparison with Z-menthyl d-tartmte.4 Z-Mentbyl&tartrate gives [MI, - 35S.1" a t 15' and - 382.5" a t 103" in the purestate and, together with its diacetyl derivative, has been examined in anumber of solvents. It is shown that the optical effect of each com-ponent optically active group in the two diacetyl derivatives is roughlytraceable in the changes of molecular rotatory power which occur onheating from 0' t o 100' and the results are ciiscussed in connexionwith the question of optical superposition,T. S. Patterson and J. Frew5 have determined the rotatory powersTmns., 1906, 89, 1884.Zrit.pJbpiku2. Chcna., 1906, 54, 385.Zeit. Ycr. dczit. Zz~ckeerincl., 1906, No. 610, 1024.Awl. B~porf, 1905, 176. Ti T m w , 1906, 89, 332STE RE0 CH El1 I STR Y. 197of I-menthyl benzenesulphonate and P-naphthalenesulphonate in alcohol,benzene, and nitrobenzene solutions at different temperatures and con-centrations ; the values for the benzenesulphonate are larger than thosefor the other ester, and in each case the highest values are obtained inalcohol solutions, the lowest in nitrobenzene, and intermediate valuesin benzene solutions.I n addition to those previously described,l P. F. Frankland andD. F. Twiss2 have determined the rotatory powers of a numberof other derivatives of tartramide; i t is notable t h a t the specificrotatory power of d-tartaric diallylamide is less than that of thedipropylamide, as this forms an exception t o the general rule that theintroduction of a double bond increases the specific rotatory power. Asimilar observation is made by P.E. Frankland and E. Done 3 in a ninvestigation on the influence of substituents on the optical activity ofnialamide; it is there shown t h a t maldi-n-propylamide has a higherspecific rotatory power than maldiallglamide.The autorscemieation of iodides and bromides of optically activequarternary ammonium bases in chloroform solution f i t st observed inthe case of phenyl benzylmethylallylammonium compounds and tlleoptical stability in aqueous solution of the corresponding salts ofthe same base in aqueous solution4 have been reinvestigated byWedekind in connexion with the iodide, bromide, chloride, andfluoride of d-phenylbenzylmethylpropylammonium. As in the firs t-mentioned case, the iodide undergoes autoracemisation in chloro-form solution more rapidly than the bromide; with the fluoride nodefinite indication of autoracemisation was obtained and the hycir-oxide in chloroform solution becomes slowly optically inverted, althoughWedekind hes previously noted that another optically active substitutetlammonium hydroxide is optically stable in aqueous solution.E.WedekindG finds t h a t the optical inversion of phenylbenzyl-methyl-, allyl-, -propyl- and -isobutyl-ammonium iodides proceeds as :tuoimolecular reaction. The molecular weight of the first compound isnormal, so that but very slight dissociation can exist in the chloroformsolution.H. Goldschmidt tloes not consider it certain that Wedekind’smeasurements completely establish that the optical inversion is due todissociation into tertiary amine and alkyl iodide ; he contributes Rthermodynamical discussion of the process of optical inversion.sE. Wedekind and E. Friihlich !’ remark that the molecular rotatorypowers previously given by Wedekintl and Jones for the opticallyTrans., 1903, 83, 1349. IDicl., 1906, 89, 1855. Ibid., 1859.Zcit. Elelctrochesn., 1906, 12, 330.Ibid., 416 and 516..i Trans., 1901, 79, 838. Bcr., 1906, 39, 474.3 Compare Weclekind, ibicl., 1906, 12, 515. EcT., 1906, 39, 4437198 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.active ion *NMeEtPh*C,H7 are not such as would be expected fromthe values obtained for the ions*NMePrPh*C7H7 and *NMe(isoC,H,)Ph.C~Hp.I n accordance with this it was found that prolonged fractional crystal-lisation of the mixed d- and Z-phenylbenzylmethylethylammoniumd-camphorsulphonates led t o the separation of a fraction, dEdA, havinga much higher rotatory power than in the previous work and fromwhich the value [MI, + 64.4' was obtained for the basic ion.The iodideof the active base undergoes optical inversion rapidly in chloroform butnot in alcohol solution.Wedekind agrees with Jones's view 1 that the so-called P-phenyl-benzylmethylallylammonium iodide is really phenylbenzyldimethyl-ammonium iodide, which is formed in the reaction between phenyl-benzylallylamine and methyl iodide by a replacement of the allyl groupby methyl ; he describes several cases of a similar kind in which an allylor benzyl group is thus displaced by methyl during the formation of aquarternary ammonium iodide. There is therefore at present noknown case of stereoisomerism amongst optically inactive asymmetricnitrogen derivatives.2have determined for purposesof comparison the rotation constants a t cliff erent temperatures and con-centrations of a large number of compounds owing their activity t othe presence of a asymmetric nitrogen atom ; the interpretation in thelight of Guye's formula of the large quantity of valuable data quotedled to no satisfactory agreement being established between theobserved and the calculated values.A. Ladenburg4 has continued work on the peculiar kind of stereo-chemical isomerism which he believes to occur amongst secondarybases like stilbazoline and coniinem5 Whilst the naturally occurringd-coniine has [u], +15*6", the base obtained by resolving syntheticconiine with a?-tartaric acid gives [aID + 19.2'; the latter Ladenburgregards as d-isoconiine. The only difference observable between t h eproperties of the t w o :bases and their derivatives is in the specificrotatory power. d-isoconiine undergoes practically complete conversioninto d-coniine OF [.ID + 15.7' on heating at 290-300".Miss 31. B. Thomas and H. 0. Jonesw. J. POPE.Awn. Report, 1905, 182.Ber., 1906, 39, 2486.Ber., 1906, 39, 481. Trans., 1906, 89, 280.Am. Report, 1904, 144

ISSN:0365-6217    

DOI:10.1039/AR9060300185

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY.THE problems of analytical chemistry cover such an exceedingly widefield, and are, if I may be permitted to use the expression, of such ttheterogeneous cha,racter, that it is ’ practically impossible to presentthis report in ths form of a continuous and connected narrative.Advances of distinct significance often consist merely in the detectionof some sour*ce of error in a more or less well known process and itselimination or in a slight modification of some existing piece ofapparatus. Trivial as these matters may appear when compared withsome of the discoveries made in other branches of our science, they arenevertheless often of prime importance to the analyst, and as such claimattention in this review. I n place of the unbroken and more readablestory which the author would have liked to present, he ie, from the verynature of the subject, compelled to deal largely with disconnected andisolated facts, and he can only hope that in consequence of the arrange-ment of the subject inatter which he has adopted he has been able topreserve in parts some semblance of sequence and continuity.Theadoption of a definite plan is as necessary for the Reporter as f o r theReader, and it is believed that the arrangement of the subject followedlast year is that which lends itself most readily to clear andmethodicaltreatment. The subjects referred to in this report will therefore badealt with under the following headings :1. Inorganic Chemistry including Electrochemical methods.2. Organic Analysis.3.Analysis of Foods and Drugs.4. Toxicological Analysis.5. Apparatus.The arbitrary character of this or indeed of any other subdivisionwill be evident, and in some cases there is perhaps no good reason whya particular process should have been discussed under one headingrather than under some other. Still the method has certain practicaladvantages and appears to the author to answer its purpose well:Inorganic Anulysis.It comparatively rarely happens that new reactions likely to be ofreal service in qualitative inorganic analysis are recorded, althoug200 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.there is unquestionably a large field still open for investigation in thisbranch of analytical chemistry, more especially in connexion with thedetection of some of the rarer elements and the easier identification oftraces of one metal in the presence of large quantities of another fromwhich it cannot be easily separated by existing methods.The import-ance of studying the nietallic derivatives of organic compounds fromthis point of view is now thoroughly recognised, and observations arefrom time to time recorded which are usuallyinteresting, if not alwaysof practical utility. Bradley finds that the hmnatoxylin reaction ofcopper, which has long been known, although but little used, is farmore sensitive than that given by potassium ferrocyanide or even bystarch and potassium iodide, and in the same paper points out thattraces of zinc in tissue ashes containing relatively large quantities ofcopper, iron, calcium, and phosphoric acid may readily be detected bytaking advantage of the fact that zinc nitroprussitle differs from all theother insoluble nitroprussicles in readily forming well defined crystalswhich can be recognised by means of the micrascope.According toGrossmann and Schuck dicyanodianiide constitutes a fairly delicatetest for nickel even in the presence of a layge excess of cobalt, althoughits sensitiveness is evidently very much inferior to that of Tschugaeff’sreagent referred t o below.For the detection of gold and platinum, more especially whenpresent in small quantities in the presence of other metals, Petersen 3outlines a scheme which appears to be capable of useful application,although it does not embody any new principle.The solvent action ofboiling sulphuric acid on platinum in the presence OF ammoniuirisulphate has been made the subject of several papers by Delkpineduring the past few years, and in a recent commnnication4 he statesthat platinum-iridium alloys are appreciably soluble in strong sulphuricacid at a temperature of 365O, and that on boiling the resulting soln-tion with ammonium sulphate the platinum is deposited, the iridiuiriremaining in solution. This solution, which appears t o containammonium iridium sulphate, exhibits the green colour becoming deepviolet on the addition of nitric acid, which is R characteristic reactionof iridium. The colour is so intense that i t is said to be possible byits means t o detect iridium in many samples of coiniiiercial ‘pureplatinum.’The detection of small quantities of yellow phosphorus in phos-phorus trisulphide (and in match heads) has been made a subjectof investigation by several chemists, and an interesting process hasbeen devised for this purpose by Schenck and Scharff,‘) depending on1 Amcr. J.Sci., 1906, [iv], 22, 326.3 Zeil. anal. Chem., 1906, 45, 342.a Bcr., 1906, 39, 3356.Conzpt. nnd., 1906, 142, 631.Bey., 1906, 39, 1522ANA4LYTICAL CHEMISTRY. 201the increase in the rate of discharge of an electroscope when subjectedt o the action of air in which the sample containing phosphorus hasbeen slowly oxidised. The method appears to be capable of being use-fully employed in toxicological analysis: and might be useful for thepurpose of controlling the purity of the air in rooms or factories inwhich phosphorus is used.The detection of sins11 quantities of nitric oxide and ozone in thepresence of one another is not an easy problem, and I?.Fischer andMarx * show that this may be done by leading the mixture into liquidair, which dissolves the ozone and solidifies the nitric oxide. Afterseparation by filtration, the two substances may be identified by theemployment of wet '' tetramethyl-base paper " (4 : 4'-tetramethgldi-aminodiphenylmethaae). The use of liquid air in this connexion isinteresting.The nitroprusside test for sulphides is not perhaps a very importantone, but it is occasionally useful, and it is well that its limits ofsensitiveness and the extent to which other acid radicles may interfereshould be understood.Following Reichard, Virgili 2 has studied thereaction, and has found that the blue coloration, which is preventedby the presence of free alkali, is also very considerably interfered withby the presence of silicates, phosphates, borates, and other salts whichare capable of yielding alkali on hydrolysis. It is, of course, wellknown that even under the most favourable conditions sodium nitro-prusside constitutes a less sensitive reagent for sulphides than neutralor alkaline solutions of lead salts. This, according to the author,appears to be. due to the fact that nitroprussides are not reagents forthe sulphide ion, but for the non-ionised metallic salt, any conditionwhich tends to prevent ionisation at the same time increasing thedelicacy of the reaction.In the quantitative section of this branch of analysis much goodwork has been done during the year.The electrical conductivitymethod has in several cases during recent years 'been successfullyapplied to the determination of the solubilities of very sparinglysoluble substances, and, working in this way, BGttgeu.3 finds that thesolubilities of the chloride, thiocymate, and bromide of silver in waterat 100" are respectively 153 x 10-6, 39 x 10-6, and 20 x gram-equivalents per litre. Every analyst knows from experience how greatan error may be introduced into estimations involving the weighingof silver chloride if that substance is washed with unnecessarilylarge quantities of hot water, but it is well to realise than an aqueoussolution of silver chloride saturated at 100" contains no less than2.18 mg.per 100 C.C. I n this connexion it is interesting t o note thatBcT., 1906, 39, 2555. Zcit. a d . Clicm., 1006, 45, 409.Zeit. pJqsiktsl. C h n . , 1006, 56, 83202 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Donaul recommends the application of the conductivity method tothe estimation of small quantities of gold and palladium in solutionsreduced by means of :carbon monoxide, and shows that even withexceedingly dilute solutions (0.0005 per cent.) the mean error is verysmall. Processes involving the employment of delicate electricalappliances are not as a rule well suited to the needs of the analyticalchemist, but they appear to the author to be worthy of special notice,as indicating a praiseworthy tendency to press new methods into theservice of analytical chemistry.For this reason the observation ofDrapier,2 that a galvanometer may be used as an " indicator " in thevolumetric estimation of silver is noteworthy. The estimation ofmoisture in substances containing other constituents which volatiliseon heating is a very common problem in the analytical laboratory andoften one of serious difficulty. I n a very interesting paper on thissubject P. V. Duprk3 describes a method based on the interaction ofthe water and calcium carbide. The resulting acetylene is measured,and the process appears to be not only accurate, but capable of wideapplication.Thus it can be employed for the estimation of water in crys-tallised salts and of moisture in cordite and i n mixtures containingvola-tile constituents such as camphor or naphthalene. There also appears tobe some foundation for the hope that it may enable the analyst todistinguish between moisture and combined water. The use of thenephelometer for the estimation of opalescent silver chloride pre-cipitates is dealt with by Wells4 and by Richards,5 both of whomindicat'e the chief precautions which must be observed in ~ephelometricwork. Horn,G and the same author and Sue. A. Blake,7 have made adetailed study of the question of sensitiveness in colorimetry, and havecalled attention t o a fact which many analysts overlook, namely, thatin every colorimetric process there is one dilution which gives themaximum degree of sensitiveness and consequently the most accurateanalytical results.I n their last communication the authors enunciateseveral generalisations in regard to colorimetric measurements whichdeserve the attention of analysts. The appearance of a further paperby Sorensen and AndersenS on the selection of a substance for thestandardisation of solutions employed in acidimetry goes to justify theuse in my previous report of .the word " perennial " as applied to thissubject. The authors still advocate the use of sodium oxalate inopposition to Lunge, who prefers sodium carbonate, and deal with theimportant question of the choice of indicator. Acree and Brunelghave also devoted attention t o this subject, but their paper, althoughMonatsh., 1906, 27, 59.Analyst, 1906, 31, 213.Ibid., 510.Ibid., 253. lbid., 1906, 36, 195 and 516.Zeit. anal. Chem., 1906, 45, 217.BuU. Xoc. chint. Belg., 1906, 20, 148.Amer. Chem. J., 1906, 35, 99 and 508.Anzs~. C ~ G I I L J . , 1006, 36, 117ANALYTICAL CHEMISTRY. 203recording some useful observations, does not contain much that isreally novel. A new indicator consisting of a condensation derivativeof methylfurfuraldehyde which appears t o possess useful properties isdescribed by Fent0n.l Several authors have dealt with the standardisa-tion of solutions employed in iodimetric analysis and two papers-oneby Bruhns 2 and the other by Riegler 3 may be read with advantage.I n the former the conditions necessary f o r obtaining accurate resultswhen using potassium dichromate and iodide are cliscussed, and it ispointed out that potassium permanganate may be advantageouslysubstituted for the dichromate.In the second paper Kiegler advancesclaims on behalf of ammonium tri-iodate as a fundamental substancefor use in iodimetry and in volumetric analysis generally. This sub-stance which has the formula (NH4)Hz(I0,), is crystalline, anhydrous,and non-hygroscopic, and is very stable both as a solid and in solution.Directions are given for using this salt in alkalimetric titrations andf o r ascertaining the strength of its solutions by means of hydrazinesulphate, with which it reacts with evolution of nitrogen, which canbe measured. Mathewson and Calvin 4 describe a method for estirnat-ing hydrogen peroxide by titration with a solution of ferrous ammoniumsulphate or vice versd, the chief point of interest being the employmentof a solution of titanium potassium sulphate as indicator, the peroxidegiving with the titanium solution, as is well-known, a deep yellowcoloration due to the formation of a higher oxide. I n a preliminarycommunication Jannasch and Zimmermann 5 describe a method f o r thequantitative separation of iodine from chlorine and bromine in whichthe mixture containing the three halogens is dissolved in a solution ofhydrogen peroxide strongly acidified with acetic acid, and the liberatediodine distilled over with steam and collected in an ammoniacal solutionof hydrazine sulphate.I n a subsequent paper 6 Jannasch deals withthe separation of bromine and chlorine, and shows that from solutionsacidified with sulphuric acid and containing hydrogen peroxide theformer halogen may be distilled over in a current of carbon dioxide,leaving the chloride undecomposed. These separations, more parti-cularly that of iodine, appear to be very complete, and the methods willno doubt be rigorously tested by chemists under the varying condi-tions of analytical practice. A further communication is promised bythe same author on the application of the hydrogen peroxide methodto the separation of the three halogens when present together and willbe awaited with interest. According t o B u s c ~ , ~ nitrous acid can bequantitatively oxidised to nitric acid by hydrogen peroxide undercertain conditions, and on this observation he has based a process for2 Zeit.nnorg. Chenz., 1906, 49, 277.Amer. Chenz. J., 1906, 36, 113.Proc. Camb. Phil. S'oc., 1906, 13, 298.Zeit. n?pw. Chenz., 1906, 19, 845.Bcr., 1906, 39, 196. Jbid., 3655. 7 B i d . , 1401204 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.the estimation of nitrite and nitrate when present together, theformer being determined volumetrically by the permanganate method,and the total nitrate gravimetrically (after oxidation by hydrogenperoxide) by means of the “ nitron ” method, t o which refercnce wasmade in my previous rep0rt.lSeyewetz and Bloch find that when an aqueous solution OF a hypo-sulphite is added to a solution of silver chloride in ammonia, reductionof the silver t o the metallic state occurs quantitatively, and assulphites, which are formed in the reaction, and thiosulphates, do notinterfere, the method can be used with advantage for the estimationof hyposulphurous acid.Manning and Lang3 have studied the question of the estimation ofboric acid, alone and in the presence of phosphoric acid, and althoughthe paper in which their results are recorded does not contain mucht h a t is new, it is deserving of the attention of analysts.The authorsdeal with the separation of the boric acid as the trimethyl ester, andits subsequent estimation either as the barium salt or by the ordinarymethod. Their results indicate that both processes are capable ofbeing employed with a higher degree of accuracy than is usuallysupposed.Methods for the detection and accurate estimation of traces of anyof the elements are always welcome, especially in view of theirimportance in connexion with many of the problems of metallurgicaland physiological chemistry, and in the last report on the progress ofAnalytical Chemistry* I referred to the fact that Tschugaeff hadsuggested the employment of a-dimethylglyoxime as a delicate test fornickel. Armit and Harden5 have now applied this method t o thequantitative estimation of very small quantities of nickel in animaltissues and other organic substances.The nickel having beenseparated by methods which are only slight modifications of those inconlmon use, is estiiiiatecl colorimetrically hy means of Tschugaefl’sreagent.The advantages of this method over that in which ainmoniumsulphide is employed are that t’he scarlet coloration is much morecliaracteristic, and that traces of iron do not interfere. It is alsomore sensitive, since a distinct reaction is given with the 1/1000 mg.of nickel in 30 C.C. of solution. Cobalt gives with the sawe reagenta yellow coloration which only interferes seriously with the nickelestimation when the amount of cobalt present is more than twice thatof the nickel. The estimation of very small quantities of manganeseis often of importance, and Tarugi 6 has described a new method basetlon the fact that manganoua hydroxide dissolves in glycerol and thatEtcZI.SOC. ehim., 1906, [iii], 35, 293.Ann. &port, 1905, 186.6 Gnxctln, 1906, 36, i, 332.Ann. hkport, 1905, 2, 190.J. Xoc. Chcm bd, 1906, 25, 397.Proc. Rog. Xoc., 1906, 77, E, 420ANALYTICAL CHEMISTRY. 205the resulting solution readily oxidises with the formation of a rubyred colour, which can be made the basis of a colorimetric process. Thereaction appears to be capable of indicating as little as 0*0000005gram of manganese.Hydrazine has, during recent years, been recommended in a numberof cases for the volumetric estimation of certain of the metals, andRiminil has described, for the estimation of mercury ancl also ofpersulphates, volumetric processes involving the use of that reagentwhich appear to be accurate, and, in the case of persnlphates moreespecially, useful.The estimation of cadmium as snlphide leaves much to be desired inpoint of accuracy, and Baubiguy deals very fully with the conditionsnecessary for the exact conversion of the sulphicle into sulphate, aform in which, as many analysts know, this metal may, like zinc,with advantage be weighed.C. Goldschmidt 3 records the interestingobservation that cadmium is quantitatively prccipitntsd whensolutions of its salts are boiled in aluminium vessels in the presenceof a trace of chromium nitrate or cobalt nitrate, the aluminiumacting catalytically just as nickel and cobalt do in the case of goldand silver respectively. Whilst the volumetric estimation of zincwould scarcely he resorted to when p e n t accuracy is tlesired, it issometimes capable of being employed with advantage in technicalwoi-k.Two papers on this subject may be usefully referred to, oneby decker^,^ on the sodium sulphide method, ant1 the other byillurmann,5 who has studied the conditions under which the bestresults can be obtained by titrating with ferrocyanide, using uranylchloride as indicator.Czerwek ti describes a method for the separation of tin and antimonybased upon the formation of a double compound of stannic acid andphosphoric acid. The method appears to be not only convenient butaccurate, and will doubtless be submitted to a careful examination.The various gravimetric methods for the estimation of calciumhave been criticised in a paper by Brunck,7 who recommends theconversion of the ignited oxalate into fluoride by treatment withhgdrofluoric acid solution.Several papers have been published during the year dealing with theuse of zinc as reducing agent for ferric salts prior to titration withbichromate or permanganate.I n this connexion the author may,perhaps, be permitted t o point out the great advantage of usingpalladium-hydrogen (charged palladium) for this purpose, and to-I Atti R. Accnd. Lincei, 1906, [v], 15, ii, 320.Compt. rend., 1906, 142, 577, 792, and 959.:: Zeit. anal. Chenz., 1906, 45, 344.ti &it. anal. Chenz.,~1906, 45, 174.B d l . Xoc. chim. Belg., 1906, 20, 164.Ibid., 505. 7 Ibid., 77206 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRP.express his surprise that so few analysts should avail themselves ofthis clean and useful method.All who regard chemical analysis as an important branch of thescience of Chemistry and not merely as a useful a r t will read withmuch interest a paper by Bruni and Padoa 1 on the conditions affectingthe precipitation and solution of metallic sulphides. These authorshave experimentally demonstrated the correctness of Ostwald’s pre-diction, based on a consideration of the law of mass action and thehypothesis of electrolytic dissociation, that by causing hydrogensulphide to react under pressure, i t would be possible to precipitatefrom acid solutions the sulphide of those metals, for example, iron,cadmium, cobalt, and nickel, which, in ordinary circumstances, aremore or less readily soluble in acid. On the other hand, by diminish-ing the pressure cadmium sulphide is found not to be precipitatedfrom solutions which yielded precipitates under ordinary conditions.Following Stahler and Scharfenberg,2 Moser a has studied thephosphate method for the estimation of bismuth and its separationfrom certain other metals, and his paper may be read with advantage.Funk4 has studied the separation of iron from manganese, nickel,cobalt, and zinc, and in his second communication shows that theformic acid process in which the iron is precipitated as a basic ferricformate is preferable to the acetate method, since the metals remainingin solution after the separation of the iron are amenable to moredirecttreatment .Jannasch and Gottschalk 5 have studied the use of ozone in quanti-tative analysis, and have shown that it affords an accuratle method forthe estimation of manganese, and that this metal may be quantitativelyseparated by its aid from a number of others, including zinc andcadmium. The reducing activity of hydrogen has been made thesubject of further study by the author of this report and H.D. Law,Gand i t has been shown that the efficiency of the hydrogen obtained bythe interaction of metals and acids is dependent on a number offactors, both chemical and physical in their nature, but that amongthese the question of “ potential )’ or ‘‘ supertension )’ plays animportant part. A special study has been made of the Marsh-Berzelius process as applied to the estimation of traces of arsenic,and i t has been shown that whilst certain metals, such as platinum,iron, and copper, lower the “potential’) a t which the hydrogen isevolved and so diminish the sensitiveness and accuracy of themethod, other metals, such as cadmium and tin, do not produce thiseffect.I n this way the so-called ‘ insensitiveness ’ of many samples1 Atti R. Accnd. Liqzcei, 1905, [v], 14, ii, 525.3 Zeit. anal. Chem., 1906, 45, 19.Bcr., 1905, 38, 3862.Ibid., 181 and 489.t i Analyst, 1906, 31, 3. J. pr. Cheni., 1906, [ii], 73, 497ANALYTICAL CHEMISTRY. 207of commercially pure zinc which frequently contain traces of iron isexplained. Several papers dealing with the estimation of arsenic bythe modified Marsh method have been published during the year, andwhilst these do not as a rule contain anything that is really new, someof the authors, notably Vdmossy,l Gautier,2 and Bishop,3 eitherrecommend the addition of platinum or copper salts as “ accelerators,”or the use of copper-coated zinc in the hydrogen generation flask.Of course, when comparatively large quantities (several milligrams)of arsenic are in question, the error introduced is not, perhaps,serious, but when fractions of a milligram have to be estimated i t isfull time that the inadmissibility of such additions was recognised.Two papers which are worthy of attention and which deal with thetitration of solutions of liydrofluosilicic acid have been published,the one by Sahlbom and Hinri~hsen,~ and the other by Schucht andMoller.5 The influence of dissociation on the results obtained bytitration with alkali under varying conditions is very interesting andinstructive.Glucinuni salts, like those of ferric iron, chromium, and aluminium,liberate iodine from solutions containing iodide and iodate, thehydroxide being a t the same time precipitated.Glasmann G baseson this fact a method for the estimation of glucinum which appears togive very accurate results. The method described by the same author7for ttie separation of glucinum and aluminium is sometimes a usefulone, but, as has been pointed out by Friedheim,& it is old and perfectlywell known to analysts.Titanium trichloride, which appears to have been first employed inanalytical procedure by Knecht, is, as is well known, a powerfulreducing agent, and Rhend has applied it to the volumetric estimationof copper.The end point is sharper than in the iodide method,lO andthe test results are good.In the electrochemical branch of analytical chemistry there is com-paratively little of importance that is new to record, Owing tothe many obvious advantages which electrochemical estimations andseparations present to the analyst, a large and increasing amount ofattention is now being paid t o the improvement of apparatus and tothe sharper definition of the working conditions necessary for success,but the greater part of such work, important though it is, scarcelycalls for special notice in this report. Foersterll shows that byworking at a potential (2.05 volts) below that at which hydrogen is1 Bzdl.Xoc. chiin., 1906, [iii], 35, 24.a J. Amer. Chem. Xoc., 1906, 28, 178.5 Ibid., 3693. ]bid., 3368. Ibid., 3366. Jbid., 3868.9 Trans., 1906, 89, 1491. lo Gerlinger, Zeit. amyew. Chew, 1906, 19, 520.11 Ber., 1906, 39, 3029.Ibid., 207.Ber., 1906, 39, 2609208 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.evolved, it is possible to obtain very good results in the electrolyticestimation of copper in solutions slightly acidified with sulphuric acid,and t o separate that metal from others (cadmium, cobalt, nickel, iron,and zinc) which reqnire higher voltages for their deposition. Priceand Judge 1 have investigated the deposition of zinc from zinc sulphatesolutions, using a rotating cathode, and fiacl that under certain definedconditions very good results can be obtained.The electrolytic pre-cipitation of gold from solutions of the chloride in presence of potassiumcyanide and of sodium siilphide, using a rotating anode, has been thesnbject of stitdy by Withrow,? who finds that the former is, if any-thing, the better electrolyte €or this purpose, althoiigh both arecapable of giving very good results. The same author has alsodevoted some attention to the electrolytic estimation of alkali halide,employing a method very similar t o that originally suggested by E. P.Smith,:: in which a silver anode is employed and the halogen weighedas silver halide. I n Withrow’s experiments, a rapidly rotating spiralcathode w : ~ employed and excellent resiilts were ohtninetl, the anodeconsisting of a silver-plated dish.In no branch of analytical chemistry is more ingenuity devotedto the devising of new appliances and to the improvement of old thanin that which concerns itself with the analysis of gases, and in nobranch is it more true that as a general rule the piece of apparatnswhich gives the best results in the hands of any operator is that t owhich the operator in question is thoroughly accustomed.It is there-fore very diacult in many cases to estimate correctly the value of anynew piece of apparatus without being practically acquainted with itsworking. Gautier and Clausmann* call attention to the difficulty inestimating carbon monoxide i n mixtures either by cuprous chlorideabsorption or by the combustion method, and advocate the employ-ment of iodic anhydride,5 a substance which is also recommended byNowicki? and by LBvy and P ~ c o u ~ , ~ for the estimation of smallquantities of carbon monoxide in air. FranzenS advocates the use ofan alkaline solution of sodium hyposulphite as an oxygen absorbentin gas analysis, and points out that in addition t o its cheapness itpossesses the advantage over the usual reagents of acting efficiently a tlow temperatures, and of not absorbing carbon monoxide.Collins 9describes an improved form of Scheibler’s apparatus for the gasometricestimation of carbon dioxide in carbonates, which eliminates severalimportant sources of error inherent in the original form, and permitsof its application t o problems in which a fairly high degree of accuracyJ.Amer. Chcna. Soc., 1906, 28, 1350.Conapt. rend., 1906, 142, 485.1 Trans. Fnraday SOC., 1906, 2, 85.3 Ibid., 1903, 25, 883.5 Compare Compt. rend., 1898, 126, 931.6 Oesterr. Zeit. Berg. Butt., 1906, 54, 6.8 Ber., 1906, 39, 2069,Compt. rend., 1906, 142, 162.J. SOC. Chcni. Ind., 1906, 25, 518ANALYTICAL CHEMISTRY. 209is demanded. Attention is drawn by Stock and Nielsen to the errorswhich may arise in the analysis of gaseous mixtures rich in one ormore constituents owing to the air, dissolved in the absorbing liquids,which is frequently present in quantities sufficiently great seriously tovitiate the results. Moureu 2 deals with the estimation of rare gases ingaseous mixtures obtained from natural sources, and describes theappamtns he employs.Organic Analysis.A good many papers have been published during the year dealingwith new reactions of organic compounds, but these, although oftenuseful, have, as a rule, such a very limited application that theyscarcely call for notice in this report.An exception may perhaps bemade in favour of the following. Sperling 3 describes a modification ofthe isonitroso-reaction of antipyrine and its more important deriv-atives which is said to be an improvement on the test as recommendedin the German Pharmacopceia. Direct tests for the identification of-the more important sugars in carbohydrate mixtures are greatlyneeded, and it is therefore to be regretted that Schoorl and vanK a l m t h ~ u t , ~ who have submitted to a critical study the colour reactionsdescribed by Pinoff,5 have arrived at the conclusion that these are notvery characteristic. Fenton 6 describes an extension of the bromo-methylfurfuraldehyde test for carbohydrates, which he published a fewyears ago, as he has found that this substance reacts readily withmalonic ester, yielding a strongly fluorescent product, which serves forthe detection of hexoses, or of compounds such as glucosides, whichyield those carbohydrates on hydrolysis.The qualitative detection ofsmall quantities of lsevulose in the presence of comparatively largequantities of dextrose (by other than optical means) is a particularlytlifficult problem, and one in which Pinoff's colour reactions appear tobe of little use, The results obtained by Mulliken in his study of theosazone test, more especially as regards the time required for theformation of a precipitate with the different sugars, have been con-firmed by Sherman and Williams,7 who have shown the influencewhich dilution and the presence of other sugars exert on the test asapplied to the detection of dextrose and Isvulose. Reference mayperhaps be made to a paper by Harang a on the detection and estima-tion of trehalose in fungi and other plants, since it involves the employ-ment of a specific enzyme (trehalase) and is a new instance of anindirect general method which is often of the greatest service inBcr., 1906, 39, 3389.Ibid., 1905, 38, 3308.C'ompt.rend., 1906, 142, 44.Bcr., 1906, 39, 280.Proc. Camb.Phil. Soe., 1906, 14, 24.J. PAnrm. Chim., 1906 [vi], 23, 16.3 Zeit. Oesterr. Apoth., 1906, [v],&, 51.7 J. Anter, Cheni. h'or., 1906, 28, 629.VOL. 111. 1210 AKNUAT, REPORTS ON THE PROGRESS OF CHEMISTRY.arriving a t a knowledge of the constituents of commercial carbohydratemixtures. The work of Hansen and others on the preparation of purecultures of the various species of Xccccharomycetes has, in fact, been ofthe greatest importance to the analyst as affording him a ready meansof obtaining the special enzymes necessary. I n the case of trehalaseit may be noted that advantage is taken of its secretion by the mouldAspergillus niger. Raikow and Urkemitsch point out that sodiumhydroxide gives a yellowish-brown coloration with nitrotoluene, butnot with nitrobenzene, and i t seems possible that the test may be ofservice in detecting small quantities of toluene in benzene.A test for‘( saccharin ” has been described by Kastle which is said to be verydelicate, and which appears to be worthy of notice inasmuch assalicylic and benzoic acids do not interfere and need not apparently beremoved. A delicate test €or indole is described by K ~ n t o , ~ and somecolour reactions for dietinguishing between proteins, indole, and scatoleare given by Steensma? who confirms the correctness of thosepublished previously by Rohde. The importance of such tests to thephysiological chemist is sufficient justification for referring to them inthis report.I n this connexion attention may perhaps be directed to amethod proposed by Herter and M. Louise Foster 5 for the quantitativeseparation of indole and scatole, the former being removed as auaphthaquinone compound. New alkaloidal colour tests are ever forth-coming, but the great majority of these are of little practical use, inthat they are either not sufficiently characteristic or are only definitewhen applied to the pure alkaloid, which is so rarely obtained inlaboratory practice. I n this branch of analytical chemistry Reichardis indefatigable, and it will perhaps suffice if notmice is taken in passingof papers by that author dealing with some new colour reactions ofberberine,G LZ new reaction for morphine,7 some new tests for cocaine,*for q~inoidine,~ and for thebaine,lO I n papers by Bredemann l1 on thealkaloids of the rhizome of Veratrum album, a number of reactions ofthe various alkaloids present are described.Lemaire describes somedistinctive reactions of alypine (benzoyltetrnmethyldiaminopentanolhydrochloride) which enable one readily to distinguish between thatsubstance and cocaine, stovaine, and other active therapeutic agents.The identification of artificial organic dyestuffs, more especially whentwo or more are present, is a problem which is daily becoming moredifficult. Various schemes have been proposed for this purpose,Chem Zeit., 1906, 30, 295.Zeit. physiol. Chent., 1906, 48, 186.5 J. Biol. Chem., 1906, 2, 267.7 Ibid., 247.10 Pharm. Centr.-H., 1906, 47, 623.1.2 Bep.Phnrm. 1906, 18, 385.Chem. Centr., 1906, i, 1575.IZlid., 1906, 47, 25.Pharm. Centr.-H., 1906, 47, 473,Ibid., 532.l1 Apoth. Zeit., 1906, 21, 41 and 53.8 Ibid., 347, and Pharm, Zeit., 1906, 51, 591ANALI’TICRT~ CHEMISTRY, 211notably by Witt, WeingWner and Green, and during the past year afurther contribution to the subject is made by Gulinoff,l who attachesspecial importance to the behaviour of the dyestuffs with variousreducing agents, which is generally recognised as affording one of thebest methods of classification.A number of investigators have, during recent years, attackedthe problem of the identification of small quantities of methylalcohol in the presence of large quantities of ethyl alcohol and withmore or less success.The majority of the proposed methods arebased on the production of formaldehyde, aud its recognitionby various colour tests. The difficulty is, however, increased bythe fact that these colour reactions are not always characteristic, andin addition a number of organic compounds other than methyl alcoholyield formaldehyde on oxidation, and Scndder and Riggs 2 point outthat this constitutes an objection to the recently published method ofLeach and Lythgoe, in which a hot copper spiral is used. Voisenet3has described an oxidation method in which the formaldehyde isrecognised by a test which is said to be quite characteristic if carriedout as recommended, but to what extent the second of the abovedifficulties may apply cannot be determined until the method has beenmore extensively tried.I n this connexion it may be noted that Leys 4has described a mercury reagent which is said t o admit of a readydistinction between acetaldehyde and formaldehyde in very dilutesolutions.That the method usually adopted for the combustion of organiccompounds in elementary organic analysis leaves much to be desiredin respect of convenience of working, neatness, and cleanliness isfully recognised, and a number of workers have introduced improve-ments more especially in the direction of employing “ contact ”substances and heating ^by electricity. I n niy previous report 5 refer-ence was made to papers by Dennstedt in which he advocated the useof an electric furnace and specially-devised tubes.These suggestionshave been criticised by Holde,G who has failed to obtain good resultsin certain cases with the form of furnace recommended by Dennstedt,but the latter author in a reply 7 draws attention to some practicaldetails, the observance of which is essential for success. The methodproposed by Carrasco,s and slightly modified by that author andP l a n ~ h e r , ~ is simpler, inasmuch as the combustion is brought about bya heated platinum spiral in an atmosphere of oxygen, and theJ. Amer. C?LC?IZ. Soc., 1906, 28, 1202.Ann. Chinz. anal., 1906, 11, 84.Ber., 1906, 39, 1615.Zeit. Parb. Text. Ind., 1906, 5, 337.3 BuZl. SOC. chin%., 1906, [iii], 35, 748.Ann,. Zeport, 1905, 195.7 Ibid., 1623.]Bid., 613.8 Atti A!. Accad. Lincci, 1905, [v], 14, ii, 608.P 212 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.apparatus is very compact and neat.The results are good, the work-ing expeditious, and the method is applicable to substances containingnitrogen, halogens, and sulphur. This method is similar in principle t othat devised by Morse and Taylor referred t o in my last report, andwhich has now been modified by Morse and Gray1 to adinit of thesimultaneous estimation of carbon, hydrogen, and sulphur. Thewpapers may be read with advantage by all chemists who are frequentlycalled on to make organic combustions, and who are working inlaboratories where the electric current is available.Vaubel and Scheuer 2 recommend for the estimation of halogens inorganic compounds a simple method in which the compound is heatedwith concentrated sulphuric acid in the presence of excess of sul-phurous acid.The halogen is obtained either as the element or as thehydracid, and is converted directly into the silver halide. This method,although not applicable to very volatile substances, appears t o be auseful one in many cases, and gives good results. For the samepurpose Stepanoff 3 proposes a method in which the substance isheated with metallic sodium and ethyl alcohol. The reaction proceedsaccording to the following general equation, in which " X " standsfor one of the halogens :RX + C2Hj*OH + Na, = RH + NaX + C2H,*ONa,and the method which is said to be almost nniversally applicable givesapparently accurate results.Some years ago Dnnstan and Carr found that the nitrogen inaconitine could not be accurately estimated by the ordinary Dumascombustion method, inasmuch as the nitrogen in the measuringvessel was always accompanied by methane.Haas4 finds that anumber of organic bases behave in a similar manner, but thatcorrect results can be obtained if lead chromate is substituted for thecopper oxide, and if the substance is mixed prior to combustion with asufficient quantity of cuprous chloride. I n view of the fact thatDumas' method is always regarded as the standard one, this com-munication is obviously of considerable importance. In order to avoidthe somewhat large percentage error inseparable from the weighing ofvery small quantities of carbon dioxide in potash bulbs, McFarlaneand Gregory advocate barium hydroxide absorption, as in the well-known Petteukofer's method, and the conversion of the bariumcarbonate into sulphate.When rather larger quantities of carbondioxide are in question, the authors make use of an ammoniacal bariumchloride solution for absorption. The principles involved are of coursewell known, but the method is one that might be more often employedAmey. Chna. J., 1906, 35, 451.Rer., 1906, 39, 4056.Chew. Nezcs, 1906, 94, 133.C'hem. Zcit., 1906, 30, 167.Trms., 1906, 89, 570ANALYTlCAL CHEMISTRY. 213in the estimation of small quantities of carbon, such as have to bedealt with, for example, in steel analysis.Watson Smith, jun,,l has introduced certain modifications intoStrache’s well-known phenylhydrazine method for the determination ofthe carbonyl groups in organic conipaunds which are said considerablyto improve the pyocess.The estimation of the percentage of methyl alcohol in commercialfornlalclehyde solutions is sometimes of importance, and for this pur-pose Blank and Finkeiibeiner 2 recomiiiend a process based on oxida-tion by means of chromic acid and the indirect determination of theamount of oxygen used.Vaniiio and Seitter’s method for the estima-tion of forrnsldehyde by oxiclation with permanganate iii acid solutionin the cold has been studied by Grossmtmn and Aufreclit,3 who findthat it gives good results if sufficient time is allowed for the com-pletion of the reaction. Formic acid is also completely oxidised inacid solutions by permanganate, but Rupp4 shows that the reactionproceeds more rapidly in alkaline solutions.For the estimation of acetone in wood spirit, crude acetone, aridsimilar liquids, Auld 6 has devised a new method depending on theformation of bromoform, its subsequent hydrolysis with alcoholicpotash, and the volumetric estimation of the bromine by iiieans ofsilver solution.This method appears to be capable of giving goodresults, and it possesses several obvious advantages over the variousniodificatiofis of the iodoform process.Jollesg has applied the bisulphite reaction to the estiniation ofacetone, and given a sufficiently lengthy period of contact the resultsare good.No year passes without cz number of new processes being put forwardfor the estimation of the reducing sugars.Occasionally some of theseare useful in special cakes, and frequently they are characterised byconsiderable ingenuity ; but generally speaking it may b e said that noprocess approaches in point of accuracy the gravimetric Fehlingmethod when properly carried out, and certainly none is so generallyaqplicable. C. A. Browne, j ~ i n , , ~ points out that the cupric-reducingpower of a sugar is constant for all concentrations if the excess ofcopper remaining in solution is kept constant, and that the ratio ofthe weights of two sugars which reduce the same amount of copperis a constant one at all concentrations. The author has determinedthe value of this ratio for a number of sugars (compared with dextroseas a standard) and finds, notwithstanding statements t o the contrary,that the “dextrose equivalent ” of a mixture of reducing sugars is*; Ibicl., 2455.CJ~ent. Arms, 1906, 93, 83.Zeit. anal. Chena., 1906, 45, 687.Ber., 1906, 39, 1326.J. SOC. Chem I?kd., 19Oti, 25, lG0.7 J. Amer. C h e m Xoc., 1906, 28, 439. ti Ber., 1906, 39, 1806214 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.equal to the sum of the ‘( dextrose equivalents” of the constituents,The disturbing effect of sucrose is dealt with in this paper, and also ina communication by Munson and Walker,l who have suggested a setof standard conditions for the carrying out of the reduction process,and have drawn up tables for the use of operators observing the con-ditions they lay clown.shows that rafinose can be com-pletely hydrolysed to melibiose and laevulose by citric acid undersuitable conditions, and has based on this fact a method for thepolarimetric estiniation of sucrose and raffinose when present together.Mlle. Talon 3 calls attention to a possible source of error in the estima-tion of sugar in liquids containing much alcohol, since during the acidhydrolysis process esters of dextrose are produced which appreciablyinfluence the results obtained by the reduction process or by thepolarimeter.The detection and estimation of adulterants in oil of turpentineconstitutes an analytical problem of some importance and frequentlyof great difficulty. The “bromine absorption” has often beenadvocated as a trustworthy test, but, as Utz4 has pointed out, thevariations in the genuine oil are great, and some resin oils so nearlyapproach turpentine in this respect that considerable proportionsmight be present, and yet not reduce the bromine value below that ofcertain pure oils.A paper has been published by Bohme 5 on thesame subject, in which an improved method is recommended for theestimation of paraffin and benzene hydrocarbons in turpentine by thewell-known sulphuric acid process. Valenta finds that methylsulphate readily dissolves aromatic hydrocarbons such as occur in taroils, but not paraffin hydrocarbons or resin oils, and has based onthis observation a method for the estimation of the former whenadmixed with the latter which promises to be of considerable service.It will be interesting to see whether the use of this reagent cannot beextended to t l e analytical examination of other hydrocarbon mixtures.I n connexion with hydrocarbon oils, attention may be directed to apaper by Ross and Leather 7 in which the problem of the valuation ofoils used for gas-making purposes is very fully dealt with.Theresults of the examination of a considerable number of oils by alaboratory method which the authors recommend are given and arecompared with those yielded in practical working,Much useful work has been devoted during the year to the study ofessential oils, not; the least important being the determination of theanalytical ‘constants’ of genuine samples of those oils, which on accountPieraerts1 J.Amer. Chem. &‘oc., 1906, 28, 663.2 Bull. Assoc. Chi7n. Sucr. Dist., 1906, 23, 1261.3 Ann. Chim. anal., 1906, 11, 244.4 Chem. Rev. Frtt. €€am. lnd., 1906, 13, 161.6 Ibid., 266. Analyst 1906, 31, 284.Chem. Zeit., 1906, 30, 633ANALYTICAL CHEMISTRY. 215of their high price are most liable to sophistication. Valuable as thisis to the analyst who is specially concerned with this branch ofanalysis, it is scarcely of suEcient general interest to justify referenceto it in this report.The accurate estimation of tannin in raw materials is another im-portant problem to the solution of which a considera6le amount ofenergy has been devoted. Wislicenusl has now arranged for themanufacture on the large scale of ‘‘ porous alumina” of uniformquality, and describes a form of apparatus by which the process ofanalysis can be best carried out.The absorptive power of thisalumina for colouring matters appears to constitute one objection t oits employment, and there seems to be an impression among those bestable to judge that it possesses no r e d advantage over the chromedhide-powder method, which in the form adopted by the AmericanLeather Chemists’ Association will probably be recognised as thestandard process. Those who are specially concerned with thisquestion will read with interest papers by Small,2 Parker and Bennett,3Procter and Bennett,4 and K ~ p e c k y . ~. Several papers dealing with the analysis of explosives have ap-peared during the year, but of these attention need only be drawn toone by Silberrad, Phillips, and Merriman on the direct estimation of‘ nitroglycerine ’ in cordite and allied explosives, and which is based onthe reduction of the saponification products of the ‘ nitroglycerine ’ andthe titration of the resulting ammonia.The estimation of indigotin in commercial indigo is obviously amatter of very great importance to the dyeing trade and judging fromseveral papers recently published the problem does not yet appear tohave been finally solved.Numerous methods have been from time t otime proposed, but only those depending on the oxidation or reductionof sulphonated indigos appear to be capable of yielding good results,and are in aaything like general use. I n a critical paper byBergtheil and Briggs it is claimed that the permnnganate methodas worked out by Rawson with slight modifications is capable ofyielding concordant and trustworthy figures.The use of bariumchloride as a precipitant is, however, shown to be inadmissible, andthe authors recommend the employment of freshiy precipitated bariumsulphate for the purpose of removing impurities. On the other hand,W. P. Bloxam * maintains that correct results cannot be so obtained,and recommends a process based on the separation of the indigotin aspotassium indigotintetrasulphonate. It is clear that, in spite of thelarge amount of valuable work done by the above chemists, a generally1 Collcgiu?n, 1906, 77.3 l b i d . , 1193. Ibid., 1203. Collegazm, 1906, 97 c t scp.J.Sot. Chenz. I d , 1906, 25, 296.6 J. SOC. Chem. Ind., 1906, 25, 628. Ibid., 729. Ibid., 735216 ,4KNTJA4L REPORTS ON THE PROGRESS OF CHERZISTRP.acceptable process has not yet been worked out, and the results offurther study of this subject will be awaited with interest.Am.!@ of Foods a i d Dmys.Dealing firkt with that most important food product, milk, severalpapers of importance to analysts have appeared during the gear. Themethod devised by T. E. Thorpe for the analysis of samples of milk(sour and otherwise decomposed) referred to the GovernmentLaboratory under the provisions of the Sale of Food and Drugs Acts,and which was noticed in my previous report has been submitted toa critical study by Richmond and Miller,2 who have shown that whilstin certain cases a somewhat closer approximation to the fresh milkvalues could be arrived a t by a n extension of the GovernmentLaboratory process, that method is capable of yielding results whichare substantially accurate.I n those comparatively rare instanceswhere unusually high proportions of butyric or propionic acids areformed, the method appears to be susceptible of improvement. It isgenerally admitted, however, that the process is one of greatpractical value, and it has to be borne in mind that i t could not becomplicated beyond a certain point without seriously reducing itsusefulness. I n this connexion it is interesting to note that accordingto Tice and Sherman3 the character of the decomposition changesoccurring in milk on keeping is largely determined by the nature ofthe added antiseptic when such substances have been used.I n thepxesence of 0-07 per cent. to 0.1 per cent. of formaldehyde, althoughbacterial action appeared to be entirely suppressed, extensiveproteolysis Loccurred with very little loss of milk-sugar, whilst inthe presence of sodium fluoride or salicylate a large proportion of thesugar underwent decomposition before any marked digestion of thecasein took place. Two other papers by Richmond are of interest inview of the preparation of so-called homogenised milk, and the veryextensive use which is now being made of dried milk or milk powder.In the first place, he gives a series of analyses which seem to showthat the Adam’s coil method when applied to the analysis of homo-genised milk gives results appreciably below those yielded by theGottlieb, Werner-Schmid, or Gerber methods, and in the second hecalls attention, itater &a, to the impossibility of extracting the f a tdirectly from milk powders and recommends the Werner-Schmidmethod. The danger of applying direct extraction methods to theanalysis of certain milk-containing mixtures, such as infants’ foods, isone which ought not t o be overlooked.1 Ann.Kq.mrt, 1905, 203.8 J. dmcr. Chcm. SOC., 1906, 28, 189.Analyst, 1906, 31, 317. ‘ A?zalyst, 1906, 31, 2i8, 219AN A LTTIC d L C H EXISTRY. 217I n his annual communication on the composition of milk Richmond 1states that the average percentage of fat in nearly 15,000 samplesanalysed during 1905 was 3.73 per cent.with 8.97 per cent. of non-fatty solids. These numbers are almost identical with those of theprevious year. For the determination of proteins in milk and ofcasein in cheese, Trillat and Sauton recommend a method based on thefact that formaldehyde renders the proteins insoluble without alteringtheir weight, and so permits of their gravimetric estimation. Schrott-Fiechtl3 has compared Gottlieb's, Gerbei-'s, and the Wollny refractometermethods for the estimation of fat in milk, and, as the result of a largenumber of analyses, has come to the conclusion that all three yieldquite trustworthy results. Siegfeld points out, however, that irkthe case of machine-separated milks, the cholesterol and lecithin whicliare extracted by the solvents used in the Gottlieb method introduce anappreciable error into the fat determination.If a simple chemicallriethod for the recognition of milk derived from diseased cows couldbe devised i t would obviously be of the highest importance from thepublic health point of view. The difficulties appertaining to thesolution of this problem will be apparent to all who have anyknowledge of the bacteriology of milk, and it will be interesting to seeto what extent a determination of the " catalase number )' as proposedby Lam in a paper communicated to the sixth International Congressof Applied Chemistry supplies this want. The detection andestimation of cocoanut oil in butter is a problem which is even moredifficult than was a t first supposed, alzd which cannot yet be said tohave been satisfactorily solved. I n my last report I called attentionto the work of K.Jensen, Kirschner, and 0. Jensen on this subject,pointing out that these authors had endeavoured to base, on thedifferences in the proportions of octoic and butyric acids occurring inbutter-fat and cocoanut oil respectively, and in the comparativelysparing solubility of silver octoate, a method for the detection andestimation of cocoanut oil. The hopes which were raised by thepublication of these papers have not altogether been realised, andmany analysts who have had much experience in this branch ofanalysis have been led to regard the so-called silver numbers as of verylittle value. Wijsman and Keijst have suggested a modification, orrather an extension, of the Jensen method in which the Reichert-Meissl distillate is divided into two unequal portions with the objectof obtaining inore widely separated solubility differences for the silversalts. The numbers given by the ,authors did not, however, appearC ' o q k m i d ., 1906, 142, 794, and 143, 61,Ibicl., 1.1 Annlyst, 1906, 31, 176.:$ Milchw. Zenh*., 1906, 2, 13.5 Chemist and Druggist, 1906, 68, 914.7 Zeit. ATnhr. GCnusSrn,, 1906, 11, 267.' AWL. RqmA, 1905, 204218 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.very convincing, and the process has since been adversely criticisedboth by Jean and by Luhrig.2 Lewkowitsch, in a private commiinica-tion to the author of this report, also states that he has obtainedconflicting and untrustworthy results.After all it would appear thatthe Polenske method and the phytosterol acetate test still furnishthe analyst with the most trustworthy indications, and if in additionthe iodine value and refraction numbers are determined, a very nearapproach to certainty is obtained. It may perhaps be pointed out inopposition to a rather widespread belief that the degree of fluidity ofthe insoluble volatile acids obtained in any of the distillation processesis of very little diagnostic value.Bellier4 proposes for the detection of cocoanut oil in butter amethod based on the precipitation of the fatty acids by means ofcopper sulphate solution, and claims that by its employment 5 percent. of cocoanut oil can be detected with certainty.The analyticaldifferences given by the author, and on which the detection ofadulteration depends, are very small, but the process will doubtless becarefully examined.A. W. Thorp5 has proposed to substitute for the methods ofPolenske and of Muntz and Coudon a simplified procedure which isreally only an extension of the ordinary Reichert-Wollny process.This is based on the same principle as that underlying the methodsabove referred to, but does not involve the use of special apparatus,and, judging from the test analyses recorded, is capable of giving veryuseful results. Jean calls attention to the somewhat extensiveemployment of Karitk or Fulwar butter (the fat obtained from theseeds of Bassia butyracea) for the purpose of adulterating butter, afact which still further complicates the analysis of that food product.He gives the analytical “constants ” of this fat, and indicates themanner in which the various butter values are affected by its use asan adulterant.I n connexion with the detection and estimation of preservativesin food-stuffs there is not much that; calls for special notice.It is well known that sulphur dioxide enters into combinationwith some of the constituents of certain foods, and that only aproportion of the amount actually present can in some instances beestimated by the ordinary distillation process.It is interesting tonote that in certain meats, for example, Holley7 was able t o recoveronly about one-fourth of the amount added as sodium sulphite.Forthe detection of fluorine in foods, Ville and Derriens propose a newZeit. Nahr. Genussrn., 1906, 12, 588. Ann. Chirn. apnal., 1906, 11, 121.Ann, Chirn. unul., 1906, 11, 412.Ann. Chiin. anal., 1906, 11, 201.Bull. s’oc. chiin., 1906, [iii], 35, 239.3 Compare Liihrig, Zeit. Nuhr. Genussm., 1906, 11, 11.Anulyst, 1906, 31, 173.’J; Anzer.. Chew SOC., 1906, 28, 993ANALYTICAL CHEMISTRY. 219method based on the change in the absorption spectrum of methEmo-globin brought about by the addition of fluorine compounds. Thetest is interesting on account of its novelty, but it remains to be seenwhether i t is capable of replacing t o any extent the methods now inuse. It is also of interest to note in passing that the well knowncolour reaction which formaldehyde gives with proteins in the presenceof sulphuric acid containing traces of certain oxidising agents, andwhich is so largely used in the testing of milk, depends on the presenceof the trytophan (indole) group, and that when that group is absent,as, for instance, in gelatin, no reaction is obtained.1 In view of thefact that in some countries the use of formaldehyde as a foodpreservative is either partially or entirely prohibited, the observationof Perrier that cider and various smoked foods may naturally containmore than 2 milligrams of formaldehyde per 100 grams is of import-ance, It is to be remarked that this observer has relied uponVoisenet’s colour reaction, and it is not impossible that the colorationshe obtained may have been due to some other substance than form-aldehyde.I n any case the observation is an interesting one to publicand other analysts who are concerned in the examination of foodstuffs under the provisions of adulteration Acts.The question of the detection of beef-fat in lard has occupied theattention of Dunlop,3 who has shown that the indications of theBelfield crystal test must be accepted with considerable caution, andthat the preseuce of ‘‘ plumose ” groups of crystals, as observed witha low magnifying power, is not to be taken as evidence of beef stearin,unless the characteristic form of individual crystals can be recognisedwith a higher magnification. I n view of the fact that lard obtained frompigs fed on cotton seed meal gives the Halphen reaction, this test is oflittle value as a proof of adultbration.Fnrnsteiner, Lendrich, and But-tenberg4 have made recent experiments on this point and have foundthat, although the lard from pigs fed on cotton seed meal often gave astrong Halphen reaction, the melting point of the acetate obtained byBomer’s method showed that cotton seecl oil itself could not have beenpresent. The glycogen in horse flesh apparently remains unchangedfor a long time, whilst that contained in beef, veal, and pork almostentirely disappears within a few days of the death of the animal, Onthis fact Martin5 bases a method for the detection of horse flesh insausages and potted meats, the glycogen being estimated by Pfluger’smethod. In this connexion attention may perhaps be directed to apaper by Pfliiger on the estimation of glycogen,G and to a series ofcommunications on the same subject by Desmouliiire.7Rosenheim, Biochon.J., 1906, 1, 233.J. SOC. Chaz. had., 1906, 25, 458.Ibid., 249.Qo?,zpt. rend., 1906, 143, 600.Zezt. Na7w. Genzcssm., 1906, 11, 1.PJugcr’s Arckiv, 1906, 114, 231.7 J. €’harm. Ckim., 1906, [vi], 23, 244, 281, and 332220 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The detection and estimation of free mineral acid in vinegar is at thepresent time of academic rather than of practical interest. Attentionmay, however, be directed to a paper by Richardson and Bowen,l inas-much as these authors deal in some detail with the influence which thealkaline and earthy phosphates in the ash exert on the results obtainedby Hehner's well-known method, and indicate the nature of theapproximate correction to be applied.Much work has been devoted from time to time t o the questionOF the estimation of the higher alcohols in spirits, and muchstill remains to be done.Veley2, has recently made a specialstudy of the Rose-Herzfeld and sulphuric acid colorimetric pro-cesses, and finds that both, but inore especially the latter, areuntrustworthy. Schidrowitz and Kaye,3 in continuation of theircritical examination of some of the better known methods, havefurther studied the Allen-Marquardt process, and are of opinion thatcarried out under proper conditions it is capable of giving quite trust-worthy results. It is shown that the usual " mineral acid " titrationwith methyl-orange as indicator may be dispensed with when itamounts to less than one-tenth of the whole, as it is not due, as isusually supposed, t o hydrochloric acid, but apparently to organicacids, some of which are known to have an appreciable effect on themethyl-orange, The same conclusion has been arrived at by Alannand Stacy,4 who have also studied the influence of temperature onthe proportion OF ethyl alcohol extracted by the carbon tetrachloride.It is in the very nature of things impossible that an exact methodshould be devised for the estimation of ft group of substances such asthe so-called higher alcohols, but there can be no doubt that, of allthe methods which have been proposed, that of Marquardt, as modifiedby Allen, is for several reasons the best.It is at least based onscientific principles, and has the further great merit of yielding actualoxidation products which can be examined and, if desired, identified.Numerous papers dealing with the analytical examination of drugshave, as usual, appeared during the year, but the majority of these,whilst undoubtedly useful, are scarcely of sufficient importance orgeneral interest t o warrant a special reference.St,an&k5 finds that betaine and choline, which frequently occurtogether in plants, can be separated almost quantitatively as per-iodides, the betaine periodide only crystallising from acid solutionswhilst the corresponding choline compound also crystallises fromliquids which are neutral or slightly alkaline.The test analyses arefairly good, and the method appears to be a useful one.I J. Soc. C h m . 1/2d., 1906, 25, 836. Ibid., 398.3 Analyst, 1906, 31, 131. J. Sos'oc. C/icnt. T?icl., 1906, 25, 1125..%it. physiot. Chenz., 1906, 47, 83ANALYTICAL CHEMISTRY. 29 1The testing of glycerol for traces of arsenic is a problem of some-what frequent occurrence, and Galimard and Verdier 1 call attentionto the fact that arsenic is sometimes present in a form (1glyceryl-arsenite), in which it cannot be detected by the direct application ofthe Marsh method, preliminary treatment being necessary.Keller’s nitric acid oxidation method for the separation of brucineand strychnine has been studied by Reynolds and Sutcliffe,2 who findthat accurate results can be obtained by the process as modified byStoeder or by Gordin if certain details of procedure to which theydirect attention are observed.The testing of disinfectants, of which there are now so manyon the market, is clearly a matter of considerable importance, andthe adoption of bacteriological methods such as that of Rideal andWalker3 marks a great advance on the unsatisfactory chemicalmethods formerly in use.I n the above-mentioned process thegermicidal value of the disinfectant in relation to that of phenol(“ carbolic acid coefficient ”) is determined in water, but Lloyd * andM. W. Blyth5 have shown that in the presence of organicmatter, suchas milk or urine, quite different results are obtained, and that two dis-infectants may occupy very different positions i n a table of relative“eficiencies,” according as the test is made with water, or with, say,diluted milk.ToxicoZogicul Analysis.Only a few communications need be referred to in this branch ofanalytical chemistry.Ipsen-Innsbruck 6 has studied atropine from the toxicological pointof view, and finds that i t is rapidly absorbed by all parts of the bodyand distributed in the blood.He also finds that the alkaloid is pos-sessed of very great sta5ility in the presence of decomposing organicmatters, and that 0.03 gram of atropine, after remaining in contactwith decomposing blood for twelve years, could still be detected. Sardnand Caffart 7 describe a method of treating blood stains for purposesof identification, in which chlorohzematin is obtained, the crjstals ofwhich can be easily recognised by the aid of the microscope.Themethod is said to work well with very old stains, and to be preferableto those in ordinary use. I n this connexion, attention may be directedto a paper by CarlsonS on the guaiacum test for blood, and to one onthe catalase test for blood stains by van Itallie.g The serum test forJ. SOC. CJiena. Ind., 1906, 25, 512.J. doc. C’iicm. hi?., 1906, 25, 405.(i Zcit. aqyem. C‘henz., 1906, 19, 141.Zeit. physiol. C‘hem., 1906, 48, 69.J. Pharm. Chim., 1906 [vi], 23, 153.J. h‘aitit. Inst., 1903, 424.Analyst, 1906, 31, 150.Conzpt. m i d . , 1906, 143, 251.Proc. K. Akad. l17ctezsch. Anaatcrdnnz, 1906, 8, 628222 ANNUAL REPORTS ON THE PROGRESS OF CHESIISTRli.differentiating the blood of different animals has also been studied byPiorkowski,l who has devised a simplified method of applying it.Bettink and van den Driessen hlareeuw have dealt with the identi-fication of chloral hydrate obtained from parts of dead bodies, andhave proposed a method for its estimation in such material which issaid t o give better results than th2t of Kippenberger.T. E. Thorpe3has devoted attention to the estimation of arsenic in wall-papers,fabrics, and similar materials, and finds that the electrolytic methodas employed in the Government Laboratory, preceded by appropriatetreatment of the substance, is capable of giving good results,This report would hardly be complete without some reference to thesixth International Congress of Applied Chemistry held in Rome a tthe end of April.More than fifty papers were presented to the sec-tion concerned with analytical chemistry, snd many more were com-municated to other sections, notably that dealing with bromatology.To one of these reference has already been made, but many have notyet been officially published, and cannot therefore be discussed. Anumber of the sections have adopted resolutions, many of whichembody most useful suggestions, although others cannot be regardedas anything but aspirations towards ideals which are scarcely likelyt o be reaiised. Of particular importance to analysts is the verymarked leaning of some of the sections towards uniformity andstandardisation of analytical procedure. It cannot be denied thatthere is much to be said in favour of the standardisation of manyarbitrary methods employed in the analysis of commercial products,more especially when, as is frequently the case, the results have t oserve as the basis of a contract between buyer and seller, or perhapsas the foundation of a criminal prosecution.On the other hand,there has been a marked tendency, which many competent analystsdeplore, to prescribe rigidIy standardised conditions for the carryingout of many analytical methods which are thoroughly well known, andwhich in skilled hands are capable OF yielding highly accurate results.I n the case of all the well known and commonly used processes, theconditions essential for accuracy have been determined and laid downby numerous workers, and no capable analyst will depart very farfrom them, although he will remember that the exact set of conditionsobtaining in one analysis are not often reproduced in another, and hewill consequently recognise that a certain amount of latitude is necessaryif the best results are to be obtained.U p to a certain point themovement in favour of " unification " and ' standardisation ' is goodand worthyof support, but beyond that point it must receive the con-Ber. Dezct. Phmrm. Ges., 1906, 16, 226.Pharm. Weekblnd, 1906, 43, 487,TTans., 1906, 89, 408ANALYTICAL CHEMISTRY. 223demnation of all who regard chemical analysis as a highly importantbranch of applied chemistry and not merely as a useful art.Apparatus.I n the body of this report reference has been made to certain newappliances, and it does not appear to be necessary to refer to theseagain.The following list contains references only to those new piecesof apparatus which have been described in recognised journals, andwhich appear to be of general utility, It may be remarked thatthe titles are not always exactly those given by the authors, but havebeen in some cases slightly altered so as to indicate more clearly thenature of the apparatus in question.“A new gas calorimeter.” C. Y. Boys (PTOC, Roy. Xoc., 1906,‘( Apparatus for removing gases from aTrated liquids before deter-K. Ulrich (Chem. Zeit.,‘‘ On vessels for collecting and transporting samples of gas.” R.“Apparatus €or the continuous registration of the results of gasB.Stollberg (Clwm.‘‘ New form of absorption tube for very soluble gases.” E. P. Per-“ Gas analysis apparatus.” John S. Haldsne (J. Hygiene, 1906,“ Modification of the Orsat gas analysis apparatus.” Louis de“ Simplified measurement and reduction of gases.’’ H. Rebenstorff‘‘ New apparatus for the examination of gases, poor in certain con-C. J. Gulich (Chern. Zeit., 1906,“ A new form of gas generating apparatus.” A. W. Gregory (Chem.“ A ‘ continuous-flow ’ wash bottle ” (Analyst, 1906, 31, 34).‘‘ A combined wash-bottle and pipette.” J. W. Hogarth (CAem.‘‘ Weighing-bottle for liquids.” K. Buschmann (Chern. Zeit., 1906,“ Modification of Maquenne’s wash-bottle.’’ Antoine Villiers (Ann.77, A, 122).mining the rjpecific gravity of the latter.”1906, 30, 90).Nowicki (Oesterv.Zeit. Berg. Hutt., 1906, 54, 62).analysis (increase of weight due to absorption).”Zeit., 1906, 30, 347).man (Chern. News, 1906, 93, 213).6, 74).Saint-Martin (Ann. Chim. anal., 1906, 11, 96).Chem. Zeit., 1906, 30, 486).stituents, by absorption methods.”30, 1302).News, 1906, 93, 27)News, 1906, 93, 71).30, 1060).Chim. anaZ., 1906, 11, 211)224 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.‘‘ A burette filling device.” Edwartl French (Chem. News, 1906,‘‘ A burette top for preventing the absorption of carbon dioxitle and“ Struthers syphon pipette ” (Analyst, 1906, 31, 247).“ New antomatic pipette.”“Dougal assay tube ” (Analyst, 1906, 31, 246).“ Filter tubes for collection of precipitates.” Samuel L.Penfieldand W. M. Bradley (Anzer. J. Sci., 1906, [iv], 21, 453).“ A delivery fnnnel for introducing liquids into vessels underincreased or diminished pressure.” T. J. Bryan (.L Amer. Chens.“ A new vacuum filter for laboratory use, and a novel method forcleaning the filtering material ” (Zeit. angew. C/t,ern., 1906, 19, 95).‘( Vacuum-filter drying apparatus.” Barth (Chem. Zeit., 1906, 30,907).“ The properties of apparatus (rings, tubes, crucibles, cbc.) made ofmagnesia.” Kurt Arndt (ClLenz. Zeit., 1906, 30, 21 1 ; compareE. Wedekind, Clien2. Zeit., 1906, 30, 329).‘‘ Porcelain-lined bomb for general laboratory use.” S. F. Acree(Anter. Chem. J., 1906, 35, 309).“ A new burner for spectroscopic work.” E.H. Riesenfeld andE. H. Wohlers (Chem. Zeit., 1906, 30, 704).“ A new sodium burner ” (Chem. Zeit., 1906, 30, 835).“ Alcohol calorimeter for coal testing.” W. H. Wallace (Engineer-ing, 1906, 81, 527).‘‘ An improved form of the William Thomson calorimeter.” ThomasGray (J. SOC. Chem. Ind., 1906, 25, 409).‘‘ A. new laboratory sink,” Heinrich Giickel (Chenz. Zeit., 1906,30, 755).“ Viscosimeter for varnishes.” E. Valenta (Chenz. Zeit., 1906, 30,583).“A new form of calcium chloride tube.” A. E. Hill (Proc., 1906,22, 87).“A new form of pofash bulbs f o r estimation of carbon dioxide inorganic combustions.” S. F. Acree (8mer. Chenz. -J., 1906, 35,309).“ Two new forms of apparatus for use in organic analysis (azoto-meter and potash apparatus).” Erwin Rupp (Zed.cmal. Chem., 1906,45, 558).“ Modification of Liebig’s potash bulbs.” R. Villiers (Ann. Clkna.anal., 1906, 11, 250).“ Improved apparatus for the continuous extraction of liquids withether.”93, 71).other gases ” (Chem. Zeit., 1906, 30, 459).Stein (Chem. Zeit., 1906, 30, 967).SOC., 1906, 28, 80).R. S. Bowman (Proc., 1906, 22, 24)ANBTJYTICAL CHEMISTRP. 225’* Apparatus for the complete extraction of liquids containitigsaccharin.” Maurice Duyk (Ann. Chim. unal., 1906, 11, 82).A modification of Foerster’s fat extraction apparatus.’’ ErnestPescheck (Zeit. nngew. Chem., 1906, 19, 1513).6‘ New form of platinum parting apparatus.” A. Jarman (Trans.Inst. Mining and Metall., 1906, 15, 625).“ Thermometer for low temperatures.” A. Stock and C. Nielsen(Bev., 1906, 39, 2066).“New method for the calibration of thermometers below Oo C.”T. W. Richards and F. G. Jackson (Zeit. physikal. Chem., 1906, 56,362).“ A temperature regulator for use with the immersion refractometer.”F. Lowe (Chem. Zeit., 1906, 30, 686).‘‘A simple form of rotating electrode for use in electrochemicalanalysis.” F. M. Perkin (Tmns. Furaday Xoc., 1906, 2, 91).(( A new electrolytic apparatus (rotating propeller-like anode).”8. F. Scree (Ameft. Chem. J., 1906, 35, 313).“ A new rheostat for electrolytic analysis.” G. Pascalis (Mon. ,S&,,1906, [iv], 20, 168).“ A modified Westphal balance for solids (particularly cements andminerals) and liquids.’’ F. 39. Williams (J. Amer. Chem. Xoc., 1906,28, 185).6 ‘ New zero adjustment for chemical balances.” J. McDowall (Chem.News, 1906, 94, 104).‘ 6 Improved Beckmanii apparatns for molecular weight determina-tions.”6‘ Portable universal stand for elementary analysis ” (Chem. Zeit.,1906, 30, 1045).6‘ The production of a high vaciiurn in the Scheihler (lesiccator.”H. C. Gore ( J . Amer. Chen?. Soc., 1906, 28, 834).6‘ Apparatus for distilling solids in a vacuum.’’ Hngo Haehn (,&it.nngew. Chem., 1906, 19, 1669).“ Shortened manometer with receivable vacuum (for distillation in nvacuum, &:.).”g C Apparatus for the estimation of snlphur and carbon with single ordouble receiver.” Arthur Wilhelmi (Zeit. Cliem. Appuratenkunde,1906, 1, 155).6‘ Jmproved apparatus for estimating total sulphur in coal gas ;modification of Dreschmidt’s method.” Everhard P. Harding (J. Amer.Chern. Soc., 1906, 28, 537).“New apparatus for the estimation of sulphur and carbon (iniron).”6‘ Percolator for me in assaying diwgs.” Frank R. Eldrecl (J. A n w .Chem. SOC. 1906, 28, 157).VOI,. 111. QJ. If. Sanders (Proc., 1906, 22, 165).Leo Ubbelohde (Chem. Zeit., 1006, 30, 966).A. Kleine (Zeit. angew. Chern., 1906, 19, 171 1)226 ANNUAL REPORTS ON THE PROGRESS OE‘ CHEMISTRY.‘‘ Improved Mayer’s apparatus for the evolution of chlorine. ” (Zeit.‘‘ A new urometer ; modification of the hypobromite method.”Nahr. Genussm., 1906, 12, 221).William M. Dehn (Zeit. anal. Chern., 1906, 45, 604).In conclusion, the author mould once again remind his readersthat the task of selecting from the enormous mass of publishedmatter those communications which appear to contain observationsof special importance to analysts is one of increasing difficulty,and? within the limits of a review such as this, many papers,embodying the results of really useful work must of necessity remainunnoticed.ALFRED C. CHAPMAN.Addendum.1Since the above mas written, I have been informed that in July,1901, H. A. Danne published, in The Chemist and Druggist ofAustrukasia, a method for the estimation of moisture identical inprinciple with Dupre’s acetylene method, referred to on page 202 ofthis report.A. C. c1

ISSN:0365-6217    

DOI:10.1039/AR9060300199

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY.STEADY progress is the key-note of the work in PhysiologicalChemistry which has been published since the date of last year’sreport. It seldom happens that an annual writer is able t o pointto any great discovery made in the preceding twelve months, andit is not my good fortune to be able t o chroniclei any such importantevent this year. Most discoveries are made so slowly, and pieceby piece, that it is difficult to assign any date a t all t o them, andthe surest knowledge is always proportional to the pains taken torender each piece accurate. Ehrlich’s views, for instance, on im-munity problems furnished investigators with a brilliant and fruit-ful stimulus to further work, and the steady flow of researches onthese lines which still continues shows that the stimulus is stilleffective.But the general theoretical results are a t present difficultto see, and it is impossible to bring anything) in the w-ay of order outof the apparent chaos. Physical chemistry, again, has its physio-logical applications ; it has enabled us to understand somethingmorel than we previously did about the osmotic processes in thebody; it has taught us that the action of salts must be viewed inthe light of the action of ions; and it has reduced the investigationof even such obscure questions as ferment action to almost mathe-matical precision.1 But here again the time is not ripe for general-isation; the physical chemists have many differences of opinion onquite fundamental questions to settle first, and until these arecleared away, the physiologists must be content to wait for the fullbenefits they expect from this new branch of science.It will therefore not be to questions of this nature that I shalldevote the bulk of what I have t o say, although they have, so far asspace is concerned, occupied so much of the Chemical Society’sJournal and its abstracts.I imagine further that it is not theobject of such a report as this t o epitomise still further the epi-tomes which have monthly made up the bulk of the Journal, butSee, for instance, E. F. Armstrong’s “Studies in Enzyme Action,” Nos. VIIand VIII of which have recently appeared (Proc. Roy. Xoc., 1905, -6, 76, 592, 600 jAbstr., 1906, i, 127, 125).Q 228 ANNUAL REPOItTS ON THE PROGRESS OF CHEMIS'I'RY.rather t o give the writer, who happens in this case t o be also auabstractor, an opportunity to enlarge upon certain aspects of thescience with which he happens to be more familiar, and t o exercisethat right of comment which is denied to him when he merelypresents an abstract.I shall naturally take the abstracts as ths foundation of suchremarks, and shall endeavour to select those subjects which appeart o be most profitable for discussion.Prot eid Chemistry and P r o t eid Me tab olism.This question still stands, and probably for many years to comewill continue t o stand, pre-eminent in its importance t o the workerswho apply themselves to the chemical side of biology.Nomenclature.-At the outset we meet with a difficulty inthe very names applied t o the heterogeneous groups of substancesincluded under the word Proteid.The difficulty has become anacute one for teachers and students, so various are the terms thatlare used by different writers. A committee has consequently beenappointed t o consider " Proteid Nomenclature," and physiologistsand chemists have sat in conclave t o formulate something they hopewill be acceptable t o all. Although their work is not yet concluded,it may not appear premature to state their main decisions.Our knowledge of the chemistry of the albuminous substances isslowly progressing under Emil Fischer's leadership, and this willno doubt in time enable one t o present a classifica,tion on a strictlychemical basis. But until that time arrives, we must be contentvery largely with the artificial classification (on the basis of solu-bility and so forth) which has hitherto prevailed.The classificationsuggested must therefore be regarded as a provisional one, which,whilst it retains the old familiar names so far as possible, yet at-tempts also t o incorporate some of the new ideas.The general name recommended for the whole group is that ofProtein. It is a t present so used in America, and to some extentin Germany, and has been definitely accepted by Fischer in thevolume of his collected papers on the subject which has recentlyappeared. The word has the advantage of admitting of the derivedwords, protease, proteose, &c., and it has, after all, the ring offamiliarity.The sub-classes, beginning with the simplest, would be asfollows : -1.Protamines.-These yield a comparatively small number ofamino-acids as their cleavage products, and are instanced by suchsubstances as salmine and sturine derived from the sperm of fishes229 PH Y S I 0 LOG I C AL C HE MI S TRY.Their most abundant cleavage products are diamino-acids ; someprotarnines yield, for instance? over 80 per cent. of their nitrogenin the form of arginine.2. Histones.-Tbese yield a larger number of amino-acids, butnot so many as those in the next classes. They have been separatedfrom blood corpuscles, and are peculiar in being precipitable fromsolution by ammonia. Classes 1 and 2 probably shade insensiblyinto one another.3. Albumins.4.Globulins.The albumins and the globulins differ from one another in theirsolubilities, the globulins being more readily salted out ” than thealbumins. They comprise the greater number of native proteins,and all possess the character of being coagulated when their solu-tions are heated.5. Sclero-proteins.-This perhaps is the most heterogeneous groupof the series; i t includes the gelatin and keratin members. Theprefix of the new word indicates the skeletal origin and often in-soluble nature of these substances. They have in tha past beencalled albuminoids by physiologists, but this word is ambiguous,and is used, and probably will continue to be used, by manychemists as equivalent to protein.Theprefix nucleo- frequently used in relation to these substances is bothincorrect and misleading.7.Conjugated proteins.-Here the protein molecule is united toa “ prosthetic ” group. The principal varieties of these are thenucleo-proteins, the gluco-proteins ( e . 9 . mucin), and the chrorno-proteins (e.9. hznioglobin).Coming next to the products of protein-hydrolysis (a term pre-ferable to proteolysis), the Committee recommend that these be clas-sified as follows:-1. Meta-proteins.2. Proteoses.3. Peptones.4. Polypeptides.Meta-protein replaces albuminate (acid-albumin, alkali-albumin).The termination ate implies a salt, and so is objectionable. Thesefirst products are, moreover, obtainable from both albumins andglobulins, and the prefix rneta- is an indication of comparativelyslight chemical alteration.The proteoses form the next stage ascleavage continues, and then come the peptones, a household wordvery unlikely ever to disappear from chemical literature. The termshould, however, be restricted t o those further products of hydrolysis6. Phospho-proteins.-This is the vitellin-caseinogen group230 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.which cannot be salted out from solution, but which, nevertheless,still give the biuret reaction.The polypeptides are still further on the down-grade; althoughmost of those we are acquainted with are synthetical products whichFischer has prepared by linking amino-acids together, some havebeen discovered as a result of digestive cleavage, and no doubt arethe immediate precursors of the final cleavage products, the amino-acids.It should, however, be noted in conclusion that this classificationi s mainly applicable to proteins of animal origin.The vegetableproteins may be arranged under the same main headings, althoughit is doubtful if a real and complete analogy exists in all cases. Thecleavage products of the vegetable proteins are in the main thegame as those of animal proteins, but the quantity of each yieldedis usually different; for instance, vegetable proteins, as a rule, givea very much higher yield of glutamic acid than do those of animalorigin. Further, there are certain vegetable proteins which havehitherto been regarded as peptones, but which do not give the biuretreaction. It seems impossible at present to bring exceptional sub-stances of this kind into any general classification, and the sameis true for those curious vegetable proteins, such as gliadin and zein,which stand apart from all other members of the group in beingsoluble in alcohol.Emil Fischer’s book, which has just been mentioned, will provea, boon to all of those who are grappling with the chemistry of theproteins, for in it, are collected his numerous memoirs on the subjectdown to the end of 1905, together with those published by his col-leagues.One searches in vain on the title-page for the legend Vol. I.But it can only be the first of a series, and already there is a goodlysupply, mainly from the pen of Abderhalden, for the second. Thisis just one of the cases, alluded to in the opening paragraph of thisreport, in which details are being steadily collected.The proteinsone by one are being taken to pieces, and the final cleavage pro-ducts identified and estimated. One cannot but admire the patienceof a worker who thus gradually plods through this routine workin order to pave the way to the final generalisation which will comein the future. Much the same sort of thing is being done in rela-tion t o the nucleic acids by Levene. The forthcoming index willbe a more trustworthy guide to all these numerous papers thanm y amateur attempt of mine to forestall it. In spite of all the hardwork involved in researches of this nature, Abderhalden has foundtime to write a, general TextrBook of Physiological Chemistry, whichis a most admirable compendium of up-to-date information, and in itsstyle rmalls that of Bunge, Abderhalden’s former master.Two nePHYSlOLOGICAL CHEMIS'L'ICY. 231books have also appeared on the Proteins, each of which has itsspecial merits; the first of these is by Dr. Schryver (Chemistry ofthe Albumens, J. Murray), and deals mainly with the purechemistry of the subject. The other, by Dr. Gustav Mann(Chemistry of the Proteids, Macmillan), started as a translationof 0. Cohnheim's work, but ended in a volume twice the size ofits German prototype. It contains a mine of references to originalresearches, and is chiefly interesting to those who deal in specula-tions of a physico-chemical kind.Globulins,--The distinction between globulins and albumins isone which is mainly based upon differences in solubility; the generalreactions of both classes are identical, and the opinion has beenfreely expressed of recent years that the differences are purely arti-ficial. This idea was first brought into prominence by Starkesome years ago, when he showed that by quite simple means theyield of globulin in such fluids as blood-serum can be increased a tthe expense of the albumin.It was further emphasised by thediscovery of certain substances termed pseudo-globulins, which, al-though they differ from albumins in the readiness by which theycan be salted out of solution, nevertheless possess the albumin-likecharacter of being soluble in water. Moll takes much the sameview as Starke, and contends, in his most recent paper,l that thenaturally occurring pseudo-globulin of horses' blood is identicalwith that prepared artificially from the crystallised albumin of thesame blood.Another paper embodying the same notion has beenpublished by Sikes,% in which he shows that, in the absence of bac-teria, the globulin of albuminous urine (especially if the fluid isalkaline) increases and the albumin diminishes when the urine iskept.But in all these cases the test used for the globulins has beenthat of solubility; there has been no attempt to ascertain whether,when an albumin changes into a supposed globulin, there has beenany chemical alteration. When we consider that solutions ofalbuminous materials are not true solutions, but colloidal solu-tions, and when we realise that the phenomena of " salting out "are properties that are shared by other colloids, it is not difficultto understand that slight dzerences of temperature, reaction, andthe like will cause a material labelled albumin to undergo smallchanges of solubility which cause it to be precipitable by reagentswhich under more normal circumstances precipitate globulins only.The molecules of a protein are unstable ones, and it is possible toimagine further that accompanying the changes of solubility someslight intramolecular changes of a chemical kind may take placeBcitr.Cheni. Physiol. Pcith., 1905, 7, 311 ; A b s t ~ . , 1906, i, 53.J. PhysioZ., 1905, 33, 101 ; Abs.fr., 1905, ii, 843232 ANNUAL IiElWKl'S ON THE PHOOKESS OF CHEMISTRY.as well.But it is not possible to imagine that any profoundchemical change can occur, and there would be a very profoundchange indeed if an albumin were in very truth transformed intoa globulin. For Abderhalden has shown that the proportion ofthe amino-acid cleavage products in typical globulins differs veryconsiderably from that obtained from typical albumins, andfurther that the difference is not merely quantitative, but qualita-tive also; for instance, the albumins do not yield glycine, whereasthe globulins do. The difference between albumins and globulinsis thus a real and fundamental one. The lessons we should reallydraw from such work as that of Starke, Moll, and Sikes are, first,that it is unwise to rely on solubility tests in any attempt t odistinguish between albumins and globulins, for solubility is avariable quantity ; and secondly, that the statement that albumincan be transformed into globulin cannot be accepted unless sup-ported by chemical analysis.A globulin, then, is a distinct entity, and although Hardy sur-mises that the globulin of blood-serum is formed by the decom-position of a more complex protein there, he has neverthelessselected it as the substance upon which to perform some very re-markable experiments in his study of colloidal solutions. The paperhe has written1 is a complex and highly technical one.In brief,he shows that globulin is an amphoteric electrolyte, and thatglobulin salts ionise in solution. If acid is added, the protein mole-cules assume an electro-positive character, and in the electric fieldthey move towards the cathode; if alkali is added, they assumean electro-negative character and move towards the anode; but inneutral solutions there is no movement, and, moreover, in normalserum " ionic globulin " is absent.The same results have also beenobtained by Pauli.2 Pauli goes further than Hardy by askingwhether the electrical charge of proteins may not possibly explaincertain physiological phenomena in connexion with protein chem-istry and assimilation, immunity, histological staining reactions, andeven fertilisation. It is easier to ask such questions than t o answerthem. One is on safer ground if one merely records the facts a t pre-sent, and the main result that a protein may act amphoterically isintelligible if we accept Fischer's view that every protein is a longchain of amino-acids, for every link of the chain is capable of actingeither as a base or an acid according as its acidic or basic groups arecalled into play.I n connexion with Hardy's work, the paper that follows it byJ. PhysioZ., 1905, 33, 251 ; Abstr., 1906, i, 121.Reitr.chern. Physiol. Path., 1906, 7, 531 ; Abstr., 1906, ii, 180 ; Xaturw.Bundsch., 21, 3, 17 ; Abstr., 1906, i, 545PHYYlOLOOlCAL CHEMISTRY. 233Mellanbyl should be read. This also emanates from Cambridge,and deals with globulins; the treatment of the subject is on ratherdifferent lines, but is based on physico-chemical conceptions.Ash Constituents of Protein.-The only other physical paper towhich I shall allude is rather an important one by Bayliss.% Igave a very full abstract of it a t the time it appeared, and so itwill only be necessary here to refer to its physiological side.Theash constituents of proteins have always been somewhat of a puzzle,but Bayliss appears to have obtained the correct solution of theproblem. They are not in chemical combination ; they are not merelyin mechanical admixture, but they are in a condition midway be-tween these two extremes, and are adsorbed in the same way thatmany dyes are adsorbed by fabrics. The main experiments weremade with gelatin, and the curve of electrical conductivity of suc-cessive distilled water extracts of gelatin is, as in the case of dyes,a hyperbola.Such a curve only approaches the axis (that is, zeroconcentration) asymptotically, or, in other words, it is impossible t owash out all the electrolytes, except by an infinite number ofchanges of distilled water, each washing removing a less percentagethan the previous one. I f such gelatin is again placed in solutionsof electrolytes, it again adsorbs them in a non-ionised condition.Adsorption is doubtless an important factor in many physio-logical processes. I n the staining of histological preparations, theevidence is in favour of the adsorption theory, and here the partplayed by electrolytes must also be taken into account I f electro-lytes are split off from living cells on death or injury, it is clearwhy such cells readily take up acid dyes; moreover, since electro-lytes are unnecessary when the substance to be stained is electro-negative, it is clear why living cells can be stained with basic dyes.The affinity of the Nissl granules of nerve-cells for basic dyes isabolished by previous treatment with neutral salts (Mayr 3), andthis is also in accordance with Bayliss’s results.It is quite certain that there is no universal law in such matters,and in the staining of cells there are cases of true chemical com-bination; and such results as those of Mncdonald * with injurednerve-fibres and neutral-red are difficult to explain by the adsorptiontheory; evidently here other factors have to be considered.Thisis freely admitted by Bayliss, who does not, like so many workersa t a new idea, seek to make it explain everything that was obscurebefore.He certainly puts forward the view that the action be-] J. Physiol., 1905, 33, 335 ; Abstr., 1906, i, 122.Biochem. J . , 1906, 1, 175 ; Atstr., 1906, ii, 344.:% Beitr. chenz. Physiol. Path., 1906, 7, 548 ; Absh.., 1906, ii, 182.Proc. Physiol. SOC., 1905, xsxvii, lxvi ; J. Physiol., 32 ; Abslr., 1905, ii, 405,545234 ANNUAL REPORTS ON THE PROGRESS OF' CHEMISTRY.tween toxins and antitoxins is possibly adsorptive, and that theunion between an enzyme and a colloidal substrate may be of thesame nature, but he does not try to make adsorption explain theuniverse.A bsorption of Protek.-Passing from adsorption to absorption,we reach surer ground, and proceed to deal with matters of morepractical interest.The old view that proteins are absorbed as pep-tones and proteoses, and that the fact of these not being discoveredin the circulating fluids is due to their being resynthesised in thecells of the living membrane of the intestine into proteins of thealbumin-globulin type, has now been definitely abandoned. Pro-teins are absorbed as amino-acids, and evidence of any specialsynthetic formation of proteins by the epithelium of the intestineis lacking (Schryver,l Leathesl); the greater part of these arenever built into living protoplasm a t all, but they are rapidlyconverted by the liver cells into urea, and this finds an easy exitfrom the body by the urine. The small amount that is needed fortissue repair is doubtless picked out of the blood and lymph by thevarious tissue-cells, and i t is there that protein synthesis takesplace, just as it is there also where internal respiration occurs.Inhis early experiments in relation to this problem, Leathes at-tempted to study it by examining the blood leaving isolated loopsof intestine in the interior of which the cleavage products had beenplaced. The loops were perfused with defibrinated blood, butin these circumstances no absorption whatever occurred, andthe intestinal epithelium underwent degenerative changes. De-fibrinated blood is not normal blood, and toxic effects have beenpreviously described when it has been used in other experiments(Brodie2). It was therefore necessary to deal with the intactanimal, in spite of the greater experimental difficulties of searchingfor absorbed products when diluted with the whole volume ofthe blood; and this is what Leathes3 in conjunction with Cath-cart has now done.They found that during absorption ofprotein cleavage products there was no increase in the coagulableproteins of the blood, but that there was a small but distinct risein the amount of non-protein nitrogen. A superficial observermight ask, Why was the rise only a small one? but the answer isobvious. Absorption is a slow process, and the amount of amino-acids absorbed is diluted with the whole volume of the blood, andfurther, as soon as it is absorbed, or shortly afterwards, it is re-moved from the blood. Many years ago Kuhne argued that theamount of amino-acids in the intestines a t any particular momentduring digestion is so small that complete protein cleavage cannotSee last year's Rrport, p.214. J. Physiol., 1900, 26, 48.3 Ibid., 1906, 33, 462 ; Abstr., 1906, ii, 181PHYSIOLOGICAL CHEMISTRY. 235be considered to occur to any great extent. He lost sight of thefact that the amino-acids in the intestine were not formed forthe purpose of accumulating there, but for absorption. So withamino-acids in the blood, they are not absorbed in order to bestored in that fluid, but are removed from it by the tissue-cellsand dealt with there, being either assimilated into protoplasm, orchanged and a t last discharged as waste material by the kidney.Since then Howell1 has, by a somewhat different method, beensuccessful also in isolating the amino-acids of the blood, especiallyafter feeding; smaller quantities of them are also present in thelymph.The Amount of Protein in Diet.-We are thus led in logicalsequence again to consider the important practical question of thenormal daily requirements of a man in so far as the protein inhis food is concerned.As is well known, it is Prof. Chittenden ofYale who is mainly responsible for raising the question, and whilstall sympathise with him in his crusade in favour of temperancein food as well as in drink, and many may confess that in thepast they have sinned and eaten too much, it is not surprisingthat his extreme views have been seriously challenged, and thatmany are asking now, would it not be equally unwise to eat toolittle? In deciding whether the Chittenden diet is one which fallsunder that description, there is a great deal more to be done inthe way of accumulating data and performing experiments beforeany decisive answe: can be given.Here experiments on animalsare not very conclusive, for if the vegetarian can point to the oxas an instance of a strong beast which thrives on diluted proteinnutriment, the meat eater can immediately point to the lion asanother vigorous animal who derives his strength from a richlyalbuminous diet. It is not, however, such a long way from theJapanese to the average European, and here accurate data are sadlyneeded. We do know that since the Westernising of Japan hascommenced, the diet of that country has altered also, and the recentprowess of the Japanese has been, in fact, accounted for by thosewho know the country by the more liberal supply of nitrogenousfood which they now ingest.A t the meeting of the British Association last summer a t York,the physiologists and economists combined to discuss this matter,and a t the Toronto meeting of the British Medical Association inAugust, the physiologists united with the doctors in a most interest-ing debate on the same subject.A t the last-named meeting wehad the advantage of listening to Prof. Chittenden himself, andalthough he was ably supported by Dr. Folin, the majority of thePmer. J. Physiol., 1906, 17, 273236 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.speakers were against his views, and doubted whether the mhimurnwas also the optimum.As an instance of the kind of experimental work which is stillnecessary, we may take that performed by seven physiologists a tUniversity College, London.1 They took their ordinary diet, andestimated the nitrogen of their urine.The total nitrogen excretedvaried from 9.6 to 16.5 grams daily, and, speaking generally, theheavier men excreted most. The influence of body weight as ;Lfactor is one which is often lost sight of, and Chittenden himselfis not a heavy person. The relation of uric acid to this was foundto be comparatively very constant, although that is somewhat of aside issue. Taking the nitrogen excreted as a measure of the proteiningested, the average intake of the seven physiologists would be93 grams daily, an amount not much below the usual Voit dietary.Atwater’s standard is 125 grams daily, and in workhouses andprisons it varies from 134 to 177 grams (see Rowntree’s Poverty,a study in Town Life).But the last-named figures are reckonedfrom bought food, and so the comparison is not quite fair, for theamount of waste is usually considerable in public institutions.Let us now turn to the question of why the minimum is notalso the optimum. Nature, as a rule, does not work in minimums,and Leathes puts it very well in his book when he says it is notconsidered unphysiololgical t o take a diet which will yield morethan the minimum of fzecal refuse, and he calculates that the dietprovided for an infant by nature in the shape of milk is, evenallowing for growth, ten times richer in protein than the require-ments of its endogenous protein metabolism would make apparentlynecessary.There is probably a real need for an excess of protein beyond theapparent minimum. I n diamond mining a large quantity of theblue earth of Kirnberley must be crushed to obtain the preciousstones.It probably is the case that among the’ many cleavageproducts of protein the majority may be compared t o this wasteearth, and we get rid of them as quickly as possible in the excre-tions, but some few may be unusually precious for protein synthesisin the body, and that in order to get an adequa,te supply of these, acomparatively large amount of protein must be ingested.It doesseem as though the large size of the liver (the riddle of the body, asLeathes terms it) is for the express purpose of dealing with thelarge amount of nitrogenous waste, much as the great capacity ofthe rectum enables the body to grapple with a large amount of fzcalrefuse.Such arguments are of more value than those so often used byPTOC. Physiol. Soc., 1906, x; J. Physiol., 34 ;?Absh*., 1906, ii, 463PHYSIOLOGICAL CHEMISTRY. 237physicians when they say that the intake of protein is for thepurpose of supplying the body with “reserve force.” Reserveforce is just one of those phrases that sound so satisfactory, butwhich it is very difficult to define. In the case of carbohydrates,we have a reserve force in the shape of a storage of glycogen; in thecase of the fats, the same is true, and the reserve is stored in theadipose tissue, but we know little or nothing of a storehouse forprotein, for the amount ingested is usually dealt with and disposeldof within a few hours after it is taken into the body.Pfliiger andhis pupil W. Seitzl have, it is true, suggested that the liver is astorehouse, not only for carbohydrates, but for proteins also, andhave supported their views by observations, partly chemical, partlyhistological, on starved and fed animals, but the idea has not a tpresent met with universal acceptance. Others have supposed thatprotein storage may occur in the muscles, a t any rate in someanimals. Be that as it may, the term reserve force is not one tobe wholly scoffed a t ; i t is not entirely meaningless, and it is after allan undoubted factor in the resistance of the body to fatigue anddisease. It is a matter of common observation how much differentpeople vary in “ stamina,” as it is sometimes called.This, in part,depends on the condition of the leucocytes or phagocytes, in parton the opsonic power of the blood-plasma, and in part on otherfactors less fully understood. It may be that the fresh supply ofprotein stimulates and activates such protective mechanisms in thebody, and certainly it is a practical fact that good feeding enablesthe body (as in tuberculosis) to repel and neutralise the deleteriousagents which produce disease. Each leucocyte may every dayundergo very slight wear and tear, but it will be more likely t oreceive the ‘‘ stitch in time” i f an abundant supply of repairingmaterial is in its neighbourhood.Some kind of attempt has already been made to work out theidea as to which of the Bausteine (to use the German phrase) ofthe protein molecule are so specially valuable for the synthesis ofprotein.The vegetable proteins do not appear to be so nutritious,t o use the popular phrase, as those of animal origin, and thisdoes not seem to be wholly due to the fact that they are not soreadily digestible. F o r are the vegetable proteins after all the sameas the animal ones? Work on their Bausteine seems t o answernd when we consider, for instance, their high yield (often over30 per cent.) of glutamic acid.The same note is also struck by twoBaltimore physicians (Lewellys Barker and B. A. Cohoe)2; theypoint out that certain articles of diet will “agree” and othersPJiiyer’s Arettiv, 1906, 111, 309 ; Abstr., 1906, ii, 241.J. Biol. Chenz., 1906, 1, 229 ; Abstr., 1906, ii, 102238 ANNUAL REPORTS ON THZ PROG€03SS OF CHEMISTRU'," disagree )' with people. On the supposition that this may be duet o the distribution of the nitrogen, they made determinations ofmono-amino-nitrogen, di-amino-nitrogen, &c. , in various foods (veal,pork, sirloin, chicken, fish, &c.), and have given their results ihtables. The differences are very striking, but their ultimate valua-tion is for the future. Still, this again is the sort of work whichmust be done before our knowledge can be based on the bed-rockof experiment.At present we can therefore only make a rough guess as to whichof the Bausteine are the diamonds; but it does appear as thoughphenylalanine and its near relative tyrosine were such; they arecomparatively scanty, and it is known that on injection into theblood stream they do not reappear as urea in the urine.We furtherknow that proteins which yield no tyrosine, such as gelatin, are ofinferior value as food. Gelatin is also destitute of the tryptophanradicle, so perhaps tryptophan is particularly useful too; and iftyrosine and tryptophan are added t o a gelatin diet, the animalsfed on it thrive better than those whose sole nitrogenous food isgelatin on1y.l Histidine and pyrrolidine have been also suggestedas being in the same category, but there again we must awaitfurther information.A critical examination of Chittenden's experiments and conclu-sions has recently issued from the pen of F.G. Benedict.2 Bene-dict's training in the Atwater laboratory would naturally prejudicehim against a revolutionary doctrine ; still, his objections are serious,and will have to be refuted before Chittenden and his comradescan urge their case successfully. But there are other subjects thatpress for consideration, and so I will be content with referringreaders to the abstract I recently supplied t o the Journal, or stillbetter to the original paper, which will amply repay perusal by thoseinterested in the subject.Protein Decomposition Products.Amino-acids.-Some interest hascentred round the question whether amino-acids occur in normalurine, and the introduction of naphthalenesulphonic chloride as areagent for their detection has rendered such an investigationfeasible. It seems to have been established that a minute amountof glycine and possibly of some other amino-acids is normally pre-sent (Embden and Reese,3 A. Lipstein: G. Fors~ner,~ Abderhalden1 Similar experiments have been made on yonng animals by Hopkins and MissWillcock (J. Physiol., 1906, 35, 88), in relation to the maize protein called zein.Zein contains no tryptophan. Zein plus tryptophan maintains growth.2 Amer. J. Physiol,, 1906, 16, 409 ; Abslr.., 1906, ii, 689.3 Beitr. chem. Physiol. Path., 1905, 7 , 411 ; Abstr., 1906, ii, 108.4 ?bid., 327 ; Abstr., 1906, ii, 109.6 Zeit.physiol. Chem., 1906, 47, 15 ; Abstr., 1906, ii, 243PHYSIOLOGICAL CHEMISTRY. 239and Schittenhelm,l F. Samuely,2 Wohlgemuth and Neuberg 3), butwhether this has any physiological significance is uncertain; theview expressed by the majority of observers is that the amountis really a negligible quantity. The importance of the inquiryarises from the study of pathological urine. I f , for instance, theamount is increased in gout, we should be provided with anotherstep in the ladder of knowledge concerning what is still an obscuredisorder. Here, unfortunately, the observers disagree, some de-scribing an increase in gout,, leuczemia, and pneumonia, but othersstating that the variations are within normal limits.A still more wide-reaching inquiry concerning the fate of amino-acids in the body is that which has been undertaken by Dakin.*It may be taken as pretty well proved that protein matter in thebody yields carbohydrate, quite apart from the glucosamine whichin some proteins is contained as a prosthetic group.Certain amino-acids, of which alanine is the one that has yielded the most positiveresults, are after administration converted into either glycogen inthe liver or sugar in the urine. The substitution of hydroxyl forthe amino-group in alanine will give us lactic acid, and lactic acidis readily formed from sugar, and so it is probable that the oppositechange from lactic acid to sugar may also occur.This, however, isonly one possibility, and certainly the more intimate chemistryof such reactions is still a matter of hypothesis only, and is difficultt o explain. Lang has shown that enzymes are present in the liverwhich remove ammonia from amino-acids, and Dakin considers thatferment activity will also explain the removal of carbon dioxidefrom their carboxyl group, as in the transformation of ornithine intotetramethylenediamine. Now if both ammonia and carbon dioxideare removed from an amino-acid, an alkyl group rich in carbon isleft, which might be further transformed into carbohydrate, or intocarbon dioxide arid water. Dakin selected a method which closelyapproximates a biochemical reaction, namely, Fenton’s method ofoxidation by means of hydrogen peroxide and a trace of acatalyst such as ferrous sulphate ; the amino-acids selected forexperiment were glycine, alanine, and leucine.All of these may berepresented by the formula NH,*CHR*CO,H, where R is either aZeit. physiol. Chenb., 1906, 47, 339 ; Abstr., 1906, ii, 470.Ibid., 376 ; Abstr., 1906, ii, 470.Ned. Klin., 1906, No. 6 ; Abstr., 1906, ii, 874.+I J. Biol. Chem., 1906, 1, 171 ; Abstr., 1906, ii, 105.The same method has been adopted by Battelli and Stern (Compt. rend., 1905,141, 916 ; 142, 175 ; Abstr., 1906, ii, 107, 184) in their investigations of oxidationsin tissues and tissue extracts. The place of the ferrous salt is in the body taken bywhat they term anti-catalase, and this disappears soon after death. Lactic, acetic,and formic acids are decomposed and carbon dioxide evolved.The method does notoxidise urea, and urea is also the chief nitrogenous end-product in the body240 ANNUAL REPORTS ON THE PROGRESS OF CHEMTSTRS.hydrogen atom as in glycine, or a methyl or isobutyl group (as iualanine arid leucine respectively). On oxidation all are readilyresolved a t the ordinary temperature into carbon dioxide, am-monia, and an aldehyde. In the case of glycine, the aldehyde pro-duced is formaldehyde, and this is the substance which is obtainedphotosynthetically in plant life, and is there the undoubted fore-runner of carbohydrate, into which it is transformed by condensa-tion, a process which has been successfully imitated in the laboratoryby Butleroff and Fischer.It was, however, found that the yieldof aldehyde was less in the case of glycine than in that of alanineor leucine; this is because it is partly oxidised into formic andglyoxylic acids. The formation of glyoxylic acid is not without in-terest, as this acid occurs in unripe fruit, and on ripening is con-verted into sugar.I n similar fashion, alanine yields acetaldehyde and acetic acid(but not pyruvic acid, the acid corresponding with glyoxylic acid),whilst leucine yields isovaleraldehyde and isovaleric acid.I think all chemists will agree that this research marks an im-portant advance, and one that should lead investigators onward.It is not until chemists are able t o repeat vital processes, by methodsthat they understand, that they can hope to comprehend what isoccurring in the hidden laboratory of the living cell. Not the leaststriking of the conditions of Dakin’s experiments is that they oc-curred at the ordinary temperature.GZyoqZic Acid.-The possibility that this substance is a productof metabolism is shadowed in Dakin’s work, and is shown to be aprobability in a later paper by the same worker.1 He was not,however, the first in this particular field, for Almagia and his col-leagues Pfeiffer and Inada had previously suggested that it is adecomposition product of uric acid, and found it in the urine,especially of people suffering from gout.I n herbivora fed on hay itis also present, and is derived there from the aromatic substances inthe food. It cannot, however, be said that the test adopted for thedetectioq of glyoxylic acid in urine is a very convincing one.Hopkins and Cole showed that the so-called Adamkiewicz reactionfor proteins depends for its occurrence (1) on the presence of thetryptophan group in the protein, and (2) on the presence of an im-purity (glyoxylic acid) in the glacial acetic acid employed.Eppin-ger3 had the brilliant idea that not only may glyoxylic acid beused as a test for tryptophan, but that tryptophan may also be usedas a test for glyoxylic acid. Subsequent observers, however (for1 J. Biol. Chem., 1906, 1, 271 ; Abstr., 1906, ii, 374.Bcitr. &em. PhysioZ. Path., 1905, 7, 4.59, 4G6, 473 ; Abstr., 1906, ii, 109.Ibid., 1905, 6, 492 ; AbstT., 1905, ii, 543PHYSIO1,OGICAL CHEhlISl'RY.241iustauce, l)akiii,l Schloss2), have pointed out that this does lrotnecessarily follow, and regard the test as untrustworthy, becausetryptophan may give the same coloration with other substancesalso.Schloss has introduced a modification of the Eppinger test, butwhether this is more satisfactory remains to be proved. Eppingerstated that the administration of various substances (alcohol,glycine, glycolic acid, sarcosine, betaine, &c.), led to the appear-ance of the acid in the urine, but this Schloss could not confirm.He only obtained a positive result when allantoin was given, andthis is by no means an unimportant result in view of Almagia'stheory of the relationship of glyoxylic acid to uric acid nietabolism.Schloss further examined the organs of the body, and believes thatglyoxylic acid when formed is destroyed in the body, especially inthe liver and brain.Whether glyoxylic acid is concerned a t all in the Adamkiewiczreaction appears questionable when one considers some results re-cently published by Rosenheim.3 He quite agrees with Hopkins andCole in regarding the reaction as due t o the presence of the trypto-phan (indole) group in the protein molecule.But he obtains whatappears to be an identical reaction both to the naked eye and t othe spectroscope when formaldehyde is added t o a protein solutionin the presence of sulphuric acid containing oxidising agents. Ac-cording to this view the impurity in glacial acetic acid responsiblefor the colour is not glyoxylic acid, but formaldehyde, and thepresence of impurities in the sulphuric acid (for instance, nitrousacid, ferrous salts) is also necessary ; these produce diformaldehyde-peroxide hydrate, and this reagent gives the test in the presenceof protein and pure sulphuric acid.I understand, however, fromDr. Hopkins that he is prepared to defend his original views, andthere we must leave) the question for the present; but until it issettled, the search for glyoxylic acid by means of tryptophan must besuspended.Lactic il cid in Intermediary Metuboli.s?n.-I mentioned lactic acidjust now as a possible intermediary between alanine and sugar in thebody. The whole question of the meaning of lactic acid is notonly fraught with interest, but also surrounded with great difficul-ties. Its close relationship to sugar is undoubted, whether we are con-cerned with the building up or the breaking down of sugar moleculesin metabolism, and yet the idea is gaining ground that the mostimportant variety of lactic acid found in the body (dextrorotatoryor sarco-lactic acid) has a protein origin, by way of such amino-acidsBeitr.ehem. Physiol. Path., 1906, 8, 445 ; Abstr., 1906, ii, 785.VOI,. 111. R' Loe. cit.3 Biocliem. J., 1906, 1, 233 ; Abstr., 1906, ii, 508242 ANNUAL REPORTS ON THE PROGRESS OF‘ CHEMISTRY.as alanine, and its compounds phenylalanine and tyrosine. G.Lusk and A. R. Mandell found that lactic acid disappears. fromboth blood and urine in phosphorus poisoning, when phloridzin glyco-suria is induced.This indicates that lactic acid produced from pro-tein (whether in liver, intestinal wall, o r elsewhere) is first syn-thesised t o sugar within the body before further distribution t o thetissues occurs. I n phosphorus poisoning this is followed by cleavageand a second production of lactic acid. But when diabetes is pre-sent, and when the mammary glands are utilising dextrose to formlactose, then the cells affected become “sugar hungry,” and alsoattract fat in greater quantity than they can burn it, and so fattydegeneration, which is really fatty infiltration, is seen. I n thediabetic organism there is therefore a complete conversion ofd-lactic acid into dextrose, and the same is true partially for i-lacticacid.The difficulties of the lactic acid question have led observers inthe past into curious mistakes ; the convulsions of puerperal eclamp-sia have, for instance, been attributed to the presence of the acidin the blood and cerebrospinal fluid.2 The acid is there, but it isobviously and undoubtedly the consequence and not the cause ofthe convulsions.Ferments.There is nothing very new or very striking to mention in rela-tion to work on enzymes during the last year.It is becoming moreand more certain that these agents act as catalysts in increasing thevelocity of chemical reactions.3 A succinct and very readableaccount of this modern view of ferment action has been writtenby Bayliss, and published in Mi. Murray’s new review, Science Pro-g r e ~ s .~ There are, of course, certain differences between enzymesand the inorganic catalysts (for instance, their destruction by a hightemperature), but, as Bayliss points out, these are all explicable ont,he hypothesis that the former are colloidal substances.I n addition to the papers of Armstrong which have been alreadymentioned, there have been others on what one may term isolatedpoints, such as the velocity of action of t r y p ~ i n , ~ the supposed iden-tity of rennin an’d pepsin,G the decomposition of caseinogen byAmer. J. Physiol., 1906, 16, 129 ; Abstr., 1906, ii, 463.This view is not altogether confined t o the past, but has again been urged byseveral investigators during the present year (Zmeifel, Munch. mcd. Woch., 1906,53, 297 ; Futh and Lockeman, Centr.Gpaek., 1906, 41 ; Abstr., 1906, ii, 472.3 See, for instance, Neilson, Arner. J. Physiol., 1906, 15, 148 ; AbStr., 1906, i,125. Oct., 1906, 281.See also same authoron Anti-trypsin, Biochem. J., 1906, 1, 474, 484 ; Abstr., 190% ii, 780.Hedin, J. Physiol., 1906, 34, 370 ; Abstr., 1906, ii, 780.Sawjaloff, Zeit. physiol, Chem., 1905, 46, 307 ; Abstr., 1906, ii, 98PHYSIOLOGICAL CHEMISTRY. 243trypsin and alkalis,l all of which are interesting in themselves, butdo not lend themselves to a general discussion.In reference to co-ferments, it is apparently becoming establishedthat these are, as hinted in last year’s report, of a simple and stablenature, being, in some cases a t any rate, inorganic in nature. Inthis relation the papers by Delezenne 2 on the activation of pancrea-tic juice by calcium salts, by Harden and Young3 on the alcoholicfermentation in which the presence of phosphates will partly, butcertainly not entirely, explain the favouring action of boiled yeastjuice, and by Loevenhart: in which Magnus’s co-ferment of lipaseis shown to consist of bile salts, should be read.Plimmer’s paper on the adaptation of the pancreas to lactose5does, however, raise a general question.The idea that the organismis able to adapt its secretions t o the calls made upon it originatedfrom the brilliant and suggestive work of Pawloff, and one of themost remarkable of these adjustments was described by Weinlandand later by Bainbridge; they stated that in animals which receivedno milk in their food, no lactase was secreted by the pancreas; butthe administration of milk or lactose to the animals educated the pan-creas to secrete the ferment necessaryfor the hydrolytic cleavage ofmilk sugar.Plimmer has now shown that this result was due to fal-lacious methods of experiment and analysis, and that this supposedadaptation does not really occur. This has certainly not killed thenotion of adaptation,6 but it has removed from it a very importantpillar of support, and this naturally leads one t o hesitate beforeaccepting other proofs, and to demand that the experiments be re-peated with more rigorous control^.^Cleavage of Peptides b y Enzymes.-This is also another importantgeneral question, although it is early days yet to attempt anygeneralisation.The peptides are numerous, and enzymes arenumerous? and t o work out all the possible combinations and permu-tations will take time; and this is the Herculean task Fischer, Abder-halden, and their colleagues * have started. Some of the peptideshyliss and Plimmer (J. Physiol., 1906, 33, 439 ; Abstr., 1906, i, 325.2 Compt. rtmd., 1905, 141, 751, 914 ; Abstr., 1906, ii, 99, 100.3 Proc. Roy. Soc., 1906, 77, 3, 405 ; Abstr., 1906, i, 470.4 Proc. Anzer. Physiol. Xoc., 1905, x w i i ; Amer. J. Physiol., 15 ; Abstr., 1906,5 J. Physiol., 1906, 34, 93 ; Abstr., 1906, ii, 239.6 There are, for instance, papers still being published in relation to i t ; see‘( Adaptation of tlie Salivary Secretion,” by Neilson and Terry (Amer.J. Physiol.,1906, 15, 406 ; Abstr., 1906, ii, 238).7 A more recent paper by Plimmer (J. Physiol., 1906, 35, 20) has already adducedevidence that other cases of supposed adaptation have no foundation in fact.8 Some of the most important papers in the series are as follow: Zeit. physiol.Chem., 1905, 46, 5 2 ; 1906, 47, 346, 359, 391, 466 (Abstr., 1906, ii, 99, 462, 464).i, 328.R 244 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.undergo cleavage, some do not, arid others are broken up only bycertain enzymes. For instance, glycyl-Z-tyrosine is readily decom-posed into its constituents by trypsin, but not by pepsin-hydrochloricacid; such an observation furnishes us with a distinguishing char-acter of these two enzymes which has for so long been lacking.Glycylglycine is not split by pancreatic juice, but it is by liverextract.Such an observation started Abderhalden on the track ofexamining the action of various tissue extracts, and there is no doubtthat a knowleldge of the part played by these tissue enzymes willteach us a great deal about intermediary metabolism. Enzymeshave in many cases been known to exhibit a " reversible action," andso it is quite possible that the same ferments which split peptidesmay also, when acting the other way round, contribute t o the syn-thesis of proteins in the tissue cells. No evidence of reversibleaction has, however, been forthcoming in the experiments hithertoperformed in. uitro.1Studies of this nature, and studies on autolysis, have establishedthe importance of the tissue enzymes; we now know that fermentswhich produce hydrolysis are not confined to the interior of thealimentary canal, but that most of the body cells are provided withferments of most diverse kinds, which assist them either in utilisingthe nutrient materials brought to them by the blood stream, or inbreaking them down previous to expelling them as waste substances.Claude Bernard, when he discovered the ferment which enablesthe liver cells to transform glycogen into sugar, little foresaw thatthis was the first of a long series which were t o be discovered manyyears later.Among such later discoveries we may mention tissueerepsin and arginase.But the best instance of all is seen in the formation of uric acidfrom nuclein; in this case we have t o deal with numerous fermentsacting in succession.Thanks t o Walter Jones in America andSchittenhelm 2 in Germany, our knowledge on this question is prettycomplete. The two observers have indulged in a certain amount ofpolemics, but those who are outside the controversy will rejoice that,after all, on the main questions involved there is agreement. Thefirst ferment to come into play is mudease, and this liberates thenuclein bases. This ferment is found in pancreatic juice, but it isnot identical with trypsin; in fact, it is destroyed by tryptic action(Sachs 3) ; it is, however, also found in the extracts of many tissues,and so the work started in the intestine is finished by the tissue cells.Abderhalden and Rona (ZeiLphysioZ.Chern., 1906,49, 31 ;'Abstr., 1906, ii, 873).Jones and Austrian (Zeit.physioZ. Chem., 1906, 48, 110 ; Ah&., 1906, ii, 561) ;Schittenhelm and Abderhalden (ibid., 47, 452 ; Abstr., 1906, ii, 465). For previouspaper, see last year's Report.Zeit. physiol. Chem., 1905, 46, 337 ; Abslr., 1906, i, 126PHYSIOLOGICAL CHEMISTRY. 245The next ferments which act remove the amino-group from thepurine bases that contain it; thus adenine (C,H,N,*NH,) is con-verted by ndenase into h-ypoxanthine (C,H,ON,) and guanine(C,H,ON,*NH,) is converted by gmnase into xanthine (C,H,O,N,).Finally, oxydases step in and oxidise hypoxanthine into xanthine,and xanthine into uric acid (C5H403N4). By examining extracts ofvarious organs, the distribution of these numerous ferments is foundto vary somewhat in different animals, although in general thespleen and the liver are the organs where they are most abundant.But the examination of such extracts has shown in addition thatthe long list is not yet complete, for some extracts in part breakup the uric acid which has been formed into simpler substances,1and the ferment which destroys uric acid is called the uricolyticferment.2 We therefore learn that the uric acid discharged inthe urine is only the balance left over when the amount destroyedis deducted hom the amount originally formed.In other words,the body possesses t o some extent the power of protecting itselffrom an excessive formation of uric acid, and so from the evilswhich would result from an accumulation of this substance.The Secretion of Urine.Bowman was the first t o put forward the hypothesis that the for-mation of urine is a double process; the glomeruli consist of bloodvessels in which there is high pressure, and consequently they havebeen looked on as a filtering apparatus where water and certainsoluble salts escape. The convoluted tubules with their secretoryepithelium are the parts of the apparatus where urea and other or-ganic substances are added to the glomerular flow.The secretingcells are able t o pick out the urea, mainly formed in the liver, fromthe blood, and transfer it to the urine.Ludwig, on the other hand, considered that practically all theurinary constituents found an exit from the blood a t the glomeruli,and that the function of the tubules was t o reabsorb some of thewater and so increase the concentration of the urine.This view hasbeen supported by the recent work of Cushny, who has put forwardevidence that reabsorption of water, and t o a certain .extent ofsome salts, occurs in the tubules. The whole tendency of modernresearch, however, apart from Cushny’s work, has been t o confirmthe original statements of Bowman, and to prove the tubules to haveas their principal function secretion and not absorption.1 See also the papers by Alinagia and his colleagues already quoted.3 The fact that uric acid is destroyed is no new discovery, however. See, forinstance, H. Wiener (Arch. exp. Path. Pharm., 1899, 42, 374 ; Absts.., 1090,ii, 153)246 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The work of Brodie and Cullis1 is a very important piece ofresearch from this point of view.They found, in a dog in whichdiuresis was produced by sodium sulphate, that the volume of urinesecreted by one kidney which was working against a small ureterpressure was greater than that formed by the other kidney whicheerved as a control; the volume of sulphate secreted on the ob-structed side was also usually in excess. A saline diuretic excitesthe cells to greater secretory activity, and does not work solely bycausing changes in the blood and in the circulation. Nevertheless,it was necessary in such experiments to exclude any artificialchanges in the blood flow through the kidney, and this was doneby making the ureter pressure sufficiently small.I f phloridzin wasemployed, the volume both of the urine and the sugar was greateron the obstructed side. Such results negative Ludwig’s view ofkidney action, for an increased pressure in the ureter. would promoteabsorption if Ludwig’s theory is true; they indicate that the glo-meruli will excrete more watler and probably more salt, and that thetubules excrete more salt when excited by a small ureter pressure.Heidenhain’s old experiment with indigo, in which he showedthat the tubules and not the glomeruli are the places where theexcretion of this foreign substance occurs, has recently been repeatedby Basler.2 This observer further introduced the indigo into thekidney calyces, but could not find that i t was reabsorbed by theliving cells of the tubules, although some ultimately diffuses back-wards into the lumen of tho tubules. But if the same experimentwas performed with sodium ferrocyanide, this salt was shortly after-wards excreted by the other kidney.This certainly shows that ab-sorption of the salt had occurred, but it does not prove that thecells of the tubules had been instrumental in the absorption; itrather appears that the salt had simply diffused into the lymphvessels or blood vessels in the neighbourhood of the injection.The mammalian kidney presents much greater difficulties to theexperimenter than the kidney of the frog; and Nussbaum, who fol-lowed in Bowman’s footsteps, utilised the fact that the glomeruli inthe latter animal are supplied with blood by the renal artery and thetubules by a different vessel, namely, the renal-portal vein, in his clas-sical experiments by which he sought to unravel the part played bythe two mechanisms. Nussbaum’s anatomical facts are undoubtedlytrue, and there is no anastomosis between the two sets of bloodvessels;if all the branches of the renal artery are tied, the glomeruli are ren-dered absolutely bloodless ; Bainbridge and Beddard 3 showed, how-l J.Physiol., 1906, 34, 224 ; Abstr., 1906, ii, 468.3 Proc. Physlsiol. Soc., 1906, ix, J. PhysioE., 34; Abstr., 1906, ii, 469 ; BiochesaPfluger’s Archiv, 1906, 112, 203 ; Abstr., 1906, ii, 468.J., 1906, 1, 255 ; Absti.., 1906, ii, 563PHYSIOLOGICAL CHEMISTRY.247ever, that undeF these conditions, although the tubules are stillreceiving blood, the kidney absolutely refuses to work a t all; forthe blood they receive is venous blood, and the loss of an arterialsupply asphyxiates the kidney and leads to death and desquamationof the renal epithelium. This may be obviated by placing the frogin nearly pure oxygen a t atmospheric pressure, and a secretion ofurine follows the injection of urea, dextrose, phloridzin, or disodiumhydrogen phosphate.Experiments on artificial perfusion lead also to similar results (MissCullis l). By quite simple operations, an arterial perfusion (by wayof the renal artery to glomeruli), a venous perfusion (by way of renalportal vein to tubules), or both (that is, a total perfusion), may be ob-tained; and the necessary oxygen supply is kept up by means ofoxygenated saline solution (Locke's fluid).Various diuretics wereadded to the perfusing fluid, and their effects noted. Phloridzinwas found to excite the tubule cells directly; they form dextrose anddischarge it into the urine. Caffeine also excites the same cells,although i t also probably has a slight similar action on the glomerularepithelium. With sodium sulphate, no flow of urine occurs unlessthe circulation through the glomeruli is maintained, and other salinediuretics act in the same way. Dextrose acts mainly on the glom-eruli, but to a small extent on the tubules. Both glomeruli andtubules are concerned in the elimination of urea, but there were somediiliculties in determining the relative importance of the two, forstrong solutions of urea kill the cells. Again, as in the dog, analysisof the urine showed no evidence of reabsorption in the tubules.Such experiments undoubtedly prove the power of secretion whichthe cells of the tubules possess.They do more than this; they showthat the old idea that the glomerular apparatus is a passive filter isincorrect, but that the cells that cover it, thin though they are, arenevertheless secretory also. At the meet'ing of the British Associa-tion in Toronto, Brodie advanced the view that the high blood pres-sure in the glomeruli is not to promote filtration a t all, but to enablethe glomerular tuft a t the commencement of each renal tube to actas a sort of force pump t o assist in driving the urine to its destination.Basler has also called attention to the high resistance the glomerularoutflow has to overcome in the narrower portions of the tubule, as, forinstance, in the loop of Henle.Whether this new idea will ulti-mately prevail it is a t present impossible to prophesy. Bainbridgeand Beddard, who concur in regarding the glomerular epitheliumas secretory, also suggest the presence of secretory nerves; nerveendings have been found by Berkeley in the renal epithelium, andit is difficult to explain diuresis following injury to the centralnervous system without assuming that these act as secretory nerves.J. Physid., 1906, 34, 250 ; Abstv., 1906, ii, 468248 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.An interesting outcome of such studies is a calculation of the workwhich the kidney does.The kidney cannot be doing more workthan its metabolism accounts for. If we suppose the kidney liveson its protein (and the figures would not be very different if wesupposed it lives on carbohydrate), we start with the following con-stants : -1 C.C. of oxygen oxidises 1 milligram of protein, and formswater, carbon dioxide, and urea (Barcroft and Brodie 1) ; in doingso it gives out 4 large calories, to adGpt Rubner's figure f o r the physio-logical heat value of albumin. I n a certain experiment the oxygenused by the kidney was 4 C.C. per minute; this was equivalent to 16calories, or to 680,000 gram-centimetres of work, and the energytransformed from potential to kinetic cannot have been less thanthat.What evidence is there of mechanical work as an offset againstthis? One way in which the work manifests itself is in the concen-tration of the urine. The urine in regard to its various constituentsis many times more concentrated than the fluid of the blood, andfrom freezing-point determinations it was found that 14,700 gram-centimetres of work were done in this way in the example just taken.No doubt if the calculation took into account each salt separately, ahigher figure than 14,700 would have been obtained, but even thenmuch of the kidney energy is left unaccounted for; we can onlysuppose that the transference of water itself a t a rapid rate throughprotoplasm is on occasion a process which involves the active meta-bolism of the cells.Micro-ch emistry.The number of workers a t this instructive and important aspect ofbiological work is lamentably small.I n addition to the paper byE. Mayr already quoted on the influence of salts on the staining andfixation of nerve-tissues, there is only one other of importancethat I can find in the year's output. This also deals with nerve-cellsand fibres, with special reference t o the distribution of chlorides inthem (Macallum and Menten ". Macallum has shown previouslythat the well-known reduction staining with silver nitrate, so muchused in histology, is due to the presence of chlorides. The transversestriations produced a t the nodes of Ranvier in nerve-fibres, andtermed the lines of Frommann, can be obtained at any portion ofthe axis cylinder, provided means are taken to allow the reagent toget a t it. These lines do not indicate, however, a pre-existing dis-tribution of 'the chlorides in alternating layers.The same appear-ance can be reproduced in capillary tubes containing egg-white, orgelatin impregnated with potassium dichromate (Boehm, Liesegang).Ostwald explains this by supposing that, when the critical concen-J. Yhysiol., 1905, 33, 52.€'roc. Roy. A'osoc., 1906, 77, B, 165 ; Abslr., 1906, ii, 182PHYSIOLOGICAL CHEMISTKY. 249tration in the advancing solution is reached, precipitation beginsand is continued until a stria is formed. This brings the solutionback to the metastable condition; then another development of thelabile condition obtains, and thus a new stria after an interstriatezone is formed.As the silver salt becomes more and more dilute,critical concentration is obtained later and later, and so new stria3are separated by interstriate zones of increasing width.The cytoplasm of the nerve cell shows the same appearances, butless intensely; this may be due to difficulty of penetration, but i tis held that probably the cell-body is poorer in chlorides than theaxon. The nucleus is destitute of chlorides.The mixture of electrolytes and colloids in the nerve-fibre wouldnot permit the ions carrying the electrical charge to travel unim-peded, and the change of potential transmitted would travel withdiminished velocity.This would bring into line the nerve impulseand the action current of nerve. It is freely admitted that cautionmust be exercised at present in drawing physiological conclusionsfrom physical data, but the following facts are very suggestive : -(1) the presence of electrolytes (chloride or chlorides) in a concen-trated degree and uniform in distribution; (2) the maintenance ofthis concentration through the impermeability of the sheaths of thefibres, and (3) the high conductivity of the axon, and the occurrenceof electrical phenomena when it is injured.Such speculations should be compared with those set forth byMacdonald in papers already referred to.Receptive Substances.I started this report with the laudable intention of avoiding, asfar as possible, speculative questions, but I find I have again landedmyself in the last section in another of those interesting regionswhere physical chemists and physiologists can meet and argue.Inthe present state of physiology it is, in fact, impossible to avoidhypothetical matters, and it is quite impossible also to conclude areport of this kind without a reference t o Langley’s recent sugges-tions on “ receptive substances.” The idea seems t o form an under-lying basis of a good deal of the work that has recently come outof Cambridge,l and it has finally found expression in the Croonianlecture which Prof. Laagley delivered before the Royal Society.2We may best approach it, as Langley himself does, by a definiteexample. Nicotine causes prolonged contraction in certain muscles1 See, for instance, H.K, Anderson on “The Action of Alkaloids on the Iris”( J . Physiol., 1905, 33, 414 ; Abstr., 1906, ii, 104).2 Proc. Roy. SOC., 1906, 78, B, 170-194. The question is also treated in J.Physiol., 1905, 33, 374 ; Bbstr., 1906, ii, 111250 BSXUAL REPORTS ON THE PROGRESS OF CHEMISTRY.of the bird even after their nerves have been cut, or after paralysishas been caused by curare. The nicotine contraction is lessened bya sufficient dose of curare, the two poisons being antagonistic, butnicotine is the more powerful. Degeneration of the motor nervesleaves these effects unaltered, but there is increased responsivenessto nicotine, and the action of curare is less marked. Under theseconditions, the axon endings are destroyed, and so the drugs mustact on the muscle itself; but as the muscles respond to direct stimu-lation, the poisons cannot be acting directly on the contractilesubstance, but on other substances in the muscle, which may betermed ‘‘ receptive substances.” This deduction may be applied t oother cases, and the majority of poisons ordinarily supposed to acton nerve-endings probably act on receptive substances in the cellsthe nerve-endings are distributed to. Adrenaline falls into thiscategory ; and secretin, iodothyrin, and other internal secretionsmay also act in the same sort of way, although the cells tiiey stimu-late may have no necessary nerve supply.These and many other speculations arising out of the generalidea are propounded, but the original papers must be consultedfor these.It will be sufficient for our purpose merely t o state whatthe general hypothesis is.It is postulated that in all cell-protoplasm two constituents atleast are present: (1) a chief Substance concerned with cell func-tion, and (2) receptive substances which may be acted on by chemicalmaterials, or in certain cases by nervous stimuli. The receptivesubstance affects, or can aEect, the metabolism of the chief sub-stance. A cell, for instance, can make motor or inhibitory recep-tive substances, or both, and the effect of a nerve impulse will thendepend on the proportion of the two kinds of receptive substancewhich is affected by the impulse.It is quite impossible to criticise such a theory a t present, forcriticism, like the main theory, must be supported by experiment.All one can say is that the theory is an exceedingly attractiveone, and one which does explain some of our present difficulties.Previous to the appearance of this new idea, physiologists wereagreed that there are only two possible ways in which a nerveimpulse can fire off such a structure as a muscular fibre, with whichits ending is in contact.One of these ways is an electrical one, theother a chemical one. The electrical theory is known as the ‘‘ dis-charge hypothesis,” and, put in the briefest possible way, it assumesthat the stimulus to muscular action is the current of action in thenerve terminal. Electro-physiologists have been fairly successful inexplaining away most of the objections which have been raisedagainst the “ discharge-hypothesis,” but they have never, t o mymind, succeeded in solving what is the greatest difficulty of all, anPHYSIOLOGICAL CHEMISTRY.251that is the mystery of inhibition. An action current, feeble thoughit is, is still a conceivable agent in rendering another tissue active.It is most difficult to understand how it can succeed in renderinganother tissue inactive, as, for instance, the vagus does the heart.An attempt has been made to explain the phenomenon of inhibi-tion by assuming differences in shape in the nerve-endings; in theordinary motor nerve terminal it has been supposed that the effecta t the entrance of the fibre, a spot which plays the part of thecathode of the terminal, is most concentrated, because the enteringpoint is a small one, whereas the anode consists of a number ofwidely-distributed points in the final branchings of the axon, andso the anelectrotonic or depressing effect is more diffused, and there-fore not so effective.Oni the other hand, the end orgm of aninhibitory fibre is assumed to be pear-shaped; the base of thepear is a t the entering of the fibre; the end organ then narrows offto a stalk, the end of which is the anode; the anode being thena smaller point than the wide cathode, anelectrotonic effects aremore concentrated, and so more effective; in fact, sufficiently so toovercome any stimulating effect the cathode would have. There is,however, very little histological evidence, and certainly not convinc-ing evidence, that inhibitory nerve-endings have such a shape as thetheory demands.Langley’s new hypothesis appears to be the first workable onein favour of the view that a nerve acts as a stimulus by producingchemical changes, and it is certainly easier to understand oppositechemical changes, or the reversal of a chemical change, than toimagine opposite electrical effects produced by differences in theshape of the nerve-ending.If, however, a muscle is rendered activeby the production of a chemical material that plays the part of astimulus, and if it is rendered inactive by the production of chemicalchanges in the opposite direction, we really only throw the maindifficulty further back; for we have still to ask how is it that thenervous impulses produce these chemical effects on the receptivesubstance or substances? Even if the presence and importance ofthese receptive substances, or intermediaries, between nerve andmusele be admitted, it may be still necessary to call to our assist-ance the “ discharge hypothesis,” or some variation of it, to explainhow the nerve affects the intermediary material.W.E. Dixon1 has already brought forward evidence that chemicalsubstances are produced in the heart when it is inhibited, and that1 Commnnicxtion to the British Association, Toronto meeting, 1906. Quiteanother aspect of the clicmicnl relationships of nervous action has been advanced byF. H. Scott (Brain, 1905, p. 506 ; Abstr., 1906, ii, 239).He considers that nerves:%re able to control changes in proteins, because of a proteolytic enzyme produced innerve-cells252 ANNUAL REPORTS ON THE PROGRESS OF CHEXISTRY.these substances can be dissolved out of the heart by alcohol, andcan then b’e used to produce inhibition in another heart. Thesubstance or substances cannot be extracted from a normally beatingheart; but we have no information as yet in regard to their chemicalcomposition. They appear, however, not to consist of potassiumsalts, to which Howell attributes such an important r6Ze in cardiacinhibition.Cuncer.I shall conclude my report by again referring to the importantquestion which I took up as the concluding section to last year’sreport. I then expressed the belief that chemistry will assistin the solution of the many problems that surround the pathologyof cancer.For instance, the important observation that the gastrichydrochloric acid is scanty or absent in this disease, even whenno actual caiicer is present in the stomach itself, cannot be meaning-less.z Investigations of the various proteins (nucleo-proteins, &c.)obtained from the tumours have not led to much a t present: butthese substances will have to be still further examined.Perhaps I was a little too positive when I stated that the parasitictheory of cancer was dead; I ought to have said that all the para-sites, animal and vegetable, held responsible by different observersfor the disease have hitherto turned out disappointments.It is difficult t o transmit the disease t o animals, and this limitsthe field of observation, but there is a transmissible disease of micewhich most pathologists agree is a form of cancer, and from thestudy of which there are great expectations. This disease was firstdescribed by Morau 4 in 1891, and subsequently by Jensen, of Copen-hagen, in 1903.It is a disease of the mammary gland; histologic-’ ally it closely resembles other cancers; it is followed by metastases(secondary tumours in other parts of the body), and it is malignant;that is t o say, it kills the mouse. Whether it is absolutely the samedisease as human carcinoma is another question, and a t a meeting1 Amer. J. Physiol., 1906, 15, 280 ; Abstr., 1906, ii, 179.2 Full papers on this point by E.Moore and his colleagues will be found i nEiochem, J., 1906, 1, 274, 297 ; Abstr., 1906, ii, 565. See also K. Sick (Arch. kliib.Ned., 1906, 86, 371 ; Abstr., 1906, ii, 565 ; Palmer, Biochein. J., 1906, 1, 398 ;Abstr., 1906, ii, 786).3 See, for instance, Neuberg, Zeit. Krebsforsch., 2, 171 ; Abstr., 1906, ii, 875.4 Conzpt. rend. A’oc. Eiol., 1891, pp. 289, 721, 801. Moran’s work came a t a timebefore cancer iesearch was in vogue ; helie5 the disease is generally known asJensen’s tumour. Jensen showed that in inoculated mice the new formation is acontinuation of the growth of the cells introduced by inoculation. The relativeimportance of the work of Morau and Jensen has been the subject of recent corre-spondence in the Lancet (Nov.and Dec., 1906), and doubt has been expressedwhether the two investigators were dealing with the same diseasePHYSIOLOGICAL CHEMISTRY. 253of the Pathological Society in Loudou a few weeks ago the experi-mental and pathological work on mice was spoken of as futile.This, of course, is the view of an extremist, and the correct attitudeshould be a more hopeful one. Curiously enough, however, in thesemice there is no fall in the secretion of hydrochloric acid in thestomach, but the reverse,l so it does appear there are grounds forhesitation in accepting the disease as identical with that in thehuman subject.A vast amount of work has been performed in relation to theJensen tumour. It is transmissible by inoculation from mouse t omouse, and already thousands of mice have borne their part in theinvestigation.I propose, however, only to deal here with the workthat has issued from the New York Cancer Laboratory a t Buffalo,because there a distinctly chemical bias has pervaded it.2 Chemistsas well as biologists have now invaded the territory of the patholo-gists, and Clowes with his colleagues have kept accurate records ofthe many thousands of mice they have had under observation.They have found that the disease may not only be given to theanimals by inoculation or injection of material from other mice, butalso that there is further distinct evidence of infectiousness in otherways. For instance, mice transferred to cages which had not beencleaned, but which had held infected animals long previously, de-veloped the disease. Such observations place this form of carcinomaon all fours with other infectious diseases, and lead one naturallyt o think that the active agent must be a living organism.Whatthe actual agent is, is still unknown, and it is necessary to exerciseextreme caution in drawing conclusions on this point. Some ofthe micro-organisms described by others are merely due to accidentalcontamination, and other supposed organisms are really artifacts.Calkins and Clowes draw attention to artifacts both in the nucleiand cytoplasm of the cancer cells, even in material fixed by Zenker’smethod (alcohol and iodine) ; the curious inclusions which theydescribe are artificial, but are found usually in the cells which areundergoing degenerative necrosis, and the method, therefore, is inone sense a valuable one in distinguishing the active cells fromthose undergoing the process of death- which is probably associatedwith a kind of fatty degeneration.Copemnn and Hake, La?zcet, 1906, ii, 1276 ; Abstr., 1906, ii, 875.The principal papers are as follows : H.R. Gaylord and G. H. A. Clomes, Mecl.News, Jan. 14, 1905 ; Xurgery, Gynmcology and Obstetrics, 1906, 2, 633 ; G. H. A.Clowes, Johns Hopkins Hos2)ttal Bulletin, 1905, 16, No. 169 ; G . H. A . Clowes andF. W. Baeslack, Med. News, Nov. 16, 1905; J. Exp. Med., 1906, 481; G. H. A.Clowes and W. E. Frisbie, Amer. J. Physiol., 1905, 14, 173 ; G. N. Calkins andG . H. A. Clomes, J. Infectious Diseases: 1905, 2, 555 ; G.H. A. Clowes, Brit. Med.J., 1906, ii, 1548 ; H. R. Gaylord, ibid., 15552.54 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The tumours, in fact, may roughly he divided into two varieties :(1) those which are growing rapidly, characterised by a high per-centage of potassium, with little or no calcium, and (2) those whichare old, slow-growing, and necrotic, characterised by a high per-centage of calcium, with little or no potassium (Clowes and Frisbie).The second class of tumours may not only be slow growing; theymay even diminish in size, and this may culminate in their disap-pearance, and the animals recover perfectly without any treatmenta t all. Bashford stated he had only seen one case of recovery in3,000 mice,l but in the experiments of Gaylord and Clowes spon-taneous recovery occurred in 23 per cent. of the cases.The retro-gression of the growth is attributed to the development of immuneforces, as in other infectious maladies, and the observation led theauthors to search for cases of spontaneous recovery in humancancer. They found fourteen apparently authentic cases in pre-vious records, but hearsay evidence of this nature is usually re-garded with suspicion, not only by lawyers, but by scientific workerstoo. I doubt if there are many medical men who would not regardthe occurrence of cancer in a human being as equivalent t o a sen-tence of death, and there are certainly none who would advise theirpatients t o trust to spontaneous cure instead of submitting them-selves t o that surgical interference which alone can avert the finaldisaster.The high percentage of spontaneous recovery in mice can bestill further increased by treatment on the lines of serum therapeu-tics. The mice which recover possess an active immunity againstfurther inoculation, and if cancer material from the Jensen tumouris mixed with the serum of the recovered mice, and then injectedinto fresh animals, quite a large percentage of the latter escapethe bad effects of the injections. Injection of the serum leads alsot o more frequent and more rapid recovery.These and similar statements require confirmation, but suchresults certainly make one feel there is hope in serum treat-ment in human carcinoma, and should still further stimulate re-search in that direction. This hopefulness, however, depends on theassumption that human carcinoma and mouse carcinoma are iden-tical or a t least similar diseases. We have already seen groundsfor doubting the identity if in one there is a rise and in the otherdisease a fall in the hydrochloric acid secreted by the stomach, forthis is an index of an altered condition in the ions of the blood.Subsequently he withdrewthis statement, as in later work (Brit. Med. J., July, 1906) he found spontaneousrecoveries i n large numbers, in some series as high as 60 per cent. Immunitydeveloped in mice .with the disease was also found by Ehrlich (Experime?ttelZeCarzinomstzcdien, April, 1906).1 Report of Imperial Cancer Research Fund, 1905PHYSIOLOGICAL CHEMISTRY. 255The relative non-malignancy of the mouse tumour is an additionalseason for making one hesitate in regarding the two diseases as thesame.Be that as it may, and only the future can decide the questicn,the results obtained by Clowes and others are important and sug-gestive; I will only add one more detail of this work, and so bringthis report.to a close.Clowes andBaeslack found that the incubation of the mouse-cancer material before it was injected into other animals altered-itsvirulence. Some of their material was, comparatively speaking, in-active; that is t o say, a large percentage of the mice injected did not“take.” I f this inactive material was kept in the incubator forsome time previous t o injection, its virulence rose, and the per-centage of affected mice increased. This, of course, is analogousto what one finds in most other infective substances.I n other cases the material was virulent a t the ordinary tempera-ture, but the virulence was lessened after incubation a t body tem-perature; this was the material obtained from necrotic tumours witha high calcium percentage. I n order to explain these results it isnecessary t o assume the existence of a toxin. The toxin acts as achemical stimulus to cell-proliferation, and its action is acceleratedby elevation of temperature; hence, comparatively inactive materialis rendered more virulent by the employment of the incubator. Butif the toxin is already abundant, it is quite conceivable that theraising of the temperature will lead, not to multiplication, but t odestruction of the cells, especially in tumours where necrotic changeshave already been initiated by other means. This autolysis willnaturally reduce the virulence of the tumour material.I n order to explain the toxin, it is necessary t o assume theexistence of some agent which will produce it, presumably a livingorganism, but on that final point we have a t present no light.W. D. HALLIBURTON

ISSN:0365-6217    

DOI:10.1039/AR9060300227

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

AGRICULTURAL CHEMISTRY AND VEGETABLEPHYSIOLOGY.THE record for the year 1905 was concerned largely with the“search for nitrogen,” or, rather, for means by which that widelydistributed, though inert, gas could be made to lend itself to theservice of agriculture. This question remains the prominent one to-day, and elver and again hopes have been quickened by some newand startling announcement, and it would seem, indeed, that theday is not far distant when the falling-off of the supplies of nitrateof soda from South America may be contemplated with resignation,and the atmosphere, with its vast store of nitrogen, be laid undercontribution to agriculture’s needs. The work of the year 1906has brought this prospect somewhat nearer, although perhaps notvery materially so, and development has hardly taken any newform.Just as the year 1905 closed a new revelation was promised asregards the behaviour of plants in relation t o their power of utilis-ing nitrogen, but closer examination has shown the views thus putforward to be untenable.At the close of 1906, there was, simi-larly, promised a new discovery, whereby at’mospheric nitrogencould be cheaply utilised. I n each case the details were not athand a t the time of writing, and so it has not been possible t o domore than merely chronicle the event. But it is evident that deepinterest must attach to researches in this direction, both from thescientific and the practical side of agriculture. The great problemis, of course, how the nitrogen of the atmosphere can be bound upin some form in which it can be transported t o the land and theremade use of just as nitrate of soda and other nitrogenous materialsare. The ways already discovered of effecting the union ofnitrogen and oxygen, which have resulted in the productionof cyanamide on the one hand and of calcium nitrate on the other,have been further exploited with the view of removing the onegreat obstacle to the general employment of these materials-namely, their cost of production.It is in this direction that thelatest discovery is stated to tend, Meanwhile, information is beinAGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 257accumulated as t o the practical uses and comparative values ofthese materials so far as their limited supply allows.I n another direction attention is being turned to the work oforganisms in the soil, and to the conditions under which some ofthese, a t least, have the power of elaborating nitrogen into formsavailable for plant use.For the moment, the direct inoculation ofleguminous crops, to which so much attention has hitherto beengiven, seems to have been dropped, and there is little that is newto record about it. But in regard to Azotobacter and other soil-organisms, much further work has been done, and our knowledgeregarding their action is beginning to shape itself into form.Similarly, inquiry has been pursued as to whether plants do not,in some cases, take up ammonia directly.I n regard to the root action of plants, more evidence has beencollected in support of the contention that there is no externalaction of the root sap itself, but that it is the excretion of carbondioxide from the roots which assists the solvent action of the soilwater.Striking proof has been afforded of the important partwhich calcium carbonate plays in respect of plant life and cropproduction, whilst the special place which magnesia occupies hasalso been investigated.The inquiry into green-manuring has been continued, and furtherresults have been obtained which bear out the conclusion previouslycome to that green crops act very variably, and that the deductionsformed from theoretical considerations are not borne out in farmpractice.Much work has also been done with regard t o the question of“strength” in wheat and what is implied by this, but strongindications are given that the solution of the problem will notcome from the chemical but from the biological side. Differentbranches of the work of the Rothamsted Experimental Station havebeen summarised in various useful ways, among which may bementioned a survey, by N.H. J. Miller,l of the amount and com-position of the drainage water through unmanured land, as recordedat Rothamsted from 1870 until the present time.A distinguishing feature of the year has been the revival ofinterest in the sugar industry, and reference is made t o severalpapers dealing with questions affecting this industry.I n India the advance indicated in last year’s report has been verymarked indeed, a thorough scheme of agricultural investigationhaving been now set on foot.An Imperial Department ofAgriculture 2 has been formed, comprising eleven different. appoint-1 J. Agric. Sci,, March 1, 1906, 377.Annual Report sf Imp. I)ept. of Agric?dture, 1904-5, C a h t t a , 1906.trm. III. 258 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.ments, included in which are those of an inspector-general, adirector, an agricultural chemist, two botanists, an entomologist,and a bacteriologist. Provincial Departments have also beenestablished in Bengal, the Punjab, and the Central Provinces,whilst the existing Departments in Madras, Bombay, and theUnited Provinces have been strengthened. I n the Bombay andCentral Provinces there is also an agricultural chemist attachedin each case to the Department.Altogether, the staff of Government experts, which four years agonumbered six throughout India, has now been increased to twenty-five.A research institute has been opened a t Pusa, in Behar, andincludes fully-equipped laboratories for research work, an experi-mental farm, a cattle-breeding farm, and a higher agriculturalcollege.The Indian Tea Association has continued its investigations withmore assiduity than ever, and, under its able expert, Dr. H, H,Mann, has put forward some really excellent work, more especiallyon the subject of the fermentation of tea. The account of Dr.Mann’s investigations shows most clearly how well-directed sciencemay be utilised for the benefit of an industry. Under the direc-tion of the Imperial Department, scientific aid has also been givento the, unfortunately decaying, indigo industry.The obituary for the year includes the names of Prof.AlexanderMuller, of Sweden and Berlin, and of Prof. Adolph Emmerling,of Kiel. The former was the organiser of the first agrico-chemical“ Versuchs-Station ” in Stockholm, and was specially known forhis work on moor soils, on the nature of milk constituents andthe influence of foods on the composition of milk, as well as, laterin Berlin, for his researches on the utilisation of sewage and thepurification of streams. Emmerling was best known for his re-searches on the formation of albumen in plants.Among publications may be noted a new edition (8th)of “ Church’s Laboratory Guide,” which has been thoroughlyrevised and practically rewritten by Prof.Edward Kinch, of Ciren-cester, also the I‘ Microscopy of Vegetable Foods,” by A. L. Winton(Connecticut, U.S.A.), which is practically an American editionof Dr. Josef Moellsr’s well-known work, “ Mikroskopie der Nah-rungs und Genussmittel.”Nitrogert.(a) Calcium Nitrate.It is €0 the direct combination, through electrical force, of thenitrogen and oxygen of the air that attention has been mainlyturned, the process briefly described in last year’s report, anAGRICULTURAL CHEMISTRY AND VIUETABLZ PHYSIOLOGY. 259resulting in the production of calcium nitrate, being the one thatseems t o offer the greatest prospects of ultimate success. Theproduct, so far as obtainable, has been tried practically, and withsatisfactory results.The entire matter of the development of theprocess into a regular industry turns purely upon the question ofcost. Though calcium nitrate has been made, and used, it cannotyet be said t o be a regular article on the market; there is ncprice quoted for it, nor is it open to anyone to purchase a supplyof it, or to use it just as he would any other artificial fertiliser forhis soil. Even where i t has been tried experimentally, it has beenprocured with difficulty, and, up to the present, it cannot be saidthat there is more than a pure “estimate” of the cost of itsproduction. I n such circumstances the whole question of thematerial becoming a regular article of commerce, and competingsuccessfully with nitrate of soda, depends entirely on its productiona t a cost which will enable the nitrogen in it to be supplied a t alower rate than the same amount of nitrogen in the form ofnitrate of soda. Though the works of Birkeland and Eyde, a tNottoden (Norway), continue to turn out a certain quantity ofcalcium nitrate, it does not seem that the process can, as yet, beprofitably worked ; otherwise, calcium nitrate made by this processwould, by now, be a regular article on the market.Other workshave been established at Ludwigshafen, and also in Italy. At aquite recent date, however, has come the announcement of a new“discovery,” with which the names of Crookes and of 5. vonKrowalski and I. Moscicki, of Freiburg, Switzerland, are associated.The details are still wanting, but we are led to suppose that thenew method really consists in some improvement, possibly intechnique, on the Birkeland and Eyde system, whereby greaterefficiency is attained, and the calcium nitrate produced a t a lowercost than before.It has, at the same time, been stated that themethods are entirely different from those in use in Norway, thatthere is a higher percentage of “ output ’’ than by any other system,and that ‘‘ pure concentrated nitric acid ” is produced. Naturallyone must await, and with interest, the further details of thisdiscovery, but, whatever be the outcome, it would seem to be fairlyestablished that the process can only be worked a t places whereenormous water power is available, and hence there is no likelihoodof England becoming a producing country.From the few recorded experiments which have, so far, been madewith calcium nitrate, the following may be noted.J.Sebelien,’ using the basic calcium nitrate suggested by R.Messel, found the results, as between this and sodium nitrateJ. Landw., 1906, 54, 159.s 260 ANNUAL REPOItTS ON THE PROGRESS OF CHEhlISTRY.yielding the same amount of nitrogen, to be somewhat variable.Where better results were obtained with calcium nitrate this wasnot infrequently proved to be due to the lime in the calcium nitrate,for, when lime was added to sodium nitrate equally good resultswere given. On a peaty soil calcium nitrate did as well withcereals as did sodium nitrate, and this was also the case with grassland.The latter experiments were carried out in Norway. Theseresults are only what one would expect, and, as has been pointedout, there is no reason why calcium nitrate should not do as wellas sodium nitrate, whilst, where lime is deficient in a soil, it mightbe expected to be superior, because of the lime it supplies t o theland. .(b) C yanaJmide,The production of calcium cyanamide has continued, and, to judgefrom the. experiments made with it, it would seem to be moregenerally obtainable than calcium nitrate, though it, too, cannot yetbe reckoned as a staple commercial product, or to have a regularmarket price quoted for it. Experiments made with it on cropshave given variable results, some observers holding that it givesequally good results as ammonium salts, others distinctly limitingits practical application to particular kinds of soil and to particularconditions. Its use on soils containing much vegetable matter(humus) is generally agreed upon as not being attended withbenefit.F.Lohnisl states that the nitrogen of calcium cyanamide israpidly transformed into ammonia in April and May, and that itsaction on crops is very like that of ammonium salts. C. vonSeelhorst and A. Miither: in carrying out pot-culture experi-ments with it, found that on sandy loams and loams it didquite as well as ammonium sulphate, but that in sand culturesi t was injurious to vegetation. They attributed this to the presenceof some calcium carbide, and showed that if iron oxide was addedto .the sand the injurious action was prevented.H. vonFeilitzen3 came to the same conclusion as regards cereals on sandysoils and loams, but states that on peaty soils calcium cyanamidehas very little effect with oats or potatoes. J. Sebelien4 likewisefound that calcium cyanamide had little effect, or was even injurious,in the case of cereals grown on peaty soils; -and with grass land,in Norway, he obtained results inferior t o those attending theuse of sodium or calcium nitrate. A. Stutzer5 has carried out potexperiments on rye with calcium cyanamide as compared withCentr. Bnkt. Par., 1905, [ii], 15, 430.Chem. Centr., 1906, i, 584.J. Landzo., 1905, 53, 329.J. La?idto., 1906, 54, 159.ti Lnndzn. VersicclwStnt., 1906, 65, 275AGRICULTURAL CHEMISTRY AND VEGETAELE PHYSIOLOGY.261ammonium sulphate and sodium nitrate, and states that 68.4 percent. of the nitrogen was recovered in the crop with ammoniumsulphate, 65.9 per cent. with cyanamide, and 55.2 per cent. withsodium nitrate. I n the last-named case the nitrate was, however,applied in the autumn, and may thus have suffered loss by drainagein winter. Paul Wagner1 also finds that in “normal soils”cyanamide works quite well, but that on acid soils and on sandyones rich in humus and poor in lime its action is uncertain. Hefurther maintains that it can quite well be used as a top-dressing,if applied about February, to winter crops. He admits that ifapplied in warm weather there may be loss of ammonia.Lohnishas already pointed out objections to the use of cyanamide: thati t cannot be used as a top-dressing, nor be mixed withsuperphosphate, owing to the mixture getting hot; that i tdeteriorates in damp weather; and that, when applied to thesoil, ammonia is evolved, which is injurious a t first t o thegermination of the seed.E. Wein 2 says, as the result of field experiments, that cyanamideis as good as ammonium sulphate, and he finds i t t o be as effectiveas sodium nitrate on peaty soils, provided that they contain plentyof calcium carbonate. I n Japan experiments have also been triedby K. As6 3 on buckwheat, sesanzzcm, hemp, and rice, with resultsgenerally equal to those from ammonium sulphate and nitratle ofsoda, provided that the soil be not rich in humus.F.Lohnis has investigated the changes which calcium cyanamideundergoes in ordinary soils. He states that i t is decomposed bycertain bacteria, ammonia and, possibly, nitrates being formed.Among the bacteria capable of producing the decomposition areBacterium 1Circhiw-i and B. Zipsiense. Pure cultures of each ofthese, however, do not severally act as effectively as do mixedcultures of the two. The decomposition does not take place inboggy soils, either because the bacteria may not be there, orbecause the cyanamide is converted by the organic acids presentinto compounds that are hurtful to vegetation. The decompositionis not facilitated either by the free admission or the exclusion ofair, so that stirring the soils has no effect in hastening the change.From these various experiments it may be regarded as fairlyestablished that under favourable conditions and with suitable soils(such, mainly, as are not rich in humus or deficient in lime) calciumcyanamide is practically nearly as good, nitrogen for nitrogen, asDeutsche Landw.Presse, Aug. 18, 1906.Chein. Cmt?-., 1906, ii, 1454.BzdI. COIL Agr. T6ky6, 1906, 7, 47.Bied. Cextr., 1906, 35, 375262 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.ammonium sulphate or soldium nitrate; but that it is non-effectivei n the case of peaty soils or those with little lime in them; also thatit does not lend itself to ready use as a top-dressing, for storage, orfor mixing with other materials. To come back to the mainquestion, that of cost, it is clear that the extended use of cyanamidemust depend on whether the nitrogen in it can be supplied ata less cost than the same amount of nitrogen in the form ofsodium nitrate or ammonium sulphate; and on this point thereis, as yet, no definit'e information. It may be added that theinformation as to the cost of producing calcium nitrate is evenless certain.It is also well t o point out that, with few exceptions,the experiments so far recorded with cyanamide have been potexperiments, and, however useful these may be as an indication,they need the confirmation of field experiments before they willcommand the attention of the practical agriculturist.Suggestions have been made as t o combining cyanamide withother materials.Thus, F. T. Shutt and A. W. CharIton1 haveformed calcium cyanamidocarbonate by passing carbon dioxide gasthrough a solution of calcium cyanamide. This pro,duct, if kept lowin amount, will not injure the germination of seeds, but if thequantity be increased above 5 milligrams per 100 grams of soil,germination is affected, and with increasing quantities is quitedestroyed. Nitrification in t h e soil is also decreased, showing thatthe nitrifying organisms in it are affected. Suggestions have alsobeen made to add t o the calcium carbide, before heating, one ormore fluorides of an alkali or alkaline earth.2 By this means, i tis said, calcium cyanamide is obtained a t a lower temperature.(c) Leguminous Nodwles.It has been mentioned that work in the direction of the inocula-tion of leguminous crops with the corresponding nodules has been,for the time, nearly put aside.The experiments instituted in GreatBritain by the Board of Agriculture in 1905, and which were carriedon in 1905, both with tnhe German (Hiltner) preparation and theAmerican (Moore), were the reverse of encouraging, and in thefew cases in which these experiments were carried on for a secondyear (1906) with a cereal crop following the leguminous onesnothing of much note has been obtained. From the Continentand America one hears also of but little more done in this direction,and, a t all events, the day has not come yet when the farmer willbuy packets of '' inoculating material " for his bean, clover, andother leguminous crops.At the Woburn Experimental Farm theTrans. Boy. Soc. Canada, 1905, [ii], 11, (3), 73.0. F. Carlson, Stockholm, Eug. Pat. 15,445, July 7, 1906AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 263experiments were continued in 1906, a wheat crop being takenafter the leguminous ones. The only further point brought out wasthat, whether sterilised soil, poor soil, or rich soil was used, thewheat crop. was in each instance decidedly poorer after tares takenpreviously than after peas or beans.H. Flamand 1 has investigated, by water-culture experiments,the influence of different salts on the process of symbiosis, asmeasured by nodule development. Peas, beans, and tares were thecrops tried, and the plants were inoculated from appropriateno,dules. Potassium nitrate (1 : 10,000) altogether preventednodule formation, but sodium nitrate only did this when thequantity was increased to 1 : 2000.Potassium phosphate wasbeneficial to nodule formation in the cases of peas and tares,potassium chloride aed potassium sulphate being less so, althoughfor beans potassium sulphate was best. Calcium and magnesiumsalts generally were beneficial to peas and beans, but only calciumsulphate for tares. It'must be said, however, that there is a gooddeal that seems contradictory in these experiments, and doubt mustbe cast upon the variable results obtained with plants so very muchalike as peas and beans.(d) Direct Utilisation of Nitrogeit b y Plants.As briefly announced in last year's report, a revolution in ourideas as to the capability of plants generally to take up nitrogenfrom the air was promised by the statement of T.Jamieson, ofAberdeeq2 to the effect -that he had discovered that not onlyleguminous plants, but cereals, grasses, &c., had the power, exercisedthrough certain structures on their leaves and leaf-stalks, of takingin directly the nitrogen of the atmosphere. Jamieson rejectedthe nitrogen theory of Lawes and Gilbert, and the " nodule " theoryof Hellriegel, and maintained that because he found on plantsin their early stages certain organs the cells of which containedalbuminous matter, the nit'rogen of this was derived direct from theair, without, any process of symbiosis. Naturally such a view wasstoutly assailed by vegetable physiologists and agricultural chemists.Its untenability was shown by Bayley Balfour, of Edinburgh, whopointed out that the above afforded no proof whatever of fixationof nitrogen, and that on this theory it might as well be assumedthat every living cell of a plant, including those of the root,possessed this same property; the presence of albuminous matter init cell was no evidence of direct assimilation of nitrogen fromBied.Centr., 1905, 34, '738.3 Ayric26lt~~1 nl Research Association, Aberdeen, Report for 1905264 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.outside. Agricultural chemists also pointed out that the theorycould not be accepted unless direct experimental and quantitativeproof were afforded of the plant being placed in an atmospherecontaining a known amount of nitrogen and of its removing fromthis a quantitative amount of nitrogen.Accordingly, we have to goback upon our former ideas, and the problem of nitrogen supplystill remains with us.(e) Nitrogen Assimilation b y Soil Bncteriu.To this subject, and more especially t o the work of the organismAzotobacter ch~oococcum, much attention has been given.R. Thiele,l while allowing that dzotobncter can fix nitrogen,expresses doubt as t o whether this is an inherent property, andwhether it may not frequently, even in normal circumstances,be lost. He has worked out the conditions of temperature mostfavourable for fixation t o proceed, and points out that fixation isless according as the most favourable temperature is onlyoccasionally attained.J.Stoklasa 2 finds that Azotobacter chroococcum possesses morepower than any other species f o r fixing atmospheric nitrogen. Bothdextrose and mannitol will serve well as culture media. The formeris the better, but the addition of a little calcium carbonate isnecessary with it. Stoklasa has estimated quantitatively theamount of carbon dioxide evolved during the assimilation process ;on an average 1 gram of Azotobacter dry substance will evolve 1-27grams of carbon dioxide in 24 hours. Under similar conditionsB. R a r t l e b i will evolve 0.6 gram, and Clostridium gelatinosum0.48 gram, so that Azotobacter is much the most active. Whendextrose is used as the culture medium, lactic, acetic, and formicacids are the decomposition products, together with carbon dioxideand hydrogen.Stoklasa considers the assimilation process to berelated to the respiratory process. He differs from Beyerinck's viewthat Radiob acter has an appreciable power of assimilatingatmospheric nitrogen, but considers it a denitrating organism ; amixed culture of Azotobacter and Radiobacter has less power ofassimilating nitrogen than a pure culture of Azotobacter, andRadiobacter will reduce the greater part of the nitricacid t o free nitrogen, whilst a certain proportion is fixedin the form of orgmic bodies, chiefly nucleo-proteins. S. F.Ashby3 has also worked on the assimilation of free nitrogen byA zotobacter chroococcum. I n making cultures of soil organisms,Landw.Tersuchs-Stat., 1905, 63, 161.Zeit. angew. Chem.,+1906, 19, 803.J. Agric. Sci. ,; 2, 'Jan. 1907, '"35AGRICULTUBBL CHEMI8TK.Y AND VEGE'l'ABLE PHYSlOLOGY. 265using mannite as a medium, he found that the greater theaeration was (namely, when less mannite was used) the greater wasthe amount of nitrogen fixed per gram of mannite oxidised.Further, when Azotobacter was present the average yield of nitrogenwas doubled. Still, fixation took place, although low in amount,even when Azotobacter was absent. The average fixation was 6.95milligrams of nitrogen for 1 gram of mannite when Azotobacterwas present., and 3.22 milligrams when it was absent. Aerationand the presence of a base would appear to give favourable condi-tions to fixation.Ashby compared the influence of magnesiumcarbonate and calcium carbonate as bases in relation to fixation.He found that magnesium carbonate delayed development a t first,but that ultimately the yield of nitrogen was larger than withcalcium carbonate. By taking soil a t different depths Ashby showedthat Azotobacter was present in greatest abundance in the soilnear the surface. H e noticed, too, that the organism would standdrying up quite well, and would produce abundant growth iffresh culture solution were poured over the mass. Hence it isclear that the organism can be carried about as dustby wind. B. Reirizel attributes the importance of a l p infixing nitrogen in soils t o their supplying nitrogen-fixingorganisms, and chiefly A zofobacter, together with carbonaceousfood.It is not the case, as has been stated, that all that algz dois t o prevent loss of ammonia in the soil.E. Haselhoff and G. Bredemann 3 ascertained that anaerobicnitrogen-assimilating bacteria (Clostridia) are abundantly present insoils and in the leaves of forest trees; the amount of assimilationis about equal t o that of Clostridium Ynsteurianum, namely, 2.74milligrams per gram of dextrose or mannite.Nitrification.S. F. Ashby3 has studied the question as t o whether anythingwill replace carbonate of lime as a base for nitrification. Kaolinand modelling clay were tried, but neither was found effective;ferric hydroxide, however, will act, but is inferior to calciumcarbonate. Ashby comes to the conclusion that a neutralammonium salt is not directly nitrifiable, but that the functionof a base is to form ammonium carbonate, which is nitrifiable.Of bases, the reaction with magnesium carbonate is greater thanwith calcium carbonate.This latter observation is confirmed byCentr. Bakt. Par., 1906, 16, [ii], 640.Landw. Jahrb., 1906, 35, 381.3 J. Agric. Sci., 2, Jan. 1907, 52266 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.S. Machida,l who found nitrification t o be favoured by magnesiumcarbonate more than by calcium carbonate.A. Miintz and E. Lain62 carried out experiments with theobject of producing nitrates in large quantity. Animal charcoalwas found t o be an excellent medium for nitrifying organisms, andwith a solution of 0.75 per cent.of ammonium sulphate tensquare decimetres produced 8.1 grams of sodium nitrate perday. If stronger solutions were used, nitrification was less active.They also tried experiments with soil to which 0.2 per cen';. ofammonium sulphate was added, and i t produced nitrates a t therate of 350 grams per cubic metre per day, which, takan t o asoil depth of half a metre, was equivalent to 1,750 kilos of sodiumnitrate per hectare. The same authors, in another communication,3show that humus, in whatever amount, is not prejudicial tonitrification, but indeed is rather favourable to it. It is not,however, necessary, as nitrification can be obtained in soils poorin organic matter. Humus seems to aid the multiplication ofnitrifying organisms, and, as a rule, a soil contains more activeorganisms and is more prone to enter into nitrification accordingas it contains more humus.Different soils showed very differenteffects as regards nitrification, and rich soils nitrified much morequickly bhan sandy or clay soils. With the same amount ofammonium sulphate a rich soil, with 17.6 per cent. of carbon, nitri-fied, at bhe end of seven days, 0.209 grams of nitrogen per kilogramas against 0.02 gram with a soil containing only 1.5 per cent. ofcarbon. Peat was found to be the best medium for nitrifyingorganisms, and by passing a 0.75 per cent. solution of ammoniumsulphate over a peat bed charged with nitrifying organisms nitrateswere formed a t a rate much in excess of anything previouslyobtained.The process of nitrification with regard to the purification ofsewage has been studied by Harriette Chick.4 The investigationswere made during the filtration of sewage.The evidence goes t oshow that nitrification takes place in two stages, and is due to theaction of two classes of organisms, the first producing nitrites andthe second converting these into nitrates. The organisms wouldseem to be the same as those which produce nitrification in the caseof soils. It may be considered strange that organisms which areso influenced by the presence of organic matter should be able tocarry on their activity; but it is pointed out that they maybe in a measure protected by other organisms with which they areThe most suitable temperature is 300.1 Bull.Imp. Centr. Ayric. Exp. Xln. Japan,.1905, 1, 1.4 Proc. Roy. h'oc,, 1906, 77, B, 241.Cornpt. rend., 1905, 141, 861. IM., 1906, 142, 430, 1239AGRICULTURAL CHEMlSTRY AKD VEGETABLE PHYSIOLOGY. 267in symbiosis, or that, while the organic matter collects mainly a tthe surface of the filter, the nitrifying organisms multiply rapidlyin the lower part of the iilter, where the organic matter is lessin amount. It has also been shown by others that if nitrifyingorganisms exist in sufficient quantity, they are able to withstandthe influence of organic matter that might otherwise destroy them.Whether the two stages of nitrification go on together o r at separateintervals depends on the condition of the sewage, whether veryammoniacal or not. If strongly ammoniacal the change intonitrates may be delayed until more of the ammonia has beenconverted into nitrites.There would appear t o be no evidencewhatever as t o the retention of free and active ammonia in cokefilters without nitrification, but that nitrification takes place rapidly.The opinion is expressed that continuous filtration is a better systemthan that of contact beds, aeration being more complete in theformer, diffusion more efficient, the distribution of the differentstages of purification better, and the facilities for cleaning greater.J. E. Purvis and C. J. Coleman1 have studied the influence ofthe saline constituents of sea water on the decomposition of sewage.They used not only sea water itself, but solutions containing thevarious salts separately, and mixed in 'the proportions in whichthey occur in sea water.The general conclusion was that bothsodium chloride and sea water hindered very greatly the productionof nitrates. Instead of the decomposition of the sewage intocarbon dioxide, water, and nitrates taking place, highly complexnitrogenous compounds seemed to remain in solution, and oxidationto proceed very slowly. The authors draw the practical conclusionthat it is a mistake to run sewage straight into the sea withoutpreviously treating it by some filtration or bacterial process.E. J. Russell and Norman Smith2 examined the question asto how far purely physical and chemical processes which take placein the soil may contribute to the formation of nitrites and nitrates,independently of the action of bacterial processes.The first pointto meet was the contention of Schijnbein that ammonium nitritewas formed during the distillation of water in air or during itsrapid evaporation. The authors repeated the experiments, andcritically discuss the work of Schonbein and his successors, andthey find no evidence whatever of the production of nitrites duringthe evaporation of water from the soil under any of the variedconditions which obtain in it. Further, they find no evidence ofthe capability of the soil to effect the combination of nitrogen andoxygen. Oxidation of free nitrogen may, they think, possibly takeJ. Xniiit. Inst., 1906, 27, 8, 433. ' J. Agric. Sci, 1. March 1906, 444268 BNNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.place by induced oxidation processes, but the evidence accumulatedwould lead to the conclusion that this is at best an unimportantsource of the production of nitrates under natural conditions.The development and distribution of nitrates in field soils hasbeen observed by F.H. King, J. A. Jeffrey, and A. R. Whitson.'I n the surface soil, to a depth of 1 foot, nitrates increased fromApril t o June, and then there was a decrease, due prnbably to rapidgrowth or heavy rains. Nitrates were much less abundant in thesecond foot of soil than in the first, and in a dry season there wasa tendency for nitrates t o accumulate near the surface. Furtherdeterminations made between November and April showed thatthere were no niore nitrates in the soil after the winter frosts thanbefore these set in.D e n i t r if; cu t ion.R.Hornberger,2 by exposing leaves of oak, beech, &c., for a,year to air and rain, found that in the majority of cases therewas a greater loss of nitrogen than gain of it.The influence of carbohydrates and organic acids on the deni-trification process has been investigated by J. Stoklasa and E.Vitek.3 The micro-organisms studied were grown in a solutioncontaining sodium nitrate, potassium, calcium and other salts,along with the particular carbohydrate or organic acid. Clos-t ridium gelatinosum produced, in the case of dextrose, ammoniamost freely. BacilZus suhtilis gave ammonia best when lzvulose orgalactose was the carbohydrate. Bacterium Hartlehi in arabinosesolutions formed much organic nitrogen, and arabinose generallyproved a better medium than xylose.Organic acids, again, wereexcellent media for the decomposition of nitrates t o elementarynitrogen, and for the formation of organic nitrogen com-pounds. Further investigation as t o the stages in whichthe action proceeded showed that the denitrification processtook place in two steps, the first being the reductionof nitrate to nitrite by means of the hydrogen formed alongwith carbon dioxide by the decomposition of the carbohydrateor organic acid through the enzyme of the micro-organisms. Fromthis it is argued that the carbohydrates in a soil are more likelyto serve for the purpose of converting nitric acid into ammoniathan as nutrients for denitrification bacteria.J.Stoklasa, J. Jelinek, and A. Ernest 4 further show, fromexperiments with sugar-beet soils, that the organic matter in the soilAgr. Exper. Stat. Univ. FViscoitsiiL, 20t7~ Animal Rcpoyt, 339.Bied. Centr., 1905, 34, 726.Y=Zeit.rZuckerind. B o h , 1906, 31, 67. Ibid., 30, 283AGRICULTURBL CHEMISTRY AND VEQEI'ABLE PHYSIOLOGY. 269is not a suitable source of carbon for denitrifying organisms, andthat nitrates are not, to any material extent, reduced ta nitrogen.When soils are well cultivated, and hence well aerated, loss ofnitrogen will not occur, though nitrates may be reduced to nitrites.Decomposition of hTitrogenous Matter in Sod.F. Lohnisl found that Bacillus mycoides and Bacterium vulgarerespectively converted within three weeks 39 and 28 per cent.ofthe total nitrogen of bone-meal into ammonia; George 8. Fraps,ssimilarly, found the organisms producing ammonia from nitrogenousfertilisers to be most active during the first week; after the thirdweek their influence decreased and nitrification was more marked.ATitrogen iiz. Rain.J. W. Leather has determined the amount of nitrogen presentas ammonia and nitrates in a year's rainfall a t Dehra Dun andCawnpore (India). He obtains the following figures for a completeyear : -iVitrogen.Parts per millioii. Pounds per acre.Rainfall, As As nitrateinches. ammonia. and nitrite. ammonia. and nitrite. Total.Dehra Dun 86.48 0'104 0.070 2.037 1 -368 3'405Cawnpore . 49'36 0'221 0.068 2-482 0.768 3.2507These figures do not differ widely from those found at,Rotliamsted, where the total nitrogen is 3.840 lb.per acre, madeup of 2.712 lb. as ammonia and 1.128 lb. as nitrates and nitrites,so that no countenance is given to a general belief that the Indianrainfall is richer in nitrogen than that of England. At DehraDun, however, where thunderstorms are more frequent; than a tCawnpore, it is noticeable that there is considerably more nitrogenpresent as nitrates. At Cawiipore the dew was also collected andanalysed, but difficulties connected with the collection are great.The results, so far as obtainable, show a total of only 0.111 lb.of nitrogen per acre during the year, this being equally dividedbetween that existing as ammonia and that as nitrates.The totaldew was 0.170 inch, and therefore, as a supply of combinednitrogen, cannot be considered of importance.H. Ingle4 has done the same in regard to the rainfall collectedCeritr. Baht. Pa?.., 1905, [ii], 15, 430.J. Amer. Chem. AOC., 1906, 28, 213.Imp. Bept. Agric. Annz6al Report, 1904-5 (Calcutta, 1906), 56, .I T ~ m s v a a l Agric. J., 1905, 4, 104270 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.a t Pretoria (South Africa.) The rainfall of 24-31 inches per annumsupplies 7.670 lb. of total nitrogen per acre, 6.587 of which occuras ammonia and 1.083 as nitrates. The total nitrogen, it will benoted, is about double that of Rothamsted, and the proportionpresent as ammonia relatively higher.N. H. J. Miller 1 in statingthe results of the Rothamsted rainfallin regard t o nitrogen and chlorine contained, gives a summary ofresults from 30 different places in tropical and non-tropicalcountries, and points out that great differences in climate do notcoincide with material differences in the amounts of nitrogenbrought down by the rain, but that, whilst in non-tropical countriesmost of the nitrogen is present as ammonia, in tropical countriesthe proportion of nitric nitrogen is relatively higher.The subject of rainfall in connexion with drainage throughuncropped land has led E.J. Russell2 to examine more closely theRothamsted results obtained respectively with the 20 inch, 40 inchand 60 inch drain gauges there. He observes that the relationbetween the evaporation from the three gauges is not constant;a t first evaporation from the 20 in.gauge is lowest, then it increases,exceeds that of the 40 in. gauge, and, after twenty years, that of the60 in. gauge as well. He attributes the variations to a “secularchange” in the drain gauges, and suggests that this is due to adecrease in t,he amount of organic matter in the soil of the gauges,and to the action of rain in washing out the finest particles, thisresulting in an increased evaporation of water.Green-Manuring.Allied t o the “ nitrogen question ” is that of the supply, throughgreen-cropping, of nitrogen to soils. The experiments on thissubject, recorded for 1903 and 1904 in last year’s report, havebeen continued a t theWoburn Experimental Farm? and the resultsfor the wheat crop of 1906 succeeding green-manuring in 1905, arenow available. Once more it appears that, contrary to theory,the ploughing-in of a non-leguminous crop (mustard) has givena better return in a subsequent corn crop than has that of aleguminous crop (tares).The green crops were cut and weighedpreviously t o being turned in, the tares giving 7 tons 2 cwt. greenproduce per acre, containing 1-05 per cent. of nitrogen, and themustard 5 tons 10 cwt. per acre, with 0.46 per cent. only of nitro-gen, the organic matter being nearly alike in amount in the two.When, however, the subsequent wheat crop came to be weighed,the results were :J. Agrie. Sci., 1, Mar. 1906, 377. Ibid., 2, Jan. 1907, 29.J. Roy. Agric.Soc., 1906, 67, 299AGRICULTURAL CHEMISTRY' AND VEGETABLE PHYSIOLOGY. 2'9 1Produce of wheat per acre, 1906.Corn. Straw.Bushels. Cwt. qr. lb.After tares ploughed in ......... .. 24'5 17 1 24After mustard ploughed in ... . . . . . , 37 '6 28 0 15Thus the leguminous crop (tares) has once again failed t o producethe larger crop which one would expect t o accrue from the largersupply of nitrogen.Humus.c- A \S. Suzukil has observed the conditions under which humusformation goes on in soils. Dry powdered oak leaves were moistenedand mixed with some humous soil; magnesium carbonate, calciumcarbonate, potassium phosphate, and other substances were thenseverally added in different flasks, and their action studied whilehumification of the leaves proceeded.The author found thathumification proceeded parallel with the Eormation of carbondioxide ; that magnesium carbonate promoted the development, andthat calcium carbonate retarded it, whilst potassium phosphate hada favourable effect.A. D. Hall, N. 13. J. Miller, and N. Marmu2 have devised animprovement in the estimation of carbon in soils and similarsubstances. Recognising that the chromic acid method of Wolffgives too low results owing t o incompleteness of oxidation, they haveproposed t o add a short tube containing red-hot copper oxide t ocomplete the combustion. They find that by this means they canconvert all the carbon into carbon dioxide, and the results agreeclosely with those of combustion in oxygen. The convenience ofthe method is that,, by adopting Brown and Escombe's modifica-tion? they can first determine the carbon dioxide present as car-bonate in a soil, and then, by attaching the copper oxide tube,they can, on the same sample and in the same apparatus, estimatethe organic carbon.Lime and Magnesia in Soils.Continued interest has been shown in the important part playedby lime in soils, and also in the significance of magnesia, and itsrelation to the lime present.The Woburn Field Experiments4afford the most striking example of the absolute need of lime ina soil, more especially under the influence of the continuousapplication of ammonium salts, these latter bringing about, inBull. Coll. Agric. Tdkyd, 1906, 7, 95.Trans., 1906, 89, 595.Phil.Trcms., 1900, 193 3, 289.J. Boy. Apic. Xoc., 1906, 67, 284, 285272 SKNUAL REPORTS ON THE PROGRESS OF CHEMISTRk'.absence of lime, an acid condition of soil and absolute sterility;fertility, however, is restored by the use of lime. This restorationwas effected by applying 2 tons per acre of lime (1897). Laterexperiments have been directed t o seeing whether smaller quanti-ties would suffice, and in 1905 lime was applied in smaller quan-tities (5 cwt., 10 cwt., and 1 ton per acre respectively) to landpreviously incapable (through the continued use of ammoniumsalts) of bearing a crop. Among the striking results may bementioned the following : -Manures per acre.Ammonium salts, without lime .................................9 , ,, with 5 cwt.lime (1905) .....................? ,, with 2 tons lime (1897) .....................Mineral manures and ammonium salts, without lime ......>, 9 , 9 , ,, with 1 ton lime3 ) >, ,, ,, with 2 tons lime(1905) ...(1897) ...Wheat,1906.BushelsCorn.3.419'226'1---Bar 1 e y ,1906.BushelsCorn.no crop11'625'41-733.944'3Incidentally these results also show that the influence of an appli-cation of two tons of lime to the acre will last for quite nine years,the dressings put on in 1897 still showing their effects. F.Wohltmann, H. Fischer, and P. Schneiderf state that manuringwith lime increases the power of decomposing nitrogenous substancesin soils, and that both nitrification and denitrification are assistedby it.M. Hoffmann2 instances experiments extending over fiveyears, and showing the general benefit of lime, even leguminousplants (lupins) profiting by it. R. Ulbricht? however, finds thatwith lupins, vetches, and serradella the application of lime producesa slightly diminished assimilation of nitrogen and phosphoric acid,the magnesia in the plants being a t the same time considerablyincreased.Investigators in Japan have continued their inquiries intothe relations of h i e to magnesia in soils as affecting theyield of crops. Thus, G. Daikuhara4 showed that the yield ofbarley in a soil having the ratio CaO : &!go : : 0.34 : 1 was doubledwhen, by the addition of calcium carbonate, the ratio was made1 : 1. The same author, experimenting with tobacco, found thatif the ratio of CaO t o MgO, in a soil of 1 : 1, was increased byliming to 2 : 1 or even 4 : 1, benefit was obtained.The latterproportion corresponds to the ratio of these constituents in theashes of tobacco. With flax and spinach S. Namikawa5 obtainedBied. Centr., 1905, 34, 805.Landto. verstbchs-slat., 1906, 63, 321.Bull. Imp. Ceittr. Agr. Exp. Stat. Japan, 1905, 1, 13,Birll. Coll. Agr. Tciky6, 1906, 7, 57.2.16id., 1906, 35, 12AGRICULTURAL CIIEMISTRP AND VEGETABLE PHYSIOLOGY. 273the best results by making the ratio of CaO to MgO 1 : 1. On theother hand, S. Maki and S. Tanakal showed that if land be over-limed, it may be benefited by adding magnesium sulphate to it.Manuring with magnesium sulphate has been tried in severalinstances (magnesium carbonate being difficult to obtain in Japan),and it is found that it has about seven times the efficacy ofmagnesite, so that when magnesium sulphate is used the ratio ofCaO to MgO should be 7 : 1, whereas with magnesite i t shouldbe 1 : 1.Interesting as these results in regard to lime and magnesia are,it has to be remembered that the experiments have been with pot-culture only, and they need the confirmation of field work. Itwould be very desirable to gather experience from field soilscontaining lime and magnesia in different relative proportions, andto ascertain if the general results obtained in pot experiments holdgood in actual practice.Phosphates.D. N.Prianischnikoff 2 has experimented on the relative value ofdifferent phosphates, I n sand culture the effect of bone meal wasabout 50 to 60 per cent.of that of soluble,phosphates, and when acrude phosphate, like phosphorite or apatite, was used, althoughgramineous crops improved very little, lupins did so considerably.I n sand cultures ammonia salts had the power of rendering evenvery sparingly soluble phosphates available for the use of plants.The same author,3 working with aluminium phosphate and ironphosphate, found that millet, vetches, and mustard, grown in sand,would assimilate the phosphoric acid from aluminium phosphate,either when merely dried or when ignited, as also from iron phos-phate if merely dried, but not if ignited. Rye and wheat, how-ever, could not utilise the phosphoric acid of crude phosphates,although lupins did as well with crude phosphate as with bonephosphate.Different processes have been suggested for rendering rawphosphates available for use.One of these is that of the WoltersPhosphat. Gesell~chaft,~ in which raw phosphates are melted in aSiemens’ furnace with alkali silicates and lime, the product beingthen led into cold water, when nearly all the phosphoric acid isfound to be soluble in citrate solution. The materials suggestedfor use are:-Tricalcium phosphate 40 per cent., silica 30 percent., lime 14 per cent., soda 16 per cent.Bull. Coll. Agr. Tiiky6, 1906, 7, 61.Landw. Versuchs-Stat., 1906, 65, 23.Bied. Centr., 1905, 34, 741.Eng. Pat. 9183, April 18, 1906274 ANNUAL REPORTS ON THE PROGRESS 0%' CHEMISTRY.The influence of phosphoric acid on straw has been observed byD.Lienau and A. Stutzer,' who conclude that it promotes thethickening of the cell wall. This effect is, however, greatlydiminished if much potassium, calcium, or nitrogen is present. Thesmaller the amount of total ash and of potassium in the straw,the greater will be the thickening of the cell walls; the appli-cation of phosphates has the effect of reducing these quantities,whilst the amount of phosphoric acid in the straw is found notto be itself dependent on the quantity supplied as manure.G. Andre2 determined a t various stages the phosphoric acidand nitrogen in the sap of certain quickly-growing annuals (Papauerand Pyrethrum), with the result that the nitrogen in the sap wasshown in general to diminish as the phosphoric acid increased.Healso found that in annuals a portion of the phosphoric acidmigrated, as soluble mineral phosphate, from the leaf to theovule, while another portion is removed in combination withnitrogenous organic substances.W. Windisch and W. Vogelsang 3 have investigated the natureof the phosphoric acid that occurs in barley grain. I n making acold-water infusion of barley they found that this containedphosphoric acid of which a considerable portion was in theinorganic state. But when the infusion was made in such a wayas t o exclude the action of enzymes, the whole of the phosphoricacid was found to be in the organic state, and they conclude thatraw barley contains no inorganic phosphates, but that these areonly produced when the organic compounds are, as in the steepingand malting processes, subjected t o the hydrolytic action of theenzymes.W. Zaleski? from eaperiments with seedlings of Lupinusangustifolius, has come t o the same conclusion regarding the actionof enzymes on proteins containing phosphorus, and shows thatinorganic phosphates are in this way produced.A. D.Emmett and H. S. Grindley5 have similarly examined thephosphorus-containing substances in flesh, and find that in beef 75per centl. of the total phosphorus is soluble in cold water, andthat one-fourth of this consists of organic compounds.This change goes on better in the dark.Landw. Yer~uchS.-Xtat., 1906, 65, 253.Conipt. yetad., 1906, 142, 106, 249.a Woch.Brau., 1906, 23, 516.Chem. Centr., 1906, ii, 893.J. Amer. Chem Soc., 1906, 28, 25AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 275Auailabaity of Phosphoric Acid in Soils.A. D. Hall and A. Amos1 have further investigated the meansof determining the amount of plant food-especially phosphoricacid-which may be reckoned as being immediately " available " forplant food. They criticise B. Dyer's citric acid method, and pointout that, although very useful, it must be regarded as purelyempirical, inasmuch as it is based on the now generally abandonedtheory of the excretion by roots of acids other than carbon dioxide.The American method of using a X j 2 0 0 solution of hydrochloricacid is similarly criticised.Both leave out of account the nature ofwhat is left in the soil, and presume that this will not in turn become'' available " until the soil has undergone a further weatheringprocess. Many circumstances, such as cultivation, the supply ofwater, the nature of the crop grown, &c., will cause variations inthe amdunts of the constituents assimilated by the crop. This hasled Whitney t o regard the soil water as the important matter ofconsideration, and as possessing a constant composition for all soils,being always in equilibrium. Hall and Amos accordingly adoptedthe plan of attacking the soil continuously with the solvent, removingthe first portion of the solution after equilibrium had been attained.The remainder of the soil was then attacked with a fresh portionof the solvent, and so on.A t first the solvent employed was carbondioxide and water, but, because of the difficulty of filtration, andthat some of the soil got into the extract, this was given up infavour of a 1 per cent. solution of citric acid. A period of twentyhours, with constant agitation, was found to suffice for the firstseparation, and to remove as much phosphoric acid as was extractedwhen the process was continued for five days. The solution wasremoved, the soil washed free of acid, and then again agitated witha further quantity of solvent. The calcium carbonate originallypresent was practically all removed in the first extraction, and nosteps were taken to restore it. I n the second extraction less thanhalf the amount of phosphoric acid was removed, in the third aboutone-half that obtained in the second, and, finally, by the time ofthe sixth extraction the quantity removed by each successivetreatment became constant.Experiments were then made on the soil to which dicalciumphosphate was added, and it was ascertained that some of thephosphoric acid soluble in the citric acid was retained in the solidstate by the soil.After a fourth and fifth extraction a point wasreached where the compound remaining in the soil was uniform.Z'mns., 1906, 89, 205.1' 276 ANNUAL REPORI'S ON THE PROGRESS OF CHEMISTRY.But this poiut of equilibrium varied in different soils, indicatingdifferences in the nature of the phosphoric acid compounds in soil.Whitney's theory of the formation in soils of solutions ofapproximately constant composition, and independently of thefertilisers used, is thus not supported, and it would appear thatthe soil water is of varying concentration in different soils.Theavailable phosphoric acid is shown by the sum of the phosphoricacid removed in the first four or five extractions; but as this hasB constant ratio to the amount dissolved in the first extraction oftwenty hours, for all practical purposes a single extraction gives asgood a result as repeated ones.G. S. Frapsl states that aluminium, iron, and calcium phosphates(as in phosphorite, vivianite, apatite, kc.), dissolve completelyin iV/5 hydrochloric and nitric acids under soil conditions.Conducting pot experiments with cow-peas he found that the plantsremoved from 17 to 60 per cent.of the phosphoric acid soluble innitric acid, and he concluded that a relation was indicated betweenthe phosphoric acid so dissolved and the needs of the soil.Potas?& and Soda.M. Berthelot,3 by treating wood ashes with 1 per cent. hydro-chloric acid and then washing with water, found that from 5 to 6per cent. of the total potassium was retained as organic compounds.He also ascertained the presence of organic potassium compouqdsin living vegetable tissues ; if digested with potassium acetatesolution the insoluble organic matter fixed a certain amount ofpotassium, and if solution of calcium acetate was used calcium wasfixed and potassium liberated.The influence of potassium manures on the quality of barleyhas been studied by several observers, and, among them, 0.Reimerhas noticed that, whilst potash increase5 the yield of grain,the amount of proteins is in no way reduced. K. As64 obtained thesame increase of grain with barley by using potassium chloride.finding, however, that potassium sulphate was more favourableto straw production; potassium, silicate was, on the whole, the bestform, and the new potassium manure " martellin " gave good resultsin this connexion. Sulphate of potash and kainite have beencompared as potassium manures for potatoes a t the WoburnExperimental Farm,5 the results of 1905 confirming thoseJ. Amer. Chcnt. Soc., 1906, 28, 823.Compt. read., 1905, 141, 793, 1182.Chem. Centr., 1906, i, 154.Bull. Coll.Agr. Tckyd, 1906, 7, 67.J. Roy, dgric. SOC., 1906, 67, 305AGRICULTURAL CHEMISTRY AKD VEGETABLE PHYSIOLOGY. 27 7previously recorded to the effect that sulphate of potashis, on a light, sandy loam, a preferable form to kainite,1 cwt. per acre of the former and 4 cwt. per acre of thelatter being respectively used. This proved to be alike the casewhether nitrate of soda or sulphate of ammonia was used as thenitrogenous manure. The relations of potassium and sodium saltsin soils and as supplied in manures have occupied considerableattention, and especially in connexion with sugar-cane and sugar-beet cultivation. J. F. Breazeale 1 grew wheat plants in solutionscontaining all necessary elements except potassium and sodium,then removing the plants to solutions with full nutrient constituentsand ascertaining the amounts of the constituents taken up.I n thisway it was found that potassium was taken up much more vigorouslywhen sodium had been left out in the first period than when it waspresent all the time. Similarly, by taking beet plants which hadbeen first grown in soil to which potassium or sodium salts had beengiven as manures, and then removing them to solutions containingfull nutrient matters, the plants to which no potassium had beengiven to the soil for some years took up potassium more vigorcruslythan where sodium had been applied. J. Urban2 has studied therelation of potassium and sodium salts in the case of sugar-beet.When sodium nitrate alone was used on a sandy humus soil therewas abnormal development of leaf, and though the total ash (leafand root) was much the same as in normal beets, it contained avery high proportion of sodium salts, much exceeding that ofthe potassium salts.So, although sodium may replace potassium inthe plant’s composition, it is a t the expense of proper root develop-ment and consequently of sugar-production. Urban attributes theabnormal composition to the great preponderance of nitrogen overpotash, the ratio of K,O to N having been 1 : 3.1, whereas heconsiders that the best ratio for sugar production is 1 : 1.Biliccc.A. D. Hall and C. G. Morrison3 have examined again the partplayed by silica in the nutrition of plants, and, while confirmingprevious conclusions as to its not being a necessary constituent ofplant food, have brought out interesting points as regards thefunctions which it exercises, and mainly in reference to the takingup of phosphoric acid.The observations have been made in respectof some of the permanent grass experiments in Rothamsted Parkand the permanent barley plots in Hoos Field. On the grass landJ. Amer. Chem. Soc., 1906, 28, 1013.Zeit. Zuckerixd. Bohni, 1906, 30, 397.8 PTOC. Roy. SOC., 1906, 77, B, 455278 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTKY.the use of sodium silicate along with mineral manures and ammo-nium salts gives, over 42 years, an annual increase of 10 per cent. inthe crop above that of a similarly manured plot without sodiumsilicate. An explanation of this is supplied by the barley plots,where sodium silicate has been employed with and withoutphosphates.Its use causes earlier formation of the grain andhastens the ripening of the crop. The omission of bot,h silica andphosphoric acid results in a poor crop (27 to 28 bushels per acre),but if sodium silicate is applied without phosphoric acid the cropis increased to 34 to 36 bushels, and more phosphoric acid is foundin the ash of the grain, although there is less in the ash of thestraw. Silica would thus appear to be able partly to replacephosphoric acid, the effect of it being that it imparts a stimuluswhich enables more phosphoric acid to be taken up by the plantfrom the soil. Barley plants were examined a t different stages ofgrowth, and it was found that, in general, only 9 per cent.ofthe silica reaches the grain in the early stages, and that, whereasordinarily the dry matter reaches its maximum about July 18-25,if no silica or phosphoric acid is supplied the dry matter doesnot reach its maximum until August 8. A series of water-culturesfurther confirmed these results and showed that while silica cannotreplace phosphoric acid it may stiniulate the plant to take upmore. And, lastly, by extracting the soil of the different plots withhydrochloric and citric acid respectively i t was shown that thesodium silicate has no direct solvent action on the soil phosphates.The ( I Rurei- ” Coizstituents of Plants and Soils.(a) Manganese.N. Passerinil grew lupins (Lupinus albus) in a soil containing0.068 per cent.of manganese, and examined the different parts ofthe plant in regard to their contents of manganese. The leavescontained 8.26 per cent. of ash, and of this ash 12.43 per cent.consisted of manganese reckoned as Mn,O,; the seed pods con-tained the next highest proportion, namely, 6 to 7 per cent. of theash (total 3.5 per cent.), and then the stems and the seeds, theroots lastly having still less. I n pot experiments, with and withoutaddition of manganese carbonate, the soil containing only 0.0002per cent of manganese, the dry matter contained 0.0095 of man-ganese when none was added and 0.0636 per cent. when it was givenas manure. T. Katayama2 showed that manganese has a stimula-tive effect on oats, barley, rice, &c., although this is not so greatBol.1st. dgmr. Scandicei, 1905, [ii], 6, 3.Bull. Coll. Agric. TGkyd, 1906, 7, 91AGRICULTURAL CHEMlSTRY AND VEGETABLE PHYSIOLOGY. ‘279as on leguminous plants. Using manganous sulphate on peas inquantity to supply 0.015 per cent. manganous sulphate to the soil,the increase was 50 per cent. in the yield of &raw and 25 percent. in that of the seeds, whereas with barley the total increasewas only 10 per cent. Quantities much exceeding the above tendedto decrease the yield. G. Salomonel confirms these results as tothe beneficial influence of a certain quantity of manganese and thetonic action_ of large amounts, and points out that the manganicsalts are more tonic than the nianganous, rnanganic acid especiallybeing hurtful.M. Nagaoka 2 obtained confirmation of formerexperiments, getting with rice a gain of 15 per cent. when usingmanganese sulphate up to 100 kilos. per hectare.(b) Copper.A. Stutzer 3 grew Trifolium pannonicum in pots with sand, gardensoil, calcium carbonate, and mineral manures. He added t o two ofthem finely-divided copper (1 gram and 10 grams) and to other twopowdered copper oxide in the same amounts, other pots receivingno copper. I n only one instance-when 10 grams of copper oxidewere used-was any injury noticeable, but here the plants eitherfailed or remained very small. Examination of the plants failedt o detect copper in them, even in the roots. W. W. Skinner hasexamined the effect on vegetation of irrigation water containingcopper salts derived from the waste products of mining operationsOne part of copper in, 800,000 has been found to be fatal t o thegrowth of corn, and as little as one part in 700 millions willretard the growth of wheat seedlings.The author concludes that 1part of copper per million is enough to condemn a water for use forirrigation purposes. He has further tested the general belief thatthe presence of carbonates and bicarbonates, by rendering copperinsoluble, will remove any danger of injury, and finds that it isnot justified, inasmuch as a considerable amount of copper remainsin solution, even if carbonates and bicarbonates are present inquantity. E. BrBa15 treated seeds with a solution prepared byboiling starch in 1 litre of 0.3 per cent.of copper sulphate solution.The seeds were soaked for twenty hours and then left to dry. Theirweight was increased somewhat, their germination was improved,and, besides the freedom from “smut ” and other diseases, the cropwas somewhat increased. (See also under mercury.)Chem. Centr., 1906, ii, 532.Bull. Co71. Ayric. Takyii, 1906, 7, 77.Lnndw. Verszcchs-Stut., 1906, 65, 285.Compt. ?-end., 1906, 142, 904.‘ J. AWIW. C ~ W I Z . +%c., 1906, 28, 361280 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.(c) Alwminium.H. Micheels and P. de Heen 1 investigated the effect of aluminiumsalts on the germination of wheat; with the result that, whilst theyfind alumina or kaolin to be beneficial, the addition of solublealuminium salts is proved to be injurious.On seedlings themselvesit would seem, from the work of H. D. House and W. J. Gies,2 thatthe injurious effect is dependent entirely on the extent of theconcentration.(d) Mercury and Silver.T. Bokorny 3 finds that a l p are killed by salts of copper, mercury,and silver if the concentration is 1 to 1 million. All other metalsrequire to be in more concentrated solution than this to do anyinjury.(e) lodine.S. Uchiyama,4 by using small amounts of potassium iodide,increased the yield of sesamurn and spinach. With sesamum heobtained an increase of 16 per cent. by using 124 grams ofpotassium iodide per hectare. This was confirmed by a fieldexperiment, and the matter has some interest owing to the commonpractice of using seaweed as manure where available.(f) Fluorine.Experiments of K.As55 with both soil and water culture seemto point to precipitated calcium fluoride as possessing some stimulat-ing action. This cannot, however, be due to hydrogen fluoride,inasmuch as this is not liberated by carbon dioxide and weak acids.AvaiJability of Soil Coiutituents.J. Konig, J. Hasenbaumer, and C. Coppenrath,6 in seeking fora method of determining the available constituents of soils, haveobtained the best results by placing the soil in a linen bag insidea copper vessel and heating the whole with water for three hoursunder a pressure of four atmospheres. The solution is thenfiltered, evaporated down, and the different constituentsestimated.Bull. Acad.roy. Be7g., 1905, 520.Proc. Amer. Physiol. S’oe., 1905, xix-xx.Chem. Zeit., 1905, 29, 1201.Bull. Imp. Centr. Agric. Exp. Stn. Japan, 1906, 1, 35.Bull. Coll. Agr. TCky6, 1906, 7, 85.Lnndzc?. Vcmmhs-Stat., 1906, 63, 471AGRICULTURAL CHEMISTRP AND VEGETABLE PHYSIOLOGY. 281Oxidation in Soils.E. J. Russell1 has continued his work on the rate of oxidationin soils and the relation this bears to their productiveness.Oxidation is due mainly, but not exclusively, to the action ofmicroorganisms, as it still goes on when the soil has been sterilisedby heating or by treatment with mercuric chloride or other re-agents. The rate of oxidation is, however, much reduced. More-over, i t does not depend on the amount of organic matter present;up to a point the presence of moisture helps; similarly, the pre-sence of calcium carbonate o r of a carbohydrate aids the rate.With partial sterilisation the rate of oxidation also increases, andthis would lead to the belief that, whilst the work of some organismsis checked, the activity of others may be favourably influenced bypartial sterilisation. This only takes place, however, underaerobic conditions, as in arable soils, but not in pasture soils,where the conditions are anaerobic.C. Schulze 2 has investigated the effect of sterilisation of soils, andfinds that whilst some substances injurious to plants are formed, thesoil constituents generally are made more available.Theresult as regards the plant will depend on the predominance of oneor the other influence.It is clear from the foregoing and the observations of others, thatthere remains still a great deal of work to be done in ascertainingexactly what changes take place in the bacterial and chemical con-ditions of different soils as well as in their physical relations,through the employment of processes of sterilisation, partial orcomplete, and that the results obtained with sterilised soils haveto be taken in conjunction with the various changes thereby pro-duced.Germination.P. Becquere13 has studied the action of carbon dioxide on seedswhich have been decorticated or perforated.When the seeds arein their naturally dry condition they will not be injured,though kept in an atmosphere of carbon dioxide; but if they arepreviously immersed in water for a, quarter of an hour they willbe all killed by exposing them to an atmosphere of carbon dioxide.0. Kamberskf? by placing seeds for forty-eight hours in contactwith a nutritive solution containing ammonium nitrate, potassiumBrit.Assoc. Reports (Section B), York, 1906.Landw. Versuchs-Stat., 1906, 65, 137.Conzpt. rend., 1906, 142, 843.Chem. Ceittr., 1906, i, 570282 ANXUAL REPORTS ON THE PROGRESS OF CHEMISTRY.nitrate, di-ammonium hydrogen phosphate, and di-sodium hydro-gen phosphate (Iszleib's solution), found that germination was re-tarded and a lower germination percentage obtained. A. Stutzerhas shown also that nitrates generally act injuriously on germinat-ing seeds; beet plants are very sensitive to nitrates, but red cloverresists their action.The behaviour of cyanamide towards germin-ating seeds has already been dealt with (page 261), but Bartsch 2 hasshown that, while the germination of mustard, oats, and barley isaffected when the seeds are sown a t the time of applying the cyan-amide, and will be still noticeable if a week intervenes, yet, if aninterval of three weeks is allowed between the application of thecyanamide and the sowing of the seed no injurious action willfollow.H. Micheels and P. de Heen3 have further found that ozonehas an injurious effect on seedlings, the roots in particular beingattacked.A ssimila tion.3'. L. Usher and J. 13. Priestley4 show that, in presence ofchlorophyll and under suitable conditions, aqueous carbon dioxideis decomposed into formaldehyde and hydrogen peroxide, formicacid being produced as an intermediate substance.This goes on in-dependently of any enzyme action, and depends solely on the properphysical and chemical conditions being present. It is possible toreconstruct this process outside the green plant. The formaldehydeand hydrogen peroxide rapidly undergo change,- and are not foundin the assimilating leaf under ordinary conditions. Working onthe leaves of Acer Negundo, B. Schultze ascertained that the in-crease in weight of the leaves, under the influence of light, was notdue only to the assimilation of starch, but also to that of proteins.But while carbon assimilation went on the production of proteinsgradually diminished.Ueuelopment.By growing green plants without carbon dioxide in an artificialsoil containing amides, J.LeGvre' showed that the dry matter ofthe plants rapidly increases, the growth being quite normal. I nabsence of light the plants failed altogether, although amides werepresent. The results go to show that the carbon dioxide of thesoil is not absorbed by the roots, or, a t least, is not utilised bythem.The oxidising power of living cells on the surface of roots wasJ. Lnndw., 1906, 54, 125.Bull, Acad. roy. Belg., 1906, 364.Baed. Centr., 1906, 35, 35.C?mn. Centr., 1906, i, 585, .I Proc. Roy. Soc., 1906, 78, E, 318.ti Compt. rend., 1905, 141 664, 834, 1035AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 283shown by experiments of M. Raciborski,l who grew plants in solu-tions which do not affect the life of the roots’ cells, but which, onoxidation, yield products either themselves coloured or capable ofcolouring suitable reagents.This power is, however, a purely localone, and is confined to the absorbent surfaces of the roots, beingstrongest near the root, hairs.The influence of light on the development of proteins in thewheat grain has been studied by J. Dumont.2 The, accumulationwas greatest under the influence of brown light, then under green,blue, and red light successively. I n the absence of light, A.Kiesel3 found not only asparagine to increase, but also otheramino-acids, especially leucine, and certain bases, such as arginine,not found in healthy plants.H. Schjerning,” in investigating the formation and changes inthe protein substances of barley during growth, ripening, and stor-ing, concludes that barley has attained its full maturity when thesoluble carbohydrates are converted into insoluble ones and thesoluble into insoluble proteins.H. T. Brown, F. Escombe, A.McMullen, and J. H. Millar5 have observed the migration ofnitrogen in barley from the endosperm t o the embryo during ger-mination. It was noticed by them that if the embryo was removedand allowed to grow in water or in a carbohydrate medium the rootexhibited a restricted development, and the embryo seemed tobe suffering from nitrogenous starvation. This nitrogen it would,in the ordinary course, derive from the endospem. The observa-tion was continued to barley undergoing the malting process, thenitrogen being determined a t various intervals in the endosperm,embryo, rootlets, &c.It was found that after nine days’ germi-nation 35 per cent. of the nitrogen originally present in theendosperm had migrated to the embryo, and must in so doinghave been converted from the insoluble protein form into solubleand diffusible compounds.The same authors continued their studies on the nitrogenousconstituents of malt that are soluble in cold water, with a viewt o ascertaining how far the quality of barley depends on these.An examination of the sprouted ‘‘ culms ” led to the identificationin them of asparagine, allantoin, betaine, and choline. The water-soluble uncoagulable nitrogens of malt have now been dividedby the authors into six classes of bodies, and their approximatepercentages have been also worked out.They consist of theCompt. mad., 1905, 141, 686. Bull. Acad. Sci. Cyacow, 1905, 338.Zcit. physio?. Chena., 1906, 49, 12.Z’rav. Laborat. Carlsbery, 1906, 6, 229.Trans. Gz6inness Research Lab., 1906, 1, part 2, 149, 169, 175, 238, 242, 284,3382% ANNUAL 13EPORl'S ON THE PROGRESS OF CHEMISTRY.following : -ammonia-nitrogen, 3.5 per cent ; malt-albumose nitro-gen, 20 per cent.; malt-peptone nitrogen, 31 per cent.; amideand amino-nitrogen, 8.5 per cent.; nitrogen due to organic bases,4 per cent.; uninvestigated bodies, 33 per cent. The conclusionis also arrived a t that, from the chemical point of view, no distinc-tion can be drawn between animal and plant proteins.The action of light on the transformation of sugars in youngplants has been studied by W.Lubimenkol in connexion withthe embryos of Pinus pinea. When these were exposed to lightof varying intensity in sterilised solutions of sucrose, dextrose,maltose, lactose, galactose, and arabinose, it was found that underthe action of the light the absorption of sucrose, dextrose, andarabinose went on, but with varying activity, diminishing as theintensity of the light increased. The light had no effect on theassimilation of maltose, lactose, laevulose or galactose.According to G. A. Calabresi 2 pentosans would seem to be formedin young plants, but t o decrease later on. I n sugar-beet, whenpentosans are high in amount sucrose is low, and, generally, inplants the pentosans are higher when nutritive constituents arelow.W.Palladin and S. Kostytschew 3 show that during the anaerobicrespiration of seeds and .seedlings a consitderable amount of alcoholis formed. Both living and frozen seeds have been experimentedwith; with frozen peas alcohol is formed whether oxygen be presentor not, but with living peas the formation of alcohol only goeson in absence of oxygen, Acetone is also found to be formedduring anaerobic respiration.W. D. Bigelow, H. C. Gore, and B. J. Howard4 have investigatedthe changes which go on during ripening in certain plants con-taining a good deal of tannin. They find that the tannin disappearsduring the ripening, passing possibly into insoluble forms. Micro-scopical examination shows that a t first the tannin is fairly uni-formly distributed through the fruit, but that, as ripening proceeds,it becomes deposited in insoluble form in special cells.&f ici-o-orgunisnts.N. L.Sohngen5 was led, by the consideration that methane,although so abundantly produced, is yet found only in traces irrthe atmosphere, t o search for organisms which were capable offeeding on the hydrocarbon. He found that if a culture-liquidCompt. re?td., 1906, 143, 516. Chcnz. Cevtr., 1906, ii, 964.J. A m e r . Chesn. Soc., 1906, 28, 688,Proc. K. Aknd. Wetcnsch. Amsterdam, 1905, 8, 327,3 Zeit. physiol. Chem., 1906, 48, 214BGltICUL'l'UltAL CHEMISTRY AND VEGETABT,E PHYSIOJAIGY.285was iniprcgnated with gardeii soil, sewage or the like, in an atliio-sphere of methane and oxygen at 38O, a slimy, pink film formedon the surface, and that this consisted of short, rod-like bacteria,which he named Bacillus metjznnicics. Within a week the methaneis nearly all absorbed, being thus utilised as a source of carbon.H. Kaserer,l working on the same subject, shows that the presenceof hydrogen and methane hinders the production of nitrites fromammonium salts. If there is a plentiful aeration, both oxidation ofhydrogen and nitrification may go on together, but, if aerationbe imperfect, nitrification will only begin after all the hydrogenhas been oxidised. V. Omeliansky2 finds that methane is producedby fermentation from cellulose, gelatin, peptone, and many othersubstances, and thinks it probable that all soils that have organicmatter will produce methane. Accordingly, i t is not possible tosay, from the mere fact of methane being produced, what thenature of the organic matter decomposed is.From the excrementsof pigeons C:. Ulpiani and M. Cingolani have isolated a micro-organism which decomposes guanine into carbamide, guanidine, andcarbon dioxide.In the fermentation of sugar-cane juice C. A. Browne4 hasnoticed that a frequent fermentation is that resulting in the for-mation of cellulose. This he has investigated and finds i t to beaerobic, being due probably to Bacterium xylintcm. From canejuice the amount of cellulose thus formed may be 7 per cent. oft'he total sugar fermented.The effect of light on bacteria has been investigated by H.'Phiele and K.Wolf.5 While the bacteria were destroyed quicklyby strong light, if the light was filtered through solutions ofnitrates or oxalic acid i t had no effect on the bacteria; if passedthrough disodium phosphate and potassium thiocyanate solutionsenough active light passed through to kill the bacteria. Fromthis the active bactericidal region was fixed. Light filtered througha piece of blue rock-salt crystal (the ultra-violet rays alone passingthrough) rapidly destroyed the bacteria.has observed the action of carbon dioxide a t highpressure on the bacteria contained in river water and in milk.Under a pressure of 50 atmospheres the bacteria are killed entirelyin twenty-four hours in the case of river water.But with milk thebacteria are not entirely destroyed, even at a temperature of 50°,although the casein is coagulated and separates out.W. HoffmannI Centr. Bnkt. Pw., 1905, ii, 15, 573. ' Atti 22. Accnd. Lincei, 1905, 14, ii, 59G.Ibid., 1906. ii, 15, 673.J. Amr. Chcm. Xnc., 1906, 28, 453.Arch. Hygiene, 1906, 57, 29.flkcth h t . C0ng.f. Appl. Chcm., Chew?,. Zeit., 1906, 30, 422286 ANNUAL REPORTS ON THE PROGRESS OP CHEMISTRY.Bnzynm,J. Stoklasa 1 has isolated several enzymes from beetroot. rheaehe identified as oxydases, invertase and glycolytic enzymes. Thelatter set up alcoholic fermentation in dextrose solutions, alcoholand carbon dioxide, as well as small quantities of acetic and lacticacids being produced.Formic acid has also been found as aproduct, and the author hints that this may give rise to thehydrogen which is evolved together with carbon dioxide, and mayplay a part in the assimilation of carbon in the chlorophyll cells,in which process formaldehyde and water are formed. The glyco-lytic enzymes are given as (a) lactolase, (b) alcoholase, (c) acetolase( d ) formilase, these causing the production of lactic acid, alcohol,acetic acid, and formic acid respectively.C. A. Brownez finds invertase in the green tops of sugar-cane,and notes that if the tops are removed when the cane is cut thediffusion of the enzyme into the stalk is prevented, and thereis less loss of sucrose. The darkening which sugar-cane juiceundergoes after expression is due to oxydases.GZwcosides and Cyanogenesis.Several investigators have continued their inquiries into thepresence in various plants of certain glucosides which, under theaction of an enzyme, gives rise t o the production of hydrocyanicacid.Numerous plants other than Phaseolus Zunntus (with whichDunstan and Henry worked) have been found to contain glucosidesof this character, and the yield of hydrocyanic acid has been quan-titatively recorded. W. R. Dunstan, T. A. Henry, and S. J. M.Auld3 find phaseolunatin in small amount in flax seed, and anenzyme of the emulsin type similar to that in Phaseolus Zmatus.They also find a glucoside and an enzyme similar to, if not identicalwith, those of I’haseoZus Zunatus, in the root of bitter cassava.L.Guignard 4 also establishes the presence of cyanogenetic glucosides inmany of the Rosaceae. He has further determined the amount ofhydrocyanic acid obtained from the ground beans of PhaseoZusZunatus, obtaining 0.052 to 0.102 per cent. with Java beans, butconsiderably less with Burmah, Madagascar, and Provence varieties.Further, he does not find, as others have done, that the whitecultivated beans are quite free froin hydrocyanic acid, and, inSixth 1nt. Congr. Appl. Cheva., Chem Zeit., 1906, 30, 422.J. Amer. Chem. sbc., 1906, 28, 453.3 Proc. Boy. Soc., 1906, 78, B, 145 and 152.-I Cow@. rmul., 1 Tf06, 143, 451, and 142, 545AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSlOLOGY. 287examining white beans that occur among Java beans he obtainsjust as much hydrocyanic acid from them as from coloured beans.He states that the poisonous properties are not removed on boiling,as this only destroys the enzyme and not the glucoside.R. R.Tatloclr and R. T. Thornson1 obtained from Java beans from 0.027to 0.137 per cent. of hydrocyanic acid. They examined seearatelythe variously coloured beans, but could arrive a t no generalisationas to the relation of colour to yield of acid. Discussing the state-ment that has been made that cyanogen is in the husk and notin the kernel, they state that this is not the case, but that thekernel has ten times as much as the husk. They examined severaldifferent varieties of beans, but only found hydrocyanic acid tobe produced from Java beans and Rangoon beans.On steepingthe beans in warm water and boiling them thoroughly, an originalpercentage of 0.009 of hydrocyanic acid falls to 0.002 and theenzyme is destroyed; in cold water the cyanogenetic glucoside isdecomposed.Kohn-Abrest 2 disagrees with the conclusion of Dunstan andHenry that there is one cyanogenetic glucoside in Phaseolus Zunatus,and considers that many are present. J. TV. Leather3 examin-ing a sample of sorghum (Sorghum vulgare) fodder whichhad proved harmful to cattle in India, found it to be immatureand t o contain 1-28 grains of hydrocyanic acid per lb. of greenstuff. The largest quantity was found in the leaves. Ilf left tomature the plant contained no hydrocyanic acid, but drying theimmature fodder in the sun produced no change in quantity.Theglucoside present was dhztrrin, as previously recognised by Dunstanand Henry. Leather confirms the presence of hydrocyanic acidin Rangoon beans and immature linseed.Foods and Feeding.K. Farnsteiner, K. Lendrich, and P. Buttenberg 4 examined lardsobtained from pigs that had been fed on potatoes, maize meal,cotton-seed meal, &c., with the result that a portion of the oilderived from the foods was shown to be deposited in the bodyfat of the animal. This was especiaIly marked in the case of maizemeal. T'he decomposition of foods in the absence of air has beeninvestigated by J. Konig, A. Spieckermann, and H. Kuttenkeuler?who find it to be practically the same in nature as when oxygenis present, although the products are different in quantity.Thegreatest loss is in the non-nitrogenous extract, although when airAnalyst, 1906, 31, 249.Agric. J . of India, 1906, 1, 220.]bid., 1906, 11, 177.Compt. rend., 1906, 143, 182.Zeit. Ndw. Geizussnz., 1906, 11, 1288 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTKT.is absent tliere is comparatively little loss of dry matter. The lossof nitrogen is very small, the proteins decomposing only slightly.The foods, in absence of air, tend to become strongly acid, but donot alter their appearance.E. Schulze,l taking potatoes, as containing a relatively largeamount-of asparagine, shows that this is converted, when consumedby animals, into amino-acids and then into succinic or malic acids,which have no value for fat production in the case of carnivorousanimals.0. Kellner,2 however, from experiments with sheep, con-cludes that asparagine may indirectly economise proteins in thecase of ruminants. Laetic acid he finds to be simply oxidised andto produce heat only.J. Konig3 has attempted to separate the various constituentsmaking up the so-called ‘( crude fibre ” in foods, and gives methodsof ascertaining the cellulose, lignin, and cutin. Lignin is separatedby digestion in the cold with hydrogen peroxide in presence ofaqueous ammonia, it being converted by this treatment into solubleproducts. Cellulose is next separated from cutin by treatment withcopper-ammonium hydroxide, it being thereby dissolved, leavingthe cutin undissolved. As the plant gets older the lignin increasesmore than the cellulose, and, broqdly speaking, the higher thepercentage of lignin and cutin the lower is the digestibility ofthe crude fibre.J.Hendrick,4 following up the work of T. B. Wood, R. A. Berry,and S. H. Collins (see AnnuaE Report, 1905, 264) has obtainedsimilar results for yellow swedes and turnips grown in the N.E.of Scotland. He finds marked variations according as the rootsare grown in different parts of the country, and emphasises (asdid the authors named) the necessity of taking a large numberof roots (100 suggested) in order to get satisfactory results. Hehas made the attempt to arrive at the value of the roots bycomparing the ratio of the soluble to the insoluble matter in thesolid matter of the roots.Crops.(a) ( ( Strength ’’ in Wheat.This subject has been further attacked both from the chemicaland the biological side.A. D. Hall5 has examined critically thedifferent constituents of the grain, with the view of finding outto which of them the quality of “strength” may be due. Buthe does not find any consistent correspondence between the pre-J, Landw., 1906, 54, 65.T7.ans. High. and Agric. SOC. of ScotEand, 1906.h?ep, Home-grown, ?.‘heat Committee (Mir’lers’ Gazette), 1906.B e d . Centr., 1906, 35, 45.3 Zeit. Nahr. Genussm., 1906, 12, 385AGRICULTURAL CHEhIISTltY AND VEGETABLE PHYSIOLOGY. 289dominance of any of these and the possession of “strength,” andis unable to go beyond the general statement that nitrogen may,as a rule, be taken as a test of “strength,” whilst the carbohydratematters do not contribute t o it.Hall finds that different stagesof ripeness do not determine “strength,” inasmuch as a crop cutdead ripe may be just as “strong” as one cut green. Nor does itfollow that a highly nitrogenous grain is of necessity a ‘‘ strong ’’one; some were, indeed,*the weakest of all from a baker’s point ofview. But it was observed that these, i f kept, became changed;their physical structure seemed to be altered, and they were thenincreased in Hall remarks on the observed “ acidity ”of flour, and finds that this is due t o the presence of a littlepotassiuni phosphate.Meanwhile the subject has been investigated further from thebiological side by R.H. Biffen 1 and with more hopeful prospects.Biffen eliniinates climatic conditions as having little or no bearingon the question, and attributes the whole to the matter of“ selection,” and looks t o the producing of “ hybrids ” to obtainthe desired quality of “strength ” combined with good yield.strength.”(b) Quality in Barley.The results obtained a t the Woburn Experimental Farm for theyears 1898-1904 on the influence of manures as affecting theyield and quality of barley have been collected and summarised?and, in general, confirm the results obtained a t the RothamstedExperimental Station. The main points as regards quality arethat this was improved by mineral manuring (superphosphate withsulphates of potash, soda, and magnesia), that farmyard manuregave very variable results, and that the best ones were obtainedwith mineral manures in combination with ammonium salts ornitrate of soda used in moderate quantities.Nitrate of soda byitself or used in excess gave a low “ weight per bushel ” and much“ tail ” corn.Industries.(a) Sugar.A considerable impulse has been given of late to the growingof sugar, more particularly of cane-sugar, and with this has comean extension of inquiry into points connected with the cultivationof the crop and the securing of the produce.H. W. Wiley3 summarises his observations on the influence ofenvironment on sugar production in the beet. Temperature heJ. Agric. Sci., 1907, 2, 1. J. Fed. Iitst. Brcwiity, 1906, 12, 408.3 U.S.A. Dept. Agric.Bid/., 1905, 96.VOL. 111. 290 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.finds to be of the greatest importance; there is little relationbetween sunshine and sugar yield, but longer daylight means moresugar; rainfall only incident,ally affects the output, but a smallyield of crop means an increased sugar percentage ; lastly, thejuice becomes purer as the percentage of sugar rises.find that sucrose is not uniformly distributedthrough the beetroot; some cells contain only water and salts,and the water is that termed by Scheibler ‘ I colloidal” water.Hence the difficulty in obtaining representative samples. Completediffusion of the juices only takes place when the pulp is finelyground and digested with cold water or hot alcohol.K. Andrlik and J./Urban2 have examined the ‘(objectionable”nitrogenous constituents in beet-root juice, and find that theseare not amide or ammonium compounds. About 70 per cent. ofthe whole of the injurious matters originally present in the rootare found in the juice. This quantity is increased by storage ofthe roots, probably owing to a breaking-down of the proteins.Experiments in sugar-beet growing in the eastern counties ofEngland3 have given in 1906 an average yield per acre of fourteentom of roots, containing 16 per centl. of sugar, with a coefficient ofpurity 87. This yield, however, is not sufficient, in the cir-cumstances of this country, t o “pay” for the manufacture ofsugar. W. D. Horn04 has inquired into the deterioration whichsugar-cane undergoes when the canes have been cut.On each ofsix successive days he cut off pieces from canes, and noticed thatthe deterioration was greater with the top part of the cane thanthe bottom, but there was also a deterioration due t o keeping.Thus, starting with 16.97 per cent. of sucrose on the first day, bythe time the fifth day was reached the sucrose had fallen to 11.86per cent.; in the first day there was a deterioration of 0.25 percent., in the next two of 1.75 per cent., and in the next two ofnearly 4 per cent. F. Watts and H. A. Tempany5 observed thechanges which sugar-cane juice undergoes when allowed to fermentspontaneously; the juice becomes acid and of a yellow colour,a dark scum rising to the surface; alcoholic fermentation sets in,carbon dioxide is given off, and quite 8 per cent.of alcohol isformed. Then acidification of the alcohol ensues, ‘( cane sugar ”being obtained. The acidification of the juice was found to be pro-duced by oxidation of the sugar by bacterial agency; this could beprevented by the addition of 2 per cent. of phenol t o the juice.1 Ez~ll. Assoe. Chim. Suer. Did., 1906, 24, 615.Zeit. Z t ~ k e ~ i i i d . Biihm., 1906, 30, 282.Bep. E. Sz~foZk CItctnzbe.1. of Aqriczrlt?s?*e, 1907.J. SOC. C?cewt. Ind., 1906, 25, 161.ICTest Ind, Bzhll., 1906, 6, 387.H. and L. PelleAGRICULTURAL CHEMIS‘L’RY AND VEGETABLE PHYSIOLOGY. 291C. A. Browne,l jun., attributes the gradual inversion of thesucrose after the cane has been cut to the invertase which existsin the green tops of the cane. He has investigated the differentfermentations, aerobic and anaerobic, which take place in thejuice.Among the former are those due t o Bacterium x y l k u m andto citromyces, and among the latter that produced by Leuconostoc,a viscous fermentation.H. Pellet2 refers to the suggestion of adding invert-sugar tomolasses to aid crystallisation of the la,tter, since sucrose is lesssoluble in invert-sugar solution than in water, but he shows thatthis is not an advantage, inasmuch as the invert-sugar brings aboutthe retention of more water, and this more than neutralises thebenefit that might accrue.(b) Tea.H. H. Mann3 in a paper entitled “The Fermentation of Tea”(part I.) gives a valuable contribution to our scientific knowledgeof the manufacture of tea.Indeed, it may be taken, in conjunc-tion with his earlier paper, (‘ The Ferment of the Tea Leaf ” (seeAnnual Report, 1904, 215) as supplying the first clear exposition ofthe scientific side of the subject. Moreover, it affords a most usefulexample of how the study of the underlying chemical principlescan be made t o contribute to the practical well-being of an impor-tant industry. Mann had shown in his earIier paper that thefermentatlion is due t o an enzyme of the nature of an oxydase,and that the, quantity in which it is present is an indicationof the quality of the tea. He now goes on to consider the variousconstituents of the leaf, t o observe the changes in them during thedifferent processes of withering, rolling, &c., and to see in what waythese affect the value of tea as a finished product.Living organ-isms, i t is shown, do not take part in the fermentation, and theirexclusion as far as possible from the fermenting room should besecured. The constituents studied in detail are (1) essential oil,(2) caffeine (or theine), (3) tannin. The quantity of essential oilpresent is very small; it is driven off a t a high temperature, andchanges into a resin on exposure t o air; it seems t o be one of thechief factors in determining flavour in tea. Caffeine exists to theextent of 3 to 5 per cent. Its presence has no bearing on themarket value of tea, although it may have on its medical value.Mann next deals very fully with the matter of tannin, and showsthat, contrary to general opinion, this is not an objectionablefeature, but that there is a close connexion between the quantityJ.Amcr. Chcnt. SOC., 1906, 28, 453.BdE. Assoc. Clzim. Xucr. nist., 1906, 24, G69.3 Indian Tea Assoc., 1906, 1 and 2.u 292 A N N U L REPORTS ON THE PROGRESS OF CHEMISTRY.of tannin that can be removed in a five iiiinutes’ extraction withboiling water and the value of tea in the market. Tannin, as i toccurs in the leaf, seems t o be combined with sugar, and thetannin undergoes oxidation during fermentation of the leaf, throughthe presence of the oxidising enzyme. The oxidised tannin willthen combine with the caffeine and other materials to form freshsubstances which are mostly insoluble in water. During the processof rolling, the soluble matter in the leaf is reduced, and so isthe amount of soluble tannin. Mann has further noticed theinfluence of light on the fermentation of tea, and finds that, whilstfermentation proceeds rather less rapidly with a. blue light, thereis no change in the percentage of tannin, but only in that of totalsoluble matter. What is of importance, however, is thickness ofspreading, and this should not exceed 1& inches in depth. Experi-ments in green-ma,nuring for tea established the usefulness ofleguminous plants, especially sau (.4 Zbizzia stipulntci).(c) Tobacco.J. Toth1 has set oat’ a new method of determining the orgauicacids in tobacco. Expressing these in terms of oxalic acid, he findsthe quantity to range from 3’6 t o 8.7 per cent., and, after trialswith 32 different samples, concluded that bad-burning tobacco wasthat which contained the most organic acids, and tiice vers&.(d) CinclL ona.D. Howard2 shows that by careful selection and cultivation theamount of quinine alkaloid in cinchona bark has been raised inJava from 4 per cent. to 10 per cent.(e) Cassava.H. H. Cousins3 has esbimated the amounts of starch obtainedat different periods of growth from 23 varieties of cassava, grownin Jamaica. He gives the produce of starch per one-tenth acreas follows:-At 1 2 months, -34 tons; a t 15 months, 54 tons; at21 months, 7$ tons.(f) Eggs.J. Hendrick4 has examined the composition of eggs preservedby the use of “wateryglass”; he finds that there is a slowdeposition of silica in the shell, but that there is no change inthe composition of the interior portion.Clwwt. Zcit., 1906, 30, 57. 2 J. xoc. c r ~ ~ ~ l t . b L d . , 1906, 25, 97.3 Jaiizaiccc Gaxtlc, Nov. 22iid, 1906, 330. J. Agric. Sci., 190T, 2, 100AORTCULTURAL CHEMISTRY AND VEGErABJ,E PHYSIOLOGY. 293H. D. Richniond 1 gives his annual statement of the compositionof milk, as obtained from good dairy farms supplying milk dailyto London, during 1905. The figures are taken from an averageof nearly 15,000 samples, and are as follows:-Fat, 3.73 per cent;solids-not-fat, 8.97 per cent.; total solids, 12.70 per cent.; sp.gr., 1.0323. The average percentage of fat of the morning milkalone was 3.54; of the evening milk, 3.91. These figures differbut very slightly from those of 1904.A. Morgen, C. Beger, and G. Fingerling2 have investigated, over aperiod of six years, the effect of adding fat, protein matter, carbo-hydrates, kc., t o foods deficient in these several constituents. Byadding fat they found the yield of milk and the amount of fatin i t to be both increased, but by adding protein matter only theyield was affected favourably, but not the fat. The yield of milkwas, however, increased more by adding a pmtein than by theaddition of fat. The addition of carbohydrates also had no effecton the production of milk-fat. The authors conclude that fat alonehas a specific action on the production of milk-fat. Further experi-ments with emulsified fats showed these to possess no advantage.Von Soxhlet3 has observed the coagulation taking place in thecase of milk that is faintly acid. A t first a coagulum is formedon boiling, and this takes place when only one-eighth of the acidnecessary to produce coagulation a t the ordinary temperature ispresent. The coagulation is due to the formation of an insolublecompound of caseinogen and calcium salts.F. Bordas,* by exposing milk to an atmosphere containing for-maldehyde, has found that air containing as little formaldehyde as 1part in 100,000 will give the reaction for formaldehyde, althoughthe milk may have been exposed for only a few minutes.J. AUGUSTUS VOELCKER.AW~YSL, 1906, 31, 176. ’ L n l t c l ~ . Yc~sz~chs-~Ytd., 1906, 64, 93, 249.Chem. Centr., 1906, i, 579. Compt. wnd., 1906, 142, 1204

ISSN:0365-6217    

DOI:10.1039/AR9060300256

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

1\IINER ALOG 1C h L CHEMISTRY.IT is impossible to begin a report on the progress of MineralogicalChemistry during the past year without making brief reference to thegreat loss this brauch of science has sustained in the untimely deathof S. L. Penfield. Equally happy as a theorist and as an experimenter,he has left in his work an enduring monument behind him. A sympa-thetic biographical notice, accompanied by a bibliography, has beencontributed by L. V. Pirrson to the pages of the American Joui-nal ofScience. I I n the person of H. A. Ward, America has also lost aveteran who, by his untiring energy as a collector, did good service inadvancing our knowledge of meteorites. By the death of W. Meyer-hoffer at the early age of forty-two, van’t Hoff has been deprived ofa fellow-worker and our science of one who did much to introduce tomineralogists and petrologists those ideas and met hods of physicalchemistry, the application of which promises such rich results in thefuture.It is, in fact, along these lines that the most important workhas been done during the past year, and it is therefore fitting that thisbranch of the subject should occupy the first place in our survey.General und Physical Chemistry of Minemls.Isalt Deposits.-J. H. van’t Hoff and his pupils have carried ontheir investigations with unabated energy. Number x l ~ i of the ‘‘ Re-searches on the Formation of Oceanic Salt Deposits ” appeared earlyin the year, and was devoted to a discussion of the conditions ofoccurrence at 83’ of anhydrite, CaSO,, syngenite, CaK2(S04),,H20,glauberite, CaNaz(S04)z, and penta-salt, Ca5K,(80,),,H20; the forma-tjon of calcium chloride and tachhydrite, CaCI;, 21\IgC12,1 BH,O, were alsoconsidered.In number xlvii the examination of the naturally occur-ring calcium compounds was brought to a conclusion by a study of therelations at 8 3 O of the triple sulphates, polyhalite, Ca,K2Mg(S0,),,2H20,and krugite, Ca,K2Mg(S0,)6,dH,0.Work on the borates was begun last year, and the relations ofAqner. J. Sci., 1906, [iv], 22, 353.3 SitmngsBer. K. Akad. W’isss. Beylin, 1906, 218, 412, 566, 653, 689MI N E R A LO G I C A TA C H E M T STRY . 295tincal and octahedral borax elucidated. The more difficult andcomplex problem presented by the double borates of calcium andmagnesium with a univalent ion has now been attacked, and therange of existence and the dissociation of NaCaB50,,8H,0 boron-atrocalcite f ally determined.'It has been shown in number xlviii that this substance splits intothe individual borates a t about S 5 O , and that i t probably was notformed in nature a t a temperature higher than 70".Incidentallypandermite, Ca,B,,O,,, 15H,O, was prepared artificially for the firsttime, together with a new substance, tricalcium borate, Ca,Bl,0,,,9H,0,not as yet obserred as a mineral. The mutual transformations of thehydrates of calcium monoborate, CaB,O,, are the subject of a separatepaper ; and number xlix of the series is concerned with the conditionsfor the artificial preparation of colemanite, (CaO)2( B20&5H,0, wbichit is shown can bc formed from the corresponding heptahydrate andsodium chloride a t 83", o r from boronatrocalcite in the same mediuma t 70".Mutua I Relution, of Fused Silicates.-The past year has witnessedgreat activity in this line of research, and the entry of Americanworkers into the field has resulted in a notable increase of ourknowledge of the calcium and magnesium silicates. I n the first place,E. T. Allen and W. P. White have succeeded in preparing artificialwollastonite having properties identical with those of the natumlmineral, and have also made a careful examination of the hexagonalcalciuni metnsilicate, termed by them pseudo-zuolkcbstonite, and ofthe relations between these two substances.They find that wollas-tonite can be readily obtained from the glass made by melting,together, a t a temperature of over 1500", molecular proportions ofquartz and calcium carbonate in a platinum crucible, which is thenrapidly chilled by placing it in water. On heating this glass to about800' to 1000" i t crystallises directly and rapidly into wollastonite,identified by its optical characters. The specific gravity is 2,915.When heated to about 1180° wollastonite changes into pseudo-wollastonite. This change is an enantiotropic one, and under properconditions reversible. The point of transformation mas determined byheating wollastonite in contact with the other form for definite perigdsa t various temperatures, and also by observing the rate of rise oftemperatureas heat was supplied to the mass, a slight absorption OCheat being noticed a t the transition point.The volume changeaccompanying the transformation is so slight that it is doubtful whichis the denser form. The reverse transformation is not so easilyeffected, and does not take place when the two forms are merelyheated in contact a t temperatures between 900' and llOOG, even if theAmer.. J. Xci., 1906, [iv], 21, 89296 ANNUAL REPORTS ON THE PROGRESS OF CHEMTSTRTheating be continued for many hours. It can, however, be broughtabout by the aid of a solvent. Calcium vanadate proved suitable, andit was found that the change into mollastonite was complete if5 grams of the silicate were heated with 1 gram of the vanadate forsome days a t a temperature of 800" to 900".Beautiful transparentcrystals were produced in this way. Analysis proved them t o benearly pure CaSiO,, and the mean specific gravity 2.913, crystallo-graphic characters 1 and optical properties, agreed with those ofwollastonite. This inversion also takes place readily in mixturescontaining excess of lime or silica, as shown by Day and Shepherd.Pseudo-wollastonite is usually considered to be hexagonal, but F. E.Wright, who has made a careful optical study of Allen and White'spreparations, thinks that it is more probably pseudo-hexagonal, its realsymmetry being that of the monoclinic system. The melting point is1 5 1 2 O , and on cooling the liquid almost invariably crystallises above1 200' as pseudo-wollastonite.The fact that the transformation takesplace at 1 180° has an important geological bearing, for it fixes an uppeklimit of temperature above which wollastonite cannot possibly havebeen formed, and neither pseudo-wollastonite nor paramorphs ofwollastonite after pseudo-wollastonite have been met with in nature.The work on wollastonite has been extended by A. 1,. Day and E. S.Shepherd2 to embrace the whole series of combinations of lime andsilica, They began by studying the properties of the two oxides.The melting point of lime is too high for any satisfactory measure-ments to be made, It can, however, be fused in the electric furnace,and on cooling crystallises with well-marked cubic strncture. Themean specific gravity is 3.316 a t 25".Silica, either in the form ofquartz, glass, or precipitated silica, when heated for a sufficient lengthof time at temperatures above 1000°, changes into tridymite. Thechange proceeds most rapidly in the case of the precipitated silica, afine state of division being favourable to the transformation. I n orderto determine the transformation temperature as accurately as possible,quartz-glass mas heated with vanadic acid, sodium tungstate, or amixture of 80 per cent. potassium chloride with 20 per cent. lithiumchloride. Below 760' quartz crystals were obtained. At 800' andhigher tridyrnite was the only product. Inversion occurs therefore atabout 800°, and the melting point of silica is really the melting pointof tridymite, although by very rapid heating quartz can sometimes bemelted without first changing into tridymite.Owing to the viscosityof the substance, it is exceedingly difficult to fix this point, but it seemsprobable that pure silica begins to melt a t about 1600".To obtain a general idea of the behaviour of mixtures of limeand silica, small portions of finely-ground mixtures of known com-1 Two crystals were measured. Anzer. J. Sci., 1906, [iv], 22, 265position were placed in A row on platinum or iricfiuin strip. Thestrip was gradually heated electrically and t'he order of melting noted.In this way two compounds ancl three eutectics were discovered.Mixtures containing more than 75 per cent. or less than S2i- per cent.of lime could not be investigated, owing to the refractory nature of thooxides.The compoonds formed are the metasilicate and the ortho-silicate of calcium ; the analogue, 4Ca0,3Si02, of tokermanite, and thetricalcic silicate, SCfaO,SiO,, could not be detected, although specialefforts were made to prepare them.Theorthosilicate, 2CaO,SiO,, melts a t about 2080", and exists in threepolymorphic forms which stand in enantiotropic relation to oneanother. The a-form, which crystallises in the monoclinic system, isthe only modification stable in cpntact with the fusion. Its specificgravity is about 3.27. Below 1410" the a-form changes into the/3-form. This unstable modification is orthorhombic, and has aboutthe same density as the a-form ; i t turns into the monoclinic y-varietya t about 675' with great increase of volume, the specific gravity ofthe latter being 2.974.The disintegration which takes place whenthe orthosilicate is cooled is thus explained. The ortliosilicate isreadily attacked by water, and this is probably the reason why it isnot found as a mineral. The three eutectics a r e : tridymite a n dpseudo-mollastonite a t 37 per cent. of lime, melting a t 1417' ;pseudo-mollastonice and a-orthosilicnte at 54 per cent. of lime,melting at 1430'; a-orthosilicate and lime a t 67; per cent. of lime,melting at 2015'.The preliminary investigation having demonstrated the existence oftwo compounds and three eutectics, the melting points of 100 gramcharges mere determined by means of a thermo-junction, or for highertemperatures by the Holborn-Kurl baum pyrometer.The results,which were plotted, fully confirmed the preliminary observations. Itwas found incidentally that pseudo-wollastonite appears to be capableof taking up small quantities of silica and of orthosilicate in solidsolution.The very important results obtained in the course of the investiga-tion of the felspars ancl of the calcium silicates naturally led theworkers in the geophysical laboratory at Washington to turn theirattention t o the compounds of magnesia :and silica, and thanks tothe labours of E. T. Allen, F. E. Wright, and J. K. Clement,l wenow possess a very complete knowledge of the metasilicate, MgSiO,.This substance can exist in four distinct cryst,il forms.I. The first crystallises in the inonoclinic system, and is the productusually obtained from fusions.It was first prepared by Ebelmen, andAmw. J. Sci.,11906, [iv], 22, 385.The properties of the metasilicate have been already clescribed298 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.is found in nature in certain meteorites. It can be made (1) bymelting together magnesia and silica in the proper proportions andallowing the liquid to crystallise; (2) by allowing the glassobtained by rapidly cooling the fusion to crystallise at 1300O ; (3) byheating any of the other forms t o temperatures from 1150" upwards ;(4) by fusing amorphous silica with magnesium tellurite or chloride ;(5) by recrystallising magnesium silicate from a flux of magnesiumchloride or vanadate, calcium vanadate or tellurium dioxide.Thefirst method is most suited for preparing the substance in quantity;the last yields the best crystals, the most satisfactory results beingobtained when the silicate is fused with magnesium chloride in acurrent of dry hydrogen chloride. The crystals resemble in somerespects those of a monoclinic pyroxene, having the characteristiccleavage angle 92O, but the ratio b : c = 0.77 is very different from thatof diopside b : c = 0.5894. They are characterised by the low extinctionangle on b (OlO), c :t= 21.So, and by polysynthetic tvinning parallelto a (100). The specific gravity is 3.192 a t 25O. The monoclinic pyroxenemet with in the Bishopville meteorite has the same properties.11. The second form is orthorhombic and identical with enstatite.It is best prepared by heating the glass to between 1000° and 1100';if the latter temperature is exceeded the first variety appears as well,often in parallel intergrowths.Obtained in this way, the substanceforms fibrous aggregates of specific gravity 3.175. The angle betweenthe optic axes is smaller than that of natural enstatite, a fact as yetunexplained, On heating to temperatures above 1260' this formpasses slowly into the monoclinic variety.111. The third form is a monoclinic amphibole, and is the leastclearly defined of the four. Its identification as a separate varietyrests on its extinction angle, maximum value ll', and on its meanrefractive index, which is much lower than that of I. It is sometimesmet with in fusions which have been rapidly cooled, and appears alsoto be produced by the action of water a t 375-475' on the nextvariety.IV.This form is orthorhombic, and is identified by the authorswith n naturally occurring amphibole to which some writers havegiven the name of kupfferite. To prepare this variety the mixtureshould be heated well above the melting point and then cooled asquickly as is possible withoui; forming glass. Measurable crystalshave not been obtained, and the identification with kupfferite restson the optical properties and the indication of cleavage a t 120".The mean specific gravity is 2.857 at 25". This variety changes intoI on heating. These four modifications stand in monotropic relationto one another, the order of increasing stability being orthorhombicamphibole, monoclinic amphibole, enstatite, monoclinic pyroxeneBI IN ER A LOG I C A 1, C H E JZ I S'I'R 17.299That this is so is shown by the fact that enstntite and the amphiboleswhen heated pass over into the monoclinic pyroxene, which cannot bechanged back without passing through the amorphous state. Further,it is found that although the first three forms can all be dissolved insuitable fluxes at comparatively low temperatures, yet they crystalliseout as monoclinic pyroxene. Lastly, it has been shown by aningenious application of Frankenheim's method that the first threeforms change into the monoclinic variety with evolution of heat. Theexistence of a monotropic relation between the two great groups ofamphiboles and pyroxenes is i n accord with the work of other experi-menters, and the formation of amphiboles in nature instead ofpyroxenes may perhaps have been due to the viscosity of the magmafrom which they crystallised, while the presence in the Bishopvillemeteorite of intergrowths of pyroxene and enstatite suggests that i twas rapidly cooled from a high temperature.Certain meta- and ortho-silicates have also been studied from a some-what different point of view by V.Paschl,' who has prepared mixedcrystals by melting the constituents together. Thus he finds thatartificial diopside and hedeiibergite from Elba mix in all proportions.The melting point curve corresponds to Roozeboom's type I, but is notquiteregular and tho specific gravities of the mixtures do not in allcases lie between those of the components.Experiments with enstatiteand diopside indicate that these substances form an isodimorphous series,with n gap exteuding from 40CaMgSi,O,, 60Mg,Si,O6, to 50CaMgSi,O,,SOMg,Si,O,. The case is similar to that of the mixed sulphates ofiron and magnesium, and the specific gravities are lower for the rhombicthan for the nionocliiiic form. The melting point curve is of type V.Artificial mixtures of the isomorphous orthosilicates, Mg,SiO, andFe,SiO,, do not give a continuous series, the gap extending from65Mg,Si0,,35Fe2Si0, to 3Mg,SiO4,97Fe,SiO,. The melting pointcurve is of type 1, but is not a straight line. Artificial mixtures ofMg,SiO, and Cs,SiO, give results indicating t h a t these substances areisodimorphous.The conditions under which quartz and tridymite crystallise fromsilicate fusions have also been studied by P.D. Quensel,, who has arriveda t conclusions in the main much the same as those reached by Day andShepherd. He found that when a mixture of 74 parts of oligoclase and26 parts of amorphous silica mas fused with small quantities of tungsticoxide, or in the presence of water supplied by driving a current of super-heated steam through the fusion, small quartz crystals were formed.The effect of adding tungstic oxide was to lower the melting point andCentr. &fin., 1906, 571.Ccntr. Xi?z., 1906, 657, 728; see also R paper by Cosmo Johiis, Geol. Mag.,1906, 3, 118300 AXNUAL REPORTS ON THE PROGRESS OF CHEMISTRY,viscosity, and to increase the size and rapidity of formation of thecrystals.On fusing silica with excess of sodium t ongstate, tridymitewas obtained, a fact previously noticed by Hautefeuille. As thereseemed reason to think that the ainountl of '' mineraliser ') present (inthis case tungstic oxide o r sodium tungstate) had an important influenceon the result, fresh experiments were undertaken in which the oligo-clase-silica mixture or pure silica were fused with from one to five partsof sodium tungstate. It was found, however, that quartz was alwaysobtained from the oligoclase-silica mixtnre at temperatures below lOOO",while if silica alone was used, tridymile or glass were formed, accordingas the temperature was kept above or below 1000°, the amount ofsodium tungstate present being unimportant.Quensel therefor0 con-cludes that the factors which determine the products are, the presenceof co-solutes, the concentration, and the existence of chemical equili-brium, and explains the forination of quartz as due to the influence ofthe constituents of oligoclase on the equilibrium between the alkalisand silicic acid. I n the case of tridymite a sodium silicate or possiblya silicotungstate is perhaps first forined, and this being unstable a t hightemperatures the silica separates dit ectly as tridymite. The rare occur-rence of tridymite in eruptive rocks, in spite of the fact that the tem-perature conditions mould favour its formation, he explains as due tothe special conditions required to produce this form, the presence ofother substances interfering with its crystallisation.Quensel finds that the melting point of tridymite is about 156G0, andconcludes from his own work and from that of his predecessors thatabove 900" i t is the stable form of silica. It can, however, exist at tem-peratures as low as 300" to 400".Quartz, on the other hand, can exist upto 1000°, but is unstable above 900'. Below 200' the hydroxides areperhaps to be considered the stable form, though quartz can exist as well.While the Americans have been breaking fresh ground in the studyof pure silicates, C. Doelter has been very active in the field he hasmade especially his own. Many pages of the numerous and lengthypapers for which he and his pnpils are responsible are occupied byadverse criticism of the views held by Vogt and of the resrilts obtainedby Day and Allen, but a certain ilmoant of fresh work along the licesalready familiar has been accomplished. Thus Doelter himself hasredetermined the melting points of a number OF nntuial felspars, and hasobtained results lower than those given by Day and Allen in their workon the artificial compounds.Further, he has reiterated his belief thatwhen silicates are melted they dissociate to a very considerable extentinto oxides, and has laid p e a t stress on the part played by viscosity,Wien. Sitxungsbe~., 3906, 115: 723 ; ililoitntsh., 1906, 27, 438 ; 2'sch. Mia.Uitt., 1906, 25, 79 and 206 ; Zeit. Eieklrocltcm., 1906, 12, 413 ; CcnfT.ililin., 1906,193MINERALOGICAL CHEMISTRY. 301crystallising power, and velocity of crystallisation in determining theparticular compounds which separate from a magma.The relation between the cornposition of the_ii;ixture and that of theeutectic is regarded by him as oE very minor importance. This pointhas been specially studied by M. VuEnik,l who has attempted to testVogt’s view in the case of certain binary mixtures, a s for instanceanorthite and fayalite, or anorthite and olivine. No eutectic structurewasobserved, but that mixture had the lowe>t melting p d u t for whichthe composition was that required by theory for the eutectic. M.V u h i k and H. H. Reiter 2 have also examined the eifect of f iising :tnumber of ternary mixtures such as anorthite, hedenbergite, andolivine; leucite, olivine, and achmite ; labradorite, aegerine, and elaolite ;albite, augite, and magnetite, &c. As can readily be imagined, theresults obtained are complex, and substances like spinel and hematitenot present in the original mixture crystallise out on cooling.Suchfacts as these they regard as evidence that dissociation of the originalsilicates has taken place. The general conclusion drawn from theexperiments is that from fusions of tLis kind minerals separate in thefollowing order : spinel, hematite, magnetite, olivine, magnetite (2),augite, magnetite (3), nepheline, plagioclase. This order is conditionedby the chemical reactions accompanying the dissociation of the silicates,as well as by the composition of the mixture and its relation to thatof the eutectic.That supersaturation may play an important part isto be gathered from the fact that magnetite can appear at more thanone stage, while viscosity, velocity of cooling, and power of crystal-lisation all have a share in determining the result. They find in theseexperiments no confirmation of Vogt’s views tts to the importanceof the eutectic in determining the order of crystallisation.J . H. L. Vogt himeelf, on the other hand, continues to insist mostvigorously that the laws of physical chemistry established by thestudy of solutions aye directly applicable to mixtures of moltensilicates, which he regards as but slightly, if at all, dissociated. Hehas recently contributed a niasterly exposition of his views to thepages of Tschernmk’s il.linernlogische ill itteilu n,g en.This begins witha brief riszcnzS of the Inws goveruitig the solidificatiou of binary andternary mixtui es, aiicl includes an account of Roozeboom’s classificationof mixed crystals. The application of these principles to slags is nextdiscussed, and van’t Hoff’s law of molecular freezing point depressionshown to hold for such cases as Akermanite and augite, melilite andanorthite, diopside and olivine, melilite and olivine. Incidentally theconviction is expressed that Doelter’s experiments in this direction arenot calculated t o throw much light on the subject.C’67ztP. jIi?t., 1906, 132. Jdrb. Nia. 1906, Beit. Bd., 22, 1%. ’ 1906, 24, 437-542302 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.I n a Eucceeding paragraph the mixed crystals formed by Mg,SiO,and Fe,SiO, are shown to belong to type I of Roozeboom’s classification,and the importance of zonal structure as indicating a slight degree ofsupersaturation is pointed out.Arguments are also adduced to showthat the mixed crystals formed by enstatite and diopside fall underRoozeboom’s type IV. The results obtained by Day and Allen areutilised in the elaborate discussion of the felspars which occupies thesecond half of Vogt’s paper and is devoted mainly to the considerationof mixed crystals composed of orthoclase, albite, and anorthite. Itis shown that whereas the binary mixture, albite and anorthite,belong to type I, the mixtures of orthoclase with albite or anorthitebelong to type V and fotm eutectics.The ternary mixture in whichall three components are present is also discussed and illustrated by adiagram. Further, the work of Schreinemakers 1 is applied to the casein which the mixture of orthoclase and albite is present with someindependent component such as quartz or olivine. Such a case mustfall either under Schreinemakers’ type d or type e, and i t is stated thatthe combination quartz, orthoclase, albite belongs to the second ofthese, and yields as final product a ternary eutectic mixture of quartzand the two kinds of mixed crystals. A full discussion of some ofthe latter points is to be given in a continuation of the paper.Deposition of Quartz from Aqueous SoZutio?zs.-J.G. Konigsbergerand W. J. Muller have attempted to throw light on the conditionsunder which quartz and other vein minerals have been deposited, moreespecially in the case of those found in the biotite-protogine of theAar. Assuming that these minerals have crystallised from solutionshaving approximately the composition of the incliisions found inthe quartz crystals of the district (see page 323) a t temperaturesbetween 120’ and 500°, they have attempted to imitate the conditionsof their formation by heating glass and obsidian with water and czrbondioxide in a steel bomb lined with platinum-iridium. The bomb washeated in an electrical oven i n which i t could be shaken and inverted.On inversion a filtering arrangement came into action which enabledthem to examine separately the crystals deposited from the solution oncooling.The composition of the glass (I) and obsidian (11) was :-SiO,.A1,0,. Fe,O,. MgO. CnO. K,O. Na,O. H,O.1. 69’21 2.48 0’45 0.52 9-84 1-98 14*91 -11. 74’3 13.0 2.6 0.3 1 -00 4’6 3 .s 0’3The glass was completely decomposed on heating with water to 360°,and quartz crystals and some opal mere found to have separated fromthe solution. The residue in the tube consisted chiefly of amorphousZeii. p7iysikal. CIWIL., 1905, 51, 569.Centy. Aliia., 1906, 339, 353MINERALOGICAL CHEMISTRY. 303silica, together with tridymite and zt little quartz. The glass was alsodecomposed if the water contained small quantities of carbon dioxide,but if much was present the glass was less readily attacked.Obsidiantreated with water was more resistant than glass, but on adding sodiumbicarbonate decomposition took place and quartz was formed. Whenheated to 420’ with a solution of the composition of the quartzinclusions, obsidian was partially converted into a substance identi-fied with aegirine-augite. Zeolites were not observed in theseexperiments. Quartz, muscovite, and adularia were all more or lessattacked by water a t 350’, and dissolved completely when heated tothe same temperature with a 20 per cent. solution of sodium carbonate,carbon dioxide escaping from the tube, which mas not quite tight. Onthe other hand, water contailling both carbon dioxide and sodiumcarbonate had very little action on quartz, adularia, sphene, muscovite,biotite, calcite, or fluorite a t 370”.The action of alkali carbonatesfirst becomes considerable a t those temperatures a t which they arestrongly hydrolysed. The addition of carbonic acid diminishes thehydrolysis, and in consequence the action of the alkali. This is inharmony with the experiments of Spezia, who found that the action ofa solution of borax on quartz was diminished by the addition of boricacid. The most important conclusion arrived a t by t’he authors is thatin the system composed of silicic acid, alkalis, and a weak acid such ascarbonic acid or boric acid in aqueous solution, the deposition ofquartz can only be explained by a change in the equilibrium point ofa reversible reaction, the acidity of the silicic acid increasing withgreater rapidity as the temperature rises than it does in the case ofthe other weak acid present.They also point out that the simul-taneous production of quartz, tridymite, opal, and chalcedony is inharmony with van’t Hoff’s rule that high valence favours the existenceof labile compounds.The Silicic Acids.-G. Tschermakl and his pupils have carried outa good deal of new work on the lines described last year, and be!ievethat they have established the existence of several new silicic acids,and thereby thrown light on the constitution of a number of minerals.Ilvaite, anorthite, and olivine all yield rnetasilicic acid, H,SiO,, andmust therefore be regarded as metasilicntes. Willemite and monti-cellite are orthosilicates. Pectolite and wollastonite both yieldH6Si,0,, and wollastonite is therefore Ca,Si,O,.Meerschaum fromAsia Minor also gave an acid, H6Si,0,. Massive and foliatedserpentine and also chrysotile were found to have the compositionH,Mg,Si,O,, but whilst the latter gave an acid, Hl,,Si4013, the former1 W i e i i . Bilximgd~cr., 1906, 115, i, 217, 697 ; Amcigcr K. Aknd. 1Viss. lVie?~.,1906, 19, 339304 AKNUAL REPORTS ON THE 1'ltOGRESS OF CHEIIISTRP.gave H8Si4012, and the same substance was obtained from thepseudomorphs of serpentine after olivine from Snarum. Chrysotile istherefore to be written l€4(MgOH)4( MgOMg)Si,O,,, ancl serpentineH,(MgOH),Si,O,,. From datolite and gadolinite a new pulverulent acid,H,Si,O,, was obtained.Heulandite, taken to be H12CaA12Si6022, gaveail acid, H,,Si,017, and must be written H,(Cr202Al,0,H2)Si~O~7,H20,the bivalent group HOAlOCaOAlOII being present. They find, more-over, that heulandite lost calcium when exposed to the action of aconsiderable quantity of water, and therefore conclude thvtt i t wasprobably deposited from a concentrated solution.to the ex-periments of F. Zambonini on heulandite and on thomsonite, by whichhe attempted to throw light- on the vexed question of the part playedby water in these compounds. The conclusion to which he then camewas that these minerals are comparable to the hydrogels described byvan Bemmelen. H e has been confirmed in this view by his recentresearches,2 which have been conducted on lines similar to thosealready described.Thus he finds that the dehydration of, and thereabsorption of water by, gelatinous silica prepared froin potassiumsilicate follows much the same course as in the case of the zeolites.The amorphous nickel ore garnierite, (Mg,Ni)SiO,,nH,O, fromNoumea, New Caledonia, on the other hand, exhibits a very differentbehaviour from heulandite and thomsonite as regards its capacity forreabsorbing water after partial dehydration a t various temperatures.This substance is probably a solid solution, and it is therefore hardlylikely that the zeolites are to be regarded as having the same con-stitution. Further, he concludes that the water taken up again byzeolites after they have been heated is more loosely held than thewater originally present, and he bases this statement on the dehydra-tioii curves of the rehydrated zeolite. Lastly, observations made ondioptase lead him to the somewhat remarkable conclusion that in thecase of this mineral we meet with a n example of solid solution.The constitution of certain silicates has also been discussed byH. C.9tLN~i1,~ who, continuing the line of research begun byF. W. Clarke, has examined the behaviour of various minerals whentreated witli strong solutions of hydrochloric acid and sodiumcarbonate both before and after ignition. H e finds that talc whichhas been strongly heated contains one-fourth of its silica in a formsoluble in sodium carbonate, the residue being completely decomposedby hydrochloric acid. He concludes that talc contains both a n ortho-and a tri-silicate radicle, and that the latter on iguition turns into anSi,O, group.Yyrophyllite he regards as a true acid metasilicate.C'unstitution of Zeolites.-Reference was made last yearAWL. Ileprt, 1905, 271. " ilIem. 12. Bccnd. Liwcci, 1906, 6, 102.J. AVLLI*. ChciiL. SOC., 1906, 28, 590MlNERALOGICAL CHEMISTKY, 305The results obtained with kaolin accord with the supposition that it isan orthosilicate, HOAl(OSiO,H,)( OSiO,Al), converted, on heating, intoA1,Si,O7 and water. Halloysite on ignition also gives Al,Si,O,,and may be regarded as kaolin combined with one molecule ofwater. McNeil has also carried out some experiments on zeolites,on the lines of those made by Steiger, but instead of using sealedtubes he has fused the minerals with various chlorides in platinumcrucibles, As the result of experiments in which chabazite, stilbite,and thomsonite were fused with sodium chloride, he believes that thesesilicates belong to the same class and have the following generalformula :R"[XR"{ Al(X Al)(XH,*AlO,H,)j],.I n thomsonite X is chiefly SiO, in stilbite Si,O,, and in chabazite amixture of both these groups.iMutua1 Relations of Fused C'hZorides.-Some fresh light has beenthrown on the m'inerals of the cerargyrite family by the work ofK.Mi;nkemeyer,l who has studied the freezing point curves of binarymixtures of AgCl, AgBr, and AgI. These three substances melt at4 5 2 O , 422O, and 552' respectively. The two former crystallise in theholohedral class of the cubic system, but the iodide is dimorphous, thecubic form being stable above 1464", whilst below that temperaturethe substance forms hexagonal crystals.I n the case of the mixtureAgC1-AgBr, the freezing point curve is of type I11 of Roozeboom'sclassification. A continuous series of mixed crystals of the same kindis formed, and a minimum freezing point lying below the meltingpoint of the more fusible constituent is reached. The minimum 4 1 2 Owas found to correspond to the mixture containing 35 per cent. ofsilver chloride. The mixtures of bromide and iodide also conform totype 111, the minimum value of the freezing point being 37i0,corresponding to the mixture containing 73 per cent. of silver bromide.I n this case the phenomena are further complicated by the transforma-tion of cubic into hexagonal crystals conditioned by the presence of theiodide. This transformation falls under type IA of Roozeboom'sscheme, the mixed crystals forming a continuous series before andafter the change, only one component being dimorphous.I n the caseof the chloride and iodide mixture the freezing point curve is of typeV. The series of mixed crystals is interrupted, and a eutectic occurscontaining 42 per cent. of silver chloride and solidifying at 211". Thechloride is only capable of taking up very small quantities of iodide,while the latter will mix with as much as 13 per cent. of chloride. Thetransformation into hexagonal crystals conforms to type III'A. Theview suggested by L.J. Spencer's study of miersite, that silver iodideJahrb. 2cl.i.l~. 1906, Bed-Bd,, 22, 1.VOL. 111. 306 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.is trirnorphous, has not received any confirmation from these experi-ments.Water of Crpta1Zisation.-The difficult question as to the manner inwhich the elements of water are cpmbined in minerals has beenattacked by W. W. Cobientzl in an ingenious way. The infra-redabsorption spectrum of water exhibits well-marked bands at theapproximate wave-lengths 1.5, 2, 3, 4.75, and 6p, those at 3 and a t 6being especially strong. Coblentz has therefore examined a largenumber of minerals to see if those containing so-called “water ofcrystallisation” show the water bands. I n the case of selenite,CaS0,,2H20, he found that these bands were strongly marked, withthe exception of that a t 4.75, the place of which was taken b y a strongband at 4.55.Anhydrite, CaSO,, on the other hand, did not show thewater bands, although in this case d s o the band at 4.55 mas prominent.This band was subsequently found t o be well shown by anglesite,barytes, and celestine, as well as by glauberike, kieserite, andthenardite; it is doubtless due to the SO, ion. Opal, heulandite,stilbite, natrolite, and scolecite all showed the water bands. Onexamining hydroxides the water bands were found to be wanting, withthe exception of that a t 3, which appears to be characteristic of thisclass of substances, This wits found to hold for manganite, gothite,bauxite, turquoise, lazulite, hydrargyllite, and diaspore.I n the case ofdatolite and azurite the band a t 3 was slightly displaced, while brucitcexhibited a complex band with maxima a t 2.5, 2.7, and 3. Tourmalineshowed bands at 1.28 and 2.82. The examination of chloritoid,clinochlore, pennine, the micas, and talc revealed no indication of thepresence of hydroxyl. On the other hand, this group probably existsin serpentine, which shoms a well-marked band a t 3p.Ne w ilii n e r CL Z s.BeZZite.-This mineral has been described by W. F. Petterd.2 Itoccurs in delicate tufts and velvety coatings lining cavities in a softiron-manganese-gossan at Nagnet silver mine, Magnet, Tasmania.Minute hexagonal scales are sometimes met with. The colour is brightcrimson to orange-yellow. Sp.gr. 5 . 5 .The following analysis is by J. D. Rlillen :8i0,. PbO. C1.0;;. SO,. As,O,. Y205. TzO,. A1,0,. C1. Total.(’09 61.6s 22.61 0.05 6.55 0.04 0.11 0.01 0.52 99.16Cl~Zo~)izaizganoh.aZite.-A preliminary account of this mineral hasbeen given by H. J. Johnst~n-Lavis,~ who found i t in the form ofcanary-yellow rhombohedra associated with halite inside a block ejected8-rI Pl~ysiunl X e x i c u , 1906, 23, 125.TaPmniiin.Noltcrc, 1906, 74, 103.IZcpovt of Xecmkwy for J1iite.c .fw 1904. Hobrirt, 1905. 83.See also A. l m r o i x , L‘o?i~pL. T W ~ . , 1906, 142, 1249MINERALOGICAL CHEMISTRY. 30'7from Vesuvius. Analysis shows that the mineral is essentially adouble chloride of manganese and potassium containing 38.97 per cent.of MnCl,,dH,O and 57.71 per cent.of KCI.ChZornatrokalite.--This name has been given by Johnston-Lavis l toa sylvite containing 12 per cent. of NaCl, found associated withchlormanganokalite.It occurs in brownpebbles, so-called "favas," in the diamond sands of Brazil, and hasbeen described by E. Hussak.2 Omitting silica (present as includedquartz grains), ferric oxide, and TiO,, the two following analyses byG. Florence lead t o the formula Ba0,2A120,,P,0,,5H,0, a portion ofthe barium being replaced by calcium and cerium, and occasionally bystrontium :SiO,. TiO,. BnO. CaO. G O . Al,O,. Fe,03. P,O,. H,O.1. 1 5 5 0.67 15'42 3.55 1-55 35.00 4.10 22'74 14.6211. 6.5 0.75 15.30 2.24 2.35 35'20 1.67 21.47 14'73Harttile.-E. Hussak has assigned this name t o a strontiumnluminium sulphato-phosphate found in flesh-coloured '' favas " in thediamond sands of Brazil.The mineral is related to svanbergite,SSr0,3A1,0,,P,0,,2S03,6 H,O, and has been analysed by G. Florence,with the following results :TiO,. A1,03. SrO. CaO. CeO. P,O,. SO,. H,O.1'42 33-66 16.80 2.80 1.02 21.17 11'53 12'53These numbers lead to the formula (Sr,Ca)0,2A1,0,,P,0,,S03,5H,0.lfyclrated Calcium CaTbonak-A deposit from the neighbourhoodof Novo-Alexandria, looking much like mould or a thin layer ofcotton-wool, has been examined by L. L. Ivanoff,* who finds that itconsists of very thin, colourless, transparent, monoclinic or triclinicneedles. When kept over calcium chloride a t 22", it loses 37.56 percent.of water, leaving practically pure calcium carbonate behind. It isto be regarded as a hydrate, CaCO,,nH,O, where n, is not less than 3.I~ertschenite.-At one or two localities in the Kertsch Peninsulathere is found a dark green or almost black mineral. The formula(Fe,Mn,TYfg)O,Fe,O3,P2O5,7H,O has been given to it by S. P. Popoffon the ground of the two following analyses :P,05. FegO,. FeO. MnO. MgO. CaO. H,O. Total.28.19 32-89 9-50 1'99 1-54 0.49 25.04 99'6428'21 32'965 9'19 1'84 1-56 0'46 24.91 99'435itTew Mercury JfiiLeraL-In 1903 A. J. Moses described two newmineral species, eglestonite and terlinguaite, both oxychlorides ofmercury, from the Terlingua district, Texas, and indicated the probableexistence of a third. The last is now under investigation by W.F.Gorceixite is a barium aluminium phosphate.Ncttzsrc, 1906, 74, 174. TscI". X i 7 t . dfttt., 1906, 25, 335.3 Ibid.) 335. Ann. Geol. Mfi?. RICSSZ'P, 1906, 8, 23.CCdI~, illill. IOOC,, 112.Y : 308 ANNUAL REPORI'Y ON THE PKOGKESS OF CHEMISTRY.Hillebrand and W. T. Scha1ler.l The preliminary examination hasrendered i t almost certain that this remarkable substance is a mercur-bmmonium salt. It has so far been shown to contain Hg,N,CI,SO,,probably 0, and possibly H. Further, P. G. Nutting has found thatit gives off a little helium on warming. The full account of this asyet unnamed mineral will be awaited with interest. I n the mean-time we may note that A. Sachs has suggested that the oxychlorideof mercuxy, 3Hg0,HgC12, described by him last year under the nameof kleinite, may be identical with the substance referred to by Hille-brand. He finds, in fact, that both the sulphur-yellow and the orauge-red varieties of kleinite yield small and variable amounts of SO, andammonia, and he suggests that a portion of the chlorine in the aboveformula is perhaps replaced by SO,, whilst oxygen is substituted byNH,.If these views are accepted, the formula of kleinite becomesMoravite.-Under this name F. Kretschmer 3 has described a newinember of the leptochlorite family, found i n considerable quantity inthe neighbourhood of Gobitschau, near Sternberg, Noravia. It occursin scales and lamells, iron-black in colour, and in physical charactersand mode of occurrence it somewhat resembles thuringite, from whichit may be distinguished by its superior hardness and lower specificgravity, as well as by its different composition.The results obtained onanalysis of two different carefully selected specimens were as follows :Si02. A1,0,. Fe,O,. FeO. CaO. MgO. K20-i-Na20. P20,. C. H,O.I. 49-30 22-71 5'04 13.99 trace 1-82 1.10 trace 0'55 4.9511. 50.69 19'62 10'42 8.30 0.84 1.46 ( 1 ) 0.93 ( 1 ) 5.02The otherHg,[ ClA so41 2P(NH,),I 3From I is derived the formula H,(A1,Fe),(Fe,Mg),Si7024.members of the group found at Gobitschau are :Thuringite, H,8(Al,Fe),(Fe,Mg),Si,0,,.Stilpnochlorane, H,,(A1,Fe),o(Ca,Mg)Si,046.Stilpnomelane, HI2( Al,Fe),(Fe,Mg)8Si,,0,7.Nepouite.-Under this name E. Glasser has recently described amineral somewhat resembling Breit haupt's connarite.It occurs inthe form of a crystalline powder a t NQpoui, New Caledonia. Fivedifferent specimens have been analysed, and the results quoted beloware in harmony with the formula 2Si0,,3(Ni,Mg)0,2H20, nickel andmagnesium being mutually replaceable in all proportions :SiO,. KO. IigO. FcO. CaO. Al,O,. H20. Total. Sp. gr.I. 32'84 49.05 3'64 1.90 0-50 0.97 9'64 9854 3'2411. 33.03 46-11 6-47 2'20 traces 1-39 10'61 99'81 3.18111. 35'05 39.99 11-80 1.22 0.58 1.13 10.05 99'82 2.89IV. 40.07 18.21 29'84 0-25 0.53 0.72 11-98 101.60 2'47V. 32.36 50.70 3.00 0.62 traces 0.69 12'31 99-68 3.202 Centr. illin., 1906, 200.4 Coiizpt. re?zd., 1906, 143, 1173.1 A ~ z c r . J. Sci., 1906, [iv], 21, 85.3 Ibicl., 293MINERALOGICAL CHEMISTRY.3090elwnite.-The formula 6Si02,6(1sIg + Fe, Ca)O, H,O has been givenby E. S. Fecloroff to a mineral of the following composition :SiO,. A1,0,. Fe,O,. FeO. MgO. CaO. Na,O. K20. H,O.49.47 6.74 0.25 6'33 16'80 17.74 0.38 0.18 2-41It occurs in the Jenashir district of the Caucasus and somewhatresembles diallage in appearance. It has three rectangular cleavages,(loo), (010): (OOl), the latter being highly perfect, but crystallises inthe monoclinic system as shown by the optical characters. The opticaxes lie in the plane of symmetry, the acute positive bisectrix makingan angle of 55' with the normal to (001).Osannite is a variety of amphibole, intermediate between riebeckiteand arfvedsonite, and is found in the gneissic rocks of Cevadaes,Portugal.The optical characters have been determined by C.Hlamatsch,2 who points out that in the amphiboles these propertiesvary with the ratio A1,03 : Fe203, and also possibly with the amount ofwater present.The aagle 2Vis 63.The following analysis is due to M. Dittrich :SiO,. Ti02. A1,0,. Fe,O,. FeO. MnO. MgO. CaO. Na,O. Ii,O. H,O, Total.49.55 0.34 0.97 16'52 20.38 1.30 0.16 0.90 6'53 0.85 1.85 99.35Otuvite is a basic cadmium carbonate containing 61.5 per cent. ofcadmium, found by 0. Schneider3 as white to reddish crusts liningcavities on two specimens from the Tschumeb mine, Otavi, GermanSouth-West Africa. The crusts consist of minute rhombohedra( r ~ ' = 80' about), which dissolve with effervescence in hydrochloricacid, and exhibit a metallic to adamantine lustre.Parutmamite.-G.F. Herbert Smith4 has proposed this name fora mineral of the same composition as atacamite, CuC12,3Cu(OH),,which he has observed on some specimens from Chili. The crystalsare of two habits, namely, rhombohedra1 and prismatic. They arefrequently twinned, and have a good cleavage parallel t o the rhombo-hedron faces. The specific gravity is 3.74. The refractive index,1.846. On heating the mineral it appears to give up its water rathermore readily than .does atacamite. According to G. T. Prior, thecomposition is :CnO. CU. c1. Ergo.56'10 14-27 15.97 14'10Pc~~~vivianite.-Radiating needle-like crystals, transparent andsomewhat blue in colour, occur in the limonite ore of the KertschPeninsula. The formula (Fe,Mn,Mg),P,O,,SH,O has been found byGorni Jozmtnl, 1905, 264.Festschrift Harry Rosedusch, Stuitgns.i, 1906, 68.3 Centr. Miqt,, 1906, 389.Illin. Mag., 1906, 14, 170310 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.S. P. Popoff 1 to agree well with the analytical results.is present.No ferric ironP,O,. FeO. MnO. MgO. CaO. H20. Sp. gr.27-01 39'12 2.01 1.92 0.48 29-41 2'66Patronite.-Under this name F. Hewett 2 has recently described adark green substance containing vanadium, which appears to occur insome quantity at Cerro de Pasco, Peru. A specimen of the crude oremas found to contain 16 per cent. of vanadium and 54 per cent. ofsulphur, with considerable quantities of silica, alumina, and iron. Itis a t present undergoing examination at the hands of Dr.Hillebrand.Rutherfordine.-This interesting mineral occurs associated withmica in German East Africa, and is an alteration product of pitch-blende. The following analysis by W. Marckmald 3 shows that it isuranyl carbonate, UOz,CO,. I n appearance it resembles uranochre.UO,. CO,. PbO. FeO. CaO. H20. Gangue. Total. Sp. gr.83.8 12.1 1.0 0.3 1'1 0.7 0.8 100.3 4'82XiZicomagnesiojuorite.-This curious mineral has been found as aloose block composed of radiating hemispherical aggregates, grey orgreen in colour, at Luppiko, in the neighbourhood of Pitkiiranta,Finland. It has been examined by P. A. Zemjat~chensky,~ who assignsto it the formula H2Ca4Blg,Si,0,F,o, which he thinks may also bewritten in the form Mg( OH)F,RiIgSiO,,Ca( OH)F,CaSiO, Fz,2 CaF,,MgF,,The fibres show straight extinction and weak positive double refrac-tion.Weinberyerite.-In the course of an examination of the Kodaikanalmeteorite, F.Berwerth5 has found a new silicate in the form ofspherules exhibiting fibrous structure, associated with diopside.bronzite, apatite, and chromite. It appears t o crystallise in theorthorhombic system, and its refraction and double refraction areboth very low. There is reason to believe that it is pseudomorphous.According t o E. Ludwig, the composition is :SiO,. TiO,. P,O,. Fe,03. A1,0,. Cr,O,. h l n 0 . CaO. MgO.42.0 0.70 0.SS 28.75 9'42 0 98 trace 3.87 4'47K,O. Nn,O. II,O. Total.2.57 3-19 2.17 99.0If we assume that the iron was present as FeO, that the wateris not essential, and that P,O, and Crz03 are due to the presence ofapatita and chromite respectively, it will be found that the compositioncan be represented by the formula NaAlSiO, + SFeSiO,, some of theThe specific gravity is 2.9125 at 20".1 Ceidr.Min., 1906, 112.3 Centr. Min., 1906, 761.a Engin. illi-niqg Jom-., 1906, 82, 385.* Zeit. Kryst. Min., 1906, 42, 209,Txh. Mia. JliLt,, 1906, 25, 179MlNERALOGICAL CHEMISTRY. 311sodium being replaced by potassium, and some of the iron by magnesiumand calcium.Ytti*ocaZcite.-A mineral described under this name by E. S. Fedoroff 1in 1905 has proved on further investigation to be identical with fluor-apat ite.2Ytlrocrasite.-This name has been assigned by W. E.Hidden andC. H. Warren a to an yttrium-thorium-uranium titanite. The materialfor analysis was derived from a single crystal weighing some sixtygrams, found about three years ago in Burneb County, Texas, whsrrethe mineral occurs in loose pegmatite. The crystal exhibited ortho-rhombic symmetry and resembled certain yttrotantalites.It was covered with a thin brown costing., the underlying materialbeing black with pitchy lustre. Optical examination of thin slicesshowed that it was not strietly homogeneous, but consisbed of istropicand of feebly doubly refracting portions. Thefollowing are the results of Warren’s analysis :Sp. gr. 4.8043 a t 1 7 O .TiO,. IVO,. UO,. CO,. (Yt,Er)203. Ce,O,, &c. Fe,O,. Tho,. UO,.49-72 1-87 0.64 0’68 25-67 2 92 1.44 8-75 1.98PbO.BInO. CaO. H,O. Total.8-48 6-13 1.83 4’46 100.57A small quantity of Cb,O, together with traces of Ta205, SiO,, and>$gO,were also found, and of the water 0.10 per cent. was hygroscopic.These numbers give the following approximate molecular ratios :H,O : R O : R”’20, : R””O, : TiO, = 6 : 1 : 3 : 1 : 16, where R O is chieflylime, R”,O, chiefly yttrium earths, and IC’”’O2 chiefly thoria. Themineral is therefore essentially a hydrous titanate of the yttriumearths and thorium, but the fact that it contains both water andcarbon dioxide, taken in conjunction with the results of the micro-scopic examination, suggests that i t may be a hydrated alterationproduct of an originally anhydrous species. The radioactivity of thesubstance has been determined by B.B. Boltwood, who finds that itcorresponds t o 10 per cent. of thorium and 2-08 per cent. of uranium.A New Zeolite.-A. Pauly4 has examined the minute grainsscattered through a quartz-sericite rock which occurs in the neighbour-hood of Hainburg. H e finds that they are isotropic and possess a goodcleavage parallel to faces of the cube. The index of refraction is1.507-1-508 for sodium light, and is therefore higher than that of anal-cime. Microchemical tests showed the presence of Na, Ca, Si, Al, andSO,. About 10 per cent. of water was driven off on heating., provingthat the mineral is not a member of the sodalite group. The specificgravity is 2.4-25. The author has been unable so far to obtainPrivate eo~nmzsirication from E.S. Fedoioff.Zeil. Kryst. Min., 1906, 42, 370.1 Borni Journal, 1905, 264.3 Amer. J. Sci., 1906, [iv], 22, 515312 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.sufficient material for a quantitative analysis, but thinks that hisresults justify him in concluding that the mineral is new.ArtiJcicd Pownation of Minerals.A number of cases of the artificial production of minerals have beenmentioned incidentally in a previous section, but R few special experi-ments deserve a separate description here.Diamond.-A useful summary of the attempts that hare been madeto obtain this form of carbon has been contributed by A. Koenigl tothe pages of the Zeitschrift f u r EZektrochenaie.obtained Mg,SiO, as a by-productwhen MgSiO, was dissolved in fluxes and allowed to crystallise.Thebest specimens were furnished by magnesium chloride. The crystalswere small, but gave fairly sharp measurements, and agreed in habit,angles, and physical characters with the natural mineral. Periclasewas also observed in some of these experiments in well-formedoctahedra.Nordensll;ioZclite.-Minute but measurable rhombohedra of this sub-stance, CaO,SnO,,B,O,, have been obtained by L. Ouvrard by passiDga mixture of air and stannic chloride vapour over calcium borate a t abright red heat.Northupite, 2 ZMgCO3,2Na2CO3,2NaCl, is probably isomorphous withtychite, 2MgC0,,2Na2CO,,Na,SO,, described by Penfield and Jamiesonlast year. To throw light on this point, A. de Schulten4 has at-tempted to prepare mixed crystals of the two substances.I n this hehas been successful, for by heating mixtures of the chloride andsnlphate of sodium in various proportions with 20 grams Na2C03 and18 grams Mg2S0,,7H,0, dissolved in 350' C.C. of water, he has obtainedcrystals containing 99, 76, 64, 28, and 6 per cent. of tychite re-spectively. He concludes, therefore, that the two substances are'perfectly isomorphous.Quartz has been produced in measurable crystals by Day andShepherd 5 by heating a mixture of ammonium magnesium chloride,sodium metasilicate, and water for three days in a steel bomb at40O-45Oo. The clear, colourless crystals attained a maximum lengthof 2 mm. They were doubly terminated and often barrel-shaped,showing rhombohedron faces passing by oscillatory developments intosteeper rhombohedra, and finally into the prisms which showed thecharacteristk! striae.I n some the + rhombohedron only was present.The angle from prism to rhombohedron was 37'48' instead ofAnter. J. Xci., 1906, [iv]. 22, 390.Forsterite.-Allen and Wright1 &?it. Elcktrochem., 1906, 12, 441.3 Compt. rend., 1906, 143, 315. Ibid., 403.5 Amer. J. Sci., 1906, [iv], 22, 297MINERALOGICAL CHEMISTRY. 3133S013’, this being perhaps due to some ingredient of the mixture heldin solid solution.Some interesting experiments on the crystallisation of quartz havealso been carried out by G. Spezia.l He suspended a long crystal andthree short prisms of quartz cut perpendicular to the axis in thelower portion of a tube containing a 2 per cent.solution of sodiummetasilicate which was kept a t a temperature of about 330’ a t theupper end, whilst the lower end remained a t about 170’. The upperpart of the solution wits in contact with a quantity of powderedquartz. After heating for one hundred days, it was found that aquantity of silica had dissolved arid had been deposited again on theprisms, converting them into more or less perfect crystals. The longcrystal had also increased in size. It was observed that quickcrystallisation appeared to favour the development of a long prismterminated by the faces of one rhombohedron. Slow crystallisation,on the other hand, gave a short prism terminated by the faces oftwo rhombohedra.Mineml Analyses.Many mineral analyses have been published during the past year.I t is only possible here to refer very briefly to some of those whichhave thrown light on the composition of rare or imperfectly describedspecies, or which are of special importance, because made on carefullyselected material of which the crystallographic and physical charactershave also been determined, For the rest, reference should be madeto the Abstracts published by this Society.Apatite.-Crystals from the Rhone glacier have been the subject ofan elaborate crystallographic and optical study by K.Busz.2 Hefinds a : c = 1 : 0.7335, and that for sodium light, W = 1.63558,~=1-63320. A second prism gave slightly different values. Theanalysis quoted below shows that the substance is a pure Auor-apatite.1’?O5. A1,0,.MnO. CaO. MgO. K20. Na,O. H,O. F. Sp. gr.41’44 0-94 0’39 54.80 0.14 0.45 0.53 0.22 2.93 3.195Traces of iron and chlorine were found.Apo,vl~ylZite.-In a preliminary communication F. Cornu 3 announcesthat the extreme members of the leucocyclite type of apophyllite are freefrom fluorine, but contain hydroxyl ; the specimens of the chromocyclitetype, on the other hand, contain fluorine. The former are opticallypositive and possess higher indices of refraction than the latter, whichare negative.Berthierite.-This mineral occurs in some quantity at Charbes, Val1 Atti R. Accnd. Sci. Toriiko, 1906, 41) 158.Ibid., 79.Centr. illin.) 1906, 753314 ANNUAL REPORTS ON THE PROGRESS O F CHENISTRY.de Till6 (Weilerthal), Alsace.gave the following results :A specimen analysed by UngemachS.Sb. Fe. As. SiQ2. Total. sp. gr.28-02 54.06 12'72 traces 5.29 100'09 4 '2 l e 4 '23On subtracting the silica, aumbers are obtained which agree wellwith the formula FeS,Sb,S3.Boleite Group.-G. Friedel 2 has published a comprehensive aceountof this group, based on an examination of specimens preserved at thegcole des Mines de Saint-Etienne, supplemented by some from thelhole des Mines de Paris. He has also been able to study Mallard'smicroscopic sections a u d some of Lacroix's preparations. He recog-nises three distinct species in the group, namely, cumengeite, pseudo-boldite, and boldite. All three cryetallise in the tetragonal system,and their chief properties are summarised below :Cumengeite ......4PbC12,4Cu0,5H@ ............ 1 *625 4.67 0'100Eoleite ............ 9PbCl2,8Cu0,3A~0l,9H~O ... 3'996 5.054 0-020Name. Formula. Parameter c. Sp. gr. Birefringence.l'seudo-boleite ... 5PbCI2,4Cu0,6H,O ............ 2'023 4 *85 0 -03 2The above formulre differ considerably from those hitherto assignedto members of the group, and are based on the following analyses, ofwhich I refers to cumengeite, I1 t o pseudo-boleite, I11 gives the com-position of pseudo-boleite on the assumption that the silver chloride pre-sent is due to admixture with boleite ; IV is the mean of two concordantanalyses of boleite made, one on material derived from the exteriorof the crystals, the other on material from the interior. Under In,IIIa, and IVa are given the theoretical percentages corresponding withthe formuls.As the analysis of pseudo-boleite was made on 0.0948gram only, and as the water yielded by this substance could only beobtained by calculation from an estimation made on a mixture ofboleite and pseudo-boleite, of which the composition was butapproximately known, the formula assigned can only be regarded asprovisional.I. Ia. 11. 111. IIIn. IV. IVn.C1 .................. 19.03 37.13CuO ................. 20'27 20.93 16 5 16.9 17.51 17.18 17'05H,O .................. 5-90 5'93 [5*5] 5.5 5.97 4.35 4.35AgCl .................. - - 1.6 - - 11-59 11.54Breunnerite.-Large rhombohedra have been observed by G. PioltiPb ..................... 54'47 z!:: ). 77.5 76.52 { f;::: 49*930.23 - - Residne ..............0.19 - 0.8 -in serpentine near Avigliana.angle is 72O29'42", whence c = 0.808642.Bzlll. Soc. franc. Min., 1906, 29, 266.The mean value of the rhombohedronThe ordinary index of re-Ibid., 14.3 Atti €2. Aecad. Xci. Torino, 1906, 41, 106631 IN ER A LOG I C A 1, C HE MI STRP , 31 5fraction determined by the Duc de Chaulnes's method is 1,715. Thecomposition is 90.47 per cent. MgCO, and 9.45 per cent. FeCO,.Traces of manganese are present, but no calcium. A specimen from theSylvester mine, Val de Villk, analysedj by Ungemach,l contained 3.1 0per cent. CaCO,, 35.08 MgCO,, 61.25 FeCO,, whilst another specimenfrom the same mine contained 58-65 per cent. CaCO,, 25.47 per cent.MgCO,, and 21.85 per cent. FeCO,, and is therefore ankerite.Two specimens from Frigido, near Massa, analysed by E.Rlanasse,2contained respectively 46.30 and 55.09 per cent. of FeO with 12-18 and5.94 per cent. MgO. The former corresponds to 2FeCO,,RlgC'O3,the latter to 5FeC0,,MgC03.Two other specimens from Bottino, Tuscany, examined by the samen n n l y ~ t , ~ had a composition agreeing with the formula 3FeCO3,I!tgCO,.Caherite.-A measurable crystal found on a specimen from Lauriunihas enabled A. Sachs4 t o determine the constants of this mineral.H e finds that i t is monoclinic, a : b : c = 0.82386 : 1 : 0.77673 ;p=106"29'. The composition of the apple-green crystals is asfollows :As,O,. KiO. COO. FeO. MgO. H,O. Total. Sp. gr.40.45 26.97 trace 1.10 6'16 25% 99.94 3T)104The mineral is isomorphous with erythrite, though the similarity ofangle is not very close.Calcite.-In the course of an interesting investigation into the causeof t h e perbistent phosphorescence exhibited by certain specimens ofcalcite from Fort Collins, Colorado, and from Joplin, Missouri, W.P.Headden 5 has made a very careful analysis of the well-known yellowcrystals from the latter locality. The results are as follows :SiO,. CO,. CaO. MgO. MnO. FeO. ZnO. Ce,O,.0.032 43.950 55,740 0.113 0.045 0'046 0.014 0.007(Di,Sm, La),O,. (Yt,Er)&.0.012 0.012Traces of SO,, P,O,, C1, SrO, A1,0,, Cr203, NH, and Na,O were observed,but no hydrogen sulphide could be detected, and of the gas evolved ondissolving 100 grams of material, all but 10 C.C.was absorbed by causticpotash. The author is inclined to attribute the remarkable phosphor-escence t o the presence of some member of the yttrium group. Speci-mens OP other colours are found with the yellow ones, and those ofBull. Soc. franq. Min., 1906, 29, 279.Men&. ,!70c. Tosc. Sci. Nat., 1906, 22, 81.3 Proc. verb. SOC. Tosc. Sci. Nut., 1906, 15, 20.5 Airier. J, Sci,, 1996, [iv], 21, 301.Ceittr. Min., 1906, 198316 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.purple tint exhibit the absorption bands characteristic of didymia, butnone of them shows the persistent phosphorescence.Celestine.-A dolomite containing considerable quantities of celestineis found at the Woolmith quarry, near Maybee, Monroe CountyMichigan. Fine crystals of the mineral are met with i n cavities in therock, and have been the subject of crystallographic and chemicalexamination by E.H. Kraus and W. F. Hunt.l Axial ratio a : b : c =0.7'781 : 1 : 1.2673. Analysis of clear, trans-parent crystals gave the following result :Sp. gr. 3.979 a t 20.5'.so,. SrO. BaO. " 0 . CaO. (Al,Fe),O,. SiO,. Total.43'58 53.75 1-26 0'1'2 0.4.5 0.15 0.22 99-5343.60 53.78 1-32 0'14 0'47 0'13 0.23 99'67Clzalnaersite. -E. Hussak,2 having received a fresh supply of thismineral from the St. John del Rey mine, has been able t o place 0.0896gram of pure material in the hands of G. Florence for n new analysis,the first having .been made on 0.016 gram only. The results quotedbelow lead to the formula CuFe,S, or Cu,S,Fe,S,.Fe. cu.S. Total.43-13 22'27 35.11 100.51Clintonite and Chlorite Group-E. Manasse has analysed ftcldoritoid (I) from Strettoia, Alpi Apuane, two specimens of ripidolite,from Calci (11) and Verruca (111) respectively, and a clinochlore fromAffaccata (IV). The results are given below :S O 2 . TiO,. Al,03. Fe,03. FeO. MgO. Ka,O. H,O.I. 25.70 0.59 30.95 - 23.44 6.12 - 6.3111. 26-14 - 23.65 - 18.38 19.48 0.5G 11.9321'80 - 28.08 12.82 trace 21.64 111. 24.93 -34.07 -- 12.86 IV. 28.95 - 21'41 3.12 -I n analysis I water was determined by ignition loss, and the iron allcalculated as FeO, although Fe,O, mas also present.DatoZite.-A valuable contribution t o our knowledge of this mineralhas been made by E. H. Kraus and C. W. who have examinedthe excellent crystals found at Westfield, Massachusetts.Thesecrystals are rich in faces, and exhibit monoclinic symmetry with thefollowing constants, a : b : c = 0.63482 : 1 : 1.26567 j p = 90'9'. Carefuldeterminations of the specific gravities of four crystals gave a meanvalue of 3.0058 a t 21.5'. This composition is accurately expressed bythe accepted formula HCaBSi05. Analyses I1 and I11 below weremade on material derived from a single crystal. Under I is giventhe theoretical composition. Crystals of this mineral found at the1 Amw. J. Sci., 1906, [iv], 21, 237.3 Proc. verb. Xoc. Tosc. Sci. Nnt., 1906, 15, 20.4 Airier. J. Xci., 1906, [iv], 22, 21.Ccntr. illis., 1906, 332MINERALOGICAL CHEMISTRY. 317Colebrook mine, Dundas, Tasmania, have been measured by C.Anderson,l who finds that they have the composition given under IV.SiO,. Fe,O,.A1,0,. CaO. MgO. R,O,. H,O. Total.I. 37-63 - - 34.95 - 21-81 5'61 -11. 37.60 0.10 0.14 34-64 0.32 21'76 5.67 100.23111. 37'58 0.10 0'16 34'74 0.31 21.94 5.76 100.59IV. 36.28 0.95 35.21 - 20.48 6'48 99-40Bzcnclasite occurs in white spherical aggregates or in tufts of radiat-ing silky needles associated with allophane and cerussite at WelshFoxdale Mine, Trefriw, Carnarvonsbire. G. T. Prior 2 finds that theanalytical results suggest the foriiiula, PbO,A1,O3,2C0,,4H,O :YbO. AI,O,. Fe,O,. (20,. H,O> 100". H,Oat100". Iiisol. Total. Sp. gr.43.20 21.39 1'61 16.45 13.60 1.41 1.80 99.46 3'25The Welsh mineral is like that from Tasmania, and shows a relation todawsonite, Na,0,A1,03, 2C0,,2H20.Fho&e.-h the course of an elaborate study of fluorescence,H. NT.Morse3 has examined the composition of the gases given offwhen fluorite is heated. I n the case of specimens from Weardalethese consisted chiefly of carbon monoxide, carbon dioxide, hydrogen,and nitrogen, with small quantities of oxygen, The two latter werenot present in the proportions i n which they occur in air, and no argonor helium was found, He concludes that the gases are due t o thedecomposition of some organic colouring matter, but that there isnothing to show that organic substances have anything to do with thefluorescence or thermo-luminescence of the mineral.Gccrizet.-The chemical composition and optical constants of a numberof garnets have been determined by AT.Seebachm4 His results aretabulated below :vI. Qrossular from Xalostoc, Mexico. Pink dodecahedra.IT. Pyrope from Colorado River, Arizona. Blood-red masses.Dark, wine-red grains.Irregular, dark-red fragments.111. Pyrope from Meronitz, Bohemia.IV. Almandine from Ceylon.VI. Melanite from Frascati.Brown-red to wine-red grains.Well-developed, black crystals.V. Alinandine from Jeypoor.VII. Andradite from Dognaczka. Green crystals.VII I. Demantoid from Polemskoi-Zawod, Urals. Rolled masses.Si02. TiO,.I. 4079 -11. 43.37 -111. 42.98 -1 v . 37'25 -V. 38-07 -VJ. 34.74 1-54TII. 36'79 -YIII. 35.37 -A1,0,. Cr,03.21-70 -20.99 2-3621.34 2.0619.43 -19-63 -5'43 -1'39 --1-54 1-32Fe,03.FeO.0.18 0'43- 10'210.95 7-803'29 35.452.16 31'5821.95 1'9929'30 0.6925-89 0'52MnO. CaO. hIg0.1.07 35-63 0-390.52 4.54 18.420-50 4-47 20.671'24 2'51 1'131.36 5'03 2-770.65 32'58 1.480.26 31-40 0.770'34 32-26 0.21Total.100.19100'411 0 0 * i i100 -30100'601 O O 3 i100.60100.45Bcc. AiLstmliaii Miis., 1906, 6, 133.Proc. Aii~er. Accid., 1906, 587. lnnug. Diss. Xcidelberq, 1906.Min. Mag., 1906, 14, 167318 ANNUAL REPORTS ON THE PROGRESS OF CHkMISTRY.All the above are the mean of two concordant analyses, with theexception of VI, which is the mean of four analyses. The mineralswere decomposed by fusion with anhydrous boric acid, and the analysesconducted by the methods developed by Jannasch and his pupils.I n the following table are given the specific gravities and opticalconstants of the minerals before fusion, the specific gravities andindices of refraction for sodium light (so far as the latter could bedetermined) after fusion, and the proportion of the fused mineralsoluble in hydrochloric acid.The molecular ratios cztlculated fromanalyses 111, V, and VII agree fairly well with those required by thegarnet formula R”3R”2Si3012, but diverge considerably from thetheoretical values in the case of analyses IV, TI, and VIII.After fosion./-- ---KO. sp. 6’.I. 3.50611. 3’715IJI. 3.679IV. 4.040Ti. 4.026v1. 3.774T1I. 3.660VIII. 3.801Before fnsion.- -.hi____pLi. pxa.1.7319 1.73641.7371 1’74171‘7417 1.74631’7724 1 *77791.7763 1.78151.8471 1.85601.8763 1’88781.8767 1.8884PT1.1’74111 *74631.75051.78251.7862136581.89901.8999sp. gr.2.8663’1903.2513.0093‘2403.2633.1713.335Percentagesolublepsi$. i n HCI.1-6205 all828472741.7667 971.8177 all1.8110 99----A few other analyses of garnet may also be recorded here.OF theseI refers to a bright red spessartite from KgrarFvet near Falun, analysedby C. Benedicksl; I1 gives the composition of a brown variety fromthe same locality ; these garnets are interesting because they containan appreciable quantity of yttria; 111 is a dark brown garnet foundin pegmatite a t Yamano, Hitachi Province, Japan ; I V occurs in brown-red crystals in mica andesite at Anamushi, Yamato Province.Theanalyses were made by Shimizu.2SiO,. A1,03. Yt,O,. FeO. MnO. CaO. IlgO. Total. Sp. gr.I. 35-67 22.50 1-19 19‘17 21-91 traces - 100.44 4‘19711. 35.36 22.34 1’23 22.01 18-80 traces - 99.74 4.068111. 36.39 23-05 - 24.77 14-21 1-57 0.67 100‘66 -IV. 36-74 20.71 - 34‘91 1.67 2.11 3.27 99’41 -GeikieEite.---A number of specimens of ferro-magnesian titanatesfrom Ceylon, including the original geikielite (analysis I below), havebeen examined by T. Crook and B. M. Jones.3 They find that thismineral contains a greater percentage of iron than was a t first recorded,and they suggest that the formula should be written (Mg,Fe)Ti03.The analyses 11 to X indicate a passage to picroilmenite, the com-position of the latter being given under XI and XII.E ~ l l .Beol. liist. Uitiv. Upsnln, 1906 (for 1904-5), 7, 271.Beitraigc 2. Xin. Japnx, 1906, No. 2, 53. Mi)/, ilIq., 1906, 14, 160MINERALOGICAL CHEMISTRY. 3191. 11. 111. IV. r. VI. VII. V l I I . IY. x. XI. XII.TiOz ... 63.77 64.41 64.78 60.02 60's; ClMl F2.25 li3.94 64.03 63'49 57'64 56.06FeO .... 6'34 5-44 5'92 5'bl 6.03 *.& i 1 9 11'5s 10.09 13'14 10.70 16-57 24.40Fe203.. 1.93 2-77 2'32 6.80 <5%9 4.95 - 0'23 - 3.54 10'17 5'433fgO ... 28-50 27'90 27.90 27'79 37.39 26-31 26.03 23'7'3 24'66 23'60 1.3 56 14'1s100.64 100.53 lOO'S.2 100'42 9R'SS 100.65 99'SB 100.07 100% 100'33 !*!)'!I4 1 O O f Nsp. gr. - 3 9 7 3'S9 3.79 3*S7 390 3.91 4.01 4'11 4.01 4.17 4'35GZaserite.-It has been maintained on the one hand that a doublesalt of potassium and sodium sulphate exists of the constant composi-tion K3Na(S04),, so-called glaserite.On the other, i t has been heldthat this name merely covers those members of the isomorphous seriesof mixed crystals formed by the t w o sulphates which contain amaximum of potassium sulphate. J. H. van't Hoff and H. Barschalllhave investigated this point and find no evidence in support of theview t h a t glaserite has a constant composition.G'yroZile.-This rare mineral has been observed by E. Hussak2 inthe form of spherical aggregates composed of thin radial leafletsoccurring in crevices in diabase a t Mogy-guassh, Siio Paulo, Brazil.The specific gravity is 2.409, and the mineral is uniaxial with negativedouble refraction. The composition is very similar to that of gyrolitefrom Skye, as shown by the following analysis of white material madeby G.Florence :__ ~ - - -___ -- -- __SiO,. Al,O,. CnO. R'a,O. K,O. H,O. Total.52-77 0'73 33'04 0.35 0'41 12.5s 99-88Under alumina is included a trace of ferric oxide. A dark greenvariety contained 7.36 per cent. Fe,03 + A1,03 and 0.32 per cent. MnO.We may note here that P. Cornu identifies gyrolite from the Hebrides,Paroc Islands, Greenland, Poonah, and Siio Pnulo with the mineraldescribed by Peli kan uuder the name zeophyllite.Hellunclite has already been the subject of a preliminary notice I)y%I7. C. Briigger, who has now published a full account based on thestudy of more than forty crystals. The mineral was found it1 a quarryopened i n a pegmatite vein on the top of a small hill calledLindvikskollen near Kragerii, Norway.The crystals belong to theprismatic class of the monoclinic system, and are for the most part agood deal altered. The freshest consist of nut-brown material withvitreous lustre, others exhibit various shades of brown, while the mostaltered ones consist of a yellow to white earthy mass. The alteration,which is probably due to hydration, does not seem to have had anyvery great influence on the relative proportions of the constituents.The purest material had the specific gravity 3.6'7 to 3.70, that of thesubstance used for analysis I1 was 3.41 to 3.33. An analysis (I) by0. N. Heiclenreich made on a small quantity of material has already&it. p,hpih.nl.C'lwn., 1906, 56, 212.Cee,Ltr*. M i i t . , 1906, i 9 ." C'mtr. 111i72., 1906, 330.Zcit. K ~ z J s ~ . Nist., 1906, 42, 41'7320 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.been published, I1 and 111 are due to L. Andersen-Bars ; tho materialused for 111 was highly altered :SiO,. A1203. Fe,03. Jlu,O,. Ce,O,. Y20,. Er,O,. Tho.,.I. 23.55 10.22 2‘64 5’69 40’1211. 23’66 10.12 2.56 5‘91 1.01 19.29 15-43 0’62111. 27.85 9-67 2.01 3’13 0.37 19.71 13’28 0’30C’aO. RlgC. Na,O. K20. H20. Total.I. 10.05 - 0’26 0.06 7.65 100-1911. 9-81 0’10 0.23 0-06 11-75 100.55\,-111. 9.97 0’13 0.41 13’09 99.93Since some 6 per cent. of the water mas expelled below 500’ and therest only a t red heat, it seemed probable that about 5 per cent.was chemically combined.This was confirmed by an experiment onthe freshest material, when 4.S6 per cent. of water was found.Accepting this value as the true percentage of water, and assumingthat the small quantities of potash and soda are due t o felspar, theratios (calculated from 11) R”O : H,O : RZ’”O3 : MiO, are very accurately2 : 3 : 3 : 4.Ca ,R ;”[ R”’(0H) J3[ 8iOJor of the type Ca,~R”’(OH)],[SiO,],. Of these two possibilities,Brogger is inclined to prefer the first on the ground of certain analogieswhich hellandite shows with guarinite, danburite, andalusite, andtopaz. Accepting this view, the composition of the mineral may berepresented thus : C’;td[$B1$-(RIn,Fe)l3[ (Y,Er,Ce)(OH),],[SiO,],.t1ibschite.-Reference was made to this mineral last year.Adetailed account of its properties and mode of occurrence has recentlyThe formula is therefore either of the typebeen published by F. C0rnu.lHueherite.-Large black crystalsLawrence County, South Dakota, werehave the following composition :\YO3. mlo. PeO.75.12 20‘54 3’01from the Comstock mine,found by W. P. Headden2 toCaO. Total.1-04 99.71Judade and h‘ephrite.-Some very valuable contributions to ourknowledge of these two minerals are to be found in the monumentaltreatise entitled “ Investigations and Studies in Jade,” issued by theexecutors of Reginald Heber Bishop. I n two vast volumes, eachweighing about sixty pounds, are embodied the results of a series ofstudies by leading American experts of the specimens contained in thegreat Bishop collection now preserved in New York.The mineralogicalportion has been edited by G. F. Kunz, and he has had the assistanceof 8. L. Penfield, P. W. Clarke, J. P. Iddings, C. Palache, L. V.Pirrson, and others. On breaking up a specimen of jadeite, whichProc. Colorado ,S’ci. Soc., 1906, 8, 174. Tsch. Mah. Mitt., 1906, 25, 249.Pyivmtcly pirrtcd, Ken. York, 1906MINERALOGICAL CHEMISTRY. 321probably came from Tibet, two small crystals mere found. Theseclosely resembled augite in shape, and enabled Penfield to determine thecrystallographic constants of the mineral. He found a : b : c =1.103 : 1 : 0.613 ; p= 72’444’. The cleavage angle was 92’58‘. Theextinction angle measured on (010) was 34” and the optic axis angle70°, one axis being nearly parallel to the Z axis of the crystal.Thisspecimen had the following composition :SiO,. Al,O,. Fe,O,. MgO. CaO. Na,O. Ii,O. H,O. Total. Sp. gr.58.80 25.37 0.33 0.25 0‘58 14.65 0.05 0’14 100-17 3.3359I n all, fifty-eight analyses of the two minerals are given, and, withtwo exceptions, these were made by P. ‘3.’. Walden and H. W. Foote.I n his discussion of the formulz to be assigned to these minerals,F. W. Clarke advances arguments in support of the view that themolecules of the pyroxenes are more complex than those of theamphiboles, and that jadeite must be represented as Na6A1,Si,,O,,.Further, he holds that it is not to be regarded as a metasilicate, but asa mixture of an orthosilicate and a trisilicate. A t the conclusion of aparagraph devoted to a discussion of the origin of jadeite considered asa lock, Pirrson sags “jadeite is a metamorphosed igneous rock, R,member of the phonolite family.The wh$e varieties are probablymetamorphosed dikes of the aplitic, leucocratic type, belonging in t h i jfamily and the darker green types those containing more iron-bearingdark silicates, like tinguaites.” The mean value of the specific gravityof all the nephrite specimens was 2-9505 ; that of the jadeites, includingsome chloromelanites, was 3.3202.Junosite.-The existence of this mineral as a separate species hasbeen denied by E. Weinschenk,l who on the ground of its opticalproperties has identified it with copiapite. H. Bockh and :K. Emszt,the discoverers of janosite, have, however, reiterated their belief in itsindividuality, laying special stress ou its specific gravity and chemicalcomposition.I n his reply Weinschenk states that a comparison ofjanosite with specimens of copiapite recently received from Copiapofully confirms his previous conclusion. Further, a specimen of janositesupplied by Bockh was found to contain 30.80 per cent. Pe,O, and tohave n specific gravity 2.17, the corresponding values found forcopiapite being 3 1-09 and 2.19 respectively,J~~mesonite.-Imperfect crystals occurring in quartz veins a tSheridan, Pennington County, South Dakota, have been analysed byW. Y. Headden.2 The percentages found are in tolerable harmonywith those required for the ordinarily accepted formula, 2PbS,Sb,S, :S.Sh. Pb. Fe. Cu. Zn. Cod Insol. Total. Sp. gr.18.90 26-99 51.15 1.30 0 2 4 0.05 trace 1’13 99-76 5’81304Ann. il‘eport, 1905, 279 ; Fold. KOzEOwy, 1906, 36, 224, 228, 359,Pr6c. CoZorado Sci. Soc., 1906, 8, 174.VOL. 111. 322 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Malacom-A specimen of this mineral examined by E. S. Kitchinand W. G. Wintersonl proved to be distinctly radioactive and tocontain argon, Taking the radioactivity of uranium oxide as unity,that of the malacon is 0*0161. This value is much greater than canbe accounted for by the iiranium present in the mineral. Afterdecomposition the radioactivity is entirely associated with thezirconium dioxide. On fusion with potassium hydrogen sulphate,100 grams of malacon gave 37.91 C.C.of gas, consisting of 33.24 C.C.of carbon dioxide, 2.82 C.C. of argon, 0.94 C.C. OF helium, 0.57 C.C. ofhydrogen, and 0.34 C.C. of nitrogen. The specific gravity is 3,908,rising to 4.232 after heating. The complete analysis is as follows :ZrO,. SiO,. Fe,Os. MgO. CaO. U,Oa. (Y,Ce),O,. H,O.67-78 22.53 4'93 0.70 0.41 0'33 0'09 1.84If the other constituents are neglected, and zirconia and silica calcu-lated t o 100, the percentages obtained agree well with those requiredfor the formula Zr3Si2010. The analytical results differ a good dealfrom those previously recorded for the substance, and from which theformula 3(Zr0,,Si02),H,0 has been derived.Meneghirnite.-A fibrous mineral found in the Gorham claim nearRochford, Pennington Cobnty, South Dakota, has been analysed byW.P. Headden.2 The ratios obtained are only approximate, butshow that the probable formula is 4PbS,Sb2S, :S. Sb. Pb. cu. Insol. Total, Sp. gr.17-51 18-20 62.85 0 *86 0.49 99.91 6'21Traces of As, Bi, Cd, and Fe are also present.iVaegite.-T. Wada 3 has published some important fresh informationabout this mineral. He states that a crystallographic examination byTakimoto has shown that in habit and angles the mineral is closelyrelated to zircon, whilst Haga has found that it contains a largequantity of zirconia, a constituent previously overlooked, probablyowing to some imperfection in the methods of separation employed.Haga's analysis is as follows :ZrO,. Tho,. SiO? (NbTa),O,. UO,. Y,O,. Total. 8p.gr.55'30 5'01 20-58 7-69 3.03 9'12 100'73 4.091Petterdite,-Under this name there mas described, a few years ago,a mineral from the Zritannia mine, Zeehan, Tasmania, which wassupposed to be a new oxychloride of lead. A careful re-examinationof this substance recently made by C. Anderson has proved that i t ismerely a variety of mimetite.Trans., 1906, 89, 1568.Beikrage z. Nin. Japan, 1906, No. 2, 23,Rec. Australia?t Mics., 1906, 6, 133.PTOC. CoZorndo. ,%i, Soc,, 1906, 8, 174MINERALOGICAL CHEMISTRY. 323Pitchblende.-The pitchblende from which rutherfordine is derived(see p. 310) is 20 per cent. more radioactive than that from Joachims-thal, and has been shown by W. Marckmaldl to have the followingcomposition :U,O,. PbO. CaO. FeO.SiO,. H,O+CO,. Gangue.87.7 7-5 2.1 1.0 0.3 0.5 0.2Plumbogurnmite. --E. Hussak 2 has published the following analysisby G. Florenceof a mineral found in the form of pebbles, “favas,” inthe diamond sands of Brazil :SiO,. PbO. CaO. CeO. Al,O,. P,O,. H,O .0.70 35-50 0.62 0‘16 24‘92 22.50 16.30The corresponding formula, 2(Pb,Ca)0,3A120,,2P,05,10H,0, is near tothat of plumbogurnmite, although it contains 3 molecules more water.Pyrochroite.-This rare mineral occurs a t Lgngban in prisms andneedles with a distinct basal cleavage. The following analysis, giveiiby H. Sjogre~~,~ agrees with the formula Mn(OH), :H,O. Sp. gr.77.3 0.4 trace 1.7 20.9 3,2435MnO. FeO. CaO. MgO.Quartz.-J. C. Konigsberger and W. J. Muller have studied theliquid inclusions in quartz crystals from the biotite-protogine of the Aardistrict, They find that for these crystals there is aconstant relationbetween the volume of the liquid and the volume of the gas in a cavity,a fact first observed by Sorby.On heating a t from 200’ to 230’ thebubbles disappear, the liquid expanding to fill the cavity. They con-clude that the included matter represents a homogeneous portion ofthe liquid phase. Its composition in the case of a specimen fromthe Biichistock appears t o be as follows :H,O. CO,. Na. I<. Li. Ca. C1. SO,. CO:,.83’4 9.5 2.0 0.7 0.2 8 0.3 1‘6 0.5 1-831. Berthelot5 has found that crystals of amethyst from Brazildecolorised by heating to 300’ regain their original tint on exposingthem for a few weeks to the action of radium chloride.He attributesthis change to the reoxidation of traces of manganese present, andsuggests that the colour of amethyst and other minerals may be dueto the action of radioactive substances. On heating smoky quartzand green fluor spar, petroleum is driven off, and in these cases thecolour is due to organic matter.n~odochrosite.-Small rhombohedra { 100) of this mineral have beenCen’entr. Min., 1906, 761.Geol. Foren. Stockholm Forhandl., 27, 37. C&nt,r. 1906, 72.Compt. rend., 1906, 143, 477.Tsch. iWi7z. Mitt., 1906, 25, 335.Y 324 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.found at S. BarthBlemy, Val d'Aosta, by F. Millosevich.1 The cleavageangle is 73"10', and the composition as follows :MllO. FeO. CaO.MgO. C 0 2 (diff.).56.00 2.04 3.33 trace 38.63Rock Xak-The blue colour observed in certain specimens of rocksalt has been the subject of much experiment and speculation in recentyears. As pointed out in a paper by F. Focko and J. Bruckmoser,2 theexplanations offered fall under three main headings. I n the first place,it is held that the phenomenon is a purely physical one due to the pre-sence of very minute fissures, secondly we have the view that it is dueto the presence of some inorganic colouring matter such as the sub-chloride of sodium or a compound of iron, and lastly that it is causedby organic material. It has, however, been shown that the blue colourcan be produced by exposing salt to the action of cathode rays or byheating it with metallic sodium, and the opinion is now widely heldthat the colour is due to the presence of subchloride or of metallicsodium.Though the latter view does not commend itself to Focke andBruckmoser or to E. Pie~zczek,~ who has found a deficiency of chlorineamounting to as much as 0.4 per cent. in the blue portions, it hasreceived strong support from the work of H. Siedeiitopf.4 This authorinvestigated specimens of salt, coloured blue by the action of sodiumvapour with the aid of the ultra-microscope and believes that he hasdemonstrated the presence of metallic sodium deposited in ultra micro-scopic fissures in the salt. These particles of sodium may possibly becovered by a very thin or " molecular " cooling of subchloride whichprotects them from the action of reagents such as chlorine. H e thinksthat since rock salt strongly absorbs Becquerel rays the blue colour ofthe mineral may perhaps be due to the sodium produced by the cumula-tive effect of the radiation absorbed during long periods of time.The gases included in certain specimens of salt from Roumania havebeen the subject of an interesting investigation by N.Costachescu.5The gases were extracted either by dissolving the salt in well boiledwater or by pnlverising it under mercury. The composition of thegases was found to vary a good deal with the method of extractionemployed, but the following points appear to be established. I n thefirst place the quantity of gas contained in a given weight of salt variesgreatly, but there is no relation between the quantity of gas evolvedand the solid impurities in the salt.Secondly, as regards the nature ofthe gases given off, the specimens examined fall into two groups, thosein which hydrocarbons are predominant and those which yield little else.A t t i A. Accad. Liizcei, 1906, [v] 15, i, 317.Tivh. Illin,. Mitt., 1906, 25, 43. Phavm. Zeit., 51, 700.Ann. Sci. Univ. Jnssy, 1906, 4, 3, 4 Phys. Zcit., 1905, 6, 8 5MINERALOGICAL CHEMISTRY. 325but nitrogen, a gas which is invariably present. Oxygen is also alwaysfound, but in smalIer proportion than the nitrogen and there is no con-stant relation between the quantities of these two elements. Carbondioxide is either absent or occurs in very small quantities. Argoncould not be detected.Methane is almost always present, but thehigher hydrocarbons appear to be absent. To account for these factsthe author suggests that the gases have been derived mainly from thedecomposition of the microscopic fauna of the lagoon in which thedeposits were laid down, and to but a limited extent from the atmos-phere through the medium of the solvent. The absence of carbon di-oxide and argon can be explained in this way, but it is difficult toaccount satisfactorily for the oxygen always observed.,S'aarcoEite.-Specimens of this mineral from Vesuvius have been sub-mitted to a careful crystallographic and optical examination byA. Pau1y.l Two pure crystals were used for analysis :SiO,. A1,0,. CaO. MgO. Na,O. K,O. Total. Sp. gr.39.34 21.63 33.70 0.36 4'43 traces 99.46 2.78cheeZite.-The crystals from Traversella have been measuredby L.Colomba who moreover has analysed specimens of differentcolours in order to test Traube's hypothesis that the ratio a : c varieswith the amount of molybdic acid present. His results are asfollows :W03. MOO,. CaO. MgO. Total. a : c.I. Colourless crystals ......... 77.03 3-15 19.73 - 99-91 1.539811. Reddish-brown crystals ... 77-35 2'46 18.33 1.67 99-81 -111. Grcenish-brown ,, ... 78.75 1.47 19.23 0.55 100*00 1.5352IV. Orange ,, ... 79-68 0.72 19.43 trace 99.83 -Since the mean value of c calculated from measurements of crystalsof the composition given under I and 111 falls about midway betweenthose accepted by Traube for pure scheelite and pure calcium molybdaterespectively, this work affords no confirmation of the view that aregular variation takes place.Siderr.ite.-Minute crystals from Prostburg, Maryland, have beenshown by W.T. Schaller3 to be pure ferrous carbonate. An analysismade on 0.1 gram of carefully selected material gave 62.01 per cent.of iron (calc. 62.07 per cent.). MnO, CaO, and MgO were proved t obe absent. A number of measurements of the crystals were made forthe purpose of defining accurately the ratio a : c forpure siderite. Themean value deduced is c=O.8241. This corresponds to a cleavageangle rr' = 73O18.6' and differs considerably from that hitherto adoptedfor the mineral, namely, c = 0.81841, rr' = 73'0'.1 Centr. Min., 1906, 266. Atti 12. Accad. Lincei, 1906, [v], 15, i, 281.3 Anav.J. Xci., 1906, [iv], 21, 364326 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.StibiotantaZite.-This very rare mineral was originally described byG. A. Goyder as occurring in water-worn fragments at Greenbushes,Western Australia. Crystals have been discovered in recent years atMesa Grande, San Diego County, California, associated,with tourmaline,pink beryl, quartz, orthoclase, and lepidolite, and have been the sub-ject of an exhaustive investigation by S. L. Penfield 1 and W. E. Ford.The mineral is an isomorphous mixture of (SbO),Cb,O, and (SbO),Ta,O,,and has a specific gravity varying from 5.98 to 7.37, depending on therelative proportions of columbium and tantalum present, and diminish-ing as the amount of the latter decreases.It crystallises in the hemi-morphic class of the orthorhombic system, though owing to twinning thecrystais simulate holohedral symmetry. I n axial ratio and habit i tshows relations with columbite. Owing to its yellow colour, highindex of refraction, and good cleavage it might be mistaken for blende.I n the following table I is the original analysis of the Australianmineral, I1 and 111 are each the means of two concordant analysesmade on separate crystals of the Mesa Grande material.(Ta,Cb),O,. Sb,O,. Bi,O,. NiO. H,O. Total. Sp. gr.I. 58-69 40.23 0 '82 0'08 0.08 99-90 7.3711. 55-33 44 26 0.33 - __ 99-92 6.72111. 50.30 49'28 0.53 - - 100.11 5-98TapioZite.-A group of distorted crystals found by W. P. Headden 2in granite near Custer City, South Dakota, were shown by S.L. Penfieldto be tetragonal pyramids (111) with small (201) planes. Twoanalyses were made :FeO. Ta,O,. Cb,O,. WO,. SnO,. Cassiterite. Insol. Total.I. 16.85 78.61 4-29 0.11 0.07 0.31 - 100.24v11. 15.60 '18.58 3'90 0 *59 - 1-29 99.96Traces of TiO, were found in analysis I and there is reason to believethat FeO is too high. The formula is FeTa,O,, a portion of the tantalumbeing replaced by columbium and taken in conjunction with the crystal-lographic characters shows that the substance is tapiolite. The specificgravity 7.2185 is low f o r a compound containing so little columbicacid. This point is discussed by Headden, who finds himself unable toexplain it.Tetrahedrite.-In the course of a description of the mines andminerals of the Val de Villd (Weilerthal), Alsace, Ungemach3 hasgiven the results of an elaborate crystallographic investigation of thebeautiful crystals of tetraliedrite found at the Sylvester mine.Twodifferent types of crystals can be readily distinguished. One (analysisI below), rich in arsenic but poor in silver, is met with in the upperportions of the veins; the other, found at greater depths, is rich insilver and poor in arsenic (analysis 11).Amer. J. Sci., 1906, [iv], 22, 61. Proc. Colorado Sci. SOL, 1906, 8, 177.BUZZ. SOC. franq. N n . , 1906, 29, 194MINERALOCIIC AL CHEMISTRY, 327The comparatively large quantities of Zn and Ri present are some-what remarkable, and the author is inclined to believe that they aredue to the presence of native bismuth and of zinc blende.Be this asit may, if the formula is calculated omitting zinc, it is found thatthe ratio R”S : R2’”S3 is 3.07 : 1 for I and 3.21 : 1 for 11.The variety of tetrahedrite previously described under the namescoppite and frigidite has been examined by E. h1anasse.l Threespecimens were analysed. The results, which are given below, analyses111, IT, and V, are in harmony with a formula of the typeTraces of tin were found in I V and V.3R2S,R’2S3 + xGR”S,R’2S3.Cu. Ag. Pb. Fe. Zn. Ni. As. Sb. Bi. S. Total. Spgr.I. 38.15 trace 0.53 3.77 5-05 - 6.75 17.47 1.63 25.58 98-93 4‘8211. 34.15 5.94 - 3.79 4-86 - 1-21 25.24 - 25-22 100-41 5-10111. 37.42 - trace 6.60 1‘72 0.23 trace 29.28 - 25.70 100.95 -1V.37’54 - trace 6’01 1.98 0.14 trace 29-54 - 25’48 100*69 -V. 30’04 - 0’26 9‘83 0.59 3.46 1.50 28.82 - 24-48 98-98 -Thuringite.-F. Kretschmer 2 has published further details as tothe occurrence of this mineral at Gobitschau, and has given three newanalyses.Thoriccnite.-In a paper published last year, W. R. Dunstan andG . S. Blake suggested that the intimate association of thoria withoxides of uranium might be a CRSI of isomorphous mixture. This viewhas been confirmed by a series of analyses of thorianite from theGalle district of Ceylon, recently published by W. R. Dunstan andB. M. Jones.3 Their results show that the proportion of the twooxides present in the mineral may vary considerably, as can be seenon comparing columns I to VII of the following table.I gives thecomposition of small crystals from Hinidumpattu, Galle District ;I1 to VI that of large lumps from the same locality, 11, I11 and IVbeing different portions of the same crystal ; VII is an analysis of alarge crystal of the ordinary variety from Balangoda. All the speci-mens contained helium and carbon dioxide. The radio-activity ofspecimen I was compared by R. J. Strutt with that of the mineralthe composition of which was given last year and found to be 1.16times as great. Column VIII contains some determinations of themore important constituents of thorianite made by E. H. Buchner inSir W. Ramsay’s laboratory in the course of an investigation into thedistribution of the radioactivity among the constituents of the mineral.In addition to the elements enumerated, small quantities of copper,tin, antimony, bismuth (?), aluminium, titanium, and zirconium wereestimated, and traces of mercury, arsenic (?), cadmium (1) and phos-Mem.SOC. Tosc. Xci. Nat., 1906, 22, 81.Proc, Boy, Xoc., 1906, 77, A , 546.Cent,.. Min., 1906, 309.Ibid., 78, A , 385328 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.phorus observed. One gram of the mineral yielded 8.2 C.C. of helium.The radioactivity is associated almost entirely with the portion of themineral soluble in nitric acid.I. 11. 111. IV.Tho, ..................... 58.84 62-16 1 66.82 -(Ce,La,Di),O, ......... 0.85 1.841 { -uo, uo, } 32’74 { ii:;:} 28.24 28.68PbO ..................... 2.56 2-29 2’29 2.50Fe,03 ................1.31 1.11 1-22 2.43..........................................CnO ..................... 0.19 0.59 0.54 -H20 ..................... 1’26 1.05 1 .OO --Insol. in HNO, ...... 0.45 0.77 0.56 0.54* u,o*.v.62-322.2427.022.992.280.502-160.87VI.63-361-1627.992.901 -270 ‘851-320.77VII. VIII.78-98 70.961-47 1.9613.40 13’12*2-54 2-420.87 2-050‘91 0.131.28 3.200.47 -Titanile.-F. Zambonini called attention last year to the unsatis-factory state of our knowledge of the composition of titanite. H e hasrecently returned to this question, and has pointed out that the com-position of specimens containing tervalent elements is better expressedby Blomstrand’s formula, 2(R,”R~’0,,TiO)0,SiO2, than by that due toGroth, who regards such titanites as consisting of isomorphousmixtures of CaTiSiO, and R,”’SiO,.Blomstrand’s formula representstitanite as containing titanyl, TiO, playing the part of a cation thus,Ti0:02Si02:Ca, aluminium, iron, yttrium, and cerium eo tering themolecule in the bivalent grouping R,“’O,. As, however, recent workon titanium, zirconium, and tin has shown that these elements readilyform complex anions, Zambonini thinks that it will be more inharmony with what is known of the general chemical character oftitanium if it is regarded RS playing a similar part in titanite. H etherefore proposes to modify Blomstrand’s formula in this sense, andregards the mineral as the calcium salt of a complex silicotitanic acidTiO:SiO,:Ca.The tervalent elements enter the molecule as two uni-valent groupings R”’0, replacing TiO.Zeolites.-Certain zeolites which occur in the amygdsloidal basalt ofthe Debaroa plateau, Eritrea have been described by E. Manasse.2Two specimens of chabtczite had a composition agreeing with theformula CaAl,Si,01,,6H20. Analyses I and 11. I Crystals of apophyllite,measured by G. D’Achiardi, agreed approximately with the formulaH7KCa,(Si0,),,4iH20. Analysis 111. The loss of water a t varioustemperatures and its reabsorption on standing in moist air werestudied in the case of both minerals.E. Manasse has also re-examined the mineral from Montecatinitermed picrothomsonite by Meneghini and A. D’Achinrdi, and has cometo the conclusion that i t is thomsonite.The mean composition derivedfrom two concordant analyses is given under IV below. Associated withAttiB. Accnd. Lincci, 1906, [v], 15, i, 291.Proc. ?:el-6. SOC. [I‘osc. Sci. Arnt., 1906, 15, 65. 3 Ibid., 20MINERALOGICAL CHEMISTRY. 329this substance is another called sloanite by Meneghini.to be identical with ncitrolite.This appearsAnalysis V.SiO,. A1,0,. CaO. Ego. K,O. Na,O. H,O. Total.I. 48.35 19.47 8.77 0.20 trace 1.05 22.13 99'9711. 46.69 20.27 9.72 - trace 0.96 22.80 100'44111. 52.84 trace 24'46 - 5'42 trace 16-48 99.20IV. 36-90 31'36 14'48 0 3 3 0.65 3.81 13.59 101'12V. 46.49 25-47 1-10 trace trace 17'05 9-76 99.87VI. 65-21 11'20 3-77 trace 6.07 14'22 100.47G. D'Achiardi 1 has referred toptilolite, a mineral from San Piero inCampo, Elba, which has the composition given under YI, and hassuggested that the mineral called hydrocastode is possibly identicalwith a pulverulent form of stilbite, containing small quantities of lithium,which he has found at the same locality.He has also given somefurther account of the zeolite which was mentioned last year as pro-bably constituting a new species.22oisite.-Striated prisms associated with prehnite have been foundat the Trace mine, Juarez district, Lower California. The opticalcharacters have been studied by 0. C. Farrington,3 and the mineralhas been analysed by H. W. Nichols.The numbers obtained agree well with the formula H,Ca,A16Si60,7,which is that usually accepted for zoisite with the addition of onemolecule of water.There is good evidence for believing that in thiscase the extra molecule of water is a primary constituent of themineral, and not the result of alteration, and the authors quote othersimilar instances.Analysis 11, which agrees with the ordinary formula, was made byE. M a n a ~ s e , ~ on a specimen from Monte Corchia, Alpi Apuane.-+Analysis I below.Traces of K and Na were also present.SiO,. A1,0,. Fe,O,. MnO. CaO. MgO. H,O. Total.I. 38.15 29.50 4-60 0 5 5 22.71 0.63 3-76 99.9011. 37'86 26'88 7.90 - 24'65 - 2-07 99'36&dioccctivity of h%aera!s.The radioactivity of minerals containing thorium has occupied theattention of several workers.B. B. Boltwood has examined thorianite, thorite, orangite, andmonazite, containing 78.8, 52, 51.1, and 4.66 per cent.of Tho, re-spectively. He has found that the activity of one gram of thoria waspractically the same in each of the four minerals. H e believes thathis results confirm t.he view that radio-thorium is a disintegrationillem. Soc. Tosc. Sci. Nnt., 1906, 22.Field Coolurnhian M i ~ s . Pub., 112 ; Gcol. Ser., 3, No. 4, 55.Proc. wrb. Xoc. Tosc. Xci. Nat., 1906, 15, 20.A?ner. J. Xci., 1906, [iv], 21, 415.Ann. Xeporf, 1905, 282330 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY,product of thorium, but that they do not lend any support to theidea that the activity of thorium in a mineral depends on the amountof uranium present. On the other hand, the available data point tothe conclusion that the quantity of actinium in a radioa,ctive mineralis proportional t o the uranium present.Similar conclusions as to theproportionality existing between the activity of thorium minerals andtheir thorium content have been arrived a t by H. M. Dadourian I andby H. N. McCoy and W. H, Ross.2Finding reason to suspect that their former estimate of the amountof radium associated with a given quantity of uranium in a mineralwas too high, E. Rutherford and B. B. Boltwood have repeated theestimation. They now find that approximately 3.8 x 10-7 grams ofradium are associated with 1 gram of uranium, a result about half thatpreviously obtained. They point out that a ton of 60 per cent.uranium ore would carry radium equivalent to about 0.35 gram ofradium bromide.Special Reactions of Minerals.F. Cornu4 has examined and tabulated the behaviour of a largenumber of minerals when finely powdered, moistened, and brought incontact with neutral litmus paper.H e finds that all the minerals ofthe kaolin and pyrophyllite groups show acid reaction, and that thesame is true of opal. On the other hand, olivine, mesolite, and talc reactalkaline. The same writer 5 bases a method of distinguishing betweencalcite and dolomite on the behaviour of these substances towardswater containing phenolphthalein. On shaking the solution with finely-divided calcite a dark red colour is produced, wbilst dolomite givesmerely a faint red tinge. V. Goldschmidtg has called attention tothe ease with which a number of minerals can be determined byfinding the loss of weight they suffer on ignition. Experiments madeunder his direction by P. Hermann on a number of zeolites show thatthese substances can be rapidly identified by heating quantities offrom 30 to 100 milligrams in a platinum spoon over a spirit lamp.Meteorites.The composition of a number of meteorites has been examinedCaiion l)iablo.-A septarian nodule found in t h i s meteorite has beenThe septa are metallic and like the mass of3 l b i d . , 1906, 22, 1.during the past year,studied by W. Tassin.7Among these we may notice the following :dmer. J. Sci., 1906, [iv], 21, 427.Tsch. Min. Mitt., 1906, 24, 417,Jahrb. Min., 1906, i, 16.Ibid., 433.7 Proc. U.X. Nat, IcIus,, No. 1497,Centr. Nin., 1906, 550MINERALOGICAL CHEMISTRY. 331the iron. The interseptal portions are made up of crystalline graphiticand amorphous carbon mixed with troilite. A lustrous motallicsubstance consisting mainly of iron (88-8 per cent.), but containingnickel, silicon, carbon, phosphorus, and a trace of cobalt, is alsopresent.Coon Butte.-This aerolite was discovered in 1905 by D. M. Barringernear Coon Butte, Coconino County, Arizona. There is some evidenceto show that its fall was observed in January, 1904. I t s generalappearance and the results of an optical examination made by G. P.Merrill suggest affinities with the meteorites from Ness County,Kansas, or with the Pultusk meteorite. J. W. Mallet has foundthat it consists mainly of enstatite and olivine, but it also containsmaskelynite and nickel-iron. The composition of all these constituentshas been ascertained, and traces of tin and copper found in the last.~stacudo.-An aerolite fell in 1882 near Estacado, on the stakedplains of north-western Texas. It has been investigated by J. M.Davison,2 who has determined the composition of the metallic portion,which amounts to 16.41 per cent., and of the stony matter, whichappears to be mainly olivine and enstatite.Kangra VccZZey.-An aerolite which is reported to have been seen tofall in the Kangra Valley, Northern Punjaub, has been described byW. N. Hartley.3 The specimen, which weighs 350 grams, appears toconsists of a crystalline ground mass of enstatite and olivine, throughwhich are scattered numerous metallic grains. A spectroscopicexamination of the metallic portion showed the presence of Fe, Ni, Co,Cr, with small quantities of Cu, Ag, Pb, and Ga. Traces of Mn, Ca,K, and Na were also detected. Ca and Mg are the principal con-stituents of the siliceous portion, accompanied by minute quantities ofFe, Ni, Cr, Ga, Sr, Pb, Ag, Mn, K, and Na.KodaikanaZ.-A new silicate, weinbergerite, has been discovered byF. Berwerth in this meteorite (see page 310).Modoc.-A fall of meteorites took place on the night of September2, 1905, in the vicinity of Modoc, a small town in Scott County,Kansas. Fourteen specimens, mostly complete individuals, have beenrecovered, and the largest of these, weighing 4.64 kilos, now in thepossession of the U.S. National Museum, has been described by G. P.MerrilL4 Under the microscope it is seen to consist essentially ofolivine and enstatite, with blebs of metallic iron and troilite. Itbelongs to Brezina’s group of veined chondritic meteorites. Analysesof the metallic portion and of the soluble and insoluble silicates havebeen made by W. Tassin.Amer. J. Sci., 1906, [iv], 21, 347.Tram., 1906, 89, 1566.Ibid., 186 ; 22, 55.J Amer. J. Sci., 1906, [iv], 21, 366332 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Shelburne.-A second stone of this fall has been described by 0. C.Farrington.South Bend.-0. C. Farringtonl has also examined a pallasiteweighing 5& lb., found in 1893 near South Bend, St. Joseph County,Indiana, and refers i t to the Imilac group. The ratio of nickel-ironto chrysolite is 21.4 to 78.6.I n conclusion, it should be noted that a great deal of interestinginformation regarding Japanese meteorites has been brought togetherby K. Jimb6.2A. HUTCHINSON.Field Columb. MISS. Pub., 109 ; Geol. Ser., 3, 2.2 Beitrage 2. Min. Japaib, 1906, No. 2, 30

ISSN:0365-6217    

DOI:10.1039/AR9060300294

出版商:RSC    

年代:1906

数据来源: RSC