摘要:

ANNUAL REPORTSON THRPROGRESS OF CHEMISTRYANNUAL REPORTSW. T. ASTBURY.Sir W. H. RI~AGG, K.B.E., F.R.S.H. V. A. BRISCOE, D.Sc.FI. M. DAWSON, D.Sc., T%.D..T. C. DKvnInrom, D.Sc.W. N. HAWOKTH, D.Sc., Ph.11,ON THEJ. KRNNI:R, Ph.D., D. Sc.U. AINSWORTH Xl I'rcmm,, AT. A.I€. J. PAGE, M.R.E., H.Sc.R. ROBINSON, IlSc., F.R.S.T,. J. SPENCER, 11. A., Sc D.PROGRESS OF CHEMISTRYF O R 1923.ISSUED BY THE CHEMICAL socrm-xdommitfae af @ublicatioir :E. C. C. BALY, C.B.E., F.R.S.0. L. BRADY, D.Sc.A.W.CROSSLEY,C.M.G., D.Sc., F.R.S.C. H. DESCH, D.Sc., F.M.S.C. S. GIBSON, O.B.E., MA.I. M. HEILBRON, D.S.O., D.Sc.J. C. IIWINE, C.B.E., D.Sc., F.R.S.T. &I. LOWRY, C.B.E., D.Sc., F.K.S.J. W. hICRAIS, Pl~.l)., F.R.S.J. I. 0. M~SSON, M.B.E., D.Sc.W.H. MILLS, Sc.D., F.R.S.J. C. PHILIP, O.B.E., D.Sc., P.R.S.R. H. PICKARD, D.Sc., F.K. S.T. S. PRICE, O.K.E., D.Sc.N. V. SIDGWICK, Sc.D., F.R.S.J. F. THORPE, C.B.E., D.Sc., F.R.S.W. P. WYNNE, D.Sc., F.R.S.6Ibbiiors ;A. J. GREENAWAY.CLARENCE SMITH, n.8~.3ssist ttir t :A. A. ELDRIDGE, B.Sc.VOl. xx.L O N D O N :G U R N E Y & J A C K S O N , 33 PATERNOSTER ROW, E.C.41924PRINTED IN GREAT BRITAIN BYRICHARD CLAY & SONS, LIMITED,BUNGAY, SUFFOCKCONTENTS.PAGEGENERAL AND PHYSICAL CHEMISTRY. By H. M. DAWSOX, D.Sc.,Ph.D. . . . . . . . . . . . iINORGANIC CHEMISTRY. By H. V. A. BRISCOE, D.Sc. . . . 28ORGANIC CHEMISTRY :--Part ~.-ALIPHATIC DIVISIOK. By W. N. HAWORTH, D.Sc., P1i.D. . 57Part II.-HOMOCYCLIC DIVISION.By R. ROBINSON, D.Sc., F.R.S. . 88Part III.-HETEROCYCLIC DIVISION. By J. KENNEE, Ph.D., D.Sc. . 126ANALYTICAL CHEMISTRY. By C. AINswoRrrr MITCHELL, 1f.A. . 157PHYSIOLOGICAL CHEMISTRY. By J. C. DBUMMOND, D.Sc. . . 177AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY.By H. J. PAGE, M.B.E., B.Sc. . . . . . . . 200CRYSTALLOGRAPHY. By U’. T. ASTBURY and Sir W. H. RRAOC, K.B.E.,F.R.S. . . . . . . . . . . . 230MINERALOQICAL CHEMISTRY. Hy L. J. SPENCER, M.A. ~ Sc.D. . 26TABLE OF ABBREVIATIONS EiIfPLOYED IN THEABBREVIATED TITLE.A . . . . .Aincr. J. Bot. . .Amer. J. Dis. Child. .Anzer. J. Hygiene .Amer. J. Physiol. .Anzer. J. Xci. . .Anxer. Min. . ,Anal. Fis. Quim. .Analyst . . .Annalcn . . .,411n. Appl. Biol. .Ann. Bot. . ..Avn. CJbina. . .Ann. Ghim. anal. .Ann. FaZsif. . .Ann. Inst. Pastew .Ann. Physik . .Adizn. Physique . ,Ann. Acport . .Ann. Xoc. ge‘ol. Bclg. .Arch. exp. Path. Pharrn.Arch. Pharm. . .Astrghp. J. . .Atti it. Accad. Lincei .Bcr. . . . .Ber. Bcut. hot. Ges. .Bcr. De1l.t. pharm. Ges.Biochem. J. . .Biochem. Z. . .IZrdnrLstotf-Chcm. .Brit. Assoc. Aep. .Brit. Med. J. . .Brit. Pat. . . .BdZ. Acacl. roy. Belg.Bull. Asso. Chim. Xricr.Bull. Xoc. chim,.Bzdb. Soc. chim. Belg.Bull. Soc. clzim. Biol.Bull. Soc. fmq. Mi?i.REFERENCES.JOURNAL.Abstracts in Journal of the Chemical Society. + Ameiican Journal of Botany.American Journal of Diseases of Children.American Journal of Hygiene.American Journal of Physiology.American Journal of Science.American 3fineralogist.Anales de la Sociedad Espancla Fisica y Quimicrt.The Analyst.Justus Liebig’s Annalen der Chemie.Annals of Applied Biology.Annals of Botany.Annales de Chimie.Annales de Chimie analy tique appliqu6e k 1’IndustriesAiiriales des Falsifications,Annales de 1’Institut Pasteur.Annalen der Physik.Annales de Physique.Annual Reports of the Chemical Society.Annales de la Socikte gkologiyue de Relgiquc.Archiv fur experimentelle Patliologie und Pharnia-Archiv der Pharmazie.Astrophysical Journal.Atti della Reale Accademia Nazionale dei Lincei.Berichte der Deutschen Chemischen Gesellschaft.Berichte dcr Deutschen botanischen Gesellschaft.Berichte der Deutschen pharmazeutischen Gesell-The Biochemical Journal.Biochemische Zeitschrift.Brennstoff Chemie.Report of the British Association for the Advance-ment of Science.British Medical Journal.British Patent.Academie royale de Belgique-Bulletiii de la ClasseBulletin de 1’Association des Chimistes de Sucreiie ctBulletin de la Socihte chimique de France.Bulletin de la Socihte chimique de Belgique.Bulletin de la Societd de Chimie biologique.Bulletin de la Soci6t6 franpaise de MinCralogie.l’Agriculture, k la Pharmacie et B la Kiologie.kologie.schaft.des Sciences.de Distillerie.Tile year is iiot iusert,eti in references to 1833viii TABLE OF ABBREVIATIONS EMPLOYED IN THE REFERENCES.ABBREVIATED TITLE.(Jhcm.and Met. Eng. . .Chem. News . . .Chem. Umschazc . . .Chem.TVee7iblad . .Chem. Ztg. . . .Chm. Z e n t T . . . ,C‘ompt. rend. . . .Compt. rend. Soc. Biol. .Compt. rend. ?‘rnv. Lab.Carlsberg . . .U.R.-i? . . . .Econ. Geol. . . .Gazzctta . . . .Geol. Fijr. F6rh. . . .Edv. C‘him. Acln . .Iuternat. Jlitt. Bodn&zcnde .Japan. J. Phys. . . .Japan. Pat. . . .J. Agric. Rea. . . .J. Agric. h’ci. . . .J. Anzcr. Chem. Soc. . .J. Amct.. Med. ASSOL*. . .J. Bact. . .J. Riol. Chem. . . .J. Chenz. Met. f o c . S. AfricaJ. Chem. Soc. Japan .J. Cliim. yhys. , .J. Exper. &d. . .J. Franklin Inst. .J. Gcn. Physiol. . .J. Ind. Eng. Chem. .J. irnst. Brewing .J. Inst. Petr. Tech. .J. Landw. . . .J. Opt. SOC. Anter. .J. Pharm. Chim. .J. Pharm. Expt. Ther.J. Pharn~. SOC.Japan.J. PlLySicaz Chem. .J. Physiol. . .J. Dr. Cham. . .J. koy. Agric. Soc. .J. Atass. YJL~s. Chem. Soc. .J. Soc, Chmn. Ind. . .J. S. African Chem. Inst. .J. Washington Acnd. Xci. .Roll. C7wm. Beihefie . .Kolloicl Z. . . . .Lnndzc.. Jnhrb. . . .Landw. Versmhs-Stal. .Lunds Uiiiv. Arsskr. . .iMcdd. o m Gronland , .illrem. CoZZ. Xci. Kyoto. .JOURNAL.Chemical and Metallurgical Engineering.Chemical News.Cheniische Umschaa auf dem Gebiete der Fette, Oele,Chemisch Weekblad.Chemiker Zeitung.Chemisches Zentntlblatt.Comptes rendus hebdomadaires des SOances d tComptes rendus hebdomadaires de SBances de laComptes rendus des Travaux du Laboratoire Csrls-Deutsches Reichs-Patent.Economic Geology.Gazzetta chimica italisna.Geologislra Fiireningens i Stockholm Fiirliandlingar.Helvetica Chimica Acta.Internationale Mitteiluugen fiir Bodeiikunde.Japanese Journal of Physics.Japanese Patent.Journal of Agricultural Research.Journal of Agricultural Science.Journal of the American Chemical Society.Journal of the American Medical Association.Journal of Bacteriology.Journal of Biological Chemistry.Journal of the Chemical, Metallurgical, and MiningSociety of South Afiica.Journal of the Chemical Society of Japan.Journal de Chimie physique.Journal of Experimental Medicine.Journal of the Franklin Institute.Journal of General Physiology.Journal of Industrial and Engineering Chemistry.Journal of the Institute of Brewing.Journal of the Institution of Petroleum Technologists.Journal fur Landwirtschaft.Journal of the Optical Society of America.Journal de Pharmacie et de Chimie.Journal of Pharmacology and Experimental T~LCT+Journal of the Pharmaceutical Society of Japan.Journal of Physical Chemistry.Journal of Physiology.Journal fur praktische Chemie.Journal of the Royal Agricultural Society.Journal of the Physical and Chemical Society ofRussia.Journal of the Society of Chemical Industry.Journal of the South African Chemical Institute.Journal of the Washington Academy of Sciences.Kolloidchemische Beihefte.Kolloid- Zeitschrift.Landwirtschaftliche Jahrbiicher.Die Landwirtschaftlichen Versuchs-Stationen.Lunds Universitets Ars-skrift.bleddelser on1 Griinland.Meirioirs of the College of Science, Kyoto ImperialWachse, und Harze.l’Acad6mie des Sciences.SociBtd de Biologie.berg.peutics.UniversityTABLE OF ABBREVIATIONS EMPLOYED IN THE REFERENCES.ixABBEEVIATED TITLE. JOURNAL.Me?lz. Jfanchester Phil. SOC. Memoirs and Proceedings of the hlanchester Literaryafb712. Poztdres . . . MBniorial des Poudres.Nin, Jfag. . . . Mineralogical Magazine and Journal of theJfonatsh. , . , , Monatshefte fur Cheinie und verwaiidte Theile andererA'aturXiss . . . . Die Natnrwissenschaften.p. . . . . . Proceedings of the Chemical Society.P-iiger's Arckiv. . . Archiv fiir die gesamte Physiologie des Mensclien undPhnrm. JVeekblad . . Phsrmaceutisch Weekblad.Pirilippine J. Sci. . . Philippine Journal of Science.Phil. Alag. . . . Philosophical Magazine (The London, Edinburgh andPhil.Trans. . . . Philosophical Transactions of the Royal Society ofPihysical Rev. . . . Physical Review.Physikal. 2. . . . Physikalische Zeitschrift.Proa. Amer. Phil. Soc. .Proc. Austral. Inst. itfin. Proceedings of the Australasian Institute of MiningNet, . . . . and Metallurgy.PTOC. K. Akad. Wetensch. Koninklijke Akadeniie van Wetenschappen te Amster-AmsteTdain . . . dani. Proceedings (English version).proc. Nut. Acad. Xci. . . Proceedings of the National Academy of Sciences.Proc. Physical SOC. . . Proceedings of the Physical Society of London.Proc. Hoy. Irish Acad. . Proceedings of the Royal Irish Academy.Proc. hoy. Soc. . . . Proceedings of the Royal Society.Proc. Soc. Exp. Biol. Jfed. .Proceedings of the Society of Experimental Biologyand Medicine.Quart. J. Med. . . . Quarterly Journal of Medicine.Kec. trav. cluim. , . . Recueil des travaux chimiques des Pays-Bas et de la8s'c.i. Proc. It. Dublin SOC.Sitzmgsbcr. Akad. W~SS. Sitzungsberichte der Akademie der WissenschaftenSitzungsber. Preuss. Akad. Sitzungsberichte der Preussischen Akademie derSoil Sci. . . . , Soil Science.Stas. sper. agr. ital. . . Stazioni sperimentali agrarie italiane.Swiss Pat. . . . . Swiss Patent.T. . . . . . Transactions of the Chemical Society.Trans. Faraday SOC. . . Transactions of the Faraday Society.Trans. Nova Scotia Inst. Sci.Trans. iioy. Soc. Canada .U.S. Pat. . . . . United States Patent.2. anal. Chem. . . . Zeitschrift fur analytische Chemie.2. angew. Chem.. . . Zeitschrift fur angewandte Chemie.2. anorg. Chem. . . . Zeitschrift fur nnorganische und allgemeine Chemie.2. Elektrochem. . . . Zeitschrift fiir Elektrochemie.2. ges. Brawzo. . . . Zeitschrift fiir das gesamte Brauwesen.2. grist. . . . . Zeitschrift fur Kristallographie.Z. Kryst. Min. . . . Zeitschrift fiir Krystallographie und Mineralogie.Z. NaJw.-Genzcss?n. . , Zeitschrift fiir Untersuchung der Nahrungs- undGenussrnittel.2. PTLysik . . . . Zeitschrift fiir Physik.2. phpsikal. Cham. . . Zeitschrift fur physikalische Chemie, Stochiometrie2. physiol. Chem. . . Hoppe-Seyler's Zeitschrift fur physiologische Chemie.Zentr. Bakt. Par. . . Centralblatt fur Bakteriologie, Parasitenkunde, undand Philosophical Society.Mineralogical Society.Wissenschaften.der Thiere.Dublin).London.Proceedings of the American Philosophical Society.Eelgique. . Scientific Proceedings of the Royal Dublin Society.Wien . . . . Wien.Wiss. Berlin . . Wissenschaften zu Berlin.Transactions of the Nova Scotia Institute of Science.Transactions of the Royal Society of Canada.und Verwandtschaftslehre.Infektionskrankheiten

ISSN:0365-6217    

DOI:10.1039/AR92320FP001

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

INORGANIC CHEMISTRY.THE output of work Ln inorganic chemistry has been well main-tained in 1923, and the prefatory remarks of the Report for 1922apply to that now submitted. As will appear, the outstandingfeatures of the year’s work are a very active and widespread discus-sion of current atomic theories as applied to the interpretation ofchemical phenomena, some interesting and important investigationsof the hydrides of boron and silicon, an extension of the work reportedlast year in the detailed study of germanium, and the discovery ofelement No. 72 with its attendant controversy as to priority inthat discovery.T7alency and Atomic Theory.The genera’l discussion of atomic theories, comprising some twoscore papers or more, must be left for consideration in other Reports,but we may properly refer briefly here to those papers which areconcerned primarily with ‘’ valency.” The Lew is-Langmuir con-ception of a static atom is, for example, applied to explain thechange of chemical properties by substitution,I the quinquevalencyof boron in acidic compounds such as HBF, and its quadrivalencyin such relatively inert substances as BF,,NH, or boron nitride.2A series of papers has been devoted t o the development of anelectronic interpretation of the structure of “ co-ordination ”compounds in general,3 and a further serres to the discussion ofthe polarity of double bonds, the existence, for example, in the ion -+- FHF, of co-ordinated hydrogen cxerting an eff cctive (co-ordination)val5ncy of 2, and kindred matters.It seems possible, however, that such discussions, based as theyare on a theory which is at hest a half truth, are of rather limitedutility. The kinetic theory of the atom, which carries generalconviction of its essential truth, continues to develop and now1 Sir J.J. Thomson, Phil. Mag., 1923, [vi], 46, 497; A., ii, 682.2 J. Boeseken, Proc. K . Akad. W-etenech. ,4mterdurn, 1923, 26, 97; A.,3 T. 31. Lowry, Chemistry and Indust~y, 1923, 42, 224, 316, 1004, 1048;4 T. M. Lowry, Trans. Farachy Soc., 1923, 18, 285; Phil. Mag., 1923, [vi],6 See, e. g., N. Bohr and D. Costerl 2. Physik, 1923, 12, 342; A., ii, 110.ii, 406.A., ii, 233, 313, 750, 849; C. H. Spiers, ibid., p. 534; A., ii, 481.45, 964, 1013, 1105; A,, ii, 480, 848; l’., 1923, 123, 822, 2111INORGANIC CHEMISTRY.29begins to find direct application to valency problems.6 It seemslikely to provide an explanation of the structure of molecules notinconsistent with, but a development of, that based upon the statticatom models.Special reference may Be made to a paper 7 showing generallyhow Eohr's theory may provide a simple and adequate explanationof the existence of all co-ordinated compounds for which Werner'sdoctrine of sixfold symmetry is most fully established. Positiveobjection to the static theories has been raised on the groundthat they fail to explain the phenomena of stereochemistry.Although these views have been adversely criti~ised,~ it seems prob-able that they represent the true line of advance toward a realunderstanding of chemical combination.In this connexion, attention may be directed to thc work of Clarkand Duane,lo who, utilising the reflection of X-rays characteristicof each element present in a compound, have been able to analyseseparately the space distribution of each kind of atom and sodetermine, in a more positive manner than was hitherto possible,the real structure of solid compounds.Thus the relative positionsin space of czesium and iodine atoms in casium iodide and tri-iodide (CsI ; CSI,) have been ascertained and a step, which mayprove very important, taken toward a new experimental methodfor the study of valency.L4tomk Weights.Boror~.-Further details have now been pEblished of the prepar-ation l1 and analysis l2 of the boron trichloride used for a determin-ation of the atomic weight of boron already rep0rted.1~Boron hydride, B,H,, prepared by heating B,H,, for five hours at95" and purified by fractional distillation a t low temperatures, hash e n decomposed by vpater thus : B,H, + 6H,O 4 El,BO, + CiH,.Measurement of the volume of hydrogen produced from a knownweight of the hydride gives values for tlhc ratio B2H6 : CiH, corre-sponding to 33 = 10.8055 & 0.0015.14J5W.Nernst, 2. ungezo. Chem., 1'323, 36, 453; A., ii, 680; W. 13. Campbell,N. V. Sidepick, T., 1923, 123, 723.S. Sugden, T., 1923, 123, 1861.T. M. Lowry, T., 1923,123, 1566; J. D. BI. Smith, Chemistry and Industry,1023, 42, 1073; A., ii, 844.lo G. L. Clark and W. Duane, Proc.Nut. Acad. Sci., 1923, 9, 117, 126,131 ; A., ii, 468, 469; Physical Rev., 1922, 20, 85; A., ii, 856.l1 A. Stock and E. Kuss, Ber., 1923, 56, tBJ, 1463; L4., ii, 560.l2 0. Honigschmid and L. Birckenbach, ibid., p. 1467; A., ii, 559.l8 Ann. Reports, 1922, 19, 31.l4 A. Stock and E. KUSS, Ber., 1923, 56, [BJ, 314; A., ii, 157.l5 Idem, 8. anorg. Chem., 1923, 128, 19; A., ii, 856.Nature, 1923, 111, 569; A., ii, 39980 ANNUAL REPORTS ON THB PROGRESS OF CHEMISTRY.Silicon.-Preliminary results obtained by decomposition ofmonosilane with sodium hydroxide, Si = 28.15, 28.16, 28.14,whilst given with reserve, suggest that the current value @i = 28-3)is too high.14Analyses of silicon tetrachloride and silicon tetrabromide, purifiedby thorough fractional distillation under exclusion of air and a tvarying pressures, give as the mean of a series differing by less than1 part in 2000 the value Si = 28.063,16 materially lower than theaccepted figure.Titanium.-Six fractions of titanium tetrachloride, taken duringthe later stages of a systematic fractional distillation directed to theproduction of a pure specimen for precise determination of theatomic weight, were collected in bulbs, which were sealed off,weighed, and broken in dilute nitric acid.The ratio TiC1, : 4Agdetermined by nephelometric titration with weighed amounts ofpure silver in the usual manner gave preliminary results rangingfrom 47.78 to 47.89, the rounded mean bting Ti = 47.9, againappreciably lower than the accepted value (Ti = 48.1).17Iron.-Using four preparations of ferric chloride, purified bysublimation in a fuspd silica apparatus, thirteen determinations ofthe ratio FeCl, : 3Ag and twelve of the ratio PeCI, : 3AgCl havebeen made.The data are concordant and give for each series thevalue Fe = 5545.18Nickel.-Pure nickelous chloride prepared from terrestrial nickeland from nickel extracted from the Cumpas meteorite has beenused for comparative determinations of the atomic weights ofterrestrial and extra-terrestrial nickel. Six and four measurements,respectively, of the ratio NiCl, : 2Ag, and two and three, respect-ively, of the ratio NiCl, : 2AgC1 confirmed the earlier finding thatthese atomic weights do not differ by an amount greater than theexperimental error.The mean value now found is Ni = 58.70.19GaZZium.-The first precise determination of the atomic weightof gallium is now fully reported.20 Gallium was extracted from 60kilos. of lead residues from the distillation of zinc and, after chemicalpurification, the metal was deposited electrolytically, and subjectedto a series of eight fractional crystallisations as metal, and the16 G. I?. Baxter, P. F. Weatherill, and E. W. Scripture, Proc. Amer. Acad.1' G. P. Baxter aad G. J. Fertig, J. Amer. Chem. SOC., 1923, 45, 1228;la 0. Honigschmid, L. Birckenbach, and R. Zeiss, Ber., 1923, 56, [B],1@ G. P. Baxter and F. A. Hilton, J . Amer. Chem. SOC., 1923, 45, 694; A .2o T. W. Richards and W. M. Creig, ibid., p. 1155; A., ii, 495.Art8 Sci., 1923, 58, 245; A., ii, 412.A., ii, 498.1473; A., ii, 560.ii, 326INORQANIU CHBMISTRY.31purest material (m. p. 29-75"> was heated for twenty-four hours ina vacuum a t 800-850" to eliminate traces of zinc, etc. Sub-sequently, in a sealed glass apparatus, the metal was combined withpure chlorine and the chloride was distilled in nitrogen, subjectedto a series of fractional sublimations in a vacuum, and fmally dis-tilled into bulbs, which were sealed. Whilst of the usual generalcharacter, the processes adopted for the solution and analysis ofthe chloride, as well as the elaborate apparatus for its purifkation,present many interesting features described in detail in the originalpaper. A final series of four analyses gave values for the ratioGaC1, : 3Ag corresponding to Ga = 69.718, 69.722, 69.707, 69.718 :rneczn 69.716, whence is deduced the rounded value Ga = 69-72Selenium-Prom determinations of the weight of a normal litreof hydrogen selenide and of the compressibility of the gas theatomic weight Se = 79.37 has'been found; but this value is regardedas subject to correction when further data are obtained.21,4ntimony.-Specimens of pure antimony were prepared fromstibnites from Peru, Bolivia, Borneo, and Hungary, respectively.After fusion in hydrogen, weighed portions were dissolved in con-centrated sulphuric acid, and the solution was diluted and titratedwith a weighed amount of potassium bromate according to thereaction : 3SbC1, + KBrO,+ 6HC1-+ 3SbC1, + KBr + 3H,O.Theslight excess of antimony remaining as trichloride was estimatedby titration with 0-O1N-potassium bromate, previously standard-ised against the same antimony, using methyl-orange as indicator.Seven concordant determinations of the ratio 3Sb : KBrO, arerecorded for each sample and the atomic weights deduced arerespectively Sb = 121.720, 122-374, 121.563, and 1210144.If,as is suggested, these differences are due to a variation of theisotope ratio in antimony from different localities, this may in partexplain the great discordance among previous determinations of theatomic weigh t.22Bercury.-Pure mercury was thrice distilled in a vacuum andconverted into chloride or bromide, and the halides were twicesublimed and once melted in quartz vessels.Weighed amounts of the halides were then reduced in ammoniacalsolution by halogen-free hydrazine and the resulting ammoniumhalide was titrated nephelometrically against weighed silver in theusual manner.Both series of debrminations (twelve of the ratio(C1 = 35.458; Ag = 107.88).P. Bruylants and J. Dondeyne, Bull. Acad. Roy. Bdg., 1922, [v], 8, 387;Sheikh D. MuaaBEar, J . Amer. em. SOC., 1983, 45, 2009; A., ii, 771.A., ii, 23632 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.HgCI, : 2Ag and eight of the ratio WgBr, : 2Ag) gave the same meanresult, Hg = 200.61.23Similar determinabions with the light and heavy Practions (d =0.999824 and 1~000164, respectively ; ordinary mercury = 1.000000)obtained by lom-temperature distillation of mcrcury in a, highvacuum gave values for the atomic weight Hg = 200.564 and280.632, re~pectively.~~Lead.-The more volatile and less volatile end fractions of leadchloride fractionally distilled in a high vacuum by Bronstedt andvon Hevesy were prepared for analysis by fusion and distillationin quartz in a current of hydrogen chloride.As a mean of tendeterminations in each case of the ratio PbCI, : 28g, they gave valuesfor the atomic weight Pb = 207.229 & 0.003 and Pb = 207.236 -&0.003. The difference between these results is of the same order ofmagnitude as the experimental error and thus affords no evidencethat any separation of the isotopes of lead has been effected.25By the same methods, lead derived from Upper Katanga, BelgianCongo, gave as a mean of three determinations Pb = 206.048,whence i t is concluded that the material is pure uranium lead.26Richards and Putzeys have extracted lead €,om several mineralsfrom the Belgian Congo, and after subjecting it to a rigorous series ofrecrystallisations as nitrate and chloride found, from the ratioPbCI, : 2Ag determined by the methods usually employed a tHarvard, Pb = 206.20.27 They conclude that this material, whichmay later be available in quantity, is probably derived from acommon primary deposit of uraninife and contains about 88 percent.of uranium lead and 12 per cent. of ordinary lead.Details have now been published of the fractionatiori of drybenzene reported last year, together with some iiew data of interest.Dried sulphur has been found to melt over a range of Cemper-ature from 116.8-118.5".Bromine dried for ten years had m. p.- 44", b. p. 118", as compared with the values - 7.3" and 59" forbromine similarly prepared but dried only for a few days.Sulphur tfrioxide dried for twenty years had the m. p. 61.5" for thea-form and changed on melting to a p-form of in. p. 15.5", thecorresponding temperatures for material not specially dried being23 0. Honigschmid, L. Birckenbach, and M. Steinheil, Ber., 1923, 56, [B],24 Idem, ibid., p. 1219; -4, ii, 493.z 5 0. Honigschrnid and M. Steinheil, ibid., p. 1831 ; A., ii, 764.3 6 0. Honigschmid and L. Birckenbach, ibid., p. 1837; -4., ii, 764.2 i T. W. Richards and I?. Putzeys, J . Amer. Chem. SOC., 1923, 45, 2954.1212; A., ii, 493INORGANIC CHEMISTRY. 3350" and 14.4".The melting points of two samples of the samebenzene dried for ten years and one month, respectively, were 6.0"and 6.4". Determinations of the vapour density of ether andmethyl alcohol, dried for ten years and boiling a t 83" and EO",gave the values 51.7 and 45, respectively, the normal values being37 and 1kZ8There has existed, apparently, some scepticism among chemistsas to the reality of these phenomena and therefore it is pertinentto remark that several workers have, in the course of other investig-ations, confirmed the effect of intensive drying in changing theproperties of liquids z9 and in inhibiting chemical reaction, forexample, between hydrogen and chlorine exposed to diffused daylight,and between hydrogen and oxygen at a red heat in glass tubes.30Even among chemists who accept them, these results are evidentlyless well known than their importance merits.A theoretical paperrecently published 3l criticises adversely the view that Raker'sobservations are best explained by a shift of the inner equilibriumof and propounds as new the alternative theory that drying" freezes " an existing equilibrium. As no acknowledgment ismade, it would seem that the author is unaware that this theorywas put forward in 1922, that the mechanism he suggests to accountfor a separation of the pseudo-components by distillation was fullyanticipated, even before such a separation was r e a l i ~ e d , ~ ~ and thatthe possible effect of condiicting the drying process a t varioustemperatures had already been foreseen.% It is, in fact, difficultto understand how the mere fixation of an existing equilibriumcan account for the change of surface tension and for the largechange of vapour pressure which have been ob~erved.~sThe low-temperature activat'ion of hydrogen previously reportednow found to be due to traces of oxygen, of which as little as0.02 per cent. can cause the effects observed.It is suggested thatthe activity arises from traces of triatomic hydrogen formed by thecombustion of the oxygen upon the surface of the platinum.3728 H. B. Baker, T., 1923, 123, 1223.29 H. M. Roberts and C. R. Bury, Z'., 1923,123, 2037.30 H. Tramm, 2. physikal. Chem., 1923, 105, 356; A., ii, 716; A.Coehnand H. Tramm, Eer., 1923, 56, [B], 455, 468, 696; A., ii, 205; see alsoA. W. C. Menzies, J . Amer. Chem. Soc., 1923, 45, 327; A., ii, 216.31 G. N. Lewis, ibid., p. 2836.32 Ann. Repor& 1922, 19, 36; A. Saits, Proc. K . A h d . Wetensch. Amster-33 A. Smits, 2. phyeikl. Chm., 1922, 100, 477; A., 1922, ii, 358.34 Idem, " Theory of Allotropy," p. 329; Ann. Repor@, 1922, 19, 36.35 H. B. Baker, T., 1922, 121, 572; Ann. Reports, 1922, 19, 36.3 7 Ann. Reports, 1922, 19, 3 8 ; A. E. Mitchell and A. L. Marshall, T., 1923,dam, 1923, 26, 266; Rec. trau. chim., 1923, 42, 826; A., ii, 547, 628.123, 2448.REP.-VOL. XX. After electrolysis of dilute aqueous sodium or potassium hydroxideor sulphuric acid, the cathode liquid has the property of reducingan alkaline silver solution.The reducing agent is unstable, one-halfdisappearing in a day, and is shown not to be ferrous hydroxide oractive hydrogen.3sThe Inert G'ases.A new method for the purification of neon, applicable to relativelylarge quantit'ies, has been described, and neon so purified has beenused to redetermine the critical temperature, - 228-7", on thethermodynamic scale .39By means of the mass-spectrograph, search has been made fornew heavier constituents of air in the liquid oxygen residues fromthe evaporation of 400 tons of liquid air. The results indicate thatif any gas heavier than xenon is present its amount is certainly notgreater than 1 partl in 1015 parts, and probably does not exceed1 part' in 2 x 1016 parts, of air.40Group I .Hydrogen produced by t)he action of hydrochloric or sulphuricacid on magnesium, or by electrolysis of aqueous sulphuric acid orpotassium hydroxide using a high cathodic current densitly, reactswith nitrogen to form ammonia.41 Similar active hydrogen, detectedby its reaction wihh cold sulphur to form hydrogen sulphide, hasbeen obtained by the burning of oxygen and hydrogen, with flameor on a platinum surface, by striking a high-tcnsion arc betweensilver electrodes in hydrogen, and by the decomposition of thehydrides of sodium, potassium, and calcium.42The rate of diffusion of hydrogen through nickel is an exponentialfunction of the temperature and directly proportional to the squareroot of the pressure.& By means of a new apparatus the followingvalues (at the temperatures stated in brackets) haJve been found forthe specific diffusion (mg.per hour per sq. cm. for a thickness of1 mm.) of hydrogen through a number of metals: Aluminiumt0.0005 (656"); zinc 0.0012 (375"); lead 0.001 (265"); copper0.011 (500") ; 0.028 (7'70") ; nickel 0.01% (500") ; 0.100 (750").4438 G. Tammann, 2. anorg. Chent., 1923, 126, 176; A., ii, 289.39 C. A. Crommelin, Rec. trav. chim., 1923, 42, 814; A., ii, 634.40 F. W. Aston, Proc. Roy. SOC., 1923, [ A ] , 103, 462; A., ii, 4S7.4 1 A. C. Grubb, Nctture, 1923, 111, 600, 671 ; A., ii, 403.42 Y. Venkataramaiah, J . Amer. Chem. Soc., 1923, 45, 261; Proc. Sci.43 V. Lombard, C m p t . rend., 1923, 177, 116; A., ii, 570.44 H. G. Deming aqd €3.C. Hendricks, J . -4mer. Chem. SOC., 1923, 45,Assoc. Vizianagram, 1922, Dee. 6; A , , ii, 235, 482.2857INORGANIC CHEMISTRY. 35X-Ray examination of the crystal structure of palladium showsthat no abrupt change occiirs 011 saturation with hydrogen, butthat the crystal lattice expands by 2.5 per cent., in good agreementwith the observed increase of 2.9 per cent. in volume. The dataindicate the existence of two crystalline phases consisting ofsaturated and unsaturated solid solutions of hydrogen in palladium,and are inconsistent with the formation of any compound.45Sodium acts on an anhydrous solution of lithium chloride inalcohol, precipitating sodium chloride and leaving in solutionlithium ethoxide, which is separated by taking advantage of itsdiminishing solubility with rise of temperature.When treatedwith hydrogen sulphide, the ethoxide yields lithium hydrosulphideas a crystalline alcoholate, 2LiHS,C,H,*OH. Some evidence wasobtained that the pure hydrosulphide results by tlhe action ofhydrogen sulphide upon metallic lithium suspended in ether, but theonly specimen so made was accidentally subjected to the action ofalcohol vapour and was thus converted into the a l ~ o h o l a t e . ~ ~Metallic sodium has also been used to reduce the anhydrous chloridesof glucinum, chromium, uranium, vanadium, and zirconium ina closed steel bomb, the metals being obtained in a fairly pure state(for example, G1 99.6 per cent., d 1.793, m. p. 1,370"; Cr 99-56 percent. ; d 6-29-6-40) and in the form of small pellets.47Triammonium hydrogen sulphate, (NH,),H(SO,),, a crystalline,non-deliquescent salt, is formed by treating ammonium hydrogensulphate with dry alcohol and washing the product with ether.48When mixtures of the salts are melted, sodium or ammoniumhydrogen sulphate reacts witlh rubidium or czesium sulphate toform the corresponding hydrogen sulphate and trisodium or tri-ammonium hydrogen sulphate.Similarly, sodium sulphate withammonium hydrogen sulphate or ammonium sulpha ie with sodiumhydrogen sulphate give mixtures of the trisodium and triammoniumhydrogen sulphates. These reactions were followed by determin-ations of the total acidity of the melts, confirmed by the resultsof extracting the powdered solid with dryAmmonium hydrosulphide, obtained by interaction of ammoniaand hydrogen sulphide in dry alcohpl or, better, in dry ether,forms white, crystalline needles.If excess of hydrogen sulphide beused, subsequent addition of ether saturated with ammonia pre-4 5 L. W. McKeehan, PhysicaE Rev., 1923, [ii], 21, 331; -31. Yamada, Phil.4 6 J. H. Jones and J. S . Thomas, T., 1923, 123, 3285.4 7 31. A. Hunter and A. Jones, Smer. Electrochem. Soc., 1923, 44, 35;4 8 H. B. Dunnielifi', T., 1923, 123, 476.Bag., 1923, [vi], 95, 241; A., ii, 427, 81.A., ii, 688.49 Idem, ibid., p. 731.G 36 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.cipitates a white, crystalline alcoholate of ammonium sulphide,(NH4),S,C2H,*OH. I f ethereal hydrogen sulphide be treated withexcess of ammonia, addition of alcohol precipitates a yellow oil,(NH4),S,2NH,, with some transparent, apparently cubic, crystalssupposed to be the normal sulphide, (NH4),s.50By the action of sulphur upon ammonium hydrosulphide in dryalcohol, orange-yellow, crystalline ammonium pentasulphide,(NH,),S,, is obtained.On exposure to air, this pentasulphidebecomes deep red, probably through formation of the heptasulphide,(NH4),S,, and finally decomposes to form hydrogen sulphide,ammonia, and sulphur; when heated in a sealed tube, it, yieldsfree sulphur and ammonium disulphide, (NH,),S,, as a yellow oilsolidifying to a yellow, crystalline mass. The cnneasulphidepreviously described could not be 0btained.~1Two investigations agree in finding that no definite hydrates ofcupric oxide exist, dehydration taking place through a series ofsolid solutions,52 but a third is held to show that, whilst t4his istrue in the presence of water, the dry hydroxide undergoes step-wise dehydration, forming definite compounds, containing 3, 4, 6, 7,and 8 molecules of CuO for each molecule of water,Fd It should benoted, however, that the granular hydroxide, owing to its compactstructure, loses water much less readily than the gelatinous hydr-oxides and thus tends to give misleading results.52Some evidence has been obtained that the blue solutions obtainedwhen concentrated aqueous alkali hydroxide dissolves cupric oxideor hydroxide, or is electrolysed with copper electrodes using a highcurrent density, contain alkali salts of cupric acid of the typeM1,cU02.54~52Reaction between excess of metallic copper and stibnite beginsa t 500" and occurs readily at 600-700", yielding a compound,3Cu2S,Sb2S3. At temperatures above 700°, this compound disso-ciates int'o antimony sulphide, which sublimes, and a residue ofcuprous sulphide, which may thus conveniently be prepared.55Complex salts of copper and thallium are described, as follows :T~,CU(SO~)~,GH,O, blue crystals ; Tl,Cu(SO,),, a yellow powder ;CuSO3,3Cu,S0~,Tl2SO3, cinnabar-red crystals soluble in aqueousammonia to a blue solution ; T~,CU(S,O,)~, a yellow, microcrystallineJ. S. Thomas and R. M.'. Riding, T., 1923, 123, 1181.51 Idem, ibid., p. 1726; compare Bloxam, T., 1895, 67, 777.52 H.33. Weiser, J . PhyGical Chem., 1923, 27, 501; E. Muller et al., Z.63 L. Losana, Gazzetta, 1923, 53, i, 75; A., ii, 321.~54 H. J. M. Creighton, J . Amer. Chern. SOC., 1023, 45, 1237; -4., ii, 492.5 5 G. Marchal, Bull. SOC. chim., 1923, [iv], 33, 597; A . , ii, 571.physikal. Clwm., 1923, 105, 73; A., ii, 566, 567INORGANIC CHEMISTRY. 37powder.56 Sodium thiosulphate, fused in its water of crystallis-ation, dissolves freshly prepared cuprous halides and cuprous thio-cyanate, giving clear, colourless aqueous solutions from which areobtained crystalline complex compounds unaffected by light.57Group I I .An improved method for the extraction of glucina from beryleffects decomposition of the finely ground mineral by fusionwith potassium hydroxide.Thc powdered melt is treated withsulphuric acid and the solution is filtered from precipitated silicaand adjusted to an acidity about 5N by addition of potassiumhydroxide. On cooling, owing to the increased solubility ofpotassium sulphate in acid of this concentration, about 90 percent. of the aluminium present separates as potash alum; furtherpurification of the glucinum is effected by known methods.58Interaction of anhydrous calcium chloride with sodium sulphatedecahydrate for eight hours at 300" and 12.5 atms. yields acompact crystalline calcium sulphate dihydrate, CaS0,,2HZO,dosely resembling natural alabaster in its texture and appearancewhen cut and polished.66Because the variation of the cubical expansion of zinc withtemperat'ure exhibits singular points a t 176" and 320", it is inferredthat this metal exists in a t least three allotropic forms.67 Detailsare published of a simple method for the preparation of stronglyphosphorescent zinc sulphide, 68 and of the production of zincnitride by the action of ammonia on zinc dust a t 650".69Measurements of the change in specific magnetic susceptibilityindicate that the dehydration of magnesium hydroxide is reversibleand that of cadmium and zinc hydroxides irreversible, but that inthe last case water lost is partly adsorbed by the oxide, some 2-3per cent. being retained a t 205".70A convenient apparatus for purifying mercury by air agitation,with or without the addition of the usual cleansing solutions, isdescribed.71The reduction of several metals of this group from their saltsby hydrogen has been investigated. By hydrogen a t 100 atms.,6 6 G. Canneri, Gazzetta, 1922, 52, ii, 266; A., ii, 74.6 7 G. Canneri and R. Luchini, Gazzetta, 1923, 52, ii, 361; A., ii, 71.5 6 H. T. S. Britton, J. SOC. Chern. Ind., 1922, 41, 3 4 9 ~ ; A., ii, 28.6 6 hl. Copisarom, T., 1923, 123, 796.6 7 L. Losana, Qazzetta, 1923, 53, 539; A., ii, 763.6 8 J. Schmidt, Ber., 1922, 55, [B], 3988; A., ii, 73.6s W. J. Bently and P. L. Stern, Science, 1921, 53, 143; A., ii, 38.70 P. Pascal, Compt. rend., 1923, 177, 765; A., ii, 861.7 1 -4. E. Dixon and J. L. McKee, T., 1923, 123, 89538 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.mercurous nitrate is reduced, a t 160", to metallic mercury and a,basic nitrate, possibly 2Hg20,N20,, and at 225", completely tothe metal; and mercuric nitrate is reduced to the mercurous saltat 170-180" and to metal a t 240-250".Cadmium nitrate yieldsa basic salt, Cd(NQ3),,7Cd0, a t 135 atms. and 220", and crystallinemetallic cadmium a t 220 atms. and 275". Zinc nitrate and sulphatewere similarly reducible, but metallic magnesium could not thus beobtained. 72Thermal studies of the systems formed by silver nitrate withmercuric iodide and by thallous nitrate with mercuric chloride,bromide, and iodide show that no double decomposition occurs,but the following compounds are formed : 2AgN03,HgI,, yellowish-green crystals, rn. p. 107"; AgNO,,HgI,, m. p. 117-118",undergoing at 52" dimorphic change marked by change of colourfrom canary-yellow to orange ; 73 T1NQ,,HgC12, m.p. 202-5" ;2T1NO3,HgCl,, m. p. 195"; T1N03,HgBr,, m. p. 152".74 A similarinvestigation of several binary systems of components capable ofsublimation discloses the existence of two compounds of mercuricchloride with ammonium chloride : HgCl,,NH4C1, m, p. 204",b. p. 350"; and HgC1,,4NH4Cl, m. p. 244", decomposing a t highertemperature^.^^Group 111.By the use of an improved process and apparatus, wherebymagnesium boride is gradually added to excess of hydrochloricacid at 40-SO", crude boron hydrides have been prepared in muchgreater quantity than formerly and purified by fractional con-densation with liquid air. The product previously supposed tobe a pure substance of the composition &HI, appears to be amixture of B4H10, B,H,, and B,H,, with silicon hydride.Tetra-borane, B4H10, has m. p. - 120" and boils at about 18"; its densityis 0.59 a t - 70" and 0.56 a t - 35"; even when pure, it decomposesrapidly a t the ordinary temperature, giving hydrogen, diborane,and several less volatile hydrides.Diborane has m. p. - 165.5", b. p. about - 92"; it does notappear to dissociate below 155"; it reacts with hydrogen bromidein presence of aluminium bromide a t 90", forming the very unstablemonobromodiborane.The hydride, B,H,, best obtained by fractionation of the pro-72 w. Ipatiev and -4. Starynkevitsch, Ber., 1923, 56, [B], 1663; A., ii, 639.A. G. Bergmann, J . Russ. Phys. Chem. Soc., 1921, 53, 181; A., ii, 636.74 A.G. Bergmann, T. A. Heiike, and F. M. Isaikin, ibid., 1922, 54, 466;75 E. Jiinecke, Rec. trav. chim., 1923, 42, 740; A., ii, 640.see also ib'id., 1922, 54, 200; A., ii, 568, 764TNORQANIC CHEMISTRY. 39ducts of decomposition of tetraborane a t loo", is a colourless,mobile liquid, m. p. - 46.9"; it has an extremely unpleasantodour and is the noxious constituent of crude boron hydrides.It is fairly stable, but.is slowly hydrolysed by water at go", forminghydrogen and boric acid.The hydride B,H,, is a colourless, refractive liquid, m. p. - 65.1",hydrolysable, as is B,H,; when kept at the ordinary temperaturein daylight, it decomposes, yielding mainly a yellow, crystalline,solid hydride.Analysis of these compounds is effected by thermal decom-position into boron and hydrogen a t a fairly high temperature;a t and below 300" they exhibit differences in stability and in thenature of the products of decomposition, for details of which theoriginal paper should be consulted.76Almost quantitative yields of boron trichloride are obtainedby the action of chlorine upon ferro-boron at 500°.77By maintaining a temperature gradient in systems of boraxand boric oxide during cooling it is possible to ensure that at somepoint in the mass conditions are such as to permit crystallisation.Thus the fusion diagram of this system has been constructed andfound to indicate the existence of two new compounds : Na20,3B203,m.p. 694", and Na20,4B,03, m. p. 783", forming solid solutionswith each other and with boric oxide.78Evidence from the cooling curves and micro-structure ofaluminium-copper alloys containing 14-2 1 per cent.of aluminiumshows that the compound AlCu,, melting with decomposition at1,016", probably undergoes change to another crystalline form,without decomposition, on cooling to about 700".79 A similarstudy of the system aluminium-iron indicates the existence of anendothermic compound, Al,Fe, and, with lower proportions ofiron, a stable phase markedly different in properties from theadjoining alloys but variable in composition. Aluminium-titanium alloys witJh up to 30 per cent. of the latter metal containhard crystals of the compound Al,Ti, m. p. 1,325", and immisciblewith aluminium.*lAqueous solutions of aluminium chloride and sodium silicatereact to form a precipitate of the composition 2A1,03,3Si0, which76 A.Stock and E. KUSS, Ber., 1923, 56, [B], 789; A., ii, 408.77 C. Mazzetti and F. De Carli, Atti R. Accad. Lincei, 1922, [v], 31, ii, 119;78 I. F. Ponomarev, J . Ruse. Phys. Chem. SOC., 1917, 49, 229; A., ii, 415.7B D. Stockdale, Trans. FaradQy SOC., 1923, 19, 135; A . , ii, 766.A , , ii, 67.N. Kurnakov, G. Urasov, and A. Grigoriev, 2. anorg. Chem., 1922,125, 207; J. Rum. Phys. Chem. SOC., 1918, 50, 270; A., ii, 75.s1 E. van Erckelons, Metall und Em, 1923, 20, 206; A . , ii, 56940 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.adsorbs silica and in presence of sufficient silicic acid is converted intothe compound A1203,2Si0,, analogous to kaolin, A1,0,,2SiO2,2H2O.Investigations of the X-ray spectra of these products and of thecourse of their dehydration indicate that the first is amorphousand that, under the conditions of experiment one compound only,A1203,2Si0,,xH,0, is formed.82Metallic lanthanum was prepared by electrolysing fused anhydrouslanthanum chloride containing small proportions of sodium chlorideand potassium fluoride, in a graphite cell which served as cathode,using currents of 40-50 amps.a t 7-8 volts. After being washedwith water, to remove adhering salt and to decompose carbide withwhich it was contaminated, the product was remelted under calciumchloride in a graphite crucible and used for determination of thefollowing properties : m. p. 826" ; 6.16 ; Brinnell hardness(500 kg.) 37; heat of combustion 1645 cal./gm.; kindling tem-perature 445".The metal is not ductile, is easily oxidised evenby dry air, but is not pyrophoric in the pure state or when alloyedwith iron?The action of water upon the product of fusion of lanthanumoxide with sodium carbonate gives only the double carbonate,La,(C03)3,Na,C03,12H,0 ; hence it appears that the various lanth-anates of sodium, potassium, and barium formerly described 84do not exist.85Similar crystalline double salts are formed by sodium carbonatewith the carbonates of cerium, praseodymium, neodymium, andsamarium.86 A series of triple nitrites of cobalt, nickel, or copperwit'h an alkali metal and a metal of the cerium or yttrium grouphas. been described.87Investigation of the emission spectra of rare-earth fractions con-taining terbium, dysprosium, and gadolinium is reported to indicatethe presence of a new element, giving a well-defined and character-istic line spectrum, for which the name zcelsium is proposed.88Group I V .Vitreous carbon, giving an X-ray spectrum containing the linesof both diamond and graphite, is obtained by exposing a heated,82 R.Schwarz and A. Brenner, Ber., 1923, 56, [B], 1433; A., ii, 569.83 H. C. ICremers and R. G. Stevens, J . Amer. Chem. SOC., 1923, 45, 614;84 C . Baskerville and G. F. Catlett, A., 1904, ii, 260.A., ii, 322.F. Zambonini and G. Carobbi, A t t i R. Accad. Lincei, 1923, [v], 32,ii, 6 3 ; A., ii, 765.g6 Idem, ibid., p. 125; A., ii, 863.87 V.Cuttica and F. Gallo, Gazzetta, 1923, 53, i, 374; A., ii, 680.8 8 J. M. Eder, Sitzungsber. Akad. W&w. TVien, Math.-natumiiss. Klass.1922,:[iia], 131,-199; A., ii, 47INORGANIC CHEMISTRY. 41chemically inert surface to the luminous flames of certain aliphatichydrocarbons. It is very pure (C = 99.06 per cent.), has dc2.07and a low electrical conductivity, and that prepared a t 1,300' isharder than carbor~ndum.~~ Pure graphite has been obtained bycarbonising filaments of artificial silk, first in coal gas at 500",then in hydrogen a t 2,200-2,500', and maintaining them a t 1,500-?,OOO" in the vapour of hexachlorobenzene, carbon tetrachloride,or light petroleum, etc., a t low pressures, or in the last two casesin the liquid state, until the cross section of the filament had verygreatly increased.After heating at 3,500" in carbon monoxide,such filaments have all the properties of pure graphite and can bebent like lead.90 Carbon produced by heating graphitic acid hasd4. 2.215 and therefore is probably pure graphite.g1By heating purified water-gas to 200-300" a t atmosphericpressure in contact with nickel, the reaction 2CO + 2H, zz CO, +CH, occurs to a considerable extent, and it is suggested that theprocess may find technical application in the manufacture ofmethane or in the partial substitution . of methane for carbonmonoxide in towns gas.92Some interesting work upon the hydrides of silicon is reported.From the study of reactions in which alcohol is in part substitutedfor water, it is inferred that when magnesium silicide is decom-posed by hydrochloric acid about 10 per cent.reacts as follows :Mg:Si:Mg + 2H*OH -+ H,Si(Mg*OH),,and the remainder yields silica and hydrogen, probably by there actionMg2Si + 4HC1 + 2H20 -+2MgC12 + SiO, + 4H,.Production of silanes probably occurs by further hydrolysis of thefirst product, for example, thus : SiH,(Mg*OH), + 2H*OH+2Mg(OH), + SiH4, and SiH,(Mg*OH), + 4HC1+ 2MgC1, + H,O +SiH,O + 2H2.93 Failure attended attempts to effect regulatedoxidation of silane by admixture with oxygen, air, or air dilutedwith nitrogen under greatly reduced pressure and at - 70" toDisiloxan, (SiH3)20, is but slightly decomposed by heating a t89 K. A. Hofmann and C. Rochling, Ber., 1923, 56, [B], 2071; A., ii, 757.y1 R.M. Burns and G. A. Hulett, J . Amer. Chem. SOC., 1923, 45, 572;92 E. 3'. Armstrong and T. P. Hilditoh, Proc. Roy. SOC., 1923, [A], 103,93 R. Schwarz and E. Konrad, Ber., 1922, 55, [B], 3242; A., 1922, ii, 846.s4 A. Stock and C. Somieski, ibid., p. 3961; A., ii, 67.- 140°.94M. Pirani and W. Fehse, 2. Elektrochem., 1923, 29, 168; A., ii, 317.A., ii, 317.25; A., ii, 307.U42 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.N O " , but phosphoric oxide decomposes it at the ordinary tem-perature, forming chiefly monosilane, hydrogen, and polymericprosiloxan, probably by hydrolysis of the type : (SiH,),O + H20 -+2SiH,O + 2H2.95Disilane at 500" suffers decomposition, analogous to the crackingof hydrocarbons, producing silicon, hydrogen, and monosilane.Monochlorosilane and hydrogen sulphide a t 150" in presence ofaluminium chloride yield hydrogen, dichloromonosilane, and avolatile compound containing sulphur, possibly SiH,*HS or (SiH3)ZS.Dichloromonosilane reacts with sodium amalgam to give mono-silane and the unsaturated, yellow polymerised hydride (SiH),.96Trichloromonosilane, prepared from copper silicide and hydrogenchloride at 300", and purified by fractional distillation in a vacuum,has m.p. - 126-5", b. p. 31.8", do 1.35. It is remarkably stableto heat and unaffected by aluminium chloride a t 175"; a t goo", itdecomposes almost quantitatively into silicon, hydrogen, hydrogenchloride, and silicon tetrachloride. It is immediately decomposedby water, yielding s6lid non-volatile silicof ormic anhydride,[HSiO],O ; it reacts with sodium amalgam readily, probablyaccording to the scheme xSiHC1, + 3xNa + 3xNaCl+ (SiH), ; andwith ammonia, in the gaseous phase at low pressures or in theliquid state at low temperatures, it forms an imide, 2SiHC1, +9NH, + [SiH(NH)],NH + GNH,Cl, which decomposes on heatingto yield mainly ammonia and SiHN.97Trisilane reacts with chloroform (4.3 mols.) at 50" to form mixturesof isomeric chlorotrisilanes according to the schemes Si,H, +4CHC1, + Si,H,Cl, .+ 4CH2Cl, ; and Si,H, + 5CHC1, -+ Si,H,Cl, +5CH2C12.98 Trisilane (silicopropane) has 0.743, m.p. - 117.4",b. p. 53"; tetrasilane (silicobutane) has d:: 0.825, m. p. circa -- go",b. p. 109".99Reference may here be made to Sosman's theory that all theforms of silica contain the same atom triplet, >Si<o aggregatedinto chains by linking of the silicon atoms.Liquid and vitreoussilica are characterised by mere assembly of such chains in juxta-position ; the crystalline forms of silica (cristobalite, tridymite, andquartz) by their systematic linking via the oxygen atoms.Investigation of the reduction of the tetrachlorides of titaniumand zirconium by sodium amalgam, magnesium, zinc, aluminium,0'95 A. Stockand C. Somieski, Ber., 1923, 56, [B], 132; A., ii, 160.96 Idem, ibid., p. 247; A., ii, 160.9 7 A. Stock and F. Zeidler, ibid., p. 986; A., ii, 412.y 8 A. Stock and P. Stiebeler, i b i d . , p. 1087; A., ii, 486.9Q -4. Stock, P. Stiebeler, and F.Zeidler, ibid., p. 1695; A., ii, 633.1 R. B. Sosinan, J . B'ralzklin In&., 1922, 194, 741; A., ii, 69INORGANIC CHEMISTRY. 43tin, arsenic, phosphorus, etc., has shown that reduction by aluminiumat about 250" affords a convenient means for the preparation of thetrichlorides, from which excess of tetrachloride and aluminiumchloride can be removed by distillation. Titanium trichloride thusprepared is a bright violet, non-crystalline powder subliming a t425"/<1 mm. to form dark violet, prismatic crystals; it is verysensitive to oxygen and moisture, and dissociates a t 450" to formthe volatile tetrachloride and a black residue of the dichloride,which is very reactive, takes fire in moist air, and decomposes waterwith evolution of hydrogen.2 Zirconium trichloride, obtained as abrown, microcrystalline solid, d1g0 3.0, and the black dichlorideformed by its dissociation a t 330" generally resemble the titaniumcompound^.^The greater part (90-95 per cent.) of the silica present in zirkitemay be eliminated by heating at 2,200" with carbon in the electricfurnace, and a crude zirconia may thus be obtained which is avaluable refractory material. Zirconium carbide is infusible in a40-50 kw.arc, but must be protected against oxidation.*Investigation of the system thorium oxide-chromic anhydride-water at 25" discloses the existence of two solid phases, the normalchromate, Th(Cr0,),,3H20, and a microcrystalline acid chromate,Th( Cr0,),,Cr03,3H20, stable in presence of dichromate or chromicacid, but decomposed by water. The normal salt is convenientlyprepared by precipitating a boiling acid solution of thorium nitratewith potassium chromate.5Germanium hydride, prepared by the action of hydrochloric acidupon an alloy of germanium and magnesium, was condensed a t-185" and purified by sublimation; it had m.p. -165"; b. 11.-126"/757 mm. When decomposed by heat, it gave 2.05 timesits volume of hydrogen; it contained 94.70 per cent. Ge and 5.29per cent. H (calc., Ge = 94-73 and H = 5.27 per cent.); determin-ations of its vapour density gave the molecular weight 76.93;therefore the hydride is proved to be GeIQ,.6An improved method is described for the extraction of german-i ~ m . ~ Metallic germanium is best prepared by reducing smallquantities of fhe dioxide ( 2 grams) in hydrogen a t 540" and fusingthe powder under sodium chloride a t 980--1,000"; with larger0.Ruff and F. Neumann, 2. anorg. Chem., 1923, 128, 81; A., ii, 863.0. Ruff and It. Wallstein, ibid., p. 96; A., ii, 668.J. G. Thompson, J . Physicad Chem., 1922, 26, 812; A., ii, 79.H. T. S. Eritton, T., 1923, 123, 1429.R. Schenck [with A. Imker], Rec. trccv. chim., 1922, 41, 869; &4., 1922,L. M. Dennis and E. B. Johnson, J . Amer. Chem. SOC., 1923, 45, 1380;ii, 855.A., ii, 570.c* 44 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.amounts of oxide, reduction is incomplete and some germaniumvolatilises. When free from oxide, the metal does not lose weightin an atmosphere of hydrogen a t 800", but it volatilises in a currentof the gas.Germanium melts a t 958*5', expands on solidification,and has dg: 5.35 ; it is very brittle and has a hardness of 6-25 onMoh's scale. A fused button exhibits a superficial resemblance toantimony, containing elongated crystals about 3 cm. long, somebounded by octahedral faces and often covered with dendriticbranches. In thermoelectric power and electrical resistance ger-manium conforms to its position in the Periodic System.8 Evidencewas obtained that germanium when heated undergoes a gradualmolecular inversion through two or more modifications between117" and 560".At 730" in oxygen, germanium is partly oxidised to a mixtureof the dioxide and germanous oxide; at higher temperatures, thelatter volatilises, thus preventing complete oxidation.Hydrogensulphide has no action on germanium below 200" and but slightaction until dissociation sets in, when the reaction between freesulphur and germanium produces germanous sulphide. Sulphurdioxide a.t 510-530" similarly yields germanium dioxide anddisulphide .At temperatures up to go", germanium is not attacked by water,50 per cent. aqueous sodium hydroxide, 1 : l-hydrochloric acid,concentrated hydrochloric acid or nitric acid, or 1 : l-sulphuricacid, and but little by concentrated sulphuric acid or 19N-hydro-fluoric acid. Dilute nitric acid oxidises the metal superficiallyto the dioxide, and 3 per cent. hydrogen peroxide slowly convertsthe metal into dioxide and dissolves it. A number of other reactionsare described in the original communication.gGermanium reacts with iodine vapour a t 250-360", yieldingthe tetraiodide, GeI,, and a little germanous iodide, GeI,, whichforms yellow, hexagonal crystals. Germanium tetraiodide crystal-lises in regular octahedra, di$4.3215, melting sharply a t 144" to aruby-red liquid; the colour of the solid varies with temperaturefrom canary-yellow at - 185" to ruby-red a t the melting point.It sublimes unchanged just above the melting point, but a t 440"dissociates reversibly into germanous iodide and iodine.It isunchanged by several months' exposure to air or by immersion incold, concentrated sulphuric acid, but dissolves slowly in 25 percent. aqueous potassium hydroxide and in concentrated hydro-chloric acid, and is decomposed by a small quantity of water.8 C. C.Bidwell, Physicat Rezy., 1922, 19, 447.0 L. M. Dennis, K. M. Treader, and F. E. Hance, J. Amer. C'hem. Soc.,1023, 45, 2033; A., ii, 769PNORGANIC CHEMISTRY. 46:It is soluble in carbon tetrachloride, carLon disulphide, and manyorganic solverits.10A complete thermal and micrographic study of the system tin-arsenic shows that these metals alloy in all proportions and formtwo compounds, SnAs and Sn3As2.11 The form of the melting-point curve for mixtures of stannic bromide and iodide and analysesof the solid phases separating from these mixtures show that themixed halides often described in the literature do not, in fact,exist.12Magnetic analysis of the stannic acids confirms the view thatthey a8re not definite corn pound^.^^Eleineiit No.7 2 .In January, Coster a i d Hevesy announced l4 that, in examiningthe X-ray spectra of a number of minerals, they had detected sixlines clearly attributable to the element of atomic number 7 2 . Theyfurther argued that the lines observed by Dauvillier l5 in a rare-earth preparation were very faint, were only two in number, differedby about 4X.u(lX.u = 10-11 cm.) in wave-length from the corre-sponding lines (La and Lp) now observed, and could not certainlybe identified with the new element Urbain claimed16 to havedetected in the same material by optical and magnetic examinationand named celtizim. Coster and Hevesy therefore exercised theprerogative of discoverers and proposed the name hafnium forelement No.7 2 . Urbain and Dauvillier replied l7 asserting thatthe lines observed by them were identical with those observed byCoster and Hevesy, quoting cases in support of their contentionthat it is possible for a quadrivalent element to be present in themother-liquors of rare-earth fractionation (a contention supportedby the observation that thorium molybdate, Th(MoOJB, is isomor-plious and miscible with cerous molybdate Is), and claiming priorityfor the name celtium. Coster and Hevesy in answer pointed out l9that there is no difliculty in effecting chemical separation of hafniumfrom accompanying rare earths and that it does not appear to yieldlo L. M. Dennis and F. E. Hance, J. Amer. Chem. SOC., 1922, 44, 2854; A,,l1 Qasim Mi Mansuri, T., 1923, 123, 214.l2 M.G. Rader, 2. anorg. Chem., 1923, 130, 325; A., ii, 867.l3 P. Pascal, Compt. rend., 1922, 175, 1063; A,, ii, 79.l4 D. Coster and G. Hevesy, Nature, 1923, 111, 79; A., ii, 80.l5 Ann. Repor&, 1922, 19, 52.l6 G. Urbain, A,, 1911, ii, 115.l7 Idem, Compt. rend., 1933, 176, 469; G. Urbain and A. Dauvillier, Nature,la F. Zambonini, AttZ R. Accad. Lincsi, 1923, [v], 82, i, 618; A., ii, 691.lo D. Coster and G. Hevesy, Nature, 1923, 111, 252; A., ii, 171.ii, 172.1923, 111, 218; A., ii, 17146 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.the optical spectrum assigned by Urbain to celtium .20 Furthercontroversy on this matter has continued throughout the year,21and the question cannot yet be regarded as settled. One hopesthat some means may be found to avoid in this case such confusionas still persists in the cases of glucinum and columbium.It is clear that our knowledge of the properties of this element isalmost wholly due to the work of Coster and Hevesy whose name,hafnium, will therefore be adopted here.Both the X-ray 22 and optical spectra 23 of hafnium have beenfully investigated, and the proportion of this element in any mixturemay be estimated by measuring the intensity of its lines in theX-ray spectrum as compared with that of lines due to knownamounts of tantalum (atomic number 71) added to the specimen.24Thus it has been found that all zirconium minerals contain hafnium,although in very varying amounts : the oxides generally contain1---2 per cent., the silicates, for example, zircon, 2-6 per cent.,whilst alvite from Kra,gero, Norway, contains 34 per cent.ofzirconia and 16 per cent. of hafnia.25 Hafnium does not occurin typical thorium minerals free from zirconium, such as Ceylonesethorianite or Norwegian orangite and thorite, or in titanium mineralssuch as rutile and ilmenite; but zirconia extracted on the largescale from fergusonite and euxenite contains 5-6 per cent. ofhafnium .Chemically, hafnium exhibits a close general similarity to zircon-ium, with which it is readily separated from the rare earths andthorium by the usual methods. $eparation of hafnium andzirconium from each other is best effected by fractional crystallis-ation of aqueous solutions of -the double fluorides with potassiumformed by fusing the material with potassium hydrogen fluoride.Hafnium is more basic than zirconium, and its phosphate is appreci-20 H. M.Hansen and S. Werner, Nature, 1923, 111, 322; A . , ii, 200.21 POT Celtium : A. Dauvillier, Compt. rend., 1923, 176, 676; A., ii, 200;M. de Broglie and J. Csbrera, ibid., p. 433; A., ii, 200; G. Urbain, Chemistryand Industry, 1923, 42, 764; A., ii, 646; Anon., ibid., p. 784; A., ii, 692;B. Rrauner, ibid., p. 884; A., ii, 692. F o r Hafnium : H. M. Hansen and S.Werner, Nature, 1923, 111, 461; A., ii, 426; D. Coster and G. Hevesy, ibid.,p. 462; A., ii, 426; H. S. King, ibid., 1923, 112, 9; A., ii, 645.22 D, Coster, Phil. Mag., 1923, [vi], 46, 956; A., ii, 807; A.khiiek, 2.Physik, 1923, 15, 31; A., ii, 449.23 J. Bardet, Compt. rend., 1923, 176, 1711; A., ii, 449; H. M. Hansenand S. n7erner, Nature, 1923, 112, 618 ; A , , ii, 807.24 D. Coster, Chem. News, 1923, 127, 65; D. Coster and G. Hevesy, Nature,1923, 111, 182; A., ii, 171.25 G. Hevesy and V. T. Jantzen, T., 1923, 123, 3218; see also V. M.Goldschmidt and L. Thomassen, Norsk Geologiak Tidsskrift, 1923, 7, 61;A., ii, 174INORGANIC CHEMISTRY. 47ably less soluble in concentrated acids than is zirconium phosphate,lout these differences do not afford a convenient means of separation.From preparations rich in hafnium, zirconium may be separatedby dissolving the oxychlorides in alcohol and adding ether, whenthe less soluble basic salt, Zr20,C1,,5H20, is precipitated.A preliminary determination, using hafnium containing 5-6per cent.of zirconium, indicates an atomic weight between 178.4and 1 8 0 ~ 2 . ~ ~Group T7.Details have been given of a more convenient process for thepreparation of potassium hydroxylamineisodisulphonate,27 and ofa technique for the preparation of hydrazine by Raschig's method.28Nitric oxide and hydrogen chloride at - 180" yield a solid havingan intense purple colour and melting a t about - 150" to a purpleliquid with an electrical conductivity about that of 0-O1N-potassiumchloride solution. The vapour pressure of the substance is notappreciably less than that of pure nitric oxide a t the same temper-ature, whence it is inferred that the complex is exceptionallyunstable and probably (in view of its colour) of the type [NOH]+Cl-.2gA study of the absorption spectra of nitrosylsulphuric acid andof the complex compounds of copper sulphate and ferrous sulphatewith nitric oxide shows that appreciable quantities of this acidremain undecomposed on dilution with water to 50 per cent.;thus one of the fundamental assumptions of,Raschig's theory of thechamber process is i n ~ a l i d a t e d . ~ ~Certain properties of ammonia have been redetermined, usingfifteen carefully purified samples containing less than 0.0001 percent.of non-condensible gases and less than 0.003 per cent. of water,as follows : freezing point, - 77.7" ; vapour pressure a t the freezingpoint, 45.2 mm.; density of the solid a t - 79", 0.817 gm./c.c.;a t - 185", 0.836 gm./c.c.31 The boiling point is - 33.41" & O ~ l " .~ 2When cooled, normal solutions of potassium hypochlorite andammonia are mixed and distilled under reduced pressure a t 3 0 4 0 " ,26 G. Hevesy, Chem. News, 1923, 127, 33; A , , ii, 570; Chemi&y and2 7 F. Raschig, Ber., 1923, 56, [B], 206; A., ii, 161; see also W. L. Semon,28 R. A. Joyner, T., 1923, 123,1114.29 W. H. Rodebush and T. 0. Yntema, J . Amer. Chem. SOC., 1923,4!5, 332;30 H. I. Schlesinger and A. Salathe, {bid., p. 1863; A., ii, 673.31 E. C. McKelvy and C. S. Taylor, U.X. Bur. Standards, Sci. Paper 465,32 F. W. Bergstrom, J . Physical Chem., 1922,26, 876; A., ii, 56.Industry, 1923, 42, 929; A., ii, 769; Ber., 1923, 56, [B], 1503; A., ii, 645.J .Amer. Chem. SOC., 1923, 45, 188; A., ii, 155.A., ii, 237.1923, 655; A., ii, 55748 ANNUAL REPORTS ON THE PRO~RESS OF CHEMISTRY.the distillate contains 10-12 per cent. of monochloroamine, NH,Cl.This substance readily decomposes, even a t 0", but it is greatlystabilised in solution by the presence of very small amounts ofammonia; and by desiccating the vapours of such a solution overanhydrous potassium carbonate and condensing the residue a t- 180", pure chloroamine is obtained as a colourless, crystallinesubstance, m. p. - 66"; it decomposes suddenly a t about - 50")forming nitrogen, chlorine, and ammonium chloride, and its liabilityto explode violently under these conditions rendered furtherinvestigation impracticableAmmonia reacts with sulphur monochloride in cold chloroformsolution, yielding mainly nitrogen sulphide, N4S4, which may beprecipitated by adding alcohol; but the mother-liquors on con-centration yield nitrogen pentasulphide, N,S,, and hexasulphamide,S6NH,, crystallising in colourless, square plates, m.p. 105".34Sodamide in liquid ammonia solution, when treated with amalga-mated aluminium, forms a definite, crystalline compound which,since it loses one molecule of ammonia above 90" in a vacuum, maybe formulated Al(NH,),NHNa,NH3.35Further work is recorded upon the additive compounds formed byammonia with the halides of the alkali metals, calcium, strontium,barium, bivalent tin, and lead.36Thenard's " black phosphorus " has been shown to be a colloidalsuspension of mercury in phosphorus and distinct from the trueblack phosphorus prepared by Bridgman.37Several phosphides have been prepared by the action of hydrogenphosphide upon solutions of metallic salts : mercurous sulphatein dilute sulphuric acid yields black, amorphous mercurous phos-phide, PHg3; mercuric chloride in ether gives pure mercuric phos-phide, P2Hg3, as a dark brown solid attacked by warm water, alkalis,and dilute acids with liberation of phosphine ; alcoholic lead acetateand ammoniacal cadmium sulphate give black, flocculent precipi-tates of the phosphides, P,Pb, and P,Cd3, which are even less~table.~SPhosphorus trichloride is obtained in almost quantitative yieldby heating calcium phosphates a t 1,000" with sulphur chloride*2 W.Marckwald and M. Wille, Ber., 1923, 56, [BJ, 1319; A., ii, 558.34 A. K. Macbeth and H. Graham, Proc. Roy. Irkh Acad., 1923, 38, 31;85 F. W. Bergstrom, J. Amer. Chem. SOC., 1923, 45, 2788.36 G. F. Huttig, 2. anorg. Chem., 1922,123,31; 124,322; 125,269; A., 1922,A., ii, 855.ii, 849; 1923, ii, 23, 72; W. Biltz et al., i b i d . , 1922, 124, 230; 1925, 127, 1;129, 1; A,, 1922, ii, 851; 1923, ii, 760, 867.s7 C. H. Hal& J. Amer. CAem. SOC., 1923, 45, 67; A., ii, 156.38 A. Brukl, 2. morg. Chem., 1922,125,256; A., ii, 75JNORBANIC CHEMISTRY. 49and a catalyst such as silica; 39 and its oxidation to the oxychloridemay conveniently be effected by passing a current of chlorinethrough the liquid and dropping in an equivalent quantity of water.40The mode of reduction of silver nitrate by hypophosphorous acidaffords further evidence in support of the hypothesis that an activetervalent form of the acid exists,41 and a detailed study of thereaction between phosphorous acid and iodine, which proves to bemuch more complex than previous worliers had supposed, providesdata which can best be explained on the assumption that phosphorousacid too can exist in an active and an inactive form, the completechange being represented : 42~ I*-+H,O I*-!-H,O %X,P04 + 2HI +-- H,PO, H,PO, ---+ H3P04 + 2H+ + 31-.(normal) (active)Crystalline tetraphosphoric acid, H6P4OI3, m.p. 34', 8% 1.8886,1iit)herto known only in the form of its salts, is obtained from phos-phoric acid by adding phosphoric oxide sufficient to make the totalP,O, 520 per cent.of the water present and allowing the syrupyliquid to stand some days.&has been obtained by the action of excess of phosphoric acid onaqueous ferric chloride.44Pure tantalic acid has been shown to be non-volatile when heatedin oxygen or on evaporation of its solution in hydrogen fluoride,and new double fluorides of tantalum with hydrogen, ammonium,and barium are described.45Arsenic trichloride, tribromide, and tri-iodide may convenientlybe prepared by treating a heated mixture of arsenious oxide andpowdered sulphur with the appropriate halogen.46Examination of the alleged antimonious hydroxides preparedfrom barium antimony1 tartrate and sulphuric acid, from tartaremetic and hydrochloric acid, and by the action of alkali carbonatesor hydroxides on antimony tri~hloride,~~ and of specimens of hydratedantimony pentoxide prepared in various ways,48 shows that nostable hydroxide exists in either case.39 P.P. Budnikov and E. A. Shilov, J . SOC. Chenz. Ind., 1923, 42, 378~;A., ii, 763.40 A. A. Vanscheidt and V. Michailovitsch, J . Rum. Phys. Chern. SOC., 1920,52, 270; A., ii, 559.41 A. D. Mitchell, T., 1923,123, 629; compare Ann. Repo~ts, 1922,19, 53.43 Idem, T., 1923,123,2241.43 M. A. Rakusin and A. A. Arseneev, Chem. Ztg., 1923, 47, 195; A,, ii, 237.44 L. Dede, 2. anorg. Chem., 1922,125,28; A., ii, 31.45 0. Hahn and K. F. Puetter, {bid., 1923,127, 153; A., ii, 773.4 6 G. Odd0 and U. Giachery, Gaxxetta, 1923, 63, i, 66; A, ii, 316.47 C.Lea and J. K. Wood, T., 1923,123, 259.48 G. Jander and A. Simon, Z . anorg. Chem., 1923,127, 68; A., ii, 772.Diphosphatoferric acid,[Fe (PO,) @3 ,24H@50 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Dissolution of bismuth in 70 per cent. perchloric acid is foundto be attended by serious danger of explosion, but it may safelybe dissolved in 40 per cent. acid. This solution, on evaporationin a vacuum, deposits small, hexagonal t'ablets of the saltBi(C10,)3,5H,0, readily hydrolysable to the bismuthyl perchlorate ,(BiO)C104,3H,0, which changes to a monohydrate, (BiO)CI0,,H20,forming hygroscopic, rhombohedra1 crystals, By solution of anti-mony oxide in hot 70 per cent. perchloric acid, small needles ofan timonyl perchlorate, (S b O)C104,2H20, are obtained .49G ~ O U ~ 171.Direct union of sulphur and hydrogen a t temperatures below 400"occurs by way of two reactions : (a) a gaseous reaction proportionalin velocity to the pressure of hydrogen, and ( b ) a surface reactionindependent of that pressure.Further study of the effect ofoxygen on this reaction, and of the direct union of sulphur andoxygen, has led to the conclusion that the surface of liquid sulphurcontains inactive (S,) molecules, and active (S,) molecules whichadsorb oxygen and then split off sulphur dioxide according to thefollowing scheme : 50+ I I - 0 2 ?2s ? -+ ? , ? + s2+2so,. s-s 7-7 s-s --., 8-sBoth hydrogen disulphide and hydrogen trisulphide dissolvelarge quantities of sulphur, a.nd the variation of solubility withtemperature shows a well-defined break a t - 1-45' when the com-position of the liquid phase approximates very closely to that ofhydrogen hexasulphide, H2S6.51Measurements of the viscosity of gaseous sulphur dioxide indicatemolecular dimensions which accord with the value calculated fora molecule S<' but not with that deduced for Langmuir's model,Further studies have been made of the oxidising action of sulphurdioxide.The observed velocities of reaction between ferrousphosphate and sulphur dioxide in phosphoric acid solution accordingto the scheme0 ,0: s* 0 . 5 24Fe(H2PO4), + 4H3P04 + SO, 4Fe(H2P04), + 2H20 + S49 F. Fichtor and E. Jenny, Helv. Cham. Acta, 1923, 6, 226; A., ii, 245.50 R.G. W. NorrishandE. K. Rideal, T., 1923,123, 696,1689,3202.51 J. H. Walton and E. L. Whitford, J. Amer. Chem. SOC., 1923, 45, 601;63 A. 0. Rankine and C. J. Smith, Proc. Phyeical SOC., 1922,35,33 ; A., ii, 66.A., ii, 315INORGANIC CHEMISTRY. 51are explained on the assumption that the primary change producesan active reducing compound, possibly a polythionic acid,54 whichlater decomposes irreversibly, depositing sulphur. The oxidisingand reducing actions of sulphur dioxide on the sulphates of molyb-denum in aqueous sulphuric acid have also been inve~tigated,~~and in this case it is suggested that the greater oxidising activityof sulphur dioxide as gas, or in high acid concentrations, may beexplained by its existence as the hydrate, S02,H20.56 Auto-oxidation of aqueous sulphurous acid, forming sulphuric acid andsulphur, is found to proceed, though slowly, a t 100" and to be auto-catalytic in its earlier stages; it is completely suppressed in3N-hydrochloric acid.57Action of a silent electrical discharge upon a current of sulphurdioxide and oxygen has yielded oxidation products as high as thatrepresented by S03,2S0,, whence it seems possible that Berthelot's" sulphur heptoxide " may have been a mixture of the trioxideand tetr0xide.5~Several physical properties of sulphur trioxide have been redeter-mined : m.p. 16-85" rfI: 0.02" ; b. p. 44.52"/760 mm. ; dzo" 1.9255;critical pressure, 83.8 atms. ; critical temperature, 218.3" ; criticaldensity, 0.633. The observations are held to indicate thatp-SO, is probably an indefinite hydration compound and not asimple polymeric modification of a-SO,.59Sodium thiosulphate and cupric nitrate in cold aqueous solutionproduce disodium tricuprous thiosulphate, 3Cu2S,03,2Na2S20,,6H20,crystallising in yellow needles which, when well washed and air-dried, are permanent. The primary reaction of formation issimply 2Cu(N03), + 3Na,S20, --t. Cu2S20, + Na,S,O, + 4NaN0,.Copper sulphate and cupric chloride give similar results, but in theformer case the yellow salt is contaminated with the salt3Cu2S0,,2Na,S0,,6H20in solid solution, and in the latter case it soon changes to a whitesalt, Cu,S20,,Na,S203,H,0, containing Cu2C12,2NaC1,H20 in solidsolution. Using excess of thiosulphate in presence of a mineralacid a t loo", the double salt is decomposed to form cuprous sulphide,3Cu,S20,,2Na,S203,6H20 + 3Cu,S + 2Na,S04 + H2S04 +250, + 25 + 5H,O, this precipitation of copper being quantitative53 S.R. Carter and J. A. V. Butler, T., 1923, 123, 2370.64 Idem, ibid., p. 2370.65 W. Wardlaw and N. D. Sylvester, ibid., p. 969. 5 6 Idem, ibid., p. 3417.57 F. Foerster, F. Lange, 0. Drossbach, and W. Seidel, 2. anorg. Chem.,6 8 F. Meyer, G. Bailleul, and G. Henkel, Ber., 1922, 55, [B], 2923; A,, 1922,1923, 128, 245; A., ii, 853.ii, 843.A. Berthoud, J. Chim. PhyB., 1923, 20, 7 1 ; A., ii, 31552 ANNUAL REPORTS ON THE PROGRESS OF CHEMXSTRT~.if sulppluric acid or nitric acid in a concentration less than N/2 isused. Under such conditions also, a reaction occurs betweensodium tetrathionate, sodium thiosulphate, and the mineral acidwhereby pentathionic acid is produced :Na2S,06 + Na2S,0, + 4HA -+ H2S,0, + 4Na'A + H20 + SO,.To account for the relatively great stability of pentathionic acidin presence of concentrated mineral acids, in sharp contrast with itsinstability in alkaline solution, it is suggested that whilst the mole-cule H,S,06 is stable, t,he anions HS601 and S,O," are veryunstable.6oPure selenium trioxide has been obtained by the action of dryozone on selenium in presence of selenium oxychloride as a solvent.After washing with carbon tetrachloride and ether, it is a pale-yellow, amorphous solid, d 3.6, decomposing at 120" to form seleniumdioxide and oxygen ; its molecular weight in phosphorus oxychloridesolution corresponds with the simple formula SeO,.A white,crystalline sublimate observed during the preparation, possiblyan allotropic modification, was not obtained in sufficient quantityfor investigation. Selenium trioxide is soluble in alcohol, butinsoluble in ether, benzene, chloroform, or carbon tetrachloride.It reacts with water and alkalis, forming selenic acid and selenates,dissolves in selenic acid, and combines directly with dry hydrogenchloride to form chloroselenic acid, the analogue of chlorosulphonicacid. Chloroselenic acid is a nearly colourless liquid, f. p. - 46",d 2.26; it fumes in air, evolving hydrogen chloride : it is insolublein ether, benzene, chloroform, or carbon tetrachloride, dissolvesunchanged in selenium oxychloride, and is dissolved and decomposedby water or alcohol.It's molecular weight in phosphorus oxy,chloride solution corresponds to the double formula (HC1Se03)2.61The solubility of a number of anhydrous metallic chlorides inselenium oxychloride has been determined and the following doublecompounds have been isolated : TiC1,,2SeOC12 ; SnCl4,2SeOC1, ;SbCI,,2SeOC12 ; FeCl3,2SeOCl2 ; KCI,SeOCI, ; RbCl,SeOCl, ;CaC1,,3SeOC12 ; MgC12,3SeOC12.Selenium nitride may best be obtained by interaction betweenselenium tetrachloride or tetrabromide and liquid ammonia ; it isan amorphous, orange-coloured powder, exploding with certaintyat 160" and more sensitive than mercury fulminate to shock; itprobably has a cyclic structure and the formula Se4N,.6360 H.Bassett and R. G. Durrant, T., 1923,123,1279.61 R. R. le G. Worsley and H. B. Baker, ibid., 1923,123, 2870.62 C. R. Wise, J. Amer. Chem. SOC., 1923, 45, 1233; A., ii, 484.133 W. Strecker and L. Clam, Ber., 1923, 56, [BJ, 362; A., ii, 152INORGANIC CHEMISTRY. 63Some new series of pliosphotungstates are described 64 includingthe simple series 3M,B,P20,,6W03,aq., of which the sodium,potassium, and ammonium salts have been prepared in the purestate.65 Investigation of the reaction between incandescenttungsten filaments and naphthalene vapour indicates the existenceof two carbides, WC and W2C.66The system chromium trioxide-nitric acid-water is simple :chromium trioxide is the only solid phase and has a minimumsolubility in liquids containing about 70-90 per cent.of nitric acid.67Group V I I .It is reported that pure chlorine is activated by the silent dis-charge, by ultra-violet light or thermally, and then reacts withozone, forming chlorine monoxide ; with sulphur, forming themonochloride ; with tellurium to form the dichloride ; and withbenzene in the dark to form the hexachloride. Active chlorineis unstable above 50" and its formation is attended by a decreasein volurnc attributed to formation of complex molecules.68Precise gravimetric determinations have been made of the com-position of constant-boiling mixtures of hydrogen chloride andwater.69 A number of new chlorites are described, including thoseof hydrazine, N,H,,HClO,, rubidium, and cmium ; mercury,HgC10, and Hg(C102), ; zinc and cadmium, Zn(C10a),,2H20 ;Cd(C10,),,2H20 ; and copper, C11(ClO2),.7O Determinations havebeen made of the solubility of the perchlorates of a number ofmetals (Li, Na, K, Rb, Cs, NH4, Mg, Ca, Sr, Ba) in water, methylalcohol, ethyl alcohol, n-propyl alcohol, n-butyl alcohol, isobutylalcohol, acetone, ethyl acetate, and ethyl ether.'lThe perchlorates of the alkali metals (except lithium), silver,and thallium are found to exist in enantiotropic forms, the transitionpoints being as follows : NaClO,, 308"; KClO,, 300"; RbClO,,279" ; CsClO,, 219" ; NH,C104, 240" ; AgCIO,, 157" ; TlClO,, 266°.72Chlorine tetroxide, (CIO,), (where x probably = Z), has been64 3'.Kehrmann and R. Jfollet, Helv.Chim. Acta, 1922, 5, 942; A., ii, 77.8 5 ldem, ibid., 1923, 6, 443; A., ii, 497.G6 Mary R. Andrews, J . PhysicalChem., 1923,27,2$0; A., ii, 327.6 7 S. A. MumfordandL. F. Gilbert, T., 1923,123, 471.b'J C. W. Foulk and M. Hollingsworth, J . Amer. C'hern. SOC., 1923, 45, 1220;'O G. R. Levi, Qazzetta, 1923, 53, i, 105, 200, 245; A., ii, 406, 421, 492.71 H. H. Willard and G. F. Smith, J . Amer. Chem. SOL, 1923, 45, 286;D. Vorlgnder and E. Kaascht, Ber., 1923,56, [B], 1157; A., ii, 487.Y. Venkataramaiah, J. Physicad Chem., 1923, 27, 74; A., ii, 149.-4. , ii, 482.Atii R. Accad. Lincei, 1923, [v], 32, i, 165, 623; A., ii, 421, 767.A., ii, 23956 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.prepared in 0-1N-anhydrous ethereal solution by the action ofiodine upon silver perchlorate; small amounts of a labile iodinecompound, assumed to be iodine tetroxide, are simultaneouslyformed, but readily decompose into iodine and oxygen.Chlorinetetroxide is stable in ethereal solution and does not volatilise withether. 73Manganese prepared electrolytically has d 7-034-7-080 ; it hasno action on cold water and very little on steam at 500" ; it burnsbrilliantly in oxygen or chlorine and when heated in a blowpipeflame forms a nitride decomposable by water with formation ofammonia,. Manganese reacts with concentrated sulphuric acidto form manganous sulphate and sulphur dioxide; and with nitricacid in a manner dependent on the concentration of the acid; 10per cent. acid gives chiefly hydrogen, and 100 per cent.acid princi-pally nitrogen peroxide as the gaseous product.74A dark red solutlion of a higher chloride of manganese, similarto Scheele's solution obtained by dissolving manganese dioxide incold hydrochloric acid, has been prepared by anodic oxidation of3M-manganous chloride solution, and is shown to contain, inaddition to this salt, only the tetrachloride, MnCl,.75Group V I I I .Preliminary experiments show that a hitherto unrecognisedfactor is operative in the corrosion of iron : 76 the rate of solutionof oxygen in water and the rate of corrosion both vary with thehumidity of the surrounding air. Apparently, the relativelyvigorous convection currents set up by the surface cooling conse-quent on evaporation into dry air materially facilitate the dis-solution of oxygen.Investigation of the system ammonium chloride-ferric chloride-water a t 25" and 60" confirms the existence of a compoundNH4C1,FeCl, described by Mohr 77 and discloses a solid,NH4Cl,4FeC1,,GH20, in equilibrium with certain solutions at GO",but shows that the supposed compound 2NH,C1,FeCl,,H20 isreally a series of solid solutions within narrow limits approximatingto this composition, and affords no evidence for Mohr's reportedcompound, NH,C1,2FeCI3,4H,O.'*In the system ferric oxide-phosphoric acid-water a t 25", the73 M. Gomberg, J . Amer. Chem. SOC., 1923, 45, 398; A., ii, 235.74 A. N. Campbell, T., 1923,123. 2323.7.i Idem, ibid., p. 892.' 6 J. A. NewtonFriend, ibid., 1923, 123, 2996.7 7 Mohr, 2. phy8ikal. Chem., 1898,27, 193.5 8 F. W. J. Clendinnen, T., 1923,123, 1338INORGANIC CHEMISTRY. 55solid phase in equilibrium with low acid concentrations isFe20,,P,0,,xH20, which adsorbs acid and at higher acid concentra-tions changes to a true compound, Fe20,,P,0,,5H20, probably aferric ferriphosphate, Fe[Pe(PO4),],5H,O. At 70°, these phasesstill exist, also the Fe20,,2P,05,8H20 and Fe203,3P205,6H20already known, and a new compound crystallising in small, pink,hexagonal plates, probably Fe,0,,3P,05, 10H20. 79Anhydrous cobalt iodide at 570-575" in a vacuum suffers somedecomposition and in part sublimes, forming black crystals of theordinary iodide and a small quantity of a yellow powder which is asecond form of the salt, termed @-cobalt iodide. This is extremelyhygroscopic and yields a yellow, aqueous solution from whichchloroform extracts iodine ; this leaves the solution colourless,but it reverts to the usual rose colour of the iodide solutions onwarming or concentration .SOThree unstable bisrnuthyl cobaltinitrites and a stable, yellowcadmium cobaltinitrite, Cd,[Co(NO,),],, have been prepared ;and triple nitrites of cobalt and lead with potassium, rubidium,ammonium, and thallium are described, the formation of thefirst-named constituting a very sensitive test for potassium.82The action of aqueous alkali and hypochlorite on a nickel saltproduces simultaneously nickel dioxide and sesquioxide. Nickeldioxide decomposes directly to nickelous oxide, Ni( OH),, whilstunder these conditicns the sesquioxide is not directly oxidisableto the dioxide; there is thePefore a limit to the oxygen content ofthe precipitate. 83By warming an aqueous solution of potassium chloroiridiatewith excess of hydrazine hydrochloride a reddish-brown solutionis obtained containing the complex acid [Ir(N2H5)C15]H, of whichcrystalline czesium and platinitetrammine salts have been prepared.84Lithium platinocyanide, variously described in the literature,is when pure a yellowish-green salt, but its colour is much changedby traces of other alkalis; it forms several hydrates, among whichthose with 4H20 and 5H20 can be characterised from the dehydra-tion curves. Lithium potassium platinocyanide, LiKPt ( CN),,2H20,forms ruby-red crystals with a characteristic blue shimmer, and ondehydration gives a yellow solid readily rehydrating on exposure. 8579 S. R. Carter and N. H. Hartshorne, T., 1923, 123, 2223.80 E. Birk and W. Biltz, 2. anorg. Chem., 1923, 128, 45; A., ii, 866.8 1 S. C. Ogburn, J . Amer. Chem. SOC., 1923, 45, 641 ; A., ii, 328.83 V. Cuttica, Gaxxetta, 1923, 53, i, 185; A., ii, 497.83 0. R. Howell, T., 1923,123, 1772.84 L. Tschugaev, Ber., 1923,56, [B], 2067; A., ii, 774.8 6 H. Terry and V. G. Jolly, T., 1923,123,221756 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The preparation of a number of new platinum ammine compoundsis reported,*6 and depolymerisation of certain inorganic bicomplexplatinum compounds has been observed. ~47H. V. A. BRISCOE.** L. A. Tschugaev et al., J. Rtiss. Phys. Chem. SOC., 1020, 51, 193; A., ii,*' L. A. Tschugaev and N. K. Pschenicyn, ibid., 1920, 52, 47; A., 1922, ii,499.866

ISSN:0365-6217    

DOI:10.1039/AR9232000028

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

ORGANIC CHEMISTRY.P A ~ T I.-ALWHATIC DIVISION.RESEARCHES devoted to problems falling within this division havegreatly increased both in volume and importance during the pastyear. Some of these have had, perforce, to receive the briefest mentionand much that is of interest is unavoidably omitted. This is to beregretted, and it is hoped that authors will appreciate that' onlylimitations of space have imposed this curtailment. The practicerecently instituted of holding over for biennial review the problemsof optical activity has again been observed, inasmuch as a period oftwo years was covered in the Report of 1922.Hydrocarbons.Current theories as t;> the genesis of petroleum are either theresult of speculation or of isolated experiments of a limited rangesuch as that performed by Xngler on the pyrogenic decompositionof fish blubber.A new survey of the factors governing the organictransformation of vegetable and animal remains into hydrocarbonsor coal is of general interest and it is illuminating to discover thatanalyses of a large number of samples of mineral oils and asphaltsfrom many quarters of the world reveal the presence of appreciablequantities of nickel either in solution or in colloidal suspension.2Sabatier and Senderens have advanced the theory that catalytichydrogenat'ion may be a factor in the production of petroleum, andthis observation lends support to their view.Catalytic hydrogenation has been studied from the point of viewof steric hindrance by selecting olefines containing side chainsdifferently situated with respect to the double linking.3 Thetheory of stcric retardation holds for this reaction, although theadditive combination with bromine is a t variance with the rule.The reduction of carbon monoxide to methane occurs in the presenceof iron as c a t a l y ~ t , ~ and provided that the pressure is increased to40 atmospheres the main reaction a t 400" is the formation of equalR.d'Andrimont, J. In&. Petr. Tech., 1923, 9, 287; A., i, 993.W. Ramsay, J. SOC. Chem. lnd., 1923, 42, 287; A., i, 737.G. Vavon and S. Kleiner, Gompt. rend., 1923, 177, 401; A., i, 891.F. Fischer and H. Tropsch, Brennstofl-Cliesn., 1923, 4, 193; A., i, 13758 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.volumes of methane and carbon dioxide from mixed gases con-taining equal volumes of carbon monoxide and hydrogen. Catalysisof the reaction leading to the formation of olefines and cyclenes bythe dehydration of alcohols is more conveniently and rapidlyconducted with the aid of sulphuric acid than with dry catalysts suchas aluminium sulphate.This inference is drawn by Senderens ina review of his work on this subject which shows that, whilsttheoretically the dry method is more efficient+ in practice the wetmethod is more advantageously operated. 'The reaction does notrequire the use of a large proportion of acid except for the purposeof attaining a mixture of such boiling point as to allow the catalyticaction to proceed.It is noteworthy that for the absorption of ethylene from gaseousmixtures chlorosulphonic acid 6 is more effective than sulphuricacid even with rapid currents of gas.Waste gases having a lowcontent of ethylene can thus be utilised to prepare ethyl chloro-sulphonate, which yields ethyl chloride or ethyl alcohol when treatedwith hydrochloric acid or water, respectively. On the other hand,the speed of fixation of ethylene with concentrated sulphuric acidis accelerated by using cuprous oxide as catalyst. An extendedinquiry into the mechanism of the Wurtz-Fittig synthesis leads toa conception of the transitory existence of a free radical as theprimary change : R*Hal + Na + Re + NaHal. In the secondphase, the radical may unite with sodium to give the sodium alkyl,RNa, or polymerise to the hydrocarbon R*R.If the conditions aresuch that a hydrogen atom is readily displaced, the radical is trans-formed into R - H or R + H. The third phase is represented bythe union of the sodium alkyl with alkyl halide, or the loss or gainof hydrogen by the radical may occur again. The last is the mainchange in the aliphatic series from ethyl upwards to cetyl, but withmethyl the radicals combine to give ethane. Complications due tosolvent may arise, for example, sodium ethyl reacts with ether inaccordance with the equation EtOEt + NaEt + NaOEt + C2H4 +C,H,. The formation of a new lead alkyl is reportedYs namely,Pb,Et,. This is a heavy, yellow oil, unstable in air, prepared byelectrolysis of lead triethyl hydroxide in ethyl alcohol.Contradictory evidence has in the past been furnished as to theti Ann.Chim., 1922, [ix], 18, 117; A., i, 9; Compt. rend., 1923, 176,W. Traube and R. Justh, Brennstog-Chem., 1923, 4, 150; A., i, 641;' H. A. Schlubach and E. C. Goes, Ber., 1922, 55, [B], 2889; A., 1922, i,T. Midgley, jun., C. A. Hochwalt, and G. Calingmrt, J . Amer. Chem. Soc.,813; A., i, 432.A. Damicns, Compt. rend., 1922,175, 585; A., 1922, i, 1105.1204.1923, 45, 1821 ; A ., i, 906ORGANIC CHEMISTRY. 69mode of attachment of hydrogen halides to isoprene, and a newinvestigation 9 makes clear the grounds of previous differences.Hydrogen bromide combines with ice-cold isoprene with the initialformation of the tertiary bromide, involving addition a t the 1 : 2positions :CH,:CMe*CH:CH, -+ CMe,Br*CH:CH2.If the tertiary bromide is kept a few hours before distillation andespecially if free hydrogen bromide is present, it undergoes isomericchange into the primary bromide, CMe,:CH-CH,Br, a productrepresenting 1 : 4 addition of the hydrogen halide in accordance withThiele’s rule.This last compound has been carefully characterised,and is found to be unusually unstable towards water with theformation of tlhe tertiary alcohol, a change which is reversible,CMe,:CH*C€I,Er + H20 e HO*CMe,*CH:CH, + HBr.An observation of fundamental importance is communicatedshowing that the additive union of ethylene and bromine is almostsuspended if the gaseous reagents are brought together in a vesselcoated internally with paraffin wax, whilst the reaction is acceleratedbeyond the rate at which it occurs on glass surfaces if the waxcoating is replaced by one of stearic acid.lO The inference is drawnthat the reactant molecules require activation with a polar catalystas a preliminary to reaction.A glass surface supplies this require-ment, and particularly so does a polar substance such as stearicacid and also, to a less extent than either of these, cetyl alcohol.The comparative effect of the surfaces in promoting the reactionis indicated roughly by the ratios 30, 20, 10, 1, respectively, forstearic acid, glass, cetyl alcohol, and paraffin wax, and if it werepossible to avoid crevices in the wa.x allowing access to the glassvessel it is suggested that the reaction would be entirely suppressed.The phenomenon is thus comparable with that observed in numerouscases where reactions between thoroughly dried gases are entirelysuspended.This view of molecular activation coupled with thekinetic theory is held to be sufficient to explain all the phenomenaof chemical reactivity without recourse to other hypotheses such asthe “ radiation theory.”Lowry’s conception of an activated unsaturated molecule isto regard the double bond as equivalent to one covalency and one9 L. Claisen, F. Kremers, F. Roth, and E. Tidze, ,7. pr. Chem., 1922, [ii],lo R. G. W. Norrish, T., 1923,123, 3006.105, 65, 288; A., i, 1050.T. M. Lowry, ibid., p. 822; compare also A. M. Berkenheim, J . R w ~ .Chem. SOC., 1917, 49, ii, 1 ; A., i, 52560 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.electrovalency, so that the resting state for ethylene acquires thepolar form indicated below :+ -CHz-CH, -+ CH2-CH, .. . . ' . (-1)The carbon atom which receives an electron assumes a negativecharacter and the contiguous carbon deprived of an electron becomespositive. Chemical union of ethylcne and bromine may thus beformulated,CH2-CH, + Br + Br -+ C H 2 B l H 2 B r-r-The idea is an alternative mode of expression of the electronic theoryof valency, and in effect the result of equation A may be shown :H H0 . .. H H .. ..cjc ++ 0 . c:c:. .. . . . . . (B) .. ..HIP H Hf -In By the two carbon atoms are linked only by two shared electronsconstituting a co-valency, whilst the negative carbon atom hasretained its own fourth electron and gained one in addition from thepositive carbon atom.Kermack and Robinson (see last year'sReport, p. 63) do not apply their theory to the simple case ofethylene and consider that the linking here is purely one of co-valency. Should the symmetrical nature of ethylene be invaded asby substitution in the case of vinyl halide, it is suggested by theseauthors that the polar conditions are set up, and their explanationof the transfer of electrons differs from that attributed by Lowryin the sense that even in this case a simple co-valency bond is notnecessarily established,I-€ II .. .. H H .. .. cjc -+ CIC. .. .. - 0 . .H C1 H C1Acetylene is regarded also by Lowry as a polar compound havinga mixed treble bond, and its combination with water is shown int<he formation of acetaldehyde :+ + &=CH+HOH -+ CH,=CH*OH + CH3-CH-6The wide difference between the reactivity of single and doublebonds is thus attributed to the development of electrovalency inthe latter.The special reactivity of the Grignard reagents is attri-buted to their polar character, I----Mg----CH,, in that they contain a- ++ ORQANIC CHEMISTRY. 61methyl-ion, and in this connexion it is now on record12 thatmagnesium alkyl halides function as electrolytes. The active phaseof butadiene is represented as CH2-CH-CH-CH,, an expressionwhich is equivalent to (I) as compared with Kermack and Robin-son's formulation (11), and it is claimed by Lowry that, in his new+ - + -H H H Hc i c i c i c*H0 .. . . . . . H H H HO D .. D . . D(11.) .. O D(I.) c:c: c: c :- 0 . 0 . D- H H H + - + - -i-formula, whilst the main polarity and unsaturation are at the endsof the chain, the alternate polarities and unsaturation exist also inthe intermediate atoms, thus providing an explanation of the attach-ment of 1 : 2- as well as 1 : 4-addenda. It would appear, however,that whilst the Lowry formula definitely excludes such a phaseas that indicated by Kermack and Robinson's representation, thelatter does not exclude the possibility of change into another phasesuch as is suggested by Lowry, and thus preserves greater elasticityas a mode of expression.The general application of Thiele's theory has been defendedagainst criticisms to which it has recently been subjected.It ispointed for example, that in the case of muconic acid, the freepartial valencies occur, not in the 1 : 4-, but in the 1 : G-posit ions,O=C(OH)2CH=GHcCH=CH"C( OH)=O,and the attachment of hydrogen occurs first on the oxygen, followedby rearrangement. Since bromine does not combine directly withoxygen, this 1 : G addition is not possible when bromine and muconicacid interact.A suggestion is made that the reactions used in earlier attempts toinvestigate the constitution of caoutchouc have been too drastic,and a new series of experiments in which hydrogen peroxide isemployed as oxidising medium leads to the proposal of a newstructural formula. 14Alcohols and Dericatives.A convenient procedure for the purification of methyl alcoholis devised 15 involving the elimination of acetone by the agency ofsodium hypochlorite, which converts the acetone into chloroform,12 N.V. Kondyrev, J . Rw8. Chem. SOC., 1920,13 3'. Ahop and J. Kenner, T., 1923, 123, 2296.14 M. C. BosweU, Trans. Roy. SOC. Canada, 1922,16, iii, 27; A., i, 350.X 6 R. C. Memies, P., 1922, 121, 2787; H. H. Bates, J. M. MIullaly, and17; A., 1922, i, 1128.H. Hartley, T., 1923,123, 40162 ANNUAL REPORTS ON TIIE PROGRESS OF CHEMISTRY.and this latter product is easily eliminated by fractional distillation.An analogous method, suitable for small concentrations of acetone,and more especially serviceable for laboratory use, is provided byutilising sodium hypoiodite, and the authors have examined thedegree of accuracy attainable by the usual method of estimatingacetone in presence of methyl alcohol.The drying of methylalcohol by magnesium and the determination of the initial hydrationhave been the subject of quantitative study,16 so that it is nowpossible by measuring the hydrogen evolved a t room temperatureand reference to a published graph to determine the progress of thedrying operation. An apparatus is also devised by means of whichethyl alcohol of 99-5 per cent. concentration may rapidly be pre-pared with the agency of calcium chloride, and an alternative formis suggested for manipulating the use of lime for the drying ofalcoh01.l~ Catalytic reduction of acetaldehyde or paracetaldehydeoccurs a t 200" when their vapours mixed with hydrogen are passedover activators consisting of finely divided copper and water-glassor of colloidal silicic acid and pumice: This enables acetylene tobe employed as a source of ethyl alcohol.Considerable interest is manifested in the mechanism which leadsto the conversion of alcohols into ethers or hydrocarbons, and inaddition to the discussion introduced jn the section on hydrocarbons,other results of value are contributed.A study of the conditionsessential to the formation of a high yield of ethers shows that theseare dependent on an understanding of the properties of binarymixtures of alcohol and water and the ternary mixtures of alcohol,ether, and water. From a knowledge of the boiling points of thesemixtures and the composition of the vapour phase in each case, thepreparation of ethers may be effected with yields of about 90 percent.by simple distillation of the alcohols with sulphuric acid, andsuccess has been attained on these lines with many alcohols.l* Theusual equationswhich purport to express the formation of ethyl ether are inaccurate,since they fail fo take account of the existence and function of thevarious hydrates of sulphuric acid which participate.19 In presenceof alcohol, the penta-, tetra-, tri-, and di-hydrates correspond with16 N. Bjerrum and L. Zechmeister, Ber., 1923, 56, [B], 894; A., i, 529.17 W. A. Noyes, J . Arner. Chem. SOC., 1923, 45, 857; A., i, 433; BadischeAnilin- & Soda-Fabrik, D.R.-P. 362537; Brit.Pat. 175238; from Chem.Zentr., 1923, ii, 478; A., i, 739.18 J. Popelier, Bull. SOC. chirn. Belg., 1923, 32, 179; A., i, 532.1s J. B. Senderens, Compt. rend., 1933, 177, 15; A., i, 742ORGANIC CHEMISTRY. 63the temperatures 110-121", 121-130", 130-145", and 145-162",respectively. Ethylene tends to be formed to the exclusion ofether a t 145". No ethylene is produced a t 130", but the effectivehydrate here is the tetrahydrate, which is surpassed by the tri-hydrate in etherifying properties. Consequently, the optimumtemperature for the production of ethyl ether is 136-138", which ishigher than that usually employed by manufacturers. The pro-duction of methyl ether avoids the complication of ethylene form-ation and it is possible here to use the still more eEective dihydrateand employ temperatures up to 160-165".The dehydrating action of phosphoric oxide 20 on alcohol vapouror ether vapour is partly catalytic and partly dependent on theformation of unstable additive products.At the ordinary temper-ature alcohol gives, with phosphoric oxide, metaphosphoric acidand the esters Et,H,P,O,, EtH,PO,, Et,HPO,, and Et3PO,, andalso dehydrates the second and third of these esters, giving a mixtureof ethyl meta- and pyro-phosphates.Evidence of the existence of an oxoniurn compound21 in thevapour phase is adduced in the case of methyl ether-hydrogcnchloride. Its formation is attributed to induced polarity in theether molecule caused by the polar molecule of hydrogen chloride.The similarity between this compound and ammonium chloride hasbeen commented on.Few criteria of purity have been recorded with such a high degreeof accuracy as those which are now available for a considerablenumber of aliphatic alcohols and ketones.22 The boiling points havebeen determined by the use of a thermo-element, and other datainclude the measurement of refractive index and density.Geometricisomerides of the crystdine dimethylhexenediol (I) have been pre-pared.23 Conversion of both isomerides into the cyclic oxide (11)occurs with iodine or by heating with sulphuric acid or potassiumhydrogen sulphate.In a series of papers by R. Delaby 24 a general procedure is describedfor obtaining alkylvinylcarbinols of the general formulaCH,:CH*CHR*OH20 D.Balareff, J . pr. Chem., 1922, [ii], 368; A., i, 287.21 0. Maass and D. M. Morrison, J. Amer. Chem. SOC., 1923, 45, 1675;22 R. F. Brunel, ibid., p. 1334; d., i, 646.23 Jul. Salkind, Ber., 1923, 56, [B], 187; A., i, 156.24 BuU. Soc. chirn., 1923, [ivl 33, 602, 753; d., i, 741 ; Compt. rend., 1922,175 967,1152; .4., i, 84, 85; Cornpt. send., 1923,176, 1326, 1898; A., i, 646.A., i, 89264 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.by the action of a Grignard reagent on acraldehyde. The substancesare of interest in that they lead to the preparation of substitutedglycerols by transformation of t,heir bromides into diacetates,followed by hydrolysis of the latter. Thus a number of alkylglycerols, OH*CH,*CH( OH)*CHR*OH, have been made available,and the experimental details leading to these results are worthy ofnotice.Aldehydes and Ketones.Systematic inquiry into sources of formaldehyde other than thatof methyl alcohol has been vigorously prosecuted since the markedadvances in this direction were reported last year.T. S. Wheelerand E. W. Blair25 have turned their attention from the catalysisof heated mixtures of ethylene and oxygen to a similar study ofmethane and coal gas, united with oxygen or ozone, but there arefew noteworthy results which register improvement on earlierrecords, although the interim reports are promising. A parallelinvestigation 26 is also in progress in which methane is oxidised withthe oxides of sulphur or nitrogen with or without silica as catalyst.With sulphur trioxide in presence of a large excess of methane a t595" a small quantity of methane oxidised entirely to formaldehyde.it is obviously an economic project to explore all the possiblecommercial uses of this reagent. -An unexpected direction 27 inwhich it has found application is in the production of its lowerhomologue, formaldehyde, which is obtained in a yield of 50 per cent.by passing one kilogram of acetaldehyde mixed with a cubic metreof air over a coil of copper wire netting.Of similar interest is theproduction of crotonaldehyde by circulation of acetaldehyde a t300" over a selection of catalysts. Meanwhile, the standard processfor the preparation of formaldehyde from methyl alcohol has beennotably improved by using as catalyst copper gauze disks packedperpendicularly to the axis of the oxidation chamber instead of themore usual copper spirals.Not only is it permissible to utilise crudemethyl alcohol of considerable acetone content, but the advantageof yield is so striking that the modification cannot be ignored, smcethe author2* claims to have increased the efficiency from 40 to70 per cent. Two independent attempts to repeat the photo-Synthetic acetaldehyde being now available from acetylene, .z5 J . SOC. Chem. Ind., 1922, 41, 331; 1923, 42, 81, 87, 260, 343; A., 1922, i,26 E. Bed and H. Fischer, 2. angew. Chem., 1923, 36, 297; A., i, 641.27 Consortium fur Elektroehemische Industrie, Brif. Pat. 178842 ; D.R.-P.P. Bobrov, J. Rw8. Phys. Chem. SOC., 1918, 50, 130; A., i, 300.1105; 1923, i, 285, 752, 997.349915; from Chem.Zentr., 1922, iv, 43; A., 1922, i, 1115; 1923, i, 752ORGANIC CHEMISTRY. 65chemical formation of formaldehyde from carbon dioxide which haspreviously been reported have met with fail~re.~g A comprehensivesurvey of the properties of formaldehyde, with particular referenceto the electrolysis and catalytic decomposition of its solution,furnishes evidence 3O of the existence and amphoteric nature of thehydrate, CH,( OH),, and these observations are extended to othersubstances containing the cnrbonyl group, such as ketones, carboxylicacids, and also carbon monoxide. A new polymeride of formaldehyde,e-polyoxymethylene, has been prepared from cc-trioxymethylenc byrepeated sublimation, and this new substance does not respond toacetylation and therefore contains no hydroxyl groups> nor does itreduce ammoniacal silver oxide.31 Paraformaldehyde gives riseto a 22 per cent.yield of glycollic acid along with methyl formate onheating a t 115" in an autoclave.Improvements in the laboratory preparation of zcetaldehyde wererecorded in the last Report, and these tlre now suppkmented byE. W e r t h e k ~ , ~ ~ who recommends that the oxida tlion of ethyl alcoholshould be conducted with a mixture containing nitric acid, sulphuricacid, and sodium dichromate, and that a stream of carbon dioxideshould be passed through the reaction mixture in order to carryover the product and prevent its furkher oxidation. For thepraparation of acetal, the use of metallic halides Is again suggestedand these are said to act as true catalysts.The catalytic synthesisof acetals from acetylene is announced as a general procedure andfurnishes moderately good results. Thus dimethylacetal anddiethylacetal are prepared by passing acetylene into the appro-priate alcohol in presence of concentrated sulphuric acid andmercuric sulphate.= Halogenation of the acetals provides a routeto a variety of useful reagents; for example, among the productsof chlorinaiion of dimethylacetal are mon ochloro- and s-dichloro-dimethyl ether, whilst the more highly halogenated ethers also areobtained on bromination. On chlorinating diethylacetal, chloralis formed. A useful variation3* of the general procedure for pre-paring the acetals of ketones is described in which ethyl orthoformatein presence of sulphuric acid is employed, and a number of aliphaticketones have responded to this reagent.A welcome addition to the available methods for the synthesis28 Emil Baur and A.Rebmann, Helv. C'him. Acta, 1922, 5, 828; A., i, 91.H. A. Spoehr, J. Amer. Chem. SOC., 1923, 45, 1184; A., ii, 452.30 2. angew. Chern., 1922, 35, 689, 698; A., i, 90.31 D. L. Harnmick and A. R. Boeree, T., 1922, 121, 2738 ; 1923, 123, 2881.32 J. Amer. Chern. Soc., 1022, 44, 2658; A., i, 14.53 J . S. Reichert, J. H. Bailey, and J. A. Nieuwlancl, ibid., 1923, 45, 1552;34 V. V. Evlampiev, J, &as. Phy8. C'hem. Soc., 1923, 54, 462; A., i, 1061.A., i, 753.REP.-VOL. YX. 66 ASNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.of aldehydes and ketones is reported as the outcome of the observa-tion that alkyl hypochlorites, which have long been known to beunstable compounds, decompose either on heating or in brightsunlight,35 and ketones or aldehydes are formed along with hydrogenchloride or alkyl chloride.This valuable observation renders itpossible to prepare aldehydes and ketones from alcohols withoutrecourse to the more usual oxidation processes. I n general terms,the reactions may be expressed as :R*CH,*OH + R*CH,*OCl + R-CHO +HC1.R,CR*OH -+ R,CH*OCl -+ R,CO+HCl.R,C*OH + R,*COCl + R,CO+RCl.Since the hypochlorites are available in quantitative yield, byadmitting chlorine to a well-cooled mixture of alcohol and alkaliwith the exclusion of light, it is apparent that this reaction willfind many applications.The behaviour of diketones in contact with tetrachlorides oftellurium and selenium 36 continues to furnish interesting examplesof co-ordination.The following compounds of the tellurium typeare given showing the behaviour of acetyl;propionylmethane.The formulae I, 11, and I11 represent intermediate phases; theproduct isolated is indicated by IVY and this on reduction withsulphurous acid loses its chlorine atoms, or, by the action of ethylchloride, is converted into an open-chain product represented bythe ethosy-derivative of 111. Some of the compounds describedin t,his communication possess germicidal properties.Several papers by Staudinger and his co-workers 37 recordadvances in the preparation and study of ketens, but their attempts3 5 F.D. Chattaway and 0. G. Backeberg, T., 1023,123, 2990.36 G. T. Morgan and H. G. Reeves, ibid., p. 444.37 C. dew. Hurd and C. Kocour, J. Amer. Chem. SOC., 1923, 45, 2167;A., i, 1060OWAJ!JIC CHEMISTRY. 67to prepare diketens have up to the present met with little success.It is of interest that the pyrogenic decomposition of methyl ethylketone leads to the formation of keten and ethane instead of theexpected methyl keten and methane.The problem of separating the constituents of wood spirit whichare usually designated as ketones has yielded interesting results.38Many of the constituents give crystalline bisulphite compounds,and among other products there have been isolated act-dimethyl-propaldehyde, CiLle,*CHO isovaleraldehyde, and AY-hexen- @-one.For the rest, it may be added that one of the first of the vitaminsto be isolated, namely vitamin-A, from cod-liver oil, is shown to becomposed of carbon, hydrogen, and oxygen, and to possess aldehydicproperties .39Acids and their Dericatives.Researches concerned with acids and their derivatives constitutea widely varied literature with which it is diflicult to cope in a limitedreview.Apart from many examples of new preparative processesof the simpler members to which reference must occasionally bemade, the group of the acids provides a rich harvest for numerousworkers engaged on the investigation of general phenomena such asthe mechanism of reaction and tautomeric change.It seems moreadvantageous to summarise the literature dealing with such funda-mental principlm rather than to register a series of isolated facts.The bromination of aliphatic acids pursues two distinct routes(1) through the enolic form of the acid, (2) through the initial form-ation of anhydride, and the latter is the more rapid of the tw0.40Theories of halogenation which are based only on the first of theseobservations are considered incomplete, inasmuch as it is shown thatbrominaticm of acetic acid in presence of red phosphorus does notproceed independently of the bromine concentration, as would bethe case if the first factor only were operative. Both factors comeinto play under the conditions described. At first, the reactionproceeds entirely through the anhydride until the concentration ofthe latter and of bromine diminishes, and with increase of thehydrogen bromide the reaction through the enolic form of the acidis accelerated and finally pursues this course to the end.Whilst the simpler view of the reaction indicated by Lapworth isfollowed when acetic acid is brominated in the presence only ofhydrogen chloride, the use of phosphorus establishes other conditions38 H.Pringsheim and J. Leibowitz, Bw., 1923, S, [BJ, 2034; A,, i, 1052.39 EL. Taka,hashi and I(. Kawaktuni, J . Chm. SOC. Japan, 1933, 44, 580;40 B. D. Shaw, T., 1923,123,2233.A., i, 968.D 68 ANNUAL REPORTS ON THE PROGRESS OF CHENISTRY.leading to a cycle of changes which may be formulated as below,although the principle of enolisation may apply to the anhydride,once it is formed :CH,*COEr + CH,*CQ,H (CH,*CO),@ 4- KBr.(CH,*CO),O + Br, = CH,*COBr + CW2Br*C0,1P.The former of these reactions, although reversible, proceeds tocompletion because the acetic anhydride is removed by the latterreaction, which is rapid41 and on exhaustion is followed by thechangeCH,*CO,H + CH,:C(OH), + CH,Br*CBr(OH),+ CM,BrCO,H -+ HBr.The best conditions for the preparation of bromoacetic acid arcfound to be those under which a trace of acetic anhydride is usedas carrier in the absence of phosphorus, when the yield of purcacid exceeds 95 per cent.of the theoretical, and analogous conditionsare applicable also to other cases.Such considerations also illuminate the mechanism of the reactioninvolved in the conversion of trichloroethylene into chloroacet'icacid4, by thc agency of 90-93 per eent. sulphuric acid, and thisncw reaction may be represented:CHCI:C'Cl, -+ CH,Cl*CCl,*SO,H -+ CH,Cl*CCl,*OH -+CH,Cl*COCl -+ CH,Cl*CO,H.I n the cam of pyruvic acid, the different phases of the bromin-ation are well defined, and in a suggestilm paper 43 the isolationof crystalline bromopyruvic acid, m.1). 59", is communicated forthe first time. With molecular quantities of acid and halogen,activation begins a t SO", but the react'ion may be cgnducted ina freezing mixture by admitting initially a trace of hydrogenbromide or sulphuric acid. The mixture soon solidifies to a massof bright red crystals; these melt and again solidify to colourlesscrystals which fume.On warming, these again melt with evolutionof hydrogen bromide, and finally solidify, on cooling, to the colour-less bromo-acid. The bromination of compounds containing thecarbonyl group thus appears to pass through a t least four stagesto its completion, and may be represented by the scheme+ HBr, - p 2 + -SH + -7HBr ~. -CIlBr ,-co -C(OH) -C(OH)Br -co4 1 Hentschel, Bcr., 1884, 17, 1286; A. Lapworth, T., 1904, 85, 41.42 L. J. Simon and G. Chavanne, C'ompt. rend.. 1923, 176: 309; A,, i, 177;&3 C. F. Ward, X',, 1023, 123, 22Oi.Bull. SOC. chim. Belg., 1923, 32, 285; A., i, 894ORGANIC CHEMISTRY. 69and there is probably an intermediate stage in which an additivecompound is formed from the bromo-acid and hydrogen bromide.Allocation of configurational formula? t o the geometric isomeridesof crotonic acid and its homologues presents difficulties whichcannot easily be surmounted.K. von Auwers and his collabor-ators 44 have endeavoured to elucidate the problem by chemicalmeans, iitilising reactions which do not obscure the various stagesof synthesis and do not involve any drastic methods of introducingthe double linking. The synthesis of yyy-trichlorocrotonic acid iseffected by condensing chloral with malonic acid, and, passingthrough the stage of the trichloro- p-hydroxybutyric acid, this isultimately dehydrated. The trichlorocrotonic acid undergoessmooth conversion into fumaric acid at 0" with sulphuric acid,and no trace of maleic acid could be detected, whilst the latteracid under similar conditions is quite stable.Moreover, reductionof the trichloro-acid to solid crotonic acid occurs readily in thecold, It is therefore concluded that solid crotonic acid is thetrans-form and isocrotonic acid is the cis-modification. Evidencebased on measurements of conductivity 45 pronounces in favourof the relationship of erucic acid to crotonic acid, and of brassidicacid to isocrotonic. Combining these results with those given above,erucic acid should be the trans- and brassidic acid the cis-modi-fication. This conclusion is contrary to that drawn from X-raymeasurements of the latter two acids,46 since the spacing of brassidicacid is longer than that of erucic acid to the extent of about 30 percent, Consequently, the former should be the trans-, and thelatter the cis-modification.The X-ray method furnishes a newinstrument for the solution of such problems, and it is abundantlyevident that many structural difficulties may be resolved by thismeans. Measurements of maleic and fumaric acids might well beundertaken in order to compare the lengths of spacings and theresults applied in the direction indicated above. The interpretationof these experimental results affords evidence from a welcomequarter that the speculation as to the tetrahedral angle of thecarbon atom harmonises well with the observed physical measure-ments and that the formulz of organic chemistry are not imaginarycreations having a limited range of truth.Speculation as to the reason for the predominance in nature ofiatty acids of the even series finds a partial explanation in the43 Annalen, 1923, 432, 46; A ., i, 546; B e T . , 1923, 56, [ B ] , 715, 533; A., i ,45 D. Holde and F. Zadek, ibid., p. 2052; A., i, 1058.4* A. Miiller and G. Shearer, T., 1923, 133, 3156; compare A. Miiller, ibid.,394, 295.p. 204370 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.persistent tendency of the dibasic acids of the even series to beproduced by oxidation. Compounds which might reasonably beexpected to yield the odd series fail to do so. For example, mono-and dj-broinoazelaic acids, on treatment with aqueous alkali toeliminate bromine, are oxidised by permanganate to adipic andsuberic acids, respectively, instead of to pimelic acid.47 Theexplanation is sought in the existence of crossed polarities in theeven members, since compounds exhibiting this relationship areconsidered to be more stable than those in which the positive andnegative charges continue to heap up to the end of the chain asis the case with the odd series of acids :+ - + --I- + - +-qH2*6H,*CH2*66*OH -- 6H2*CH2-66*OHCH2*CH2*CH2*CO*OH CH2<CH2*CH2*CO*OH + - + -+ + - +- - + - +- - I - - +-Suberic acid (even).Pimelic acid (odd).It is contended that the form of the electronic theory expoundedby Lowry fails to lend itself readily to the interpretation of theexistence of stereoisomerides of compounds containing conjugateddouble linkings, of which ad-dibromomuconic ester is an example.Three crystalline, stable forms have been isolated,4* and theseappear to be genuine geometric isomerides, and only a t high tem-peratures is any interconversion observed.The mobility of thelinkings suggested by a formula such as Lowry would ascribe tlothis substance is held not to be consonant with these observations,and it would seem that the double linking maintains its locationas a persistent reality scarcely expressed by the type of unionrepresented as a single unit of co-valency modified in the waysuggested by Lowry’s theory.Tautomeriam or reversible isomeric change of the kind representedby ethyl acetoacetate and definable as the movement of a mobilehydrogen atom may be regarded as the “aliphatic” yepresent-ation (I).Benzene exhibits another kind, the “ aromatic ” repre-sentation (11), which requires no such transference of hydrogen.Diflering from the keto-enolic type, there is a third kind of mani-festation (111), in ‘which t,he occurrence of a semi-aromatic OTnormal form is postulated(1.) CH--C=O C=C-OH.(11.1 CH--CH=C€I + CHZCH-CH.(111.) R*CH-C=C z+= R*C=C-CH.4 7 W. A. P. Challenor and J. F. Thorp, T., 1923,123, 2480.4 8 E. H. Farmer, ibid.. p. 2532ORGANIC CHEMISTRY. 71It is suggested by J. F. Thorpe49 that intermediate phases of (I)and (111) should be capable of manifestation :(HI(Ia.1 CH--C=O += C - P O + C=C-OH.The former of these expressions has not yet been realised experi-mentally, but the latter is represented by the series of the glut-aconic acids in which the ccnormal" type of isomeride is theintermediate phase.Feist's contention that the isomerism of thesubstituted glutaconic acids is of the usual geometric kind isresisted, and the evidence in the cases of ap-dime thylglutaconicacid and p-phenyl- a-methylglutaconic acid is reviewed by Thorpeand W00d.50 The fact that ozone yields degradation productspointing to two forms only of each of these acids is consideredinsufficient proof, since the analogous case of the constitution ofbenzene cannot be decided by such means. It is claimed that Peist'sproducts are those which are anticipated if the esters of the isomericp-phenyl-a-methylglutaconic acid reacts in the " normal " form.The view that Feist's two acids, m.p. 155" and El", are the trans-and cis-forms and that the two other acids, m. p. 120" and lo$",obtained by Thorpe and his colleagues are impure specimens ofthese forms is opposed to the fact that they are obtained by thehydration of a pure anhydride which has been recrystallisedrepeatedly. Thorpe and Wood regard Feist's acids as the trans-labile and cis-forms, and their own two other acids as the normaland cis-labile formsCO,H$Me $!HNe*CO,H *YMe-CO,H gMe*CO,HYPh fiPh 4;HPh YPhCH,*CO,H CH*CO,H *CH*CO,H CH2*C0,Htrancl-labile, m. p. 165". c b - , m. p. 151'. normal, m. p. 120". cis-labile,(1.1 (11.) (Feist) (111.) m. p. 108' (IV.)The anhydride obtained from (11) differs from that of (111) and(IV), although their melting points are similar, but they reactdifferently on hydration, since Thorpe and Wood's anhydride passesinto (111) and (IV), and is, moreover, partly converted into Eeist'sanhydride on distillation, and thereafter into (11).It seems to thepresent writer that a fumaroid form of (11) should also exist, namely, -Phof?CH''e*Co2Hy and, moreover, that the application of theCO,H*CH49 T., 1923, 123, 1361.60 J. F. Thorpe and A. S. Wood, ibid., p. 6272 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.method of X-ray measurement to these acids would have specialinterest.With the object of investigating the influence of various groupsin effecting alteration of the tetrahedral angle between two sub-stituents on the same carbon atom, the behaviour of severalCHBr*CO,Et p-substituted dibromoglutaric esters of the type E>C<CHBr.C02Ethas been studied.51 Where a and b are methyl and ethyl, the esterloses ethyl bromide on distillation and passes into the lactoneMe>C<CH(CozEt)*? The free dibasic acid exists in cis- Et CHB~------CO'and trans-forms, arnd changes by the agency of sodium carbonateinto the analogous lactonic acid. In contact with methyl alcoholicpotash, the dibromo-ester resembles the dimethyl analogue inyielding a cydopropane derivative,Etwhich exists in cis- and trans-forms.The methoxyl group in thiscompound is eliminated in the usual way with hydriodic acid, butthe expected hydroxy-ring acid suffers fission and passes into theopen-chain pp-methylethyl-cc-ketoglutaric acid, Me Et>C<cHz.c6,H, CO*CO,Hwhich yields as.-methylethylsuccinic acid on distillation. Whena and b are both methyl groups, a quantitative transformationoccurs into pp-dimethylketoglutaric acid.The first evidence ofstability of the cyclopropane ring occurs when a and b are bothethyl groups, and in this case the keto-acid and the hydroxy-ringacid are tautomeric, and t,his is borne out in the dipropyl series.The larger alkyl groups in the latter produce a widening of theangle between the two a-residues, and confer greater stability on thecyclopropane ring. Similar principles are operative when sodiumhydroxide reacts with tribromo-pp-dipropylglutaricwhen the keto-acidCO--+ p r 2 d >O (111.1 Pr2C(I) leads to the substituted succinic acid (11),C02H\CHBr*CO,H \CH.CO,Hby loss of carbon monoxide and finally to the p-lactone (111) byelimination of hydrogen bromide.This p-lactone is a stable61 B. Singh and J. F. Thorpe, T., 1923,123,113; F. R. GOSS, C. K. Ingold,and J. F. Thorp, ibid., p. 327; L. Bains and J. F. Thorpe, ibid., p. 1206.62 L. Bains and J. F. Thorpe, ibid., p. 2742ORGANIC CHEMISTRY. 73crystalline compound ; the lactone ring is opencd by boiling withdilute alkali, and closes again on neutra.lisation a t O", so that thelactone is regenerated, as is not usually the case with p-lactones.The effect of the two propyl residues is to cause the carboxyl andp-hydroxyl groups to become approximately the same distanceapart as in a 7-hydroxy-acid and hence the p-lactone assumes astability comparable with that of 7-lactones.The condensation of pp- and ap-dimethylacrylic esters withoxalic ester occurs in the y-position by the agency of potassium~ t h o x i d e .~ ~ Thus the ap-substituted ester reacts as follows :C( O€I):CH*CH:CiVIe*C02Et -+ CH,*CH:CMe*CO,Et + IC0,Et C0,EtThis corresponds to a Claisen condensation in which the usualrequirement of hydrogen atoms in the a-carbon atom is dispensedwith owing to development of the necessary hydrogen activity a tthe 7-carbon atom. The doubly unsaturated product of thecondensation changes into an a-pyrone in contact with concentratedhydrochloric acid, whilst the analogous pyrone from the pp-dimethyl-acrylic ester is produced direct from the condensation with oxalicester.I n the same paper, an improved method of preparing thecyanohydrin of methyl ethyl ketone is described. The sameauthors contribute an interesting example of the reduction of anunsaturated ester a.nalogous in its mechanism to the pinacolinformation.54 Ethyl ethylidenemaloiiate undergoes reduction withpalladium and hydrogen to give the expected ethyl ethylmalonate,but with sodium amalgam the change is represented by the following :CI-I,*yH*CH (C0,E t)2CH,*CH*CH( CO,Et),2CH3*CH:C(C02Et), +A discussion of the mechanism involved in the reaction betweenaldehydes and sodium cyanoacetate is communicated which favoursthe adoption of formulze displaying ap-unsaturation in all suchcases .55RCHO + CH,(CN)*CO,X --+ R*CH:C(CN)*CO,X.The addition to such products of reagents like potassium cyanide,sodium bisulphite, or hydroxylamine is regarded as diagnostic ofthe ap-type of unsaturation and these tests are utilised in supportof the validity of this view.On the other hand, analogous cases53 Lucy Higginbotham and A. Lapworth, T., 1923, 123, 1325.5p Ibid., p. 1618.55 A. Lapworth and J. A. McRae, T., 1922, 121, 1699, 2741; S. F. Birch,G. A. R. Kon, and W. 8. G. P. Norris, T., 1923, 123, 1361.D74 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.are known where similar products display tautomerism and existequally in their py-unsaturated forms, a condition which is prob-ably more especially operative where a cyclic ketone participatesin the reaction with the cyanoacetate.Halogen Compounds.A reinvestigation of the conditions operative in the chlorinationof methane has led to an appreciation of the value of adequatemeans of control, and the causes of the departure from the step-wise reaction are discussed in detail.56 A yield of methyl bromideamounting to 96 per cent.is made available by the use of 1.25 mols.of methyl alcohol, 1 mol. of potassium bromide, and 3 mols. ofsulphuric acid diluted with a third of its weight of water. Thisappears to be the most economical procedure for preparing thereagent. An excellent yield of pure bromopicrin is obtainable byexposure of aqueous picric acid and bromine in presence of sodiumcarbonate to direct sunlight for a few days. The reaction pro-ceeds also in the absence of light, but takes longer, and the sodiumsalt of picric acid seems to be the active agent.It is now shownthat the yellow, explosive compound produced from bromopicrinwith 50 per cent. potassium hydroxide is not a potassium salt ofbromonitromethane, but is s.-dipotassium tetranitr~ethane.~' Theaddition of an ester of hypobromous acid to an olefinic 58 linkingoccurs readily in presence of acids, particularly formic acid, withthe use of bromotrinitromethane, thus :-CH:CH* + KO-CHO + CBr(N02), + *CH(O*CHO)*CHBra +CH(N02)3*In the section on hydrocarbons, examples will bc found of themode of attachment of halogen and halogen acids to olefhic com-pounds, and these are more advantageously placed under thathead, since their chief interest lies in an explanation of thebehaviour of double linkings. Numerous communications havebeen made during the year on the mode of preparation and pro-perties of such additive compounds, and references to a few of theseare now given.The action of pure bromine on propylene gives riseto a yield of 90 per cent. of propyleno bromide and 4 per cent. ofapy-tribromopropane. The, presence of metallic iron as catalystleads to 40 per cent. of the latter product and 17 per cent. ofa@-tribromopropane, whilst with ferric bromide or aluminium as56 A. Schleede md C. Luckow, Ber., 1922, 66, [BJ, 3710; A., i, 83.6 7 L. Hunter, T., 1923, 123, 543.6 8 E. Schmidt, R. Schumacher, and R. Asmus, Ber., 1923, 56, [B], 1239;A., i, 645ORGANIC CHEMISTRY. 75catalyst the latter two bromopropanes are produced in the pro-portion 8 : 33.Rules for conducting such brominations 59 aregiven and represent an extension of the substitution rules ofMarlcovnikov, Stadel, and V. Meyer.In a paper by A. E. Favorski60 various examples of intra-molecular rearrangement of hydrocarbons and their halogen deriv-atives are given, and from these it is concluded that a conditionof strain may develop between the carbon linkings, leading todissociation. Tertiary carbon atoms multiply joined to other atomsoften undergo rearrangement resulting in the transposition of theirelements, and one example from many may be quoted :CH,Me*CMeBr*CH,Rle +-- CH,Me*CMe,*CH,Br +CH,Me*CH,* CMe,Br.The spontaneous decomposition of unsaturated aliphatic iodo-chlorides has been studied,61 and in the case of p-chloroethyleneiodochloride the products are iodine monochloride, trichloroiodo-ethane, am@@-tetrachloroethane, and a dichloroiodoethane, and ofthese the first two are the principal products.The changes consistof several rearrangements involving the elimination and subse-quent addition of the halogen atoms.Under the hydrocarbon group there are also recorded the resultsof an investigation on the mechanism of the Wiirtz-Fittig reaction.&4 contribution to the study of the behaviour of sodium withorganic substances in liquid ammonia solution62 may here bementioned. Treatment of an organo-magnesium compound, suchas magnesium ethyl iodide, in ethereal solution with dry ammonia 63gives rise to a substance analogous to sodamide, but more easilyobtainable and having constant properties :A study of the properties of the magnesylamine has been made andthis would appear to be a useful reagent for the preparation oforganic amides.New methods for the preptrrat'ion of as-dibromobutane 64 shouldprove useful in synthetic work, and these are described by twoindependent investigators.B.K. Mereshkowsky, Annalen, 1923, 431, 113, 231; A., i, 527, 643.6o J. Ru88. Phys. Chem. Soc., 1918, 50, 43; A., i, 430.61 L. B. Howell, J. Amer. Chern. SOC., 1933, 45, 182; A., i, 174.62 C. A. Kraus and G. F. White, ibid., pp. 768, 779; A., i, 456, 457.63 G. Odd0 and E. Calderaro, Gazzetta, 1923, 53, i, 64; A., i, 448.64 C. S. Marvel and A.L. Tanenbaum, J . Amer. Chern. SOC., 1922, 44,2645; A,, i, 2; J. von Braun and G. Lemke, Ber., 1922, 55, [B], 3626; A.,i, 2.D* 76 ANNUAL REPORTS OK THE PROGRESS OF CHEMISTRY.Carbohydrates.General.-New sources and methods of preparation of sugars andtheir derivatives are made available,65 among which may bementioned arabinose, rhamnose, xylose, galactose, fructose, maltose,trehalose, raffinose, and gluconic acid. The sodium derivative ofglucose which has so frequently figyred in the literature is nowshown to be merely an additive compound of glucose and sodiumethoxide.66 Improvement in the technique of the oxidation ofsugars with nitric acid continues to lead to the isolation of newsugar derivatives. At atmospheric temperature the reactionfunctions in several unexpected directions.It seems clear that thesecondary alcohol group may pass with ease into a keto-group,and this is more especially the case with the fifth group of a he~ose,~'thus emphasising the special character of this group which haspreviously been observed in other connexions.Monosaccharides and GE ucosides.-A reinvestigation of the acetonederivatives of sugars appears to reveal several anomalies requiringexplanation, and in the discussion which has arisen as to thestructure of these compounds the observation that trimethyleneglycol68 condenses with acetone invites caution in drawing con-clusions. A constitution of glucose diacetone is given which isin conflict with that previously assigned to this compound on thebasis'of its meth~lation.~~ Much confusion would be avoided if itwere always possible to decide which of the various oxide linkingsis present in the sugar which combines with acetone.This fundamental problem of the structure of sugars is receivingthe attention it merits, and it appears to be established thataldoses can exist either as 1 : 4- or 1 : 5-oxides (butylene or amyleneoxides), the equivalent form for ketoses being 3 : 5- or 3 : 6-oxides.Which of these two forms will possess the greater stability maydepend on such factors as torsional strain and variation of tet'ra-hedral angle, considerations such as have been applied to thePp-&substituted glutaric acids by Thorpe, Ingold, and others.Itis by no means to be accepted that the different configurations ofthe hydroxyl groups displayed by the various hexoses will always65 T.Swann Harding, Sugar, 1922, 406; 1923, 82, 124, 175, 240, 308, 350,406, 476; A,, i, 898, 1062, 1064; A. Blanchetibre, Bull. SOC. chim., 1923, [ivl,33, 345; A., i, 539; L. Bert, ibid., p. 733; A., i, 754; D. H. Brauns, J . Amer.Chem. SOC., 1923, 45, 833; A., i, 441.66 cf. Zemplh and A. Kunz, Ber., 1923, 56, [B], 1705 ; A., i, 897.137 H. Kiliani, Ber., 1922, 55, [B], 2817; A., 1922, i, 1111.68 J. BGeseken and P. H. Hermans, ibid., p. 3758; A., i, 86; compare69 K. Freudenberg and A. Doser, Ber., 1923, 56, [B], 1243; A., i, 652;Rsc. trav. chim., 1922, 41, 722; A., i, 177.P. A. Levene and G. M. Meyer, J. BioE. Chem., 1922, 54, 805 ; A., i, 92ORGANIC CHEMISTRY.77lend themselves to the development of the same degree of stabilityof the oxide ring, and hence it is to be expected that some sugarswill be more stable as the 1 : 5-oxide than as the 1 : 4-oxide form.The adoption of either the butylene- or amylene-oxide structureto represent the normal and the so-called 7-sugars may well resultin the possible allocation of a 1 : 4-oxide formula to the latter inthe case of some simple sugars. Meanwhile, it is demonstratedthat the dextrorotatory tetramethyl 7-fructose 7O isolated frommethylated sucrose has the 2 : 6-oxidedisaccharide section).yH2*OMer-y*OH0 [YH*OMe],Lt,'HCH,*OMestructure (I) (see underyo&oxidation [YHooMe12+ C;H*OHC0,H(111.) (I. 1 (11.1Te tramethyl y -f ruc tose Tetramethyl fructose Dimethbxyhydroxy-(dextrorotatory). (laevorotatory).glutaric acid.,4 second example of this type of linking is found in the case ofxylose, since trimethyl xylose gives an inactive specimen oftrimethoxyglutaric acid on oxidation.71 This methylated sugarhas therefore the constitution CH( OH)*[CH*OMe ],*CH,, although itsproperties correspond with those of a normal sugar and not witha y-form. Conversely, to the normal or lworotatory form oftetramethyl fructose is given the usual 2 : &oxide formula (11),inasmuch as it is degraded by oxidation 72 with nitric acid to thedimethoxyhydroxyglutaric acid (111), which has been isolated asthe ethyl ester. The normal tetramethyl galactose conforms,however, to the 1 : 5-oxide type, as is demonstrated in an investig-ation based on the Hudson rule as applied to the rotation of itstetramethylgalactonolactone. 73 Evidence of the structure of a lessstable variety of this sugar is, however, awaiting publication bythe present writer, and this appears to have the constitution of a1 : 4-oxide.Confusion as to the meaning of the term y-sugar may well arise,since only substitution derivatives of this type have hitherto beenisolated.Strictly speaking, the term might be restricted to thatstructural form of a sugar or its derivative which corresponds inproperties with the earliest example published by E. Pischer and-0-170 W. N. Haworth and W. H. Linnell, T., 1923, 123, 294,7 1 E. L. Hirst and C. B. Purves, T., 1923, 123, 1352.72 J.C. Irvine and J. Patterson, T., 1922, 121, 2696,73 J. Pryde, T., 1923, 123, 180878 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.described by him as 7-methylglucoside. The free y-glucose shouldpresumably possess the same internal structure as its glucoside,were it capable of isolation, but it is suggested '* that such a sugarmay be incapable of real existence, and that the abnormal activityassociated with the properties of a 7-sugar may find its only infer-pretation in the aldehydic or ketonic phase of a monose.The synthesis of substituted n-hexanes containing hydroxyl aswell as a ketone or aldehyde residue so constituted as to beequivalent to a de-oxygenated hexose continues to be of service inpresenting analogies with sugars.The two following compoundshave been preparedY75CH,*CH,*CH( OH)*CH,*CH( 0H)CHOCH2( OH)*CH,-CH,*CH( OH)*CO*CH,,and the former of these gives rise to two semi-acetals with methylalcohol containing in the one case a 1 : 2-oxide and in the other a1 : 4-oxide structure, and these exhibit different rates of hydrolysisin accordance with the experience with sugars, and, moreover,2 mols. of the aldehyde condense to give an anhydride analogousto a biose. The second compound formulated above furnishes adicyclic anhydride which, although containing an ethylene oxidering (1 : 2-oxide), is unusually resistant to fission, whilst it haspreviously been shown that the amylene-oxide or 1 : &ring is, insimilar compounds, remarkably sensitive to hydrolytic agents.The constitution of E-glucosan is again a subject of controversy,and the formula originally assigned by Pictet is supported byevidence adduced from methylati~n.'~ Trimethyl glucosan isfound to give rise to a reducing sugar on boiling with water, andthis appears to be 3 : 5 : 6-trimethyl glucose, since it forms a crystal-line osazone.The authors have not, however, taken the necessaryprecaution of estimating the methoxyl content of their osazone,and have confined their analyses to an estimation of nitrogen. Theexpulsion of a methoxyl group during osazone formation is not anunknown experience, and such an occurrence would invalidate theauthors' reasoning. Earlier workers,77 on the contrary, diagnosedthe sugar as 2 : 3 : 5-trimethyl glucose and modified the Pictetformula for Z-glucosan to harmonise with this result.Other newfacts relating to methylated hexoses include the isolation of acrystalline tetramethyl a-galactose and of a crystalline 2 : 3 : 6-tri-74 J. C. Irvine, T., 1923, 123, 898.7 5 B. Helferich and A. Russe, Ber., 1923, 56, [B], 759; A., i, 301; B.Helferich and R. Weidenhagen, ibid., 1922, 55, [B], 3348; A., 1922, i, 1115;M. Bergmann and A. Miekeley, Annalen, 1923, 432, 319; A., i, 1053.7 6 M. Cramer and E. H. Cox, HeEv. Chipn. Acta, 1922, 5, 884; A,, i, 94.7 7 J. C. Irvine and J. W. H. Oldhaan, T., 1921, 119, 1744ORGANIC CH3EMISTRY. 79methyl p-methylglucoside. ' 8 Exchange of the glycerol residue forthat of a hexose is reported in the case of olive oil, which, on heat-ing with a-methylglucoside in presence of sodium ethoxide, formsa mono-oleate of the glucoside, whilst in the case of mannitol adioleate of this hexitol is isolated.79 With both examples, thereaction is accompanied by internal dehydration of the carbo-hydrate chain.Anhydromethylglucoside mono-oleate and mannitandioleate are homogeneous compounds, and following methylationand hydrolysis give rise to methylated anhydro-sugar derivatives.A structural formula proposed 80 for mannitan (11),is confirmed by a series of reactions involving the formation of thefuran derivative (I) by decomposition of mannitol hexaformate,and the reduction of the compound (I) to 2-ethyltetrahydrofuran.The claim is made of the discovery of a new method of characterisingthe acids derived from sugars, depending on the observationthat dibasic acids derived from hexoses and monobasic acids frompentoses give colour reactions with ferric chloride, whilst the mono-basic acids from hexoses do not do so.A synthesis of pentamethylarbutin 82 has been achieved by the condensation of tetramethylglucose in benzene with quinol monomethyl ether in presence ofhydrogen chloride and anhydrous sodium sulphate. Arbutin isthus shown to contain the normal glucose residue.Disuccharides and Trisaccharides.-A new constitutional formulahas been applied to sucrose and experimental evidence brought toits support in two papers 83 which outline a study of the structureof the fructose unit isolated by hydrolysis of methylated sucrose.This fructose derivative has already been the subject of earlierwork, and the presence of an ethylene-oxide linking was favoured,although alternative formula? mere kept in view.It is now demon-strated that the oxidation of tetramethyl 7-fructose, a cleavageproduct of octamethyl sucrose, leads to two simple degradation78 H. H. Schlubach and K. Moog, Ber., 1923, 56, [B], 1967; A., i, 1063.7s H. S. Gilchrist, Rep. Brit. A~woc., 1922, 357; A., i, 297.P. van Romburg and J. H. N. van der Burg, Proc. K . Akad. Wetenech.81 L. J. Simon and A. J. A. Guillaumin, Compt. rend., 1922, 175, 1208;82 A. K. Macbeth and J. Mackay, T., 1923, 123, 717.83 W. N. Haworth and W. H. LinnelI, T., 1923,123, 294; W. N. Haworthand J.G. Mitchell, ibid., p. 301; compare M. Bergmann, Ber., 1923, 56, [B],1227; A., i, 654.Amsterdam, 1923, 25, 335; A., i, 85.A., i, 23980 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.products, both of which afford guidance as to the constitution.Oxidation with nitric acid furnishes a trimethoxyvalerolactone (XI)which, on further oxidation, gives rise to a trimcthoxyglutaricacid (111), whilst direct oxidation of the sugar with permanganateproduces a dimethoxybutyrolactone (IV) :vH,*OMe(p2H rY0 H*OMe (iH*OMe0 yH*OMe O$JH*OMe * TH*OMe * CH*OMe 1 CH*OMe I VH*OMe FH*OMe LbH,LbH, LCH, CO,H(1.) (11.) (111.) W.)On the basis of these results, tetramethyl y-fructose receives theformula (I), since it is apparent that the dibnsic acid (111) couldonly be produced if the lower terminal carbon atom in (I) yielded acarboxyl group by reason of the opening of the six-membered ring.Applying these facts to sucrose, the following constitrution is givento this disaccharide :rYooH yH*O&Ie [Yo YH-OMer-0-1 r-0-CE2( OH)*CH( OH)*CH*[CH*OH],-CH-O-$!*[ CH*OH],-CH,CH,*OH(glucose unit).(fructose unit).By observation of the mutarotation of the glucose which is liberatedby the hydrolysis of amygdalin with emulsin, the biose of amygdalinhas been recognised 84 to be a glucosido-p-glucose, the structure ofwhich had already been elucidated by Haworth and Leitch.Gent,iobiose has also been the subject of a constitutional study, andthe fact emerges that this sugar is identical with that occurring asthe biose of a m ~ g d a l i n .~ ~ Heptamethyl methylgentiobioside under-goes hydrolysis to the easily recognised, crystalline 2 : 3 : 5 : 6-tetramethyl glucose, and to the 2 : 3 : 5-trimethyl glucose, thelatter being identified as its crystalline p-glucoside. It thereforefollows that gentiobiose has the structure shown below :r - O i p r - 0 7 CH,( OH)*CH( OH)*CHfCH*OH],*CH*O*CH,*CH( OH) *CH*[ C'H*OH],*CH*OHand the linking between the two glucose units is of the P-type.The structure is thus identical with that of maltose which, how-ever, diff ers stereochemically and is glucosido- a-glucose, whilstboth structurally and stereochemically amygdalin biose is the same84 R. Kuhn, Ber., 1923, 56, [B], 857; A., i, 589.W. N. Haworth and B.Wylam, T., 1923, 123, 3120ORU ANIC CHEMISTRY. 81as gentiobiose. Proof of this is also’furnished by synthesis ofhepta-acetyl amygdalinic acid. Arising from the allocat,ion of thisconstitution, it is now seen that the trisacchzride, gentianose, hasthe following formula, since gentianose yields sucrose and gentio-biose respectively with emulsin and invertase.sucrose. gentiobiose.Methylation of raffinose has led to the elucidation of its structuralformula by anabgous methods. Hendecamethyl rafiose giveson hydrolytic cleavage three methylated hexoses, which are recog-nisable as 1 : 3 : 4 : 5-tetramethyl y-fructose, identical with thatobtained from sucrose, 2 : 3 : 5-trimethyl glucose, identical withthat derived from maltose, gentiobiose, and amygdalin, and2 : 3 : 4 : 6-tetramethyl galactose, which had previously beenisolated from lactose.The constitution of raffinose is thus indi-cated, and may be represented by the formula 86r - * 1 r - 0 1 r - 0 1CH~~[CH.~H],.C-O~CH~[CH.OH]~~CH~CH(~H)~CH~~O~CH~[CH~OH]~~CH~I 1 ’--CH,-OH glucose galactose -- fructoseIt follows that raffinose contains a sucrose residue as well as aresidue representing melibiose.PoZysaccharides.-The study of the constitution of starch hasbeen advanced by the active inquiry of many workers, and, althoughfinality is still far from achievement, the publications of the yearhave cleared the ground of numerous pitfalls for the unwary andopened up a path which should lead to substantial progress. Muchconflict of opinion might have been avoided even in recent workha,d it not been that investigators have tended to disregard valuableevidence which is to be gathered from some of the earlier literatureon this subject.It has long been recognised that the nature of the materialcomprising the inner portions of the starch granule differs fromthat of the outer portion.The former of these is known under66 W. N. Haworth, E. L. Hirst, and D. A. Ruell, T., 1923, 123, 312582 ANNUAL REPORTS ON THE PROGRESS OF CHEMXSTRY.different names, among which are granulose, amylocellulose,amylose; and the name amylopectin has been given to the outermaterial. The purer starches (for example, from potato, arrow-root) contain almost exclusively these two ingredients, whilstother specimens from rice, wheat, and barley contain also hemi-cellulose,s7 which, in the case of rice starch, may occur to theextent of 18 per cent.The need for caution in selecting initialmaterial intended to serve a's a basis for experimental investigationof the structure of the starch molecule is thus apparent. One istherefore impressed by the searching inquiry into the problemundertaken by Ling and Nanji,s8 who have achieved results ofposit,ive and outstanding value. Basing their work on the earlierobservations of Baker, 89 who showed that ungerminated barleydiastase effects cleavage of starch speedily into crystalline maltoseand a-amylodextrin, they have followed biochemical methods forseparating the two starch ingredients. With precipitated, desic-cated barley diastase a t 50°, the amylose constituent is quanti-tatively converted into maltose, leaving the amylopectin unchanged.Baker's a-amylodextrin is a simpler depolymerised product ofamylopectin, from which the phosphoric ester groups have beenremoved, and Baker's product is now designated ap-hexa-amylose,Malt diastase, however, effects the cleavage of amylopectin a t70" into a trisaccharide or hexatriose which is a t one and the sametime a-glucosidoisomaltose and p-glucosidomaltose, a new productof degraded starch of signal importance.This breaks down withdifferent enzymes to give either isomaltose or maltose. It is clearthat the degradation of amylopectin may be expressed thus:amylopectin + ap-hexa-amylose + a trisaccharide (hexa-triose) --+ isomaltose or (alternatively) maltose.The structural formula assigned tentatively to isomaltose isrepresented by I, and that of the triose by 11, the ringed carbonatoms indicating the reducing or potential reducing groups :- 0 1CH2( OH)*FH*CH*[CH*OH],* @H*OHP ? (I.) isoMaltose.6 H* [ CH*OH],*CH*CH (OH) *CH,*OH137 D. H. F. Clayson and S. B. Schryver, Biochem. J., 1923, 17, 493; A., i,88 A. R. Ling and D. R. Nanji, T., 1923,123, 2666; compare L. Maquenne.89 T., 1902, 81, 1177.1066; S. B. Schryver and Ethel M. Thomas, ibid., p. 497; A., i, 1066.Compt. rend., 1923, 176, 804; A,, i, 442ORGANIC CHEMISTRY. 83r - 0 1CH,(OH)*~H*CH*[CH.OH],.OH.OH is.Maltose I p ?(11.1 @ H*[CH* OH],*CH*CH (OH)*FH,CH,(OH)*CH(OH)*CH*[CH*OHJ2*@H P 1 L 0 - J-0-The structure allocated to isomaltose will doubtless be revised,inasmuch as this formula is already appropriated by cel1obiose.wConsidering the synthetic methods employed in obtaining iso-maltose from glucose, it is not inconceivable that one glucoseresidue in this biose possesses an amylene-oxide structure, and inthis case the attachment of the p-linking of the second glucoseunit may be through the hydroxyl group associated with the fourthor sixth carbon atom.Certainly isomaltose cannot be the p-ana-logue of maltose, since this formula is already allocated togentiobiose .gThe authors assign a formula to the basal unit of the amylo-pectin constituent of starch which represents this as @-hexa-amylose. The grouping of the six glucose units in this formulais based on the structure given to the hexatriose (11), and may berepresented in skeleton as a hexagonal formula in which each sideis occupied by a glucose residue as follows :0 *<.\The lettering a t the angles indicates the type of the stereochemicallinking, and the lefters along the sides show the structure of theunits, A and B together representing one isomaltose residue, andC and C one maltose residue.Hydrolysis along the dotted linewould give rise to two molecules of the triose (11).As to the structure of polymerised amylose, the second consti-tuent of pure starch, which amounts to about 60 per cent. of thewhole, it is made abundantly clear that, since this gives rise to aquantitative yield of maltose on treatment with diastase, thewhole of the gluoose residues are of the a type.Ling and Nanjiagain suggest a hexa-amylose structure showing lines of cleavageby depolymerisation into a tetra- and a di-amylose to conformwith the known behaviour.So W. N. Haworth and E. L. Hirst, T., 1921,119, 193.S1 W. N. Haworth and B. Wylam, T., 1923,123, 31208.4. ANNUAL REPORTS ON THE PROCTRESS OF CIIEMISTET.It thus appears possible to reconcile their views on this basiswith those of Pringsheim and of Karrer. Pringsheim92 has longcontended that a-hexa-amylose (which is considered to be idcnticalwith Ling and Nanji’s depolymerised amylose) is a trimeric di-amylose, and Karrer 93 strongly maintains that a diamylose is thebasal unit of starch and is to be recognised as anhydromaltosc.The second or p-series of amyloses has been the subject of con-troversy. Pringsheim’s ?-hexa-amylose is similar to Ling andNanji‘s ap-hexa-amylose from amylopectin, and whilst Pring-sheim’s investigation shows this to be a dimeric triamylose,[(C6H1006)3]2, Karrer protests that it is a simple triamylose. Differ-ences are thus narrowed down to a slender issue, and the review ofthe research describing the isolation of a triose from this unit ofstarch will still further harmonise the outstanding disagrceinent.Ling and Nanji express their difficulty in interpreting Irvine andMacdonald’s experiments 94 on this basis, and hesitate to attemptany reconciliation with their own experiments, especially inview of the fact that the latter authors used rice starch, and thisusually contains an appreciable quantity of hemicellulose whichmay have confused the issue.In the absence of quantitativefigures it is not possible to interpret these results as having referenceonly to the amylopectin constituent, although there is apparentlysome relationship between the triamylose formula of Irvine andMacdonald and the triose formula (11) outlined above.The polyamyloses obtained from starch and glycogen are charac-terised by the ease with which they undergo depolymerisation totheir fundamental substances when acetylated, and also by theresistance they present to complete methylati~n.~~ These propertiesare opposed to those displayed by tetraglucosan and tetralcmo-glucosan, which can be ncetylated under similar conditions withoutundergoing any depolymerisation, and are methylatecl with unusualease.These facts demonstrate that the structure of starch is inno way concerned with the glucosans.Last year the isolation of celloisobiose was reported as a newcleavage product of cellulose, but this is now shown to be a mixtureof cellobiose and a new trisaccharide, procell~se.~~ The latter is92 H. Pringsheim and K. Goldstein, Ber., 1923, 56, [B], 1520; A., i, 899;compare H. Pringsheim and W. Fuchs, ibid., p. 1762; A., i, 965; also “ DiePolysaccharide ” (H. Pringsheim), 1923, 167.93 P. Karrer, HeEv. Chim. Acta, 1923, 6, 402; A., i, 655; Ber., 1922, 55,[B], 2854; A., 1922, i, 1119.94 See Annual Reporhs, 1922, 81 ; also J.C. Irvine, T., 1923, 123, 898.96 H. Pringsheim and K. Schmalz, Ber., 1922, 55, [B], 3001; A., 1922, i,96 G. Bertrand and (Mlle) S. Benoist, Compt. rend., 1923, 176, 1683; 177,1118.85; A., i, 756, 757ORGANIC CIIEMISTRY. 85a by-product obtained in the usual process of preparing cellobioseocta-acetate, and the determination of its constitution should behelpful in deciding the structure of the unit of cellulose. A con-stitutional formula for cellulose was discussed in the last Report(p. 82) and a more detailed account of the experimental work onmethylated cellulose is now c o n t r i b ~ t e d . ~ ~ Mannan, which occursin vegetable ivory, gives rise on methylation with methyl sulphateto a dimethyl mannan, from which by hydrolysis a laxorotatorydimethyl mannose has been isolated.9s This sugar conforms tothe stable type of mannose despite its unexpected sign of rotation,since it gives the normal crystalline tetramethyl cc-methylmannosideon further methylation.Nitrogen Corn po 21 nds.The volume of new researches on nitrogen compounds of thealiphatic series increases from year to year, and the reporterexperiences difficulty in writing an adequate epitome of importantresults.More than a hundred references have been consultedand the space available does not allow of the mention of morethan tt few of these. Fortunately, a number of the importantnitrogen compounds relating to physiological and agriculturalchemistry will be reviewed in the separate sect'ions devoted to thesebranches of the work.A new laboratory preparation of hydrocyanic acid in largequantities is described,99 in which potassium fcrrocyanide, sulphuricacid, and water in the proportions 10 : 5 : 8 are recommended, anda novel form of apparatus is given.A new synthesis of this acidis mentioned from ethylene and nitrogen under the influence ofthe silent discharge, and in a theoretical paper,2 the properties ofhydrogen cyanide are considered to be those represented simul-taneously by an ammonocarbonous acid, a formaldehyde of theammonia type, and of a compound related to ammonia as thehypothetical formic anhydride is to water, and this thesis is ablydeveloped. A study of the behaviour of cyanamide in both acidand alkaline solution explains the action of the latter reagent asbeing due to its hydroxyl-ion, the products being carbamide andthe dimeride dicyanodiamide, and the effect of acids is explainedon the ionic theory.Other workers regard the polymerisation ofD7 J. C. Irvine and E. L. Hint, T., 1923, 123, 618.O8 J. C. Patterson, ibid., p. 1139.Og E. Fritzmann, J . Rum. phy8. Chern. Soc., 1920, 52, 227; A,, 1922, i,1128.L. Francesconi and A. Ciurlo, Gazzetta, 1923, 53, i, 327; A., i, 764.E. C. Franklin, J . Physical Chem., 1923, 2'9, 167; A., , 447.H. C. Hetherington and J. M. Braham, J . Amer. Chem. SOC., 1923, 45,824; A., i, 44786 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.cyanamide to dicyanodiamide as an example of the " urea dearrange-ment," a change which is shown to occur with carbamide, thio-carbamide, guanidine, and their derivatives.4appears on examination to containno ethylenic bond nor is it to be regarded as a strong base.Itcombines additively with three molecular proportions of phenolor of the cresols.An almost quantitative yield of acetamide is available 6 if equalmolecular proportions of ammonium acetate and glacial aceticacid are heated for thirty to fifty minutes a t a temperature justbelow the boiling point and then slowly distilled. The temperatureof the issuing vapour from the fractionating column is not allowedto exceed 104", and thus a residue of pure acetamide is obtained.A yield of 54 per cent. of glycine may now be derived from thereaction involving the condensation of formaldehyde with ammon-ium cyanide and hydrolysis of the resulting nitrile with 40 per cent.baryta, and the characteristics of the two crystalline forms ofglycine are described.Hydrolysis of a solution of glycine undernew conditions is shown to lead to the formation of ammoniumglycollate.8 Methylglyoxime has not hitherto been isolated instereoisomeric forms, but the announcement of this result is nowmade.9The claim that amines, pyridine bases, and alkaloids may beobtained by photosynthetic methods is criticised on the groundthat Baly, Heilbron, and Stern subjected their exposed solutions ofammonia, and formaldehyde to a heat'ing process with excess ofhydrochloric acid as a means of isolating their products. It isshown that this last procedure alone, without exposure of thesolutions to light, leads to the formation of the methylamines andtheir simple condensation products with formaldehyde, a reactionwhich is already well known.10 These simple compounds undergocolour reactions and other tests which resemble those previouslyrelied upon in the claims of the earlier workers.Methylamine condenses with formaldehyde and n-butyl alcoholHexamethylenetetramine4 T.L. Davis and H. W. Underwood, J. Anter. Clzern. Soc., 1922, 44, 2595;A., i, 22; T. L. Davis and K. C. Blanchard, ibid., 1923, 45, 1816; A., i, 902.R. Pummerer and J. Hofmann, Ber., 1923, 56, [B], 1255; A., i, 759.W. A. Noyes and W. F. Goebel, J . Amer. Chem. Soc., 1922, 44, 2286;A , , 1922, i, 1127.7 A. R. Ling and D.R. Nanji, Biochem. J., 1922, 16, 702; A., 1922, i,1124; C. A. Brautlecht and N. F. Eberman, J . Amer. Chem. SOC., 1923, 45,1934; A., i, 1001.8 E. Baur, HeZv. Chim. Acta, 1922, 5, 825; A., i, 97.lo 0. W. Snow and J. F. S. Stone, T., 1923, 123, 1509.A. Dorabialski, ISZY Zjazd Chemikdw Pobkich, 1923, 25; A., i, 754ORGANIC CHEMISTRY. 87in presence of potassium carbonate with the formation of aa’-di-n - b u t ox ytrime t h y lamine, NMe ( CH,* 0- C4H9) ,, which should provea useful synthetic agent. Other interesting examples of thepreparation 11 of allrylamino-ethers are given by following thesame procedure, among which are dimethylaminomethyl isobutylether, CHMe,*CH,*O*CH,*NMe,, and diethylaminomethyl n-butylether, Et,N*CH,*O*C,H,. The latter is easily decomposed bywater, whereas its methochloride is remarkably stable towardshydrolytic agents.The alkylamino-ethers condense with organo-magnesium compounds according to the scheme R,N*CH,- 1 O*C,H, + R’MgOHal + R,N*CH,R‘ + C4Hg*O*Mg*Hal and with theuse of appropriate Grignard reagents prepared from allyl chlorideor isoamyl bromide the following compounds have been isolated :Ay-butenyldiethylamine, CH,:CH*CH,*CH,*NEt, ; &methyl-%-amyldiethylamine, CHMe,*CH,*CH,*CH,*NEt,. The reaction is avaluable one and is general in its application.The perhalides of the three simplest tetra-alkylammonium halideshave been prepared l2 by adding the appropriate halogen in alcoholor acetic acid to a similar solution of the quaternary salt.Theseproducts are interesting examples of the rnultivalent natureof the halogens : NR,X,, NR,X,, NR,X,, NR,X,, NR,X,,.Similar examples of perhalides of the phenyltrimethylammoniumtype are described by another author,l3 and among other propertiesmentioned, one bhich was used as a means of determining con-stitution is of interest. This is the successive detachment of someof the halogens either with acetone or ethyl malonate. Thesecompounds yield halogen on heating and give rise to a salt of theammonium radical.An interesting generalisation has been reached with regard tothe behaviour of mixed alkyl sulphides towards cyanogen bromide. l4In the cases which have been st’udied, the smaller alkyl radical iseliminated as alkyl bromide, whilst the larger one remains associ-ated with sulphur as the thiocyanate, C,H7*S*C4Hg + CNBr ++C,H,Rr + C,H,*S*CN, but, on the other hand, the benzyl radicalis more readily detached from sulphur than the smallest alkylgroup.A warning is given against the use of potassium cyanideas a means of preparing ally1 cyanide from allyl bromide, sincethe alkaline nature of this reagent leads 15 to the rapid isomerisationof allyl cyanide to crotononitrile :CH,:CH-CH,*CN -+ CH,.CH:CH.CN.l1 G. M. Robinson and R. Robinson, T., 1923,123, 532.l2 F. D. Chattaway and G. Hoyle, ibid., p. 654.l3 H. McCombie and T. H. Reade, ibid., p. 141.l4 J. von Braun and P. Engelbertz, Ber., 1923, 58, [B], 1573; A., i, 893.lG K. von AUWBIS, ibid., p. 1172; A . , i, 66188 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The addition of ammonia or alkylamines to ally1 cyanide furnishesa ready means to the synthesis of P-aminobutyronitriles.If thealkylamines used contain not more than three carbon atoms,isomerisation occurs into crotmionitriles. Reduction of thesep-aminonitriles provides an easy route to the ay-diamino( or alkyl-amino) - butanes .16A method leading to the synthesis of p-nitroethyl alcohol and itschloroamino-derivatives is worthy of notice, as this interestingcompound is now available by a process involving the degradationof nitrotrimethyleneglycol,~7 whilst the synthesis of a number ofnew aminohydroxy-acids l8 is described either from keto-alcoholsby t,he cyanohydrin method or from olefinecarboxylic acids by thefollowing stages : olefinecarboxylic acid + P-methoxy- cc-acetato-mercuric ester -+ P-methoxy- a-bromomercuric ester + a-hrorno-p-methoxy-acid --+ a-amino- p-hydroxy-acid, and the new methodwill probably prove valuable in the purely aliphatic series.W.N. HAWORTH.PART II.-HonrocYcrm I)I~ISION.Reactions and Preparative Methods.Reduction.-Numerous special investigations of the scope andmechanism of the process of catalyt'ic hydrogenation are still beingprosecuted, whilst the application of the method to the elucidationof structural problems has become a commonplace. Nevertheless,a graded set of standard procedures is as much a desideratum asever, and a close examination of all the operative factors is necessary. .For example, it has been shown that, in the hydrogenation of naph-thalene in presence of platinum black, the course of the reductionis very much affected by the proportion of oxygen present in thecatalyst or the hydrogen emp1oyed.l I n the complete absence ofoxygen, the hydrocarbon is not reduced.In presence of the mini-mum amount of oxygen, the product is tetrahydronaphthalene.If the oxygen is present in small relative amount, the chief productis decahydronaphthalene without detectable intermediate stages,but if the oxygen content of the catalyst is considerable, then thetetrahydro-derivative is again predominatingly produced. Thel6 P. Bruylants, Bull. SOC. chim. Belg., 1923, 32, 256; A,, i, 762.1 7 R. Wilkendorf and M. TrBnel, Ber., 1923, 56, [B], 611 ; A., i, 288.l* N.E. Zelinsky and E. F. Dengin, Ber., 1922, 55, [B], 3354; A., 1922, i,1126.1 R. Willstiitter and F. Seitz, Be?-., 1923, 66, [B], 1388; A., i, 771ORGANIC CHEMISTRY. 89explanation advanced is that spongy platinum poor in oxygencontent induces reduction through intermediate phases of relativelysmall stability, and it is thought that these must include dihydro-naphthalenes such as the I : 5-isomeride in which the hydrogen isattached to both nuclei. If such highly unsaturated substanceshave more than a momentary existence, they become perhydro-gcnated. These unstable dihydronaphthalenes are, however, evenmore readily dehydrogenated by platinum rich in oxygen and inthese circumstances can only be produced in minute amount.The more stable intermediate in the production of tetrahydro-naphthalene is thought to be I : 2-dihydronaphthalene.It is impor-tant to notice that under conditions favourable to the formation ofdecahydronaphthalene from napht>halene, tetrahydronaphthalene isbut slowly reduced. High yields of ar-tetrahydro- a-naphthol andcz-ketotetralzydronaphthalene from a-naphthol and of ar-tetra-hydro-a-naphthylamine from a-naphthylamine have been obtainedby applications of the Sabatier-Senderens method a t temperaturesof 100-1 10" and 135-14G0, respectively.2 The catalytic hydro-genation of phenetidine in the presence of nickel salts and underpressure yields a number of products, of which the chief are thetwo stereoisomeric 4 : 4'-diethoxyphenylcyclohexylamines,OEt*C6H,onTH*C6H,,*OEt.3The stability of the ethoxyl group is interest'ing, but a more straight-forward process is the reduction of o- or p-aminophenol to respectiveaminocyclohexanols, which is accomplished in presence of reducednickel at 180" and GO lig.pre~sure.~ Under the correct conditions,Rosenmund's method of preparation of aldehydes by catalyticreduction of acid chlorides has now been shown to be applicableto unsaturated substances. Thus o-chlorocinnamaldehyde isobtained from o-chlorocinnamoyl ~hloride.~ A process for thepreparatim of phenylhydrazine IVhich has been patented has somesuggestive features. Aniline is diazotised in the presence of anexcess of sulphurous acid and the solution reduced a t a zinc or tincathode.6 It is noteworthy that the action of hot alcoholic potass-ium hydroxide on benzophenones often effects reduction to therillated benzhydrol arid particularly that benzhydrol is obtainedin this manner from 3bromobenzophenone.The reaction is2 S. Iiornatsu and R. Nodzu, X e m . Coil. Sci. Kyoto, 1923, 6, 177; A . ,i, 782.J. von Braun and E. Hahn, Ber., 1922, 55, [B], 3770; A . , i, 102.J. B. Senderens and J. Aboulenc, Compt. rend., 1923, 177, 168; A.,I<. W. Rosenmund, F. Zetzsche, and G. Weiler, Ew., 1923, 56, [ B ] ,H. Wachi, Japan Pat. 40194; A., i, 67.i, 919.1451 ; A., i, 79990 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.inhibited by the presence of a hydroxyl, ethoxyl, or amino-groupin the para-position to the carbonyl.7Oxidation.-The introduction by Gadamer of mercuric acetateas an oxidising agent especially applicable to the removal of hydro-gen from hydrogenated heterocyclic bases and alkaloids has provideda valuable resource in a particular field, but apparently lead tetra-acetate has even more useful properties.Indeed, it appears tobe unique among oxidising agents, since the characteristic effectis to replace labile hydrogen by the acetoxy-group or to add twosuch groups to a double bond. Some of the more interestingexamples are among aliphatic compounds, but it may be notedhere that toluene may be converted into benzyl acetate, diphenyl-methane into benzhydryl acetate, and, naturally most readilyof all, triphenylmethane into triphenylcarbinyl acetate.8The oxidation of aromatic amines to nitroso- or nitro-compoundsby means of monopersulphuric acid or Caro's acid has alreadyproved a serviceable method in the case of nitroamines and hasnow been applied to the aminoanthraquinones.The l-amino-anthraquinones yield nitroso-derivatives, whilst S-nitroanthra-quinone is obtained from 2-aminoanthraq~inone.~ This nitro-anthraquinone was not previously accessible.Halogenation.-It has been shown lo that the simultaneousaction of pyridine and bromine on many substances leads to theformation of quaternary pyridinium bromides. Thus quinolyields quinolpyridinium bromide, C,H,( OH),-N( C,H,)Br, by meretreatment in pyridine solution a t a low temperature with a mole-cular proportion of bromine, also dissolved in pyridine.Underdifferent conditions, pyridine or quinoline may be employed toeffect a control of bromination either in addition or substitution.The most certain method is to employ ready-formed quinolinedibromide hydrobromide as the brominating agent in acetic acidsolution, but it usually suffices to add the calculated amount ofbromine solution from a burette to a solution of the substance andof a mineral acid salt of pyridine or quinoline in acetic acid. Thetermination of the reaction is indicated by the production of ayellow coloration clue to the presence of the dibromide hydro-bromide. The normal dibromide of safrole was readily obtainedin this way and the preparation of mono- and di-bromo-7 P. J. Montagne, Rec. trav. chim., 1920,39, 339; 1922, 41, 703; 1923, 42,499; A., 1920,i, 394; 1923, i, 227, 801.8 0.Dimroth and R. Schweizer, Bey., 1923, 56, [B], 1375; A., i, 744.0 E. Kopetschni, D.R.-P. 363930; from Chem. Zentr., 1923, ii, 1029;A., i, 1021.10 E. de B. Barnett, J. W. Cook, and E. P. Driscoll, T., 1923, 123, 503ORaANIC CHEMISTRY. 91pyrogallols, monobromocatechol, and bromotyrosine presented nodficulty.11Decompositions.-The formation of lactones by the action ofiodine on the silver salts of substituted glutaric acids has beenstudied in the alicyclic series. The normal case is illustrated bythe following example :(jH2<CH2*CH2>C<CH2*co!2Ag 2% (J~2<CH2*CH2>C<cH2'~CH,*CH2 CH,-C0,Ag CH,-CH2 CH2*C 0 + 2AgI + CO,.Silver cis-hexahydrohomophthalate yields hexahydrophthalide,?H2*CH2*FH'CH2>0, and it is interesting that the same substanceCH,*CH,*CH--COis obtained, although in smaller yield, by the action of iodine onthe silver salt of the trans-acid. Silver cis-hexahydroisophthalateundergoes the reaction, but a remarkable exception has been foundin silver camphorate, which is changed by iodine into camphoricanhydride.l 2 The cherished belief that alkali metals are inactivetowards ethers must now be somewhat modified. Diphenyl etherreacts exothermally with sodium a t 180-200", with formation ofphenol and benzene, together with small relative amounts of diphenyland products of higher molecular weight. The ethyl ethers ofphenol and the naphthols are similarly decomposed above 200",whilst benzyl ethyl ether reacts with sodium a t 140°.13Another investigation has brought to light still more strikingphenomena of a similar type.The ethers having the formuhPh,C:CH*CPh,*OEt, CPh,*OEt, CPh,*OPh, CHPh,*OEt,CHPh,*O*CHPh2, Ph,C( OMe),, CPh,*SPh, are all decomposed whenshaken in cold anhydrous ethereal solution with potassium powderor sodium-potassium alloy in the sense of the equationR0O.R' + 2K = RK + KOR'.14Quite unexpectedly it was found that the isomeric hydrocarbonsCHPh,*CHPh2 and CPh,*CH,Ph suffer fission in similar circum-stances, although they are stable individuals exhibiting no tendencyto dissociate. The disruption of the bond by the alkali metalis attributed to its character as a weakened valency. Fundament-ally, an alkali met'al must be regarded as a donator of electrons,and in the reporter's view the occurrence of the reaction shows thatl1 K.W. Rosenmund and W. Kuhnhenn, Ber., 1923, 56, [B], 1262; A.,i, 782; K. W. Rosenmund, W. Kuhnhenn, and W. Lesch, ibid., p. 2042;A., i, 1095.12 A. Windaus, F. Kliinhardt, and G. Reverey, Bw., 1922, 55, [B], 3981:A., i, 111; M. Bredt-Savelsberg, J. pr. Chem., 1922, [ii], 105, 149; A., i, 1097.13 P. Schorigin, Bw., 1923, 56, [B], 176; A., i, 207.l4 K. Ziegler and F. Thielmann, ibid., p. 1740; A., i, 92192 ANNUAL REPORTS OW THE PROGRESS OF CHEMISTRY.the carbon atom which becomes separated from oxygen is one whichhas a tendency to acquire an electron. This tendency ir due inmost of the above examples to its union with tjhe key-positivephenyl groups.From this standpoint the fission and reductionof s-tetraphenylethane by potassium is cori*elated with the factthat tetraphenylethylene is readily reducible but difficult to oxidiseor brominate. Alkyl gronps are key-negative and tetramethyl-ethylene is difficult to reduce, but absorbs bromine with avidity.I n this case, the unsaturated carbon atoms tend, not t o acquire,but to give up electrons. The reversibility of the benzoin condens-ation has been experimentally proved. The equilibrium constantbetween benzaldehyde and benzoin a t 79" in 95 per cent. alcoholin presence of sodium cyanide. is about O ~ 2 P l i . l ~ Closely relatedis the observation that benzil, furil, ankil, and piperil may bereadily ammonolysed under the influence of ammonium cyanide.16Thus benzil is practically quantitatively coiiverted into benzamideand benzaldehydecyanohydrin.Condensations and Additive Syntheses.-Brief reference may bemade to the fact that Tollens's well-known synthesis of polyhydroxy-compounds by the action of excess of formaldehyde on ketones oraldehydes in the presence of calcium hydroxide has been extendedto cyclic ketones.According to the conditions, cyclohexanone yieldseither 2 : 2 : 6 : 6-tetrahydroxytetramethylcycZohexan-l-ol,(cH,*OH),.~.ca(OM)*F(cH,.oH,,CH,*CH,-CW2or acetals derived by further condensation with formaldehyde.With limited amounts of formaldehyde, it is possible to obtain theketo-alcohols. cycloPentanone with much formaldehyde yieldsinsoluble amorphous products and with 4-6 molecular proportionsit is converted into 2 : 2 : 5 : 5-tetrahydroxytetramethylcycZo-pentan-l-one.This substance is unchanged by reagents for thecarbonyl group, but its bismethylenc ether can be reduced to asecondary alcohol. Menthone, carvone, and camphor are inactivetowards formaldehyde.17 The condensation of aldehydes withsubstances containing the group -CH,-CO - in presence of alkalinecat,alysts is one of the most useful of synthetical methods, but inmany cases it is difficult to devise a suitable means of protection ofphenolic hydroxyl groups the presence of which frequently involvesa tendency of the products to resinify. It is now suggested that15 E. Anderson and R. A. ,Tacobson, J .Amer. CJbem. SOC., 1923, 45, 83G;A., i, 467.1 6 H. D. Dakin and C. R. Harington, J. Biol. Chem., 1923, 55, 487; A . ,i, 583; compare A. Lachman, J. Ainer. Chem. SOC., 1923, 45, 1522; A.,i, 785.Y17 C. Mannich and W. Brose, Rer., 1923,156, [B], 833; A . , i, 665ORGANIC CHEMISTRY. 93the methosyuletliyl group may serve the purliose, aiid o-cuniaralde-hyde, for example, is prepared by condensing o-methoxymethoxy-benzaldehyde with acetaldehyde in the usual manner followed by ashort hydrolysis with boiling 50 per cent. acetic acid containing 0.3 percent. of sulphuric acid.l8 I n the course of an examination of cymenederived from different sources, it has been incidentally noted thatthe “ cymcne ” prepared from toluene and isopropyl bromide withthe help of aluminium chloride is a meta-compo~nd.~~ Thymolis said to be obtained in satisfactory yield by hydrolysis with super-heated steam of the sulphonated thymol which is the product ofthe condensation of polysulphonatecl m-cresol and isopropyl alcoholin sulphuric acid solution at 90O.20 The use of a halogenalkyltolnene-p-sulphonate €or the introduction of halogenalkyl groupsinto phenols and amines was noted last and it has now beenfound that towards the Grignard reagent also the sulphonic estergroup is more reactive than the halogen.22 An example is theproduction in 75 per cent.yield of p-chloroethylphenylacetylei.,e,CH,ClCH,*CiCPh, from CH,Cl*CH,*Q*SO,*C,H, and CPhi C-MgBr.Unsymme Lrically substituted benzoiris may be prepared 23 by takingadvantage of tho interaction of aromatic aldehydecyanohydrinsand aryl magnesium salts in ethereal solution.The processgives moderate yields, and may even be applied to the produc-tion oE o-hydroxybenzoin from salicylalclehydecyanohydrin andmagiiesiurn phenyl bromide. Purfuraldehydecyanohydrin andmagnesium phenyl bromide yield isobenzfuroin,which is stated to be not identical with E. Pischer’s benzfuroin.24The latter must therefore have the constitution C4H,0*CO*CHPh*OH,and if these individuals or a similar pair can really be isolated insuch a simple manner in a pure condition, a study of their equilibriumin prescnce of zlliali should prove of much interest. The chemistryof the indones has been little investigated, largely, no doubt, becausethese substances are not very readily accessible.2 : 3-Diphenyl-indone is obtained in 89 per cent. yield when the dibromide of benzyl-ider,edeoxybenzoin is heated a t 140-145°.25(1413,0*CH( OH)*COPh,Is H. Pauly and K. Wikcher, Ber., 1923, 56, [ B ] , 603; A., i, 342.l9 I(. von Auwers and H. Kolligs, Ber., 1922, 55, [B], 3872; A,, i, 99.2O Howard st Som, Ltcl., and J. W. Blagden, Brit. Pat. 1923, 197848;2 1 Annud Reports, 1922, 93.22 H. Gilman and N. J. Bcaber, J. AMY. C‘hent. SOC., 1923, 45, 839; A.,Y. Asahina and &I. Terasaka, J. I’liu.i*ne. WOC. Japan, 1923, No. 494,A., i, 781.i, 453.210; A , , i, 1023.21 E. Fischer, Annulcn, 1882, 211, 288.z 5 A. P. Ct16khur, J . EI~PE. Phyq. Clterm. SOC., 1916, 48, 1827, 3., i, 45494 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY./\ CPh / BryHPh ' ' CPhBr -+ +2HBr \/\/ co coDiazotisation.-In presence of a large excess of aqueous hydro-chloric acid and nitrous acid, triaminomesitylene suff em twofolddiazotisation, and the product was isolated as aminomesitylene-bisdiazonium chloroaurate.26 This interesting result renders itprobable t'hat under ordinary conditions not more than two amino-groups attached to one and the same benzene ring can be diazotised.It may mean that the benzene ring cannot carry more than twodiazonium groups, and this is the emphatic opinion of the authors.Apparently the only alternative explanation is that the directattachment of two oniucm groups to the nucleus distributes a positivecharge which inhibits the amino-group from attracting a proton.Substitution and Orientation.In comexion with the theory of Reddelien that substitutionin aromatic compounds is preceded by the formation of additiveproducts, it is of interest to note that a mixture of t4e compositionPhNOB,H,$04 slowly crystallises, when coold to -loo to --20°,in pale green needles, m.p. 11". The substance is sufficientlystable to be capable of crystallisation from an ethereal solution.27Prom observations of the electrical conductivity of sulphuric acidsolutions, it is concluded that p-nitrotoluene is about half as stronga base a 2 : 4-dinitroaniline. Dinitro-compounds are not basicand when added to sulphuric acid diminish its elecbical conductivity.A careful examination of the products of nitration of benzaldehydeby the method of thermal analysis has been made.28 About 19per cent.of the product is o-nitrobenzaldehyde and this accordsclosely with the conclusions previously derived, in all probability,from works practice in the manufacture of Patent Blues. Thenitration of p-fluorobenzoic acid yields, to the extent of 80 per cent.,4-fluoro-3-nitrobenzoic acid, but p-fluoronitrobenzene is alsoformed.29 The fluorine atom accordingly finds a place among thegroups which have a sufficiently powerful directive influence toinduce displacement. The difficulty of achieving consistencyin the interpretation of orientation results among complex benzenederivatives is well illustrated by the outcome of a research on the26 G.T. Morgan and G. R. Davies, T., 1923, 123, 228.27 $. Cherbuliez, Helv. Chinb. Acta, 1923, 6, 281; A., i, 452.28 0. L. Brady and S. h i s , T., 1923, 123, 484.29 H. Rouche, BuX Acud. wy. B e . , 1921, 534; A., i, 214ORGANIC CHEMISTRY. 95nitration and bromination of 2 : 3-dialkyloxybenzaldehydes.30Brominstion is found consistently to occur in position 5, but nitrationoccurs in positions 5 and 6 in the 2-ethoxy-3-methoxy-derivativesand in position 6 in the case of 2 : 3-dimethoxybenzaldehyde.31Another difficult case is furnished by the nitration of 2 : 3-dinitro-chlorobenzene,32 which yields a considerable proportion of 2 : 3 : 5-trinitrochlorobenzene (I). There is evidently some overlappingin the operation of the various factors controlling orientation, andwe are not yet in a position usefully to discuss these examples.The nitration of sulphonated m-cresol gives a product which yields2-nitro-m-cresol (11) on hydr~lysis,~~ or 3-methoxytoluene-4 : 6-disulphonyl chloride may be converted into the 2-nitro-derivative(111) and then into 2-nitro-m-cresol by hydrolysis with acids oralkalis .ac1 Me(1.1 (11.) (111.) -The latter device, which was elaborated in connexion with workon the preparation of the four isomeric m-tolyl methyl ether sul-phonic acids, may frequently prove serviceable in attempts tointroduce substituents in unusual or unfavoured positions.Somefurther abservations in connexion with phenols may now bereviewed. The existence of the so-called " di-iodophenol iodide " 35obtained by the action of iodine on an alkaline solution of phenolhas been repeatedly denied,36 but is now reaffirmed.37 The sub-stance occurs in dark violet-brown leaflets, m.p. 12Y, and is bestobtained by the prolonged action of cold sodium hypoiodite onphenol. A by-product is tetraiododiphenylenequinone,0 :C&&12:C6H212:0(Lautemann's red), and the same two substances are said to beGbtained by the oxidation of tri-iodophenol by means of potassiumpersulphate in presence of sodium carbonate. The perplexing30 W. Davies, T., 1923, 123, 1575; W. Davies and L. Rubenstein, ibid.,p. 2839.31 W. H. Perkin and R. Robinson, T., 1914, 105, 2389.32 A. F. Hollemann, Proc. Acad. Amsterdam, 1922, 25, 223; Chem. Abstr.,33 G. P. Gibson, T., 1923, 123, 1269.94 R.D. Haworth and A. Lapworth, T., 1923, 123, 2982,36 Messinger and Vortmann, A., 1890, 1473.96 Bougaylt, A., 1908, ii, 738; Wilkie, A,, 1911, ii, 546; 1912, i, 346; Hunter3 7 G. Vortmann, Ber., 1923, 56, [B], 234; A., i, 206.1922, 16, 4193.and Woollett, A., 1921, i, 23896 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.feature is that the constitution (IV) assigned to " di-iodophcnoliodide " is that of a tautomeric form of t,ri-iodophenol. This seemshighly improbable, and if the substance exists it must surely havetwo iodine atoms on one of t'he carbon atoms in the o- or p-positionsso as to give it blocked hydroaromatic character. In the caseof the action of bromine or hypobromites on thymol, a s i d a rmatter has been cleared up during the pa,st year.co CMe CMe CMeA /\BrY 7Br2 ol' Br? YRr, A BrC YHBr/\O h CH OC CH HG co I8 E1 HC CH\/ CPrS\/CPrS(1-1.)The product to which the formula (V) had beenproves to be impure dibromothymol, and its partial insolubilityin solutions of alkali hydroxide was due to admixture with tribromo-p-menthadienone (VI), which is best prepared by the action of calciumbromohypobromite on thymol in aqueous solution.39 It has beenfound that C-alkylation of phenols is the rule ratlher than the excep-tion when alkyl halides and the sodium derivatives of phenols areallowed to interact a t elevated temperatures in non-dissociatingsolvents, for example, in benzene or toluene.40 A note of cautionmust be sounded, because the groups which have been introducedare allyl, benzyl, and cinnamyl, which are of a special type.Thesubstitution occurs preferentially in tlhe ortho-position. As anexample, phenyl cinnamyl ether is obtainable from cinnamylbromide and sodium phenoxide in alcoholic solution, but in benzene,o-cinnamylphenol is exclusively formed. It is interesting to notethat the phenyl etlhers of o- or y-nitrated phenols are more reactivethan the allryl ethers.41p-2 : 4-Dinitrophenylhydroxylamine, (KO,),C,H,*NH*OH, can beobtained by the action of hydroxylamine in alcoholic solution on2 : 4-dinitrodiphenyl ether.42 It has marked acidic properties andforms intensely coloured ammonium and phen ylammonium salts.There has been much activity in the development of the chemistryof the simpler naphthalene derivatives, but no orientation rules inthis series have yet been propounded which will satisfy all or nearlyall the requirements. The suggestion that directive suhstituents88 Dannenberg, A., 1903, i, 338.39 H.Jost and F. Richter, Ber., 1923, 56, [B], 119; 4., i, 208; compareCrowther and McCombie, T., 1913, 103, 539.40 L. Claisen, 2. angew. Chem., 1923, 36, 478; A., i, 1094.4 1 W. Borsche, Ber., 1923, 56, [B], 1488; A., i, 780.42 €bid., p. 1434; A,, i, 778ORGANIC CHEMISTRY. 97should be divided into a quinonoid type (o-, p - ) and a non-quinonoidtype (m-) 43 leads to exactly the same results as the theory of inducedalternate polarities, but presents no special advantages. It isthe effect of the fusion of the rings which remains ambiguous,apart from the obvious enhancement of the reactivity of the a-positions which reaches the maximum in the 9- and 10-positionsin anthracene. A monosubstituted naphthalene is analogous to atrisubstituted benzene, and the material necessary for a completesolution of the orientation problem is not yet at our disposal in eithercase.,4 careful re-examination 44 of the sulphonation of naphtha-lene has shown inter aKa that at higher temperatures, for examplea t 180°, the disulphonic acid predominatingly formed is the 2 : 7-isomeride, and not the 2 : 6 as a t present believed. The latteracid is stated to yield a sparingly soluble anhydride on heatingwith water a t 135" in a closed vessel. A reaction new to the naph-thalene series is the formation of a diazonium compound of theprobable constitution HOG H < r 2 by the action of nitrous acidon a solution of naphthalene-2-sulphonic acid in sulphuric acidcontaining a trace of mercuric oxide or selenium.The benzeneoriqntation rules as interpreted in terms of the polarity theoriesare followed in the bromination of 2-nitronaphthalene to the 5-bromo-derivative 45 (in the corresponding nitration position Salso is attacked) and in the nitration of aceto-p-naphthalide inglacial acetic acid solution, when the nitroxyl enters in the firstplace the 1-, 8-, or 6-position in order of irnp~rtance.~~ %Nitro-aceto-(3-naphthalide has not been found among the products ofthe reaction. A number of new hydroxynaphthoic acids have beenobtained, and in the course of the work the literature has beensomewhat extensively revised.The sulphonation of a-naphthoioacid with 98 per cent. sulphuric acid a t 100" gives a mixture of the5-, G-, and 7-sulpho-a-naphthoic lllnder similar conditions,p-naphthoic acid yields 5-, 7-, and 8-sulpho- p-naphthoic acids,the former in largest relative amount. At l(iO", 'i-sulpho-p-naph-thoic acid is the main pr0duct.~8 Clearly the relatively weakcarboxyl group does not exert a very decided orientating influence.The various sulphonaphthoic acids are best obtained from a- andp-naphthylaminesulphonic acids by means of the Sandmeyerreaction.43 V. Veself end M. JakeEi, Bull. Soc. chim., 1923, [iv], 33, 955; A., i, 911.44 H.E. Fiere-David, J . SOC. Chem. Ind., 1923, 42, 4 2 1 ~ ; A., i, 1190.45 V. Veselg and M. Jeke6, Bull. SOC. chim., 1923, [iv], 33, 952; A., i, 911.48 Ibid., p. 942; A., i, 918.47 F. A. Royle and 6. A. Schedler, T., 1923, 123> 1641. '* C. Butlsr and F. A. Royle, aid., p. 1649.so3REP.-VOL. XX. 98 ANXUSL REPORTS ON THE PROGRESS OF CHEbiISTRT.Natural Products.Chrysanthemum cirierarict?joliurn contain? an insecticidal principlewhich is called “ pyrethron.” Higher alcoho!s, sn oily substance,and a solid and a liquid acid may be obtained from it, whilst an esterprepared from the liquid acid and the oily substance has theinsecticidal properties of the original material. This liquid acid.,termed pyrethronic acid, has the remarkable constitutionWhen reduced with hydrogen in presence of platinum black, ityields a dihydro-derivative, and the glycol obtained by the actionof perrnanganate may be further oxidised to trans-caronic acid bymeans of chromic acid.Ozonisation of the acid yielded caronicacid and its semialdehyde, propionic acid, and propaldehyde.Oil of milfoil contains a curious hydrocarbon, a-zrbene, c1$&8,which apparently yields a sodio-derivative.50 Catalytic reductionproduces a dicyclic hydrocarbon, C1&&8, and oxidation by means ofalkaline permanganate leads to the formation of acetone and(pro bab!y ) meth ylphthalic acid.The annexed formula? are provisionally suggested and, as indicatedby the dotted lines, these may be derived in skeleton from threeisoprene units.orThe constitution of capsaicin has now been completely elucidated.It will be recallcd that the substance has been proved to be tlicvanillylamide of a decenoic acid and the ambiguity was inconnexion with the constitution of the acid fragment.Catalyticreduction of capsaicin yields dihydrocapsaicin, which is as pungentas the original substance. Dihydrocapsaisin is identical with7-methylnonovanillylamidc prepared synthetically. This fixes thecarbon skeleton and the position of thc double bond follows fromthe oxidation of the decenoic acid by means of potassium pcr-manganate to isobutyric and adipic acids.51 Capsaicin is there-fore v-methyl-k-nonenovanillylamide,CH~e,*CII:CH.[CH,l,*CO*~€~*CH~*C~H~*( OH) *OMe.Tnxine, a coiistitucnt of the yew, Il’axzis baccccta, readily yields49 R.Yamamoto, J . Chem. SOC. Japan, 1923, 44, 311; A., i, 1010; comparo50 R. E. Kremers, J. diner. Clzem. Soc., 1923, 45, 717; A., i, 454.5 1 E. K. Nekciz aiid L. E. Damon, IbSd., p., 2179; A., i, 1108.A . , 1919, i, 4G5ORGANIC CHEMISTRY. 99cinnamic acid in several ways and its behaviour is expressed bythe following provisional formula :~ ~ ~ e 2 ~ C ~ ~ h ~ C ~ 2 ~ C ~ ~ ~ ~ The oxidation of the terpene derived from Indian turpentine (exPinus Eonyi folin, Roxb .) by means of potassium permanganate inacetone solution has furnished results which go far to justify theassignment of the d-A3-carene structure (I) to it.53 The more impor-tant products are cis- and trans-caronic acids, a dibasic acid,C8H1204, probably cis-homocaronic acid (II), and two dibasichydroxy-acids, Cl,Hl6O5 (111), which are a-hydroxy-acids, and byfurther oxidation yield isomeric keto-acids, C,H,,Q, (IV).Inview of the simultaneous formation of cis- and trans-caronic acidsthere can be little doubt that the isomerism of the pairs of acidsC1,H1,O, and C,H140, is also stereochemical. Only one of theketo-acids was obtained in sufficient quantity to demonstrate thatit is a methyl ketone. On treatment with alkaline hypobromite,bromoform and the acid (11) were obtained. The course of thedegradation is shown in the following scheme :CMe CMe*OH CMe*OH/\\/\OH$ VH, --.)./\\/\yo VH2 ~ (1.1 YH QH2 --3ACH, CH\/\CII, CH CH CHCH--CMc, CH-CMe, CH--C‘Mc,(hypothetical itzterndiutc stages.)CO,H COMe CiMe*OH\ A FH,, f- HO,C $!H2H0,C CH H0,C CE1 HO& cH\\/\p2 f-\/\CH--CMe,(11.1 (IV.1 (111.)Thc higher-boiling fractions of this variety of Indian tur-pentine contain a sesquiterpene, d-longifolene, which possessesa stable molecular structure very difficult to break up.54 It isalmost inert towards potassium permanganate, but may be oxidisedby means of chromic acid with formation of longifolic acid and,under some conditions, isolongifolic acid, C14H2202, as well as ana-diketone, C16H2202, to which the not very euphonious named-longif-1 : 2-dione has been assigned. Longifolic acid is extremelys2 E. Winterstein and A. Guyer, 2. physiol. Chern., 1923, 128, 175; A , ,i, 942; compare A., 1922, i, 672.53 J.L. Sirnomen and M. G. Reu, Z’., 1923, 123, 549; cf. J. L. Sirnomen,IndianB’orest Records, 1923,10, iv, for occurrence of d-A3-carene in the essentialcil from the oleo-resin of Pinus Mevkasii.64 J. L. Sirnomen, T., 1923, 123, 2642.CH--CMc2\/\C€€--C&ie2E100 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.stable, certainly saturated, and therefore tricyclic. Longifdioneyields a quinoxaline, a monoxime, and similar derivatives and isoxidised by a mixture of nitric and sulphuric acids to a dibasicacid, C16H2404, which yields an anhydride. The simultaneousformation and the properties of longifolic acid and longifdionecannot be explained on any. simple hypothesis, and in the absenceof further information structural speculations are premature.On dehydrogenation with sulphur, many sesquiterpenes yieldthe hydrocarbon cadalene, which has already been proved to be4 : 7-dimethyl-l-isopropylnaphthalene, but another group of thehydrocarbons on similar treatment gives eudalene, a methyliso-propylnaphthalene not identical wit,h any of the apocadalenes .Eudalene has now proved to be l-methyl-7-isopropylnaphthaleneand bas been synthesised 55 by a method which need not be detailed,as it is similar to that used in the case of ~ a d a l e n e .~ ~In order to develop the sesquiterpene skeleton from that ofeudalene, it is necessary to introduce one more carbon atom insuch a position that the group containing it must be ejected whena naphthalene derivative is formed.If the further condition bcadded that the structure must be divisible into isoprene units,there is only one solution, which is shown below under the heading“eudesmol type.” It is instructive to note how the skeletons ofeach of the classes of hydronaphthalenoid sesquiterpenes containthe three-isoprene chain of farnesol. The head to tail union ofisoprene residues which is characteristic of tho aliphatic terpenesis repeated. It is curious that both the cadinece and eudesmolskeletons can be opened in two ways so as to givc tlhe farnesolchain, but only one of these is indicated.Cadinme type. Eudmol type.C1 : cC55 L. R ~ ~ i c k a and M. Stoll, Hdv. c‘him. AcLa, 1922, 5, 928; A., i, 119.56 AM. Repor&, 1922, 118ORUANIC CHEMISTRY.101The constitution IV is assigned to a-selinene, which on oxidationyields a tricarboxylic acid (V),57 The fact that the latter canbe readily esterified and the ester hydrolysed is held to prove thatthe carboxyl groups are not attached to tertiary carbon atoms,and in that case the eudesmol-typc skeleton receives experimentalsupport,.CH, CH,YH, YMe QH,-CH CH CH/\/\\/\/CH, CMeCH, CH, /\7\6p z p e FH2 (V.)\ACO,H*CH CH C0,HCH, CO,HThe chemistry of pimaric and abietic acids is being activelypursued, but the results are not yet such as can be usefully reportedin detail.A crystalline dimethyl shellolate, C17H2406, is obtained by esterific-ation of the resin acids of shellac,58 but beyond the fact that shellolicacid is dibasic and contains two hydroxyl groups and a doublebond, few facts are known which can be brought to bear on thequestion of its constitution.Ring Closure, Alicyclic groups.Although citral is an ap-unsaturated aldehyde, it yields a hydr-azone which' is semi-stable, being converted into citralpyrazoloneonly on di~tillation.~~ This pyrazolone yields p-cymene of a highdegree of purity when it is heated with fuming hydrochloric acidin a sealed tube.On distillation over alkali hydroxide in presenceof platinum, the pyrazolone decomposes as shown in tihe annexedscheme :An attempt to prepare methylenecyclopropane by the thermaldecomposition of cyclopropylme t h yltrime th ylammonium hydroxide,X~>CHCH2*NMe,*OH, led mainly t'o the production of cyclo-propylmethyldimethylamine.Under f avourable conditions, theyield of hydrocarbons was about 6-5 per cent., and after the gases5 7 L. Ruzicka and M. Stoll, Helv. Chim. Acta, 1923, 6, 846; A., i, 1216.6 8 C. Harries and W. Nagel, Ber., 1922, 55, [B], 3833; A,, i, 120.s@ N. I(ishner, J . Rt48.9. Phy8. them. SOC., 1918, 60, 1; A., i, 385102 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.were treated with bromine methylenecyclopropane dibromideand a larger relative amount of tjhe tetrabromide of butadienecould be separated.60 Posthumous honours are to be paid to theLadenburg “ prism ’’ benzene formula, since an attempt to syn-thesise substances cont’aining this particular “ caged ’’ ring systemis in progress.6l There are numerous alternatives in connexionwith the order of ring-closure, and the most promising of theseinvolves the production of cyclopropylcydopropane deriv (z t’ ives.An ingenioixs method has been elaborated whereby suitable com-pounds of this type become moderately accessible.A re-examin-ation of the products of the action of six molecular proportions ofphosphorus pentachloride on mucic acid led to the isolation of thestereoisomeric methyl and ethyl csters of m’-dichloromuconicacid, two in each case, in much improved total yield.62 Thesccsters react with ethyl sociiomalonate as shown in the followingscheme, the stereoisorneridcs giving identical solid products.CO,R*CCI CCl*CO,R j “02R*y>~H.C~<p+CO,R(CO,R),C c(co,R), \ / / 2CHNs(CO,R)CH*CH (1.1The hexaca,rboxylic ester (I) yields on hydrolysis with alkali acrystalline sodium salt from which the hexacarboxylic acid is readilyobtaked.The decomposition of the malonic acid groupingsproved difficult, but the tetracarboxylic acid (11) has neverthelessbeen obtained in a pure condition.kBefore the later stages can be attempted, an investigation of thestereochemistry of this acid is necessary, the form I11 being thatwhich should be most; readily convertible into the “ caged ” system.The camphor mine still proves inexhaustible and attention mayhe drawn to the following investigations, the results of whichcannot be given in detail : Preparation of a ring homologue of cam-60 N. J. Demjanov and M. Dojarenko, Rer., 1923, 56, [ B ] , 3208; A . , i, 1192.61 33.H. Farmer, T., 1923, 123, 3.388.62 Ibid., p. 2631ORGANIC CHEMISTRY. 103phenilone,62 of G-mctliykamphor and its derivatives,c4 and of phenyl-apocamphor.6JA passing reference must also be made to the careful work whichhas been carried 0x6 on the stercoisomeric pinanes.66Optically homogeneous l-pinene yields on hydrogenation the purehydrocarbon piwane, but impure d-pinene or r-pinene yields amixture.The pure stereoisomeride, termed pinocaniphane, is obtained fromd-pinene by way of pinocamphone, the hydrazone of which is heatedwith alkaIi hydroxide. A number of investigations converge onthe formation of derivatives of 1 -ketotetrahydronaphthalene from7-aryl-rrz-butyric acids. When phcnylbutyryl chloride is treatedwith aluminium chloride according to the method of Kipping andHill,G7 the yield is said to be only about 10 per cent.of that theorctic-ally possible. When a methyl group is present in varied positions,the yield rises to 70--'iG per cent.GsAt loo", the dehydration of phenylbutyric acid may be accom-plished by sulphuric acid, the yield being about SO per cent. of thetheoretical.69 The rcaction does not occur in this example a tthe ordinary temperature, and a systematic survey 7* has shownthat l-ketotetrahydronaphthalene derivatives are produced bythe action of cold concentrated sulphuric acid only on those7-phcnylbutyric acid derivatives which bear a substituent in thep-position and in addition contain a second carboxyl group. Itis suggested that an anhydride is first formed, and that this reactswith sulphuric acid so as to give a mixed anhydride of the carboxylicacid and sulphuric acid, the process being completed by the elimin-ation of sulphuric acid.Alternatively, the nuclear hydrogen maymigrate to the carbonyl group of the anhydride.-Although the cycloheptane ring is not distinguished by its easeof formation, it would appear that the structure, once formed,is relatively unstrained. trans-cycZoHeptanesyjil-ocyclopp.opane-f : 3-dicarboxylic acid (IV), in respect of its stability to mineral acid,stands intermediate between the related compounds derived fromcydopentane and cyclohexane. 7163 P. Lipp, J. pr. Chem., 1922, [ii], 105, 50; A., i, 1105.64 S. S. Nametkin and (hllle) A. M. Chuchrikova, J.Izus3. P7)ys. Chcni. Xoc.,G 5 M. Bredt-Savelsberg, Ber., 1923, 56, [B], 554; A., i, 348.O6 8. S. Nametkin, J. Russ. Phys. Chern. Soc., 1922, 54, 177; A., i, 811 ;O7 T., 1899, '75, 144.6R F. Mayer and G. Stamm, Ber., 1923, 56, [B], 1424; A., i, 802.6s F. Krollpfeiffer and W. Schafer, ibid., p. (320; A., i, 343.70 A. J. Attwood, A. Stevenson, and J. F. Thorpc, T., 1923, 123, 1T65.'1 J. W. Baker and C. K. Ingold, ibid., p. 122.1915, 50, 264; A., i, 586.A. Lipp, Ber., 1.923, 56, [R], 2095; A., i, 1214104 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.It is the cyclopropane ring which is affected, and the results areinterpreted in accordance with the theory of the effect of attachedgroups on carbon-to-carbon valencies to which reference has beenmade in previous reports.The conclusion that the cycloheptanering is unstrained, and therefore in all probability lies in morethan one plane, has also been reached from the observation of theclose relation of a representative of the series with a tricyclononanederivative. When set up on the models, the tricycEononane struc-ture is seen to be almost necessarily stable and free from valencystrain, and it is argued that the ready formation of the simplerring-system from it shows that this also must be free from strain.Whatever may be thought of the validity of this reasoning, therecan be no doubt in regard to the great interest of the investigationnow under discussion.72 Any one of t.he products obtained by thecondensation of formaldehyde and methyl malonate yields more orless methyl dicyclo-[I, 3, 31-nonane-2 : G-dione-l : 3 : 6 : 7-tetra-carboxylate (V) when boiled with concentrated methyl-alcoholicsodium meth~xide.'~ The best results are obtained by using amixture of methyl methylenebismalonate (1 mol.) and methylmethylenemalonate (2 mols.).QH2*Q ( CO2&Ie)*7 0CO-C(CO,Me)* xH*co2Me H,~H2*CH2*CH2>c<'H*c02H Co2Me,YH YH2H2*CH2*CH2 bH*C02H1 (V.1The tetracarboxylic ester yields dicyclononanedione (PI) onhydrolysis by means of hot dilute hydrochloric acid.The disemi-carbazone of this diketone is converted by 10 per cent. ethyl-alcoholicsodium ethoxide solution at 220" into dicyclononane, which occursin feathery, plastic crystals melting a t 145-146". Reduction ofdicyclononanedione with sodium amalgam produces the corre-sponding disecondary alcohol and the pinacol (VII), which is atricyclononane derivative and belongsof associated cyclic systems.CH,--CH-CO~ o - C H - ~ H ,to t'he "caged" ring typeT2 H.Meerwein, F. Kid, G. Klosgon, and E. Schoch, J . p ~ . Chem., 1922,'* H. Meerwein and W. Schurmann, Annalen, 1913, 398, 196; A., 1913,[ii], 104, 161; A., i, 221.i. 869ORQANIC CHEMISTRY. 106The tetracarboxylate (17) yields a disodio-derivative which reactswith bromine (5 atoms) to give methyl dibromodicyclononanedione-tetracarboxylate (VIII). It is very noteworthy that this substancemelts at 142” with elimination of bromine and production of methyltricgclononanedionetetracarboxylate (IX).(VIII.)The tricyclo-ester is also obtained by the thermal decompositionof the copper derivative of V and in several other ways, best ofall.by treatment of the monobromo-derivative of V with sodiummethoxide, This tricyclononanedionetetracarboxylic ester takesup two molecules of methyl alcohol when it is treated with methylalcoholic sodium methoxide. The last-formed bridge remainsintact and the product is a methyl cycloheptanehexacarboxylatefor which there are three possible formu1:e. Numerous furtherderivatives of these interesting substances have been prepared.It should be pointed out that the configuration of the cycloheptanering obtained by opening up the tricyclononane system is one whichhas screw asymmetry independent of the substituents.Tautomerism.An addition to the literature which will be generally welcomedis the “Report on Some Eew Aspects of Tautomerism,” by J.F.Thorpe and C. K. Ingold, published under the auspices of the UnionInternationale de la Cbimie Pure et A p p l i p d e . The brochure is anadmirable summary of the more important developments in thework of the School which has so successfully attacked some of themost difficult theoretical problems of Organic Chemistry.Riny-chain ?‘aut0merism.-~4lthough not strictly speaking a caseof tautomerism, the properties of 4 : 5dimethoxyphthalonic acidhave an interest of a related character.74 The substance crystallisesfrom water with 2H,O, and one of the molecules of water is lostat 100”. The anhydrous acid crystallises from an ethereal solutiondried over sodium sulphate.What is remarkable is the dif3Eeringbehaviour of these specimens towards acetyl chloride. The hydratedacid (I) is converted into the yellow anhydride (11), whereas theanhydrous acid (111), which is called dimethoxy-$-phthalonic acid,is transformed into an acetyl derivative (IV).74 W. H. Perkin and (Miss) C. Kuroda T., 1923, 123, 2094.E106 ANXUAL REPORTS ON THE PROGRESS OF CHEMISTRY.coThe products of the action of alkalis on ad-dibromo- pp'dialkyl-glutaric esters have been examined in many new cases, the mainobject in view being the determination of the effect of varying thesubstituents R, R' on the equilibriumIt will be recalled that when the groups RR' are both hydrogenor methyl, the keto-acid alone can be obtained, whilst if RR' ispentamethylene the hydroxy-ring acid constitutes the whole product ;further, that an equilibrium is set up in presence of concentratedpotassium hydroxide solution when R and R' are ethyl groups.It has now been found that RR' = MeEt 75 and RR' = tetra-methylene 76 present cascs similar to t<hat where R and R' are methylgroups, but that when R and R' are propyl groups there is againan equilibrium in presence of potassium hydroxide.77 This is morein favour of the hydroxy-ring acid than was found to be the casein the diethyl series.These resiilts strongly support the hypothesisof the gonal relations of t'he carbon valencies. Widening of-theangle in one pair of valencies narrows it in the other, and it is, ofcourse, the reduced natural angle of the valencies which bringsthe carbonyl group in these ketoglutaric acids into closer proximitywith the methylene group in the P-position, and so favours theformation of a cyclopropane ring by aldol condensation.In thoseexamples where the keto-acid is dehitely favoured, the actionof alcoholic potassium hydroxide produces alkyloxycyclopropanederivatives, as shown in the scheme :The instability of the hydroxy-ring acids is, however, demon-75 B. Singh and J. F. Thorpe, T., 1923, 123, 113.76 E. W. Lanfear and J. F. Thorpe, ibid., p. 1683.77 L. Rains and J. F. Thorpe, ibid., p. 1206ORGANIC CHEMISTRY. 107strated by the fact that these alkyloxy-derivatives are convertedby acid hydrolysis into t,he open-chain keto-acids.The interchangebetween hydroxy-ring and keto-acid modifications in presence ofpotassium hydroxide is now formulated in the following manner(R = Et or Pr) : 76This hypothesis, which implies that a case of ring-chain tauto-merism is fundamentally intra-annular, is entertained on account ofthe fact that there is evidence available which shows that the trans-and not the cis-forms of the hydroxy-ring acids undergo fission.The view formerly tentatively expressed that Ealbiano's acid,C02H*CHMe*CMe2.CO*C0,H, exhibits twofold ring-chain tauto-merism has now been modified, because there is no sufficient evidenceof the existence of a hydroxy-ring (cyclopropane) pha~e.7~ Theargument is too complex to be usefully summarised, but the con-clusion drawn is that the behaviour of this and related trialkylatedacids is to be expressed by the scheme :C( OH)*C02HCR, 0CHR*COCO*CO,H J -.- I \RC~~<CHR*CO,H I IThree-carbon Systems.--A detailed investigation of $methyl-cplopropene-1 : 2-dicarboxylic acid and its derivat,ives 79 has fur-nished results of corisiderable theoretical importance which it isprobably not too much to say establish firmly the correctness inbroad outlines o€ the concept'ion of the glutaconic acid system whichis due to J.F. Thorpe. In the open-chain glutaconic acids thepossibility of cis-trans-isomerism always presented a loophole, butthe characteristic features of the system have now been found tobe reproduced in the case of a substance which, on the ordinarytheory, cannot exist in cis- and trans-forms.The preparation ofthe cyclopropene acid by known methods has been so much improved'* I(. C. Psndytt and J. F. Thorpe, T., 1923, 123, 2862.F. R. Qoss, C. K. IhgoId, and J. F. Thorpe, iW., pp. 327, 33420E' 108 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.that 1 kilogram may be obtained from 6 kilograms of ethyl aceto-acetate. If a conventional symbol is to be assigned to it, theexpression (I) must be chosen for the following reasons inter alicz :-(i) The formula is in harmony with all known methods of form-attion, for example, from bromoisodehydracetic ester and fromax'-dibromo- P-methylglutaric ester under the influence of alkali.Still more interesting is the synthesis of the acid by the removalof two hydrogen atoms from each of the three stereoisomeric methyl-cyclopropanedicarboxylic acids (11, 111, IV).C0,HMe IC0,HICO,HMe I(11.1 CO2H (111.1 '[trans] [ (trans)-cis](IV.1[(cis) -cis](ii) The cyclopropene acid is not affected by mild reducing agents,but yields p-methylglutaconic acid whcn heated with hydriodicacid with or without the addition of phosphorus.(iii) The additive properties of the substance characterise it asan ap-unsaturated acid.(iv) The acid is oxidised by alkaline permanganate to malonicacid, and its esters yield an ozonide which furnishes ethyl acet,yl-oxaloacetate (V) on reduction.*The statement of Feist 80 that the acid exists in two forms, m. p.200" and m.p. ,189', has been challenged, since the latter is shownto be an impure specimen of the former. We should probably,on this and other evidence, be quite satisfied with the formula Ifor the acid, even although attempts to produce similar substancesof the typesC*CO,HRC&"ZH CR*CO,II and nZC<&cO,Khave invariably been fruitless, were it not for the fact that thebehaviour of the esters can only be explained by the adoption ofa special structural theory which has a repercussion on our view of* In this reaction the " normal'' ester exhibits the more unsaturatedcharacter md the fact that it absorbs ozone more rapidly than the labileester is of very great importance. It is this observation which renders thehypothesis that the acid and its " normal " ester are A*-derivatives untenable.Ber., 1893, 26, 750ORaANIC CHEMISTRY.109t,hc acid itself. Esterification by means of the usual agents givesa mixture of three esters-the ‘’ normal,” the “ labile,” and the“ enol ” esters-to which the symbol VI and the constitutions VIIand V I I I have been respectively assigned.(VI.) (VII.) (VIII.)These esters have been proved to be in equilibrium with oneanother, and in a hot alcoholic solution containing a mineral acidthe following mixture is obtained :Normal ester s Labile ester =S= Enol ester(95%) (5%) (trace)In sodium ethoxide solution a t 60”, the equilibrium is stated tobe represented by the scheme (ethyl esters) :Normal ester =s= Labile ester Z-S= Enol ester += Sodio-derivativeThe “ normal ” ester, m.p. 38-39’, possesses the closest relationto the free acid, being the sole product of the action of ethyl iodideon the silver salt. It is the form into which the others tend tobe predominatingly transformed, and is characterised by itsstability towards additive reagents (except ozone) and by itsinability to yield a sodio-derivative without previous conversioninto the “ labile ” isomeride. The ‘‘ normal ” and ‘‘ labile ” esterscan be separated by fractional distillation in a vacuum, but whenthe “ normal ” ester is distilled under the ordinary pressure, thepure “labile” ester condenses in the receiver. The “labile”ester is distinguished from the “ normal ” ester by the fact thatit rapidly yields a yellow sodio-derivative (of the enol ester) whentreated with cold dilute alcoholic sodium ethoxide.The enolester is distinguished from its isomerides by its yellow colour, itssolubility in cold dilute sodium hydroxide, and by the immediateand intense coloration which it gives with ferric chloride.The series is seen to be precisely analogous to the “normal,”“ labile,’’ and “ enol ” forms of glutaconic acids or their deriv-atives in the aliphatic series. Since cis-frans-isomerism is hereprecluded, the existence of the “ normal ” forms may be regardedas established, These “ normal ” glutaconic acid derivatives havetwo of the chief characteristics of benzenoid or aromatic systems.I n the first place, they are readily formed, often by unusual reac.tions, and show a great tendency to preserve their type, and inthe second place there is a decided reduction of the unsatumted(40%) (trace) (trace) (60%110 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.character evinced by the double bond.It might be added thatthey often exhibit considerable crystallising power. For thesereasons the “normal ” forms have also been described as semi-aromatic. The elucidation of the iiatlure of these substances isaccordingly a matter of importance in connexion with the theory ofaromatic types. It is not, perhaps, surprising that little progresshas been made in this directionthe first thing was to provideconvincing proof of the existence of the normal forms. Never-theless the following remarks of the authors of the paper underdiscussion may be quoted as an indication of the type of hypothesiswhich they tend to adopt :-“ In the ‘ normal ’ formula, as in allformulze of the normal glutaconic type, the mobile hydrogenatom is placed a t the centre of the three-carbon (glutaconic) system,in order to indicate that this three-carbon system represents theextent of what may loosely be described as the orbit of the hydrogenatom.Thus the ‘normal’ formula is essentially a dynamicformula. . . .’’ It is difficult to grasp exactly what this theoryimplies, unless it is a return in a particular case to the oscillationhypothesis of Laar. The reporter is not aware of any experimentalevidence which is better interpreted on such a view than on thatwhich ascribed the stability of the normal forms to a relativelystatic molecule and a.co-ordinated hydrogen atom. Is not thefact that the “ labile ” ester is produced by heating the “ normal ”ester an indication that the internal molecular energy of the formeris the greater 1cycZoPropene itself, CH2<EH has been obtained by the thermaldecomposition of cyclopropyltrimethylammonium hydroxide.81The gas may be condensed to a liquid by means of ether andsolid carbon dioxide. It is extremely unsaturated, polymerisingin light and absorbing oxygen. It unites very energetically withbromine and forms an iodide when treated with an alcoholicsolution of iodine.It is natural that search should be made for examples of three-carbon tautomerism outside the glutaconic acid series and anexample has been found in cyclohexenylacetone (IX), which isthought to be tautomeric with cyclohexylideneacetone (X).CH’61 N, J.Denjanov and M. Dojarenko, Ber., 1923, 56, [B], 2200; A., i, 1188ORGANIC CHEMISTRY. 111Reactions corresponding to both forms were already known, andit has now been found that the distinct chlorides of pure A~-cycZo-hkxeneacetic and cyclohexylideneacetic acids give one and thesame ketone when condensed with zinc methyl iodide.82Furthermore, the ketone gives a weak coloration with ferricchloride in alcoholic solution, and with alcoholic sodium ethoxidegives an orange-yellow solution of a sodio-derivative, which is trans-formed by ethyl iodide into the ethyl derivative (XI). Thissubstance was synthesised by an independent method.The tautomerism which is proved by these experiments doesnot appear to be that which involves the individuals IX and S,but is rather between X and the enol form of IX, which is, in itsturn, in equilibrium with IX.It is therefore in all probabilitya case of tautomerism analogous to that of anthrone, that is, keto-enol tautomerism where the methylene and carbonyl groups areseparated by a double bond or an equivalent system.The tautomeric character of the indene nucleus has long beensuspected, but experiments now placed on record offer a proof thatthe system is mobile to a t least the same extent as a typicalbenziminazole. 83 5- and 6-Methosyhydrindamine hydrochlorides(XII) yield, on heating, one and the same methoxyindene (XIII)and ammonium chloride.CH, CH2\/\/[MeO]/\/\ I 'H, &feo('(\cHCH\/\/(XII.) .(XIII.)This is called the " symmetry " test for mobility.CH*NH,,HClThe methoxy-indene yields isomeric benzylidene derivatives and thus satisfiesthe " substitution " test. Only the " fission " test failed to pro-vide evidence of tautomerism, because the 'only significant oxidationproduct isolated was the methoxyhomophthalic acid derived fromthe first figured component of the equilibrated mixture (XIII).Obviously indene may have a constitution analogous to that ofa normal glutaconic acid. A remarkable observation was madein the course of the work. p-Nitro- p-phenylpropaldehyde,NO,*C,H,*CH,*CH,*CPO, was obtained by the action of aluminiumchloride on pnitro- p-phenylpropionyl chloride in thionyl chloridesolution.The yield was only 15 per cent. of that theoreticallypossible, but 75 per cent. of the chloride usgd was recovered inthe form of the corresponding acid.62 S. F. Birch, G. A. R. Kon, and W. S. G. P. Norris, T., 1923, 123, 1361.as C. K. Ingold and H. A, Piggott, ibid., p. 1469112 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The Theory qf Aromatic Typcs.Opinion is crystallising in connexion with the problem of theconstitution of benzene, but unfortunately it is also exhibitingthe property of polymorphism, Those who regard the questionfrom the point of view of an attempt to employ the electronictheory of valency as a generalisation in organic chemistry appearmore and more to converge on the idea that there are groups ofelectrons which by their association confer a new factor of stabilityon the molecule.If we take it that systems possessing aromaticcharacter are such as exhibit reduced unsaturation of the com-ponent parts coupled with a tendency to formation and to pre-servation of type, then molecular nitrogen, compounds containingthe carboxyl group, glutaconic acids, cyclopentadienes, thiophen,and benzene can all be regarded as aromatic and also as containinggroups of two, four, or six electrons which have a special function.This theory is on safe ground so long as it is not too ambitiouslyemployed. Attempts to deduce space models on an electronicbasis are, fiowever, almost useless unless such models accommodateall the known facts, including the molecular symmetry of fused ordissolved benzene derivatives and the reduced symmetry of thecrystal molecule^.^^ We conclude that the time has not yet arrivedwhen the electronic theory of benzene can be stated in preciseterms and this is not surprising when it is considered that thephysical meaning of the simple non-polar linking has not yet beensatisfactorily explained.Indeed, the whole electronic theory ofvalency must be employed at the present time in a symbolic fashion.Quite a different point of view is that of those chemists who, em-ploying the conventional valency symbols, regard the aromaticcompounds as tautomeric systems comprising different individualsto which precise constitutional formula? can be assigned.85 Thereporter does not share the conviction that a complete solutionof the benzene problem is possible along these lines, but theclassical theory combined with the hypothesis of intra-annulartautomerism has been made the basis of much valuable experi-mental work, a prominent position among which is occupied byan extremely interesting comparison of the properties of thecyclopentadiene and benzene nuclei.86 Previous work 87 had led64 Compare B.Orelkin, J . Rus.4. Ph98. Chern. Soc., 1923, 54, 493; A.,66 Compare W. A. P. Challenor and C. K. Ingold, T., 1923, 123, 2066;66 C. K. Ingold, E. A. Seeley, and J. F. Thorpe, {bid., p. 853. *' E H. Farmer and C. K. Ingold, T., 1920, 117, 1362 ; E. H. Farmer,C. K. Ingold, and J.F. Thorpc, T., 1922,121,128; Ann. Reports, 1922,19,112.i, 1082.C. K. Ingold, ibid., p. 2081ORGANIC CHEMISTRY. 113to the conclusion that there exists in certain five-carbon nuclei atautomeric condition characterised by exchanges ( A ) which maybe compared with those postulated in the benzene series betweenDewar and Kekul6 phases of the molecule (B).-g-yx-Ez - -$--cx_yz7 -c-CY-cw -c-CY=CWWhen the group CR, is CMe,, in a certain series of the abovekind, the experimental verification of the analogy with benzeneis difficult on account of the stability of the bridge-bond. If,however, the group is cyclohexylidene, theory indicates a weakeningof the bridge, and this conclusion has been justified by experiment.**These cyclohexanespirocyclopentadiene derivatives were thereforeselected as a group of compounds which should simulate thoseproperties of benzene derivatives which can be laid to the accountof the severance of a para-linking.It was, indeed, found innumerous cases that the normal mode of oxidation led to theproduction of diketones, the p-quinones of the five-carbon nucleus.One example may be cited. The hydroxy-acid (I) is quantit-atively converted by an alkaline solution of potassium ferricyanideinto the quinonoid compounds (I1 and 111).The action of halogens on the cyclopentadienes is shown insuitable cases to involve two kinds of aromatic simulation, thatis, (i) formation of substitution products or preservation of type,and (ii) the formation of blocked perhalogenated derivatives.These points may be briefly illustrated by a consideration of thecourse of the bromination of the acid IV.8 8 C.:K<Ingold md J.F. Thorpe, T., 1919, 115, 120114 ANNUAL REPORTS ON THE PROGRESS OF CHEMTSTRP.The first bromine atom enters the position shown in V and thesecond in the remaining ortho-position to the hydroxyl group.I n the case of both the bromo- and the dibromo- (VI) acid, oxidationproducts were obtained indicating the predominance of the bridgedphases, but including also some derivatives of aconitic acid, whichmay be regarded as obtained from the double-bonded phases. VIis converted by further bromination into the blocked tribromo-acid (VII), which on oxidation is converted into a bromohydroxy-semi-quinone (VIII).The reaction doubtless takes place throughthe intermediate figured below, this substance being spontaneouslyreduced by alkali by a reaction analogous to that characteristicof otlher cyclic compounds containing the group -CO-CBr,-CO-.A very notewort,hy transformation is the conversion of the bromo-enolic acid (V) into the dienol (IS), which is effected by boilingalkali :Compounds of this type exhibit analogies with resorcinol andthe formation of 1 : 3-dihydroxy-compounds from a 1 : 2-brorno-hydroxy-derivative is compared with the production of resorcinolfrom o-bromophenol by the action of alkali a t high temperatures.The reaction in both cases is attributed to the hydrolytic fissionof a bridge-bond, but it should be noted that the bridge assumedin o-bromophenol is not the one which a consideration of its pro-perties as a phenol would require on this hypothesis.The inter-pretation given above is that of the authors, but in view of theimportance of the subject it may not be out of place to suggestthat the experimental data may also be explained on the basis ofthe formulaIfor the cyclopentadiene nucleus. In the course of reactions, thefour electrons represented by the dotted lines can regroup them-selves in such a way as to increase or decrease the value of thebridge partial valency. The fkal solution of this constitutionalproblem is probably beyond the reach of the ordinary methodsof organic chemistry and must await some definite advance iORGANIC CIIEMISTRY. 115technique, possibly in connesion with the analysis of crystals.It is not too optimistic to look forward with confidence to thetime when the electronic distribution in t'he molecules of carboncompounds will be disclosed by physical methods.Molecular Rearrangement.Some examples of the enlargement of the rings of quinones bythe Beckmann transformation have been re~orded.~g p-Benzo-quinonemonoxime yields a henzenesulphonyl ester which breaksdown on heating and subsequent treatment with sulphuric acidso as to form the substance I, which has pronounced acidic pro-perties.co<cH:cHoNH CH:CH*YO c6H4<LEgG> C6H4 c 6 H 4 < ~ ~ : ~ ~ > C 6 H 4(1.1 (11.1 (111.)-4nthraquinonemonoxime is converted by a mixture of phos-phorus pentachloride and acetyl chloride into the cyclic amide (11),which yields an oxime capable of transformation into phthal-o-phenylenediamide (111).Numerous investigations of the courseof pinacol-pinacolin and semi-pinacolic transformations have beenpublished during the year and some generalisations have emerged.It is, for example, definitely shown that ethyl and benzyl groupshave a much greater migrational aptitude than the methyl gr0up.mI n the case of allcylnydrobenzoins, OH*CHPh*CRPh*OH, theaction of sulphuric acid may lead either to a phenyl a-alkylbenzylketone, COPh-CHRPh, by dehydration (" tertiary "-OH reactive)or to a benzhydryl alkyl ketone, CHPh,*COR, by migration(" secondary "-OH reactive). When R is a group of strong " satura-tion " capacity, for example, methyl, isobutyl, or phenyl, theformer type of reaction occurs.On the otlher hand, when R =ethyl, n-butyl, propyl, isoamyl, both types of reaction occur. Theinfluence of the nature of the group R may make the secondaryhydroxyl more reactive than the tertliary.91 The relative freedomof the cycloheptane ring from strain, to which reference is madeabove, is regarded as the explanation of the formation of seven-rings in the Wagner-type rearrangement of certain cyclohexanederivatives. The following comparison nevertheless proves thatthere is more resistance to overcome in passing from six- to seven-ring members than is the case in the enlargement from five tosix.9289 E. Beckmann and 0. Liesche, Ber., 1923, 56, [B], 1; A., i, 232.90 M.Tiffeneau and (Mlle) J. Levy, Compt. rend., 1923,176, 312; A., i, 213.Q1 M. Tiffeneau and A. Or&hoff, ibid., 1922, 175, 964; A., i, 113.92 H. Meerwein and J. Schiifer, J . pr. Chern., 1922, [ii], 104, 289; A., i, 324116 ANNUAL REPORTS ON THE PROQRE~S OF CHEMISTRY.>CMeH2*CH CH, CMegH2~cH:>CMe*CHMe*oH -+ CH2<CH,,CH,sole product.FH2*CH2*CH2CH2<CH2*H>CCHMe,CH <CH20CH 2>CMe*CHMe*OH / ClH2*CH2*CMe2cMe2 CH2*CH2CH2*CH2This may, however, have something to do with the fact that itis much easier to introduce a double bond into the cyclohexanethan into the cyclopentane ring. Thus cyclopentane is passivetowards fuming sulphuric acid under conditions whereby hydro-aromatic hydrocarbons are readily 0xidised.~3 On the other hand,1 : l-dimethylcyclohexane, which is not hydroaromatic, resistsdehydrogenation to a much greater extent than cyclohexane.Itis not affected by passage over very active platinised asbestos at300 *. 94The reduction of ow-dibromo-1 : 1 -dimethylcyclopropane (IV)with zinc dust and alcohol leads to a hydrocarbon, C5H8,95 whichhas now been found to yield lmulic and succinic acids on oxidationand therefore is methyl-A1-cyclobutene (V) or, much less probably,methylene~yclobutane.~~ This shows that the process cannotproceed by way of the spiro-compound (VI) and provides anadditional argument against the validity of the tricyclene explan-ation of the Wagner-Meerwein transformation of borneol.CH2Br H2$Me CH2>C<CH2XH2*cH bH2 bH,(V.1 WI.182>c<CH213r(W.1The tricyclene hypothesis is, however, very frequently employed,and has been advanced in order to explain the complex rearrange-ment which fenchocamphorol (VII) suffers when it is heated withpotassium hydrogen sulphate.The product is santene (YIII).Iv~~C/'~\CH, H2C/I \CH*OH(VII.1 1 CMe, 1 11 AH2 I (VIII.)H&\I ,OH2 ?IIeC,\ ,CH,CH CHCHa- and p-Fenchocamphorol and camphenilol can yield the same93 N. Zelinski, Ber., 1923, 66, [BJ, 1718; A., i, 907.94 N. Zelinski and (Frl.) N. Delzova, ibid., p. 1716; A., i, 907.95 N. Zelinski, Ber., 1913, 46, 160.98 0. K. Ingold, T., 1923, 123, 1706ORGANIC CHEMISTRY. 117tricyclene (IX), which by rupture of one of the bonds (a) yields theunstable intermediate (X) and then santene (XI).97(IX- ) (X- 1 (XI.1The rearrangement of fenchocamphorol to santene can, however,be readily represented on the reporter’s cyclic partial valencytheory,98 the ring involving eight members. It has been urgedas an objection to the tricyclene hypothesis that, since tricyclereis symmetrical, it cannot give rise to an optically active product.Ruzicka and Liebl consider that this object’ion cannot be main-tained, because in the case of the transformation of active linaloolinto active terpineol, the asymmetric centre is changed from onecarbon atom to another, and on any hypothesis there must bean intermediate stage which is symmetrical. One is grateful forsuch an excellent illustration of the advantages of the cyclic partialvalency theory of migration.In accordance with this view thechange in question is to be represented in the following manner :CMe,=CH*CH,*CH,*CMe (OH)*CH=CH,.1 OH- (a)( c ) ; [ (d)CMe2-CH*CH,*CH,*C~e-CH-CH 2 ---- (6)If (a) and ( b ) unitc, the result would be to produce geraniol. Ter-pineol results from the addition of (a;) to ( c ) and (b) to ( d ) , givingthe stage XII.CMe;----OH. .I /CMe2-OH /(XII. CH-CH2-CH2-&lk CH-CH,-CH,-CMe WII. 1.’”’.. CH 2- .----CH.y \cH,-cH~~This, by further rearrangement in the same sense, yields terpineol(XIII), the whole process being continuous.Owing to the fact that the intermediate is a “caged” ring(cineole-type) the terpineol formed not only can, but must, beoptically active unless, of course, racemisation occurs before orafter the transformation.Several papers deal with the mechanism of the conversion ofbenzil into benzilic acid under the influence of alkalis.Thisreacttion is regarded from two points of view, that is, as an internalIt cannot occur during the change.*’ L. Ruzicka and Fr. Liebl, Hdu. C h h A&, 1923, 6, 267; A., i+ 476.98 Mem. Manchester PM. SOC., 1920, 84, No. 411s ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.oxidation-reduction presenting points of analogy with the additionof an organo-metallic compound to (z ketone or alternatively as apinacol-pinacolin-type rearrangement preceded by addition ofthe reagent to both carbonyl groups. The former theory is tosome extent supported by tfie discovery that a definite compound,C14HIo02,KOH, can be isolated by trituration of the componentsunder pyridine or benzene.This substance is decomposed bywater with regeneration of benzil and potassium hydroxide. It isslowly converted at O", in a few hours at the ordinary temperature,and very rapidly a t 80" into potassium benzilate, so that it appearsto be a true intermediate product in the transformati~n.~~ Asimilar compound of potassium methoxide and benzil is stable,whilst another investigator finds that the additive product ofsodium ethoxide and benzil breaks down in cold alcoholic solutionwith formation of benzaldehyde and ethyl benzoaf'e.1 The factthat only one molecule of the reagent is requisite in order to trans-form one molecule of the diketone emerges as the result of stillanother research.2These facts are embraced by the hypothesis that the reaction isa rearrangement of the negative ion of the additive compound,PhV(0H)COPhowThe charged =C(OH)-O- group strives to stabilise itself bybecoming a true ion of a carboxylic acid. To do this, it loosensboth a hydrogen atom and a phenyl group, which add on to theneighbouring carbonyl. An intermediate stage can be repre-sented on the partial valency theory by the expression\OaThe Cannizzaro reaction can be explained in a precisely similarmanner. The additive product Ph-CH(0H)-0)K gives up twohydrogen atoms in order to accommodate the negative charge inthe benzoic anion.Stereochemistry of Diphenyl Dericatizws.Benzidine and some of its derivatives condense with isophthal-aldehyde, and terephthalaldehyde to form coloured, extremelyG.Scheuing, Ber., 1923, 56, [B], 252; A., i, 231.1 A. Lechman, J . Amer. Chem. SOC., 1923, 45, 1509; A,, i, 784.a A. Sch6nberg and K. T. Keller, Ber., 1923, 68, [B], 1638; A., i, 928ORGANIC CHEMISTRY. 119sparingly soluble substances which may have the followings tru c t u e s :andThese compounds may, however, be polymerides.3 Some furtherdetails in connesion with the isomeric oo-dinitrobenzidines havebeen recorded.* An independent synthesis of the isomeride obtainedby hydrolysis of the product of nitration of diacetylbenzidine hasconfirmed the view that this substance is 3 : 5’-dinitrobenzidine.Furthermore, the tetra-amino-compounds obtained by reductionof 3 : 3‘- and 3 : 5’-dinitjrobenzidines have been found to be differentsubstances, although they yield the same diquinoxaline on condens-ation with benzil.The observation that 7-6 : 6’-dinitrodiphenicacid (I) can be resolved into optically active components hasbeen followed up, and further examples of eiiantiomorphous diphenylderivatives have been found.The isomeric 6 : 6’-dinitrodiphenic acids yield on nitration onlyone 4 : 6 : 4’ : 6’-tetranitrodiphenic acid (II), which is regarded asthe 7-variety because it may be resolved.5 An attempt was thenmade to produce a stereoisomcride of this acid by oxidation of2 : 4 : 5 : 7-tetranitrophenanthraquinone. The latter substance,however, could not be obtained by nitration of 2 : 7-dinitrophen-anthraquinone, since, for some reason, one nucleus resists nitration.The product was 2 : 4 : 7-trinitrophenanthraquinone (111) andthis yields, on oxidation, 4 : 6 : 4’-trinitrodiphenic acid (IV), whichwas resolved into opticzlly active modifications.6NO,/-\ /-\\ /(111.)- 2\ - /--,/No2NO2 NO,/-\ /-\NO, (11.)”O2\-/-\./ C02H C0,HNO,/-\& /-\ No2\/--\/NO2 (IV.)C0,H C0,H3 R.Adams, J. E. Bullock, and W. C. Wilson, J. Amer. Chem. SOC., 1923,45, 521; A., i, 378.0. L. Brady and G. P. McHugh, T., 1923,123, 2047.6 G. H. Christie and J. Kenner; T., 1922, 121, 614.6 Idem., T., 1923, 123, 779120 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.This shows that one nitro-group in the o-position to the couplinglink suffices to ensure stability of the asymmetric configurationof the diphenic acids.Furthermore, the resolution of 6 : 6'-dichloro-diphenic acid has been successfully accomplished and thereforenitroxyl groups are not to be regarded as necessary componentxiof resolvable diphenic acids.7 It is very curious that an anhydridecannot be obtained from 4 : 4'-dinitrodiphenic acid or diphenyl-2 : 6 : 2' : 6'-tetracarboxylic acid. This discounts the value of theargument against the KauAer diphenyl configuration, which mightbe advanced as the result of the observation that diphenyl-3 : 5 : 3' : 5'-tetracarboxylic acid cannot be deh~drated.~Triphenylmethne Ileriratices.Triphenylmethyl chloride reacts with alcohols in the presenceof anhydrous pyridine with formation of ethers, CPh,-OR.Theseethers crystallise well, and may possibly be employed for thecharacterisation or even the purification of alcohols. lo Theyare quite stable to boiling alcoholic alkali, but are hydrolysed bydilute methyl-alcoholic hydrogen chloride in the cold. The pro-ducts are the alcohol R-OH and triphenylcarbinyl methyl ether.The reactivity of groups attached to the triphenylmethyl residueis exemplified in a series of double decompositions.ll Triphenyl-methylcarbinol gives moderate yields of triphenylmcthylamine,CPh,*hTH,, and triphenylmethylaniline, CPh,*Pu'HPh, when treatedin boiling acetic acid solution with ammonium or aniline acetate,respectively. Triphenylmethylaniline is converted by heating in asealed tube with alcoholic ammonia into triphenylmethylamineunder conditions which leave triphenylcarbinol unaffected. Simi-larly, triphenylmethylamine yields triphenylmethylaniline by theaction of an excess of aniline.o-Hydroxytriphenylcarbinol exhibitsa reversible colour change in solution a t temperatures between 50"and 110". This is supposed to be due to the formation of a quinonoidform and the hypothesis is supported by the fact that above 100"the expected o-fuchsone (I) rearranges to 0-phenylxanthane (11).0 0G. H. Christie, C. W. James, and J. Kenner, T., 1023, 123, 1948.J. Schmidt, Ber., 1903, 36, 3743.H. Burton and J. Kenner, T., 1923, 123, 1043.10 B. Helferich, P. E. Speidel, and W. Toeldte, Ber., 1923, 56, [B], '766;11 P. I. Petrenko-Kritschenko and A.Gandelman, J . Rws. Phg8. Chem. SOC.,A., i, 331.1917, 49, 413; A., i, 554ORGANIC CHEMISTRY. 121This is a type of quinonoid addition familiar in connexion witho-Hydroxytriphenylrethyl the chemistry of the azine-dyestuffs.could only be isolated in the form of a polymeride.12The Anthraccne Gozip.To the already strong evidence that in substitution reactionsit is the enolic modification of a phenol which is reactive mustnow be added the outcome of a striking experiment with phenyl-anthrone (I). This substance is non-fluorescent in acetic acidsolution, and therefore does not contain an anthracene nucleus.It should be mentioned that derivatives of the enol form, forexample, the methyl ether, exhibit powerful fluorescence in solu-tion.Phenylanthrone was found to be unattacked by nitric acidin acetic acid suspension under conditions more vigorous thantlhose which suffice to transform phenylanthranyl acetate (11) intoa mixture of phenylnitroanthrone (111) and phenylhydroxyanthrone(IV). Phenylnitroanthrone alone is formed in the facile nit'rationof phenylanthranyl methyl ether in acetic acid s01ution.l~CHPh Ph NO,*CPh OH*CPh(1.1 (11.1 (111.) (N.1Phenylanthrone is, convenienfly prepared by the condensation ofbromoanthrone and benzene in the presence of aluminium chloride,and on reduction with zinc dust and ammonia it is very readilychanged to phenylanthracene. The above reactions are attributedto 9 : 10-addition involving the rupture of the " bridge bond"which is sopposed to connect these atoms.The important pointis the 9 : 10-addition, not the theory of the mechanism of it, thesole recommendation of which is its convenience. The relations ofanthracene with anthraquinone are exhibited clearly enough bymeans of a " bridge " bond, but this is scarcely true of pyreneand pyrenequinone, of dianthranol and dianthraquinone, and ingeneral of heteronuclear quinols and quinones. It is now suggestedthat " bridge " bonds, being unsaturated, may be conjugated.If, however, conjugation as an explanation of additive phenomenais to be admitted at all, in what respects, it may be asked, doesthe " bridge," essentially a device for avoiding conjugation, offerany advantages? When anthrone is reduced by means of zincand hydrochloric acid, it yields a mixture of dianthranyl (V) and12 M.Gomberg and D. Nishida, J. Amer. Chem. Soo., 1923, 45,190; A,, i, 212.l3 E. de R. Barnett and J. W. Cook, T., 1923,123,2632132 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.an a-pinacolin to which the ethylene-oxide structure (VI) has beenassigned.The intermediate pinacol derived from anthrone loses water intwo directions. When the substance VI is hwated in acetic acidsolution with hydrochloric acid, it probably adds on water withreproduction of the pinacol, which is immediately dehydrated withformation of diant8hranyl. This behaviour coupled with therefusal of the substance to form an acetate or benzoate is regardedas proving the ethylene-oxide structure.14 It is, however, quiteconceivable that the substance is a real kcto-pinacolin with aseven-ring (VII), because it seems very probable that the pinacol-pinacolin transformation is reversible, although the equilibriummay greatly favour the phacolin.I n such a case as the presentone, the irreversible conversion of the pinacol into an aromaticsubsta.nce would ensure the transformation of the whole of theproduct, however small the proportion of pinacol in the equilibratedmixture.The fact that the arylarninc salts of the anthraquinone mono-and di-sulphonic acids exhibit a great tendency to crystalliseand are sparingly soluble in water and alcohol h i s of much practicalinterest.For example, pure methylaniline can be separated from a mixturecontaining not too much dimethylaniline by taking advantage ofthe sparing solubility of methylaniline anthraquinone-2-~u1phonate.l~The dry distillation of sodium anthraquinone-2-sulphonate wasexamined in 1885,16 but the nature of the products has only recentlybeen e1u~idat~ed.l~ The chief substances formed are 2 : 2’-dianthra-quinonyl ether and the corresponding sulphide, which is an orsnge-red substance.Michlcr’s ketone and anthrone condense together slowly inboiling benzene solution in presence of phosphoryl chloride withformation of a product from which 4’ : 4”-tetramethyldiamino-anthrafuchsone (VIII) can be isolated in 62 per cent.yield.13 Thisis a briek-red substance which gives bright blue salts of the usual1 4 E. de B. Barnett and M, A. Matthews, T., 1923, 123, 380.16 A.G. Perkin and W. G. Sewell, J. SOC. Chem. Ind., 1923, 42, 27T; A . ,16 A. G. Perkin and W. H. Perkin, T., 1885, 4’9, 679.1 7 A. G. Perkin and W. G. Sewell, T., 1923, 123, 3032.18 F. A. Mason, ibid., p. 1546.i, 234ORGANIC CHEMISTRY. 123quinonoid iriphenylmethane type. The colour-salt is readilyhydrolysed by water, but with formation of a substance of muchdarker colour than thc fuchsoiie, and this is thought to be animmonium base. In the salts the anthrone nucleus is probablyin the enolic form ; ths acylated salts are of a very similar character.The further investigation of the remarkable class of free radicalsknown as the l-aroyloxanthronyls has led t o a modified conceptionof their nature. These substances, of which l-p-chlorobenzoyl-oxanthronyl lins been investigated in greatest detail, were firstobtained by the reduction of 1 -nroylanthrauuinones with aluminiumbronze in sulphuric acid solution.constitution is that expressed by theIThe simplest view offormula IX.their(IX.)The suggestion which rcplaces this view is that the hydrogenatom is co-ordinately attached to two oxygen atoms, with theresult that the free valency is shared by two carbon atoms as shownin the expressionThese substances therefore contain two carbon atonis which aretogether septavalent.l9 The experimental side of the work scarcelylends itself to summarisation, but a new method of preparationapplied to the parent substance of the group may be mentioned.1 -Benzoylanthraquinone is made from the chloride of anthra-quinone-1 -carbosylic acid and benzene by the action of aluminiumchloride and then reduccd by zinc dusf and glacial acetic acid to1 -benzoylanthraquinol (X).This undergoes what is called '' dis-proportionation " on treatment with hydrochloric acid in accord-ance with the scheme :H19 R. Scholl and H. Eliilile, Ber., 1923, 56, [B], 918, 1065; A., i, 584, 6891% ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Benzoyloxanthronyl (XI) occurs in bluish-violet needles, m. p.192-193', and exhibits the behaviour of a univalent radica1.mMiscellaneous.p-isoPropylphenylacetaldehyde (incorrectly designated as p-cymyl-acetaldehyde) has been prepared and found to possess a strong odourof vervain.,l The existence of monomeric quinonehalogenmethidesappears to have been definitely proved.22 The action of phosphoruspentabromide on 3 : 5-dibromo-4-h ydroxybenzaldehyde yields thebenzylidene bromide (I), which is fransformed into 3 : 5-dibromo-GHBrCquinonebromomethide (11) by short treatment with cold alcoholor by shaking an ethereal solution with aqueous sodium acetate.This substance is unimolecular, but polymerises rapidly in hotbenzene solution.It is hydrolysed with remarkable ease withformation of the original hydroxy-aldehyde. An interestingexplanation of the formation of purpurogallin 23 is shown in thescheme given below : 24In the first place, a quinonoid addition and in the second abenzil-benzilic acid-type transformation is postulated, The pro-duct (I) then loses carbon dioxide and hydrogen, yielding in turnthe substance (11) and purpurogallin (IIT).20 R.Scholl, H. Dehnert, and H. Semp, Ber., 1923,56, [ B ] , 1633; A . , i, 807.21 L. Bert, Compt. rend., 1923,177, 550; A., i, 1101.22 H. Lindemann, AnmEen, 1923, 431, 270; A., i, 686.23 A. G. Perkin, P., 1913, 29, 364.16 R. Wibtiitter aad H. Heiss, Annden, 1923, 433, 17; A., i, 1212ORGiQNIC CHXMIS'I'RY. 125The conversion of purpurogallin into purpurogallonc is supposedto be due to a second benzilic acid transformation as follows :The .conclusion has been drawn25 that the isomerism of the" saturated " and " unsaturated " silicohydrocarbons, Si4Ph,,produced by the action of sodium on diphenylsilicon dichloride 26is very probably to be expressed by the formula IV and V,respectively.SiPhz*SiPh,'IV*) h?h2*kiPh,-SiPh,*SiPh,*SiPh,*SiPh,- (v,)In addition to the facts already known in regard to the gapwhich exjsts between the reactivities of the isomerides and whichhave been confirmed and extended by striking new observations,it has been found that the iodide, Si,Ph,I,, derived from theunsaturated silicohydrocarbon, reacts with magnesium ethylbromide with formation of diethylocfaphenylsilicotetrme, Et,$i,Ph,.On the other hand, decaphenylsiliootetrane, Si,I?h,, could not beob6ained by an analogous reaction.27 It seems that there is roomfor the ethyl groups, but not for phenyl.An intermediate in theformation-reaction of the two silicohydrocarbons is probablySiPh,Cl*SiPh2*SiPh,*&PhzCl, and this may lose two chlorineatoms so as to form a ring or, on account of steric hindrance, thecompound containing two tervalent silicon atoms.Cuprous phenyl, CuPh, is obtained as a white powder by theaction of magnesium phenyl bromide on cuprous iodide.Onwarming in benzene solution, it is quantitatively decomposedwith formation of diphenyl and a copper mirror.28In closing this series of Reports, it is desired to add an expressionof a sense of deep indebtedness to all the colleagues who havelightened an onerous task, and especially to the Abstractors, whosecareful summaries of long and often difficult memoirs have greatlyfacilitated the work, even in the numerous cases where referenceto the original was necessary.R.ROBINSON.26 3. S. Kipping, T., 1923, 123, 2590.26 F. S. Kipping and J. E. Sands, T., 1921, 118, 830.F. S. Kipping, T., 1923, 133, 2598.28 R. Reich, Compt. r e d . , 1923, 177, 322; A., i, 972126 ANNUAL REPORTS ON THE PROGRESS OI?' CHEMISTRY.P-4RT III.-HETEROCYCLIC DIVISION.THE volume of work falling within the purview of this Report issomewhat smaller than that dealt with last year, and, with theexception of important papers on morphine and its congeners,includes little of outstanding value. Nevertheless, a number ofobservations have been made, the collective signifkance of whichwould seem distinctly interesting a t the present time.The chemistry of pyrrole derivatives seems now sufficientlycomplete to encourage the hope that the examination of chlorophylland haemoglobin may soon enter on a fresh stage.Some Conditions of Jlolecular Stability and Reactivity.Those theories of organic chemistry which are concerned withmolecular structure are founded on the hypothesis that stabilityis very closely associated with molecular saturation.The corollaryof this view that any molecular structure will tend to assume tlhemost saturated condition has not always received the attention itdeserves. For example, it seems never to have been suggested thatthe immediate transition of synthetic dihydroquinaldine intoquinaldine and its tetrahydro-derivative in the Doebner and Millerreaction is due to the more saturated character of each of the lattercompounds :CH,\/vCHMe/' /\ /\/\FH, 'I + I I y>\l<;e -+ I/\/\NH\/\/NH NSimilarly, when 1 -metliyl-2-propyldihydroquinoline is distilledunder .atmospheric pressure, it suffers partial decomposition intomethane and 2-propylquinoline : 1Failure to realise the probability that this might occur was respon-sible for the erroneous statement that the tetrahydro-derivativeprepared from the supposedly pure dihydro-compound could existin stereoisomeric forms.2 Again, the hydrochloride of acetophenone-anil is converted at 180" into 4-phenyl-2-methylquioline :1 J.Meisenheher and M. Schiitze, Rer., 1923, 56, [B], 1353 ; A., i, 839.2 >I. Freund and E. Kessler, J. pr. Chem., 1918, [ii], 98, 233; A., 1918,J E, Knoeveiiagel and 0. Gcas, BEY., 1922, 55, [Sj, 1329; A., 1922, i, 751.i, 283ORGANIC CHEMISTRY.127N NH NSimilar tendencies on the part of dihydropyridine derivatives havefrequently been observed, and are discussed in a paper in whichit is shown that the pyridine (11) and its hexahydro-derivative (111)are formed in place of the dihydro-compound (I) which would beexpected : 4COPhCH*CNCPh -It has recently been suggested that the general readiness withwhich morphine dcrivatives decompose into derivatives of phen-anthrcne and of aminoethanol is similarly due to the tendency toproduce an aromatic nucleus. The irnportlant conclusion , revo-lutionary in the discussion of the constitution of these a81kaloids,has therefore been drawn that the ethanamine grouping must bcattached to the nucleus which cventually becomes aromatic at acarbon atom (13 or 14) which is not provided with a hydrogenatom or hydroxyl group.The forinulae (IV) and (V), respectivelyassigned to codcine and a-~ethylnzorphimethine, illustrate thesepointis. rjE. P. Kohler and B. L. Souther, J . d m e r . Cfienz. SQC., 1022, 44, 2903;A., i, 2-43.J. M. Gullniicl and Pu. Robinson, ?I., 1923, 123, 980. The formation ofraudalene when eudesinol or selinene is heated with sulphur (L. Ruzicka,J. Xeyer, and M. Mingazzini, Helv. Chim. Actn, 1922, 5, 349; A., 1922, i, 560;Ann. Reports, 1922, 18, 118) invol:-ea the extrusicn cf a methyl gicup dua toa similar causa128 ANNUAL REPORTS ON THE PROGRESS OF CHXMISTRY.The same paper contains a discussion of yet other modes in whichthe same fundamental tendency manifests itself.6A familiar process by which the molecules of unsaturated com-pounds tend to become more saturated is that of more or less well-defined association with other unsaturated molecules. It waspointed out in a previous Report 7 that in such cases four-memberedrings are frequently formed and that, from the kinetic point ofview, a reaction between two molecules is more likely to occur thanone between three. In agreement with this, dimethindiazidines,for example (I), have been prepared by direct combination ofazomethines :In other cases, the formation of such an intermediate product ist4e most plausible explanation of the attainment of an equilibriumwhich can be reached from either side.8 For example,In another in~tance,~ the symmetrical dimeric form is stable a+law temperatures, and is only completely broken down a t 250" :In all such cases the resulting equilibrium represents, if theinfluence of surrounding media be for the moment neglected, acompromise between the tendency towards more complete satur-ation and instability of the resulting ring structure, just as tauto-merism may be due to an equilibrium between two conditions ofequal molecular saturation or between one of greater saturationand some particular source of instability inherent in that condition.10Some interesting observations have been made during the yearwhich would seem to fall in this category.Acetylpapaverine(R = Me in 11) has a considerable tendency to pass into the ammon-ium base, coralyne (R =Me in ID), but aqueous solutions of6 Compare, for example, p.992.Ann. Reports, 1920, 17, 97.6 C. K. Ingold and H. A. Piggott, T., 1922, 121, 2793. * Idem, T., 1923,123, 2746,lo F. Allsop and J. Kenner, JW., p. 2306ORGANIC CHEMISTRY 6 129homocoTalyne, on the other hand, arc very unstable and graduallydeposit propionylpapaverine : l1The formation of the products (I) and (11) by bromination of allyl-veronal12 suggests that this and the open-chain compound (111)are ring-chain tautomerides :lp3-yO TH-7070 7Ef2 +(I. 1 (111.)70 YEt, frC,H5Br,*NH CN C3H,*NH CNThe result of the decomposition by heat of 4-hydroxy-7 : 9-dialkyl-4 : 5-dihydrouric acid l3 points to .a similar conclusion :A reaction interesting from some of the above points of viewoccurs when 4-nitro-2-aminodiphenylarnine is treated with benzil.The stilbazonium derivative usually obtained from such condens-ations is also obtainable in tzhis case as a sulphate (111), if a solut,ionof the intermediate anil (I) in concentrated sulphuric acid becautiously diluted with water ; excessive dilution, however, causesseparation of the original anil, although the +-base (11) is pre-cipitated from solutions of the salts on addition of ammonia.Thefollowing equilibrhm t'herefore apparently exists :11 W. Schneider and E. Nitze, Ber., 1923, 56, [El, 1036; &4., i, 701.12 0. Diels, Annalen, 1923, 432, 115; A., i, 950.13 H. Biltz and R. Lemberg, ibid., p. 137; A., i, 955.REP.--VOL.XX . 130 ANNUAL REPORTS ON THE PROGRESS OFN NI *N;I-I NCHEMISTRY.N(111.)No2f)/\CPh(N.) \/\/ WOPhTHc'aaHs'oH N02')/NCPh + C,H,-CO,Et + H,NPh (v.) NPhBut the anil also hae a slight tendency to form the derivative (IV).The stability of such dihydrobenziminazoles would, however, seemto be slight in comparison with that of the benzjminazoles (forexample, these have so far resisted attempb a t direct reductionto dihydro-derivatives) and consequently when the an2 (I) isboiled with alcoholic hydroehloric mid, the products are Pot stilb-azonium salts, but 5-nitro-1 : 2-diphenylbenziminazole (V) andethyl benzoate, arising from the irreversible reaction indicated.The result depends on the very slight basicity of the stilbazoniumhydroxide, and therefore is not observed when 4-chloro-2-amino-dipheaylamine or 4-nitso-ootphenylenediamine is treated withbenzil.14Saturation as above considbred is one form of what has beentermed '' chemical neutralisation," which was mentioned in lastyear's Report in connexion with the formation of cyclic compoundsfrom hydrazodicarbon-mono- and -di-thiocarbonamides under theinfluence of alkali or acid.A more extended investigation of thisquestion l6 has revealed some exceptions to the suggestion thatthese alkaline or acidic reagents respectively give rise to the form-ation of acidic or basic products. Thus methyl thiosemicarbazide-dithiocarbonate (VI) furnishes 2-amino-5-methylthiol-1 : 3 : 4-thio-diazole (VII), whether it be heated alone or treated with either acidor alkali :The explanation is that in general such reactions occur in twostages; the first consists in the removal of, for example, ammonia14 K.Brand and E. Wild, Ber., 1923, 56, [B], 105; A., i, 251.l5 Ann. Reports, 1922, 19, 130.16 F. Arndt and F. Bielich, Ber., 1923, 56, [B], 2276; A., 1924, i, 22;E. Fromm, Annulen, 1923, 433, 1; A., i, 1239OWANIC CHEMISTRY. 131or, as in the example quoted, methyl mercaptan, whilst in thesecond, internal condensation of the unsaturated compound oocursaccording to the above-mentioned suggestion, when alternativesare open. In certain cases, however, only one course is possible,and the result may then be at variance with the view indicated,The underlying idea of the theory of induced alternate polarity isclearly also one of neutralisation.An interesting application ofthis theory has been made to explain the formation of (I) and (11)by the nitration respectively of tetrahydrocarbazole in concentratedsulphuric acid solution and of its N-acetyl derivative.H 2NO, /\-/\& 3-, NO2 332/-\-AH2(1.1 (/,+)Y)H2 I +I IL IH, (11.1\/\/\/-NAc H, * H2 wHso,The justification for considerkg the orienting influences to betransmitted in the manner indicated by the signs of polarity,rather than more directly through the aromatic nucleus, lies inthe observation that the ethylenic linking in tetrahydrocarbazoleis specially reactive. For example, the pinacol (In) is obtainableunder certain conditions of nitration, and, it may be noted, passesinfo the spko-compound (IV) when heated alone or with aceticanhydride.17Another reaction, noteworthy from the same point of view, consistsin the formation of N-p-nitrophenylcarbazole (V) by heatingpotassium carbazole with the usually inert nitrobenzene a t thelow temperature of 45-50’ :+ -The result becomes perhaps more sign*lficant by contrast with the1’ W.R. Perkin and S. G. P. Plant, T., 1923, 123, 676.F 132 ANNUAL RXPORTS ON THE PROGRESS OF CHEWISTRY.fact that the analogous synthesis of p-chlorophenylcarbazole, bythe aid of pchlorobromobenzene (VI), requires a temperature of210°.18 The reactivities of the 2-methyl group in 2 : 3-dimethyl-chromone (I) 19 and of the 3-hydrogen atoms in 6-methylthio-chromone and -flavanone (11) are also readily interpreted in termsof the theory of polarity.0 S S(1.1 (111.) (11.)The hydrolysis of the condensation product (111) of the tlrioffavanonewith nitrosobenzene to the original compounds rather than toaniline and the corresponding diketone is very striking. Thepolar effect of the phenyl group is alone indicated in (11), becauseit is this, superimposed on those of the other atoms, which deter-mines this result.Thus, the diketone is obtainable from methyl-thiochromanone by the method under discussion.20 Again, when3-acetyl-2-methylnaphthachromone (IV) and anelogous compoundsare treated w-itli alkali, the “positive” acetyl group is replacedby hydrogen : 21In yct another direction, 4-hydroxy-7 : 0-dialkyl-4 : 5-dihydrouricacids are obtained when the corresponding glycols are heated withphosphorus tribromide :NH-66 NH-COCO C(0H)-NR --+ CO CH--NRNH--C(OH)*NRI -I + 1 11 +I - >co I I >coNH- C(OH) -mA review of reactions of this type leads to the conclusion thatphosphorus trihalides react with enolic hydroxyl preferentially in18 (2.and M. dc Montmollin, Helv. Chiwz. Acta, 1923, 6, 94; A,, i, 373.1s I. R I . Heilbron, H. Barnes, and It. A. Morton, T., 1023, 123, 2659.20 B. Amdt and others, Ber., 1923, 56, [B], 1269; 9., i, 526; F. Krollpfoiffer91 IV. ScIinoider and (Miss) H. Bode, ibid., p. 1062; A., i, 699 ; St. v.and H. Schultze, ibid., p. 1810; A., i, 1113.Kbstaneeki and A. Rczycki, Ber., 1901, 84, 102; A., 1901, i, 222ORGANIC CHEMISTRY.133such a manner as to replace it by hydrogen. Correspondingly, thechlorine atom of 5-chloro-q- or -iso-uric acids, or of 5-chloro-4-hydroxydihydrouric acids exhibits " positive ' ' properties.22 Theformation of 2 - bromoglyoxaline from 2 : 5 -dibromo-4-carboxy-p-bromoanilide (p. 143) would seem to be another reaction of thiskind.Valuable as these points of view are, however, they must beregarded only as approximations to the fundamental principle ofmaximum entropy, and it is not dBcult to find examples whichsuggest that the reactions of organic chemistry will be properlyunderstood only when a more exact application of this principlebecomes possible. The various results obtained by reducinghydroxycodeinone 23 illustrate this point :Non-ketonic, non-phenolic pro-duct.SnC1,+ HCI Hydroxycodeinone + H, -- -+ Ketonic, phenolic.Ketonic, non-phenolic.Again, 2-bromothiophen, resulting from the action of cyanogenbromide on thiophen, is probably accompanied by some 2-cyano-t h i ~ p h e n , ~ ~ so that the cyanogen bromide apparently does not reactaccording t o a perfectly definite distribution of polarity, Thereare similar indications that absolute rules cannot be laid down inregard t o the relative strengths of attachment of groups to thesame atom.As is well known, much attention has been bestowedon this question in recent years, and a survey25 of the resultsobtained in a variety of directions points to the definite conclusionthat aliphatic groups are more easily detached than aromatic.The exact opposite is, however, observed in the reaction of aceto-phenoneanil already referred to, whilst, among open-chain com-pounds, the mode of dehydration of glycols, involving ultimatedetachment and migration of groups, varies with the conditionsemployed : 26Wld heat or -+ R,CArCHO. Ar>CH*COR R $n~Ex HOGRa2*CHAr*OH GCidz2 H.Biltz and R. Lemberg, Annulen, 1923, 433, 137; A , , i, 956.23 Compare E. Speyer, ibz'd., 1923, 430, 1 ; A , , i, 127.24 W. Steinkopf, ibid., p. 78; A., i, 124.25 J. v. Braun and K. Moldaenke, Ber., 1923, 56, [B], 2165; A., i, 1193.* & M. Tiffeneau and (Mlle) J. Ldvy, BUZZ. SOC. chhim., 1923, [iv], 33, 735;A., i, 588134 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.I n this connexion, a paper may be noted in which the results ofheating various alkyliodides of 1 -methylglyoxaline a t 260-300°are communicated.Bor example, l-methylglyoxaline isoamyl-iodide (I) furnishes equal quantities of isoamyl- and methyl-glyoxalines , but the latter alone results when the benzylbromidederivative is heated : 27CH-meaCH + fjH----N >CHR"-me>CH1 CH---N~ \ c 5 H l ~ f -+ ZH-N CH-W5H11)(1.1Ring Formation.When the hydrochloride of o- y-chloropropylbenzylamine (1) isheated a t 100" with dilute sodium hydroxide solution for a shorttime, a base, most probably homoisoquinoline (11), is obtained.The result is perhaps attributable to the readiness with which, inthe first place, irreversible internal quaternary ammonium chlorideformation occurs, even during the possibly infrequent phases inwhich the molecule assumes a configuration favourable to such areaction :By contrast, a reaction of more complex character does not takeplace between two amino-groups in the same relative position : 28The formation of 4-ketotetrahydro-1 : 5-heptabenzthiazine (111)by heating ,8-o-aminophenylthiolpropionic acid would also seemto illustrate the influence of internal salt formation as an aid tothe synthesis of large ring stmct'ures : 2927 J.Sarasin, Helv. Chim. Acta, 1923, 6, 370; A., i, 710.28 J. v. Braun and F. Zobel, Ber., 1923, 56, [B], 690; &4., i, 371.29 F. Mayer and C. Horst, ibi&., p. 1415; A., i, 844ORGANIC CXEMISTRY. 135Whereas the condensation of indigotin with phenylacetyl chlorideyields Lake Red Ciba B (IV), only one molecular proportion ofethyl malonafe can be condensed with indigotin.Nevertheless,the product is converted by treatment with phenylacetyl chlorideinto (V)?CO---CPhFive-membered Heterocyclic Structures.In some respects, the thiophens are intermediate between theolefines and the benzenes. Thus, usually only additive products areobtained by the action of reagents on olefines, whereas, althoughthose of bromine and of merouric chloride with thiophens may beisolated in certain cases, they readily pass into substitution deriv-atives, such as are alone obtained from benzene. On the otherhand, cyanogen bromide only reacts with benzene and naphthaleneabove 200°, and not a t all with unsaturated compounds like ethylfumarate or ethyl cinnamate, but thiophens are easily convertedby this reagent into 2-bromo-derivatives, accompanied by smallamounts.of the corresponding nitriles. 2 : 5-Derivatives of thiophenare only attacked with difficulty by this reagent. The superiorreactivity of the a- over the p-position in thiophen is also illustratedby the fact that 2 : 5-dimethyl- and -diphenyl-thiophens alone ofthe 2 : 5-derivatives examined, form thienyl mercurichlorides, andreact relatively sl0wly.~1 2 : 2’-Mercurydithienyls have been pre-pared by treating the corresponding mercurichlorides with sodiumstannite, sodium iodide, or sodium thiocyanafe.2 1 CHX(HgC1)CH:C(H~C~)>SThe formation of the cyclic compound (I) from 2 : 5-thienylene-dimercurichloride is the more interesting, since scarcely any cyclicmercuric compounds have been previously ~repared.~aPosner and a.Pyl, Ber., 1923, 56, [ B ] , 31 ; A., i, 252.Society of Chemical Industry, Basel, D.R.-P. 260243 of 1913; T.al W. Steinkopf, Annalen, 1923, 430, 78; A,, i, 124.88 W. Steinkopf, W. Btelenberg, and H. Augestsd-Jensen, ibid., p. 41;A., i, 12136 ANNUAL REPORTS ON THE PROGBESS OF CHEMISTRY.Only thiophens with two free a-positions exhibit the indophenhereaction. Since, further, the analogous condensation product ofthiophen with ethyl mesoxalate has a bimolecular formula, theconstitution (11) has been assigned to indophenine. The alternativeformula (111) does not accord with the indigoid character of indo-phenine, or with the formation of 2 : 2'-dithienyl from thiophenand sulphuric acid.33EH-fiH C NH ,\Y< /J\ -1 ,\7?7\/\/\,\ (11.) ( I c=c c: I ( I c/\/ co h ~ = i ; l ~ 1 2 "& \c7\{\co A I(111*)8~-CH IBiphenylene sulphide, found in coal tar, has not hitherto been easilyaccessible by synthesis, but it can now be readily prepared byboiling diphenyl sulphoxide in toluene solution with sodamide.34When acetophenoneanil is fused with sulphur at 240°, 2 : 4-di-phenylthiophen is obtained, and selenophens may be similarlyprepared : 35Phf-EHC6H,*N:$!*C,H, --+ [C6H,*C(SH):CHJ + CH CPhMe \S/The development of general methods for the preparation ofvarious types of substituted pyrroles has continued.Amino-derivatives, hitherto unknown, have been obtained by hydrogen-ation of cold alkaline alcoholic solutions of suitable benzeneazo-pyrroles in presence of platinum.Although the products are strongbases, 4-amino-2 : 3 : 6-trimethylpyrrole, which alone was examinedin these respects, did not react with phenylcarbimide, or acidchlorides, and could not be methylated.36Cyanopyrroles also had not previously been prepared, but arereadily obtainable from oximes 37 of the aldehydopyrroles, whilsttreatment of their hydrazones or semicarbazones with sodiumethoxide in the usual manner provides a convenient source ofalkylpyrr~les.~~ The failure to obtain phyllopyrrole from 3-aceto -6-aldehydo-2 : 4-dimethylpyrrole is an isolated exception to this33 W. Schlenk and (Miss) 0. Blum, Aniaalen, 1923, 433, 95; A., i, 1235.34 A.Schonberg, Ber., 1923, 56, [BJ, 2275; A., 1924, i, 39.S 5 M. T. Bogert and P. P. Herrera, J . Amer. Chem. Soc., 1923, 45, 238;313 H. Fischer and F. Rothweiler, Ber., 1923, 56, [B], 512; A . , i, 391.37 H. Fischer and W. Zerweck, ibid., p. 519; A., i, 364.38 H. Fischer and M. Schubert, ibid., p. 1202; A., i, iO7; H. Fischer,A . , i, 240.B. Weiss, and M. Schubert, ibid., p. 1194; A., i, 703ORGANIC CHEMISTRY. 137statement.39 A new synthesis of haematic acid also depends in thefirst place on that of an aldehydopyrrole : 40MeE-E.CH.0 MeG-fi*CH:C(CO,Et),CO,R*C\/CMe + CO,R*C\,CMe -+NH NHMeg-fi*CH,*CH( CO,H), MeC=$XHZ*CHa*C02HCO,R*C,/CMe + Ob\/CONH NHIn view of this importance of aldehydopyrroles, the successfulapplication of Gattermann’s synthesis to N-methyl- and N-phenyl-pyrroles is note~orthy.~lThe object of all this work is of course the perfection of methodspermitting closer inquiry into the manner in which the variouswell-recognised alkylated pymole nuclei are united in the molecularstructure of biologically important pigments.Bilirubin, whichfrom its oxidation to htematic acid &I known to contain a p F o l enucleus, has now been shown42 to contain, not a methylimino-group, but an imino-group, which undergoes methylation when thisdibasic acid is esterified by means of diazomethane.m Since thisbehaviour is reproduced by the pyrrolenyl derivative (I) (althoughnot by the analogous furfurylidene derivative), of which thesynthesis is indicated, it is concluded that bilirubin contains aMet+ CH + CHO0C6H4*OH + c * ~ ~ < ~ ~ ~ ~ ~ - C 6 H pyrrolenyl nucleus connected with a pyrrole nucleus through asingle carbon atom.Bilirubic acid, obtained from the pigmentby reductive degradation, had aIready been formulated as anunsymmetrical methene conforming to this description, Com-pounds of this typeM have now been prepared by the action ofhot dilute mineral acid on 2-aldehydopyrrole~,~~MeG-fiH HC-CMe MeE-SHCH0.C CMe + Me(!!\/b=CH-C,/CMeCO,R*g-fi*OH >--NH (1.1 NN,HCl NH\/ NHH. Fischer and H. Ammann, Ber., 1923, 66, 2319; A,, 1924, i, 78.40 W. Kiister and H. Maurer, a i d . , p. 2478.*l H. Fischer and K. Smeykal, ibid., p. 2368.42 W. Kiister and W. Maag, ibid., p.65; A., i, 242.43 Compare W. Kuster and others, 2;. physiol, Clzem., 1915, 94, 136; A .44 H. Fischer, Ber., 1912, 45, 1979; 0. Pilofy and Thannhauser, ibid.45 H. Fiecher and W. Zerweck, loc. 03.1915, i, 829.p. 2393; A,, 1912, i, 646, 926.F135 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.or on the tripyrrylmethanes (obtained when the pyrroles aresubjected to the Reimer-Tiemann reaction) : 46COMe-fi-fiMe Mey=y*COMeMeC,,C-CH=C\/CMeNH N,HClAB a fukther step, these and other dipyrrylmethenes have beenshown to furnish complex copper, zinc, and nickel, but not ferric,salfs, in which the atom of the metal is united to two pyrrole nucleiby principal and to two pyrrolenyl nuclei by subsidiary valencies.The copper salts resemble that of mesobilirubinogen in exhibitingthree absorption bands, whilst the zinc complex salts show afluorescence corresponding to that of urobilin.47The thermal decomposition of cyclic bisimines 48 has been appliedto the preparation of pyrrolidine by heating the quaternary ammon-ium bromide prepared from 1 : 4-dibromobutane and the noweasily accessible copellidine 49 (using preferably the stereoisomeridewhich furnishes the less soluble hydrochloride) for twenty-fourhours with ammonia at 170-180" : 5oThe interval of 80" between the boiling points of pyrrolidine andcopellidine renders their separation easy.A new synthesis of proline depends on the condensation oftrimethylene dibromide with ethyl aminornalonate : 51Br.[CH,],*Br + yH(CO,Et), 4 Br[CH,],*C(CO,Et), ~NH2 kH246 H.Piscker and H. Ammann, loc. cit. ; compare 0. Piloty, W. Krannieh,and H. Will, Ber., 1914, 47, 2531; A., 1915, i, 461; H. Wiedmann, Ddss.,Munich, 1920.4 7 H. Fischer and M. Schubsrt, Ber., 1923, 58, [B], 2379.48 Compare Ann. Beport8, 1922, 19, 127.49 Hijchster Farbwerke, D.R.-P. 34 7820, 349184, 349267.6o J. v. Braun, G. Lemke, and (Miss) A. Nelken, Ber., 1923, 56, [B], 1564;51 N. J. Putochin, ibid., p. 2213; A., i, 1225.A., i, 840ORGANIC CHEMISTRY. 139The Gattermann and Hoesch syntheses have been successfullyapplied to 2-methyl- and 2-carbethoxy-indoles, but indole itself isnot reactive.52The discussion of the alleged cases of isomerism in the isatinseries has been continued. Thus, it is claimed that to the isomericforms of isatlin and 4-hydro~yquinaldine~ two forms of ketodihydro-indazole but at the same time it is admitted that thealleged isomerides are polymolecular in various solvents includingphenol.This result is ascribed to association, but it has been verypertinently objected that such a view is inapplicable whFn hydr-oxylic solvents are concerned, and that the compounds in questionare in reality polymerides of the simple compounds. 54The formulation of the supposed isomeric forms of ethyl isato-genate as an additive compound with ethyl alcohol 55 has beenaccepted and confirmed by analysis, but a t the same time theexistence of isomerides of carbethoxy- and nitro-phenylisatogenis affirmed, and in the latter case it is shown that an additivecompound with ethyl alcohol can also be obtained under somewhatdifferent experimental condition^.^^The preparation of pehnaphthindigotin has now been achieved,57and in two papers 58 the identity of a- and P-indines with iso-indigotin is independently demonst,rated.Ethylene oxalate decomposes a t 240" largely into ethylene andcarbon dioxide, but also to a considerable extent into ethylenecarbonate and carbon monoxide :Other products include a~etaldehyde.~~It has not been possible to synthesise optically active forms ofthe ketothiazolidines (I) or of the rhodanines (11) owing to theirtendency to enolisation.I n the case of the diketothiazolidines (111),however, this tendency is sufficiently restrained to permit optical52 R.Seka, Ber., 1923,'fis, [BJ, 2058; A., i, 1125; H. Fischer and I<.58 G. Heller qnd W. Kohler, ibid., p. 1596; A., i, 850.64 A. Hantzsch, ibid., p. 2110; A., i, 1226.6 6 Compare Ann. Reports, 1922, 19, 135.56 P. Riiggli, A. Bolliger, and W. Leonhardt, Helv. Chim. Acta, 1923, 6,5 7 S. Dutt, T'., 1923,123, 224; compare Ann. Reports, 1922, 19, 131.68 A. Wahl and W. Hansen, Compt. rend., 1923, 1'56, 1070; A., i, 607;0. Dornier and Jh. Martinet, Bull. SOC. chim., 1923, 33, 779; A,, i, 852.Pisbor, ibid., p. 2313; A., 1924, i, 86.594; A., i, 833.69 M. Tilitscheev, Ber., 1923, 56, [B], 2218; A., i, 1173.F 2140 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.activity to be observed when the synthetic products are isolatedwith sufficient rapidity.60Stereochemical considerations have also led to the synthesis ofanother thiazole derivative (IV).The failure of all attempts toresolve this compound into optically active components 61 accordswith the considered opinion of one of the foremost workers on thesubject of asymmetric tervalent nitrogen that ‘‘ the asymmetricsaturated tervalent nitrogen atom can give rise only in very specialcases, if ever, to the existence of stereoisomerides.” 62The +-base derived from benzothiazole methiodide (I) is not thecarbinol (11), but the monobasic acid (111), which is reconvertibleinto sslts of the true benzothiazole base by treatment with acid,and is also easily oxidised by iodine or alkaline ferricyanide to thedisulphide (IV) : G3HIIKOH -+(111.)J.IEvidence that (11) is an intermediate product in the above changeis obtained by the formation of small amounts of methylbenzo-thiazolone (V) when the methiodide is treated with alkaline hydrogenperoxide. When the disulphide is heated with phenylhydrazine,the asymmetric bis-2-methylbenzothiazoline-1 : 1 -spiran (VI) is6o S.Kallenberg, Ber., 1923, 56, [B], 316; A., i, 247.62 J. Meisenheher and M. Schutze, ibid., p. 1353; A., i, 839.a W. H. Mills, L. M. Clark, and J. A. Aeschlimann, T., 1923, 123, 2363.B. Groth and B. Holmberg, ibid., p. 289; A,, i, 246ORGANIC CHEMISTRY. 141s sproduced. If, in place of the hydrazine, an alkyl salt of a basecontaining a reactive methylene group be employed, the latterreacts with the formic acid to produce carbocyanines and similardyestuffs.Thus, in t’he case of ethylquinaldinium nitrate anddi-o-formylethylaminodiphenyl disulphide, pinacyanol is produced.At the same time, however, another reaction occurs with formationof dyes of the isocyaninc type : 64/\ ,SH SSimilar results are obtained when 1 -methylbenzothiazole ethiodide,lepidine ethonitrate, or 4-phenyl-2-methylthiazole methiodide isemployed.652 : 6-Dimethylbenzbisthiazole (I) has been prepared from thedithioacetyl derivative of m-phenylenediamine by oxidation withalkaline potassium ferricyanide solution :S Sf- C,H,(N:CMe*SH),N(1.1CMeThe formula (I) is preferable to (11) because the actual product isreadily formed, and yields a monomethiodide in the same manneras the product obtained from 2 : 6-diaminotoluene, which neces-sarily corresponds to (I), whereas the product from 2 : 4-diamino-toluene, which must be of the type (11), is much less readily formed,and furnishes a dimethiodide. There is an indication, however,$hat a small proportion of (11) accompanies (I).,,64 W.H. Mills, L. M. Clark, and J. A. Aeschlimann, T., 1923, 123, 2362.05 W. H. Mills and W. T. K. Braunholtz, ibid., p. 2504.66 S. R. K. Edge, T., 1922, 121, 772; 1923,123, 153, 1011142 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Derivatives of benzoisothiazole have been prepared for the firsttime from 2-chloro-6-nitrobenzaldehyde. The disulphide (111).obtained from this compound by treatment with sodium sulphide,is converted by prolonged treatment with bromine into thebromide (IV), which yields 5-nitrobenz-4' : 5'-isothiazole (V)wheh boiled in benzene solution with concentrated aqueousammonia solution :CH CHThe salt (VI) is produced if aniline be employed in place of2-Phenylbenzoselenazole is best prepared by boiling benzylidene-aniline with selenium : G8N NHSeAlthough it is now well recognised that many heterocyolic amino-compounds are diazotisable, the value of the reaction for syntheticpurposes is frequently v e v limited.Thus, 4-iodo-3 : 5-dimethyl-pyrazole is much more conveniently prepared by direct substitutionthan from the diazonium compound. Again, aminomethyl-furazan, when diazotised, at once furnishes the diazoamino-compound. 70Substitution of bromine for hydrogen in 4-methyIglyoxalineoccurs first in the 5- rather than in the 2-position, because themonobromo-derivative obtained differs from that prepared bybrominating ethyl 4-methylglyoxaline-5-carboxylate and subse-quently removing the carboxyl group.71 Bromination of glyoxaline-5-carboxyanilide also occurs first in the 4-position, but 2-bromo-6 7 K.Fries and G. Brothuhn, Ber., 1923, 58, [BJ, 1630; A., i, 842.68 M. T. Bogert and Yu-Gman Chen, J . Arner. Chern. SOC., 1922, 44, 2362 ;69 G. T. Morgan and I. Ackerman, T., 1923,123, 1308.70 G. Ponzio and G. Ruggeri, Gazzetta, 1923, 53, i, 297; A., i, 553,7 1 F. L. Pyman and G. 3%. Tirnmis, T., 1923, 133, 494.A., 1922, i, 1182ORGANIC CHEMLSTRY. 143glyoxaline may be obtained by hydrolysing 2 : 6-dibromoglyoxabe-4-carboxy-p- bromoanilide with sufficiently strong hydrobromicacid solution a t 150" : 72H'hr (x = C6H,Br*NH*CO*)2 : 5-Dibromoglyoxaline may be obtained under milder conditionsof hydrolysis.Although there is no statement as to whether thisis similarly convertible into the 2-bromo-compound, the reactionby which this is produced may probably be compared with thedisplacement of iodine from o- and p-iodoanilines by means ofacid.73 This analogy between reactions of glyoxaline and benzenederivatives is clearly seen in the ready convemion of 4-nitro-1 : 5-dimethylglyoxaline into a 2-bromo-derivative (I), as contrasted withthe non-formation of (11) by similar procedure.(I. ) (11.)In (II), which can be prepared by albylation in the manner indi-cated, the bromine atom occupies a para-position with respect tothe nitro-group, and therefore is mobile, whilst in (I) the meta-orientation of the bromine atom and the nitro-group involves thenon-reactivity of the halogen atom.?* Again, 5-nitro-4-methyl-glyoxaline resembles the nitrotoluenes in its reactivi y towardsbenzaldehyde, which provides a very satisfactory method ofpreparing 5-nitroglyoxaline-4-carboxylic acid : 75A compound isolated from human urine has been suspected tobe 4-glyoxalylaminoacetic acid,76 and this view has been sub-stantiated by the synthesis of this lower homologue of histidine : 77VHO MI2*$ HCN NH,*$ H*CO,Hc/\ HF! M HN-CHHCI c/\ ---+ KGN+NH,CI(3/\ HF! 8 +Hf: R HS-CH HN-CH72 H.King and W. 0. Murch, T., 1923,123, 621.78 Compare Ann. Reporb, 1922.19, 100.74 F. L. Pymsn and G. M. Timmis, loc. cit.75 A. Windaus and W. Langenbeck, Ber., 1923, 66, [B], 683; A., i, 386.76 R. Engeland, 2. physiol. Chem., 1908, 57, 49; A., 1908, ii, 1056.77 C. P. Stewart, Biochem. J . , 1923, 11, 130; A., i, 486144 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.p-Glyoxalylisopiperidine (I) has been obtained by the gradualaddition of methylal to a solution of 4-p-aminoethylglyoxaline a t100" : 78CH,O CH2/\Indoisooxazole-7-carboxylic acid (11), prepared by the action ofhydroxylamine on oxindole-3-a-thiolacetic acid, is the first instanceof a compound in the molecule of which indole and oxazole ringsare fused together : 79A preliminary account has been given of the formation of As-methyldihydroarsindole from p-phenylethylmethylchloroarsine : 8OAIC&-3The Pyrone Croup.2 : 4-a-Chromenes have been obtained by condensing phenolswith a/?-unsaturated ketones : 81CRAs usual in such reactions, resorcinol and m-dimethylaminophenolgive more favourable results than the simple phenols.Similarly,phloroglucinol condenses remarkabIy easily with ethyl formate orethyl orthoformate in presence of hydrogen chloride to form thexanthylium salt (I), but simpler phenols react less readily : 8278 Society for Chemical Industry in Basel, S&8 Put. 92297 ; A , , i, 156.79 Ch. Granacher and A. Mahal, Helv. Chim. Acta, 1923, 6, 467 ; A., i, 713.80 E. E. Turner and F. W.Bury, T., 1923,123, 2489.81 Chemische Fabriken vorm. Weiler-ter Meer, D.R.-P. 357755; A., i, 114.82 D. D. Pratt and R. Robinson, T., 1923, 123, 739ORGANIC CHEMISTRY. 146O H ~ ) O H H% OH()"" + \ \/OEt OH $2\/OHBaicalin, a colouring matter present in the roots of Scutellariabaicalensis, is converted by hydrolysis into glycuronic acid andbaicalein, which appears tto be identical with synfhetic 5 : 6 : 7-trihydroxyflavone (IT) .P3The Pyrimidines.The loose combination between the alloxan and dialuric acidcomponents of alloxantin is illustrated by its decomposition ontreatment with diazomethane into products to which formuls (I)and (II) are assigned. These are also formed when alloxan anddialuric acid or their di-N-methyl derivatives are separately treatedwith diazomethane.The formula (111) for alloxantin is consideredto be a better expression of such results than the older ones.Me?-70 Mey-$lO YH-CO 7 O - F70 g*OMe Y O L0<::roH*8 y oMeN--C*OMe NH-60 oWeC-NH y o f?o>CH,MeN-C.0(I. ) (11. ) (111.)It should be noted that compounds analogous to (I) are obtainedby the action of diazomethane on phenanthraquinone, benzil, andother a-diketones. 84A number of syntheses of purine derivatives based on Traube'swell-known procedure has been published, together with certainimprovements in detail.85The oxidation of 4-hydroxy-7 : 9-diethyl-4 : 5-dihydrouric acidby means of ferric chloride, and other mild reagents, yields a product,to which the formula (IV) is assigned.86yo N- rH-70 I tC O I HY-----NEt >co -+ $!-O-y--NEt>Co (IV.)NH-C(OH).NEt N H -C( OH)*NEt*a K.Shibata, 8. Iwata, and M. Nakamura, Acta Plqtochim., 1923, 1,64 H. Biltz and H. Paetzold, Annalen, 1923, 433, 64; A., i, 1233.8 5 W. Traube, <bid., 432, 266; A., i, 1136.H. Biltz and R. Lemberg, ibid., p. 177; A., i, 957.105; A., i, 691 ; G. Bargellini, Gazzetta, 1919, 49, ii, 47; A., 1919, i, 645146 ANNUAL REPORTS ON THE PROURESS OF CHEMISTRY.However satisfactory this may be from &me points of view, itwould appear to be open to serious objection on stereochemicalThe Pyridine Group.The sodarnide method of preparing 2-aminoquinolines has beenapplied to the preparation of 1 -aminoisoquinoline, and alsoof 2-aminonicotine, 2 : 6-diaminopyridine, and 6-amino-2-methyl-pyridine.Nitration of such aminopyridines occurs principally inthe 5-, but also in the 3-position, whilst sulphonation and bromin-ation take plaoe in the 5-position. Hydroxy- and halogen deriv-atives may be prepared from the amines by diazotisation, whilstsecondary amines result from heating their hydrochlorides. 872-Hydroxypyridine is produced when pyridine vapour is passedover potassium hydroxide a t 320°, whilst an 80 per cent. yield of2-hydroxyquinoline is similarly obtained a t 225O, In this reaetiogalso, the 2-position is exclusively attacked, so that %methyl-quinoline is recovered unchanged after similar treatment. 88The condensation of saturated aliphatic aldehydes with ammoniagives rise to a number of pyridine derivatives.Thus from acet-aldehyde 2- and 4-picolines, 2-methyM-ethyl-, 4-methyl-3-ethyl-,and 2 : 3 : 6-trimethyl-pyridines have been obtained.89 The bhiefproduct of the decomposition of cyanoacetyl chloride, which occursslowly even a t the ordinary temperature, is 6-chloro-Z : 4-di-hydroxynicotinonitde : 90cocl co C*OHg r O U n d S ./CN + /\VHz YHCNCIC\, c 0N-+ c-The first representative of the pyridine methides has been pre-pared by treatment of pyridine methosulphate with sodiumhydroxide and is also obtained by decomposition (which occursslowly even at the ordinary temperature) of the cyano-derivative9 7 A. E. Tschitschibabin and others, J. Rus8. Phys. Cltem. SOC., 1921, 50,471, 483, 492, 495, 497, 502, 512, 519, 522, 534, 543, 548; A., i, 694-600,604, 613; J.P. Wibaut and (Miss) E. Dingemanse, Rec. trav. chirn., 1923,42, 240; A., i, 486.(1) :88 A. E. Tschitschibabin, Ber., 1923, 56, [B], 1879; A., i, 1121.89 A, E. Tschitschibebin and others, .J. h 8 8 . Phy8. Chem. SOC., 1923, 54,402, 411, 413, 420,428; A,, i, 1121, 1128, 1123; cornpareAnn. Reports, 1906,3, 168.90 G. Schroeter and Chr, Seidler, J. pr. Ghem., 1922, [ii], 105, 165; A.,L 1124ORGANIC CHEMISTRY. 147Me co2Roco2R Me <Me HNMepyridone.The methide occurs in two interconvertible modifications, respec-tively reddish-yellow and yellow, and corresponding possibly tothe two formulae (11) and (111). By catalytic reduction, a dihydro-derivative results, which differs from the known compound derivedfrom (11), and hence is assumed to be (IV).Atmospheric oxidationfurnishes a black compound of uncertain constitution, which maybe a polymeride of the expected pyridone, but is not obtainablefrom it.91The elimination of ammonia from pyridinecarboxylic acids byreduction with sodium amalgam in warm alkaline solution probablydepends on the formation of a dialdehyde, which then undergoesa Cannizzaro rearrangement.meronic acid, the change may be represented :For example, in the case of cincho-CH,-t]H-CH*CO,H --+kH0 C02HbH0CH*CO,HCH YH*CO,H 60 CH,/\\/0It will be noticed that (V) contains a grouping somewhat similarto that in pjmole, which latter is easily converted into the oxime,of succinaldehyde. Further, 6-phenyl-2-methylcinchomeronic acidhas been shown to furnish the acid (I).92yH2-$!H---$'H2COPh C0,H COMe (I.)'1 0.Mumm and G. Hingst, Ber., 1923, 56, [B], 2301; A., 1924, I, 83.compare H. Weidel and J. Hoff, Monatsh,, 1802, 13, 678; A,, 1893, i, 114.0. Mumm and K. Brodersen, Ber., 1923,56, [B], 2295 J A,, 1924, i, 82 148 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Against the view that apophyllenic acid is a 4- rather than a3-betaine derivative of cinchomeronic it has been urgedthat a comparison with the behaviour of 2 : 6-dimethylcinchomeronicacid is inadmissible, since in this the 3-carboxyl group is stericallyprotected. The methiodide of 3-methyl 4-ethyl cinchomeronateyields a mixture of 3- and 4-betaines, in which t’he former pre-ponderates in spite of the very much easier alkaline hydrolysis ofthe 4-ester group.It is ttherefore maintained that betaine formationfrom the free acid will occur in the 3-p0sition.~*The interaction of 4 : 4’-dipyridyl with cyanogen bromide hasbeen investigated. This reagent is known readily to open thepyridine r.ing95 but for the first time in the present instance aprimary additive product (11) has been obtained. By treatmentof dipyridyl with two molecular proportions of cyanogenbromide and excess of aniline, the normal dianilidodianil dihydro-bromide (ID) is 0btained.~6In confirmation of the views previously expressed on tlhe con-stitution of the coloured quinhydrones obtained from the reductionof various pyridine derivative^,^? tetrabenzyldipyridylviolet iodide(I) is converted in acetic acid solution by absorption of atmosphericoxygen into the corresponding dipyridyldibenz yl salt :Attempts to prepare mixed salts of the type (I) from, for example,dibenzyltetrahydrodipyridyl and dilutidyldiiodobenzylate havefailed, tetrabenzyldilutidylviolet iodide being formed in the instancecited.9893 Compare Ann.Repor&, 1922, 19, 147.94 A. Kirpal and E. Reiter,. Annalen, 1923, 433, 112; A., i , 1225.95 Compare Ann,. Reporte, 1905, 2, 149.86 W. KBnig (with G. Ebert and K. Centner), Ber., 1923, 56, [B], 751;97 Compare Ann. Reports, 1922, 19, 150.0 8 B. Emmert and 0. Varenkamp, Ber., 1923, 56, [B], 491; A . , i, 383.A., i, 303ORGANIC CHEMISTRY. 140The Quinoline Group.It has been previously supposed that the Skraup and Doebnerand Miller syntheses depend in the h t place on the addition ofthe aromatic amine to the double bond of an unsaturated aldehyde.The behaviour of the ketoanils previously discussed 99 wouldsuggest that this is not quite correct, but that it is rather the anil(for example 11) of such an intermediate product from which thequinoline ring is formed.Further evidence in favour of this viewis supplied by the easy conversion of the anil of P-anilinoacraldehyde(111) into quinoline when its hydrochloride is heated with zincchloride : 1c1\(11.1 (111.)The formation of quinolines by condensation of o-aminobenz-aldehyde with bromoacetophenone, acetonylphthalimide, orphenacylphthalimide,2 or diphenylsulphonylacetone is an obviousspecial form of the Friedlaender synthesis.More interesting, asinvolving an imino-condensation, is the reaction represented asfolIows :CHThe amino-group in the product is not diazotisable, but may bereplaced by hydroxyl.quinolinederivatives has shown that, whilst 6-, 7-, and 8-methylquinolines,like quinoline itself, suffer reduction of the pyridine ring exclusively,An extended study5 of the catalytic reduction ofSee p. 127.W. Konig, Ber., 1923, 56, [B], 1853; A., i, 1127.G. Uargellini and S. Berlingozzi, Qazzetta, 1923, 53, i, 3 ; A., i, 482;S . Berlingozzi, -4tti €2. Accad. Lincei, 1023, [v], 32, i, 339; A., i, 847.J. Triiger and P. KGppen-Kastrop, J . pr. Chem., 1922, [ii], 104, 335;A., i, 368.J.Troger and K. v. Seelen, ibid., 105, 208; A., i, 1127.J. v. Braun, W. Gmelin, and A. Schultheiss, Ber., 1923, 66, [BJ, 1338;A., i, 836160 ANNUAL REPORTS ON THE PROQRESS OF CIFEMISTRT.substitution of this ring, as illustrated by the cases of 2-(4)-, 3-(33)-,and 4-(33)-methyl-, of 2 : 3444)- and 2 : 4-(80)-dimethyl-, and2 : 3 : 4-(80)-trimethyl-quinolines~ renders it; more resistant, so thatto a certain extent (indicated by the bracketed figures of per-centages) Bz-tetrahydro-derivatives are produced. As would beexpected, tetrahydroacridine (49) and 2 : 3-trimethylenequinoline(48) exhibit a similar behaviour.6 It seems to have escaped theinvestigators concerned that these results are in noteworthy contrastwith the fact that, so far as the point has been examined, substitu-tion in the pyridine nucleus renders this more susceptible to attackby oxidation, especially in acid solution.7w-Trichloro- and o-tribromo-derivatives are readily preparedfrom quinaldine by addition of halogen to the base in glacial aceticacid solution, and subsequently boiling the mixture for a fewminutes.s This is not surprising when it is remembered that thehydrogen atoms concerned are “ positive,” like those in ethylmalonate and similar easily halogenated compounds.The interesting suggestion9 has been made that the colouredforms of salts of di- and tri-quinolylmethanes are not truly quinon-oid, as represented, for example, by (I), but rather that they containa hydrogen atom which is simultaneously within the spheres ofMe Me/\/\ / / \ (A, :(>,,I &)=cH*cH:.iI-( x,! ’\ L HNH NMe IMeN N(1.1 (11.1influence of the two nitrogen and the central carbon atoms, becausethe absorption spectrum of the compound (I) does not agree withthat of the N-methyl derivative, but rat,her with that of $40-cyanine iodide.Other reasons advanced seem less forceful. Forexample, the reactivity of both the methyl groups in (IT) is easilyexplained by the known tautomerism of the isocyanines, and is nota sufficient reason for supposing that a formula with two pyridinenuclei is preferable-although workers on tautomerism may verypossibly prefer this reason on other grounds. Similarly, theformation of isonitro- and oximino-derivatives by direct action ofnitric and nitrous acids respectively can be met by the quinonoidformula.J. v.Braun, A. Petzold, and A. Schultheiss, Ber., 1923, 56, [ B ] , 1347;A., i, 836. ’ Compare, for example, W. v. Miller, Ber., 1891, 24, 1900; A., 1891, 1094.* D. L. Hammick, T., 1923, l.23, 2882.a G. Scheibe, Ber., 1923, 56, [B], 137; A., i, 250ORGANIC CHEMISTRY. 151As mentioned in last year's R,eport,lo the methylene derivat,ive(111) had previously been suggested as a possible intermediary inthe typical condensations of 2-methylquinolines. At the sametime, it was recognised that such a methylene derivative might be/\ /\(111.) Me1 (me) Me Imore easily formed fromprovide an explanation ofquaternary ammonium salts, and hencetheir superior reactivity. An illustrationof this is supplied in the condensation of quinaldine met.hiodidewith formaldehyde in hot alcoholic solution to the derivative (IT),previously suggested as the intermediate product in the formationof dimethylcarbocyanine (V). Its conversion into the latter wasactually achieved by treatment with hot alcoholic sodium hydroxide,but the yield was increased tenfold by the presence of a quaternaryammonium salt.The importance of the latter in the usual prepar-ation of the dyestuff i8 already known, but its function is not clear,since in the experiments under consideration the composition ofthe product is independent of the nature of the salt used.11The corrected formula for cryptocyanine l2 has been justified,and in the same paper a new general method of preparing carbo-cyanines and isocyanines is des~ribed.1~The formation of methylene derivatives has also been assumedto explain the interesting dealkylation which occurs when quin-aldinium alkyliodides are treated simultaneously with a molecularproportion eaob of sodium hydroxide and aryldiazonium chloride :In support of this view, vinyldimethylamine is also known to10 Seep.166.la Ann. Reports, 1921, 18, 139.13 W. H. Mills and W. T. K. Braunholtz, T., 1923, 128, 2804.11 Miss I?. M. Hamer, CT., 1923, 123, 246152 ANNUAL REPORTS ON !CHI3 PROGRESS OF CHEMISTRY.couple,l* and it has been found possible to isolate (VI). Somewhatcuriously, however, the investigation is not rounded off by showingthat the last compound couples, or whether coupling with Vinyl-dimethylamine involves dealkylat~ion.15An examination of the syntheses of tetrahydroisoquizloline fromphenylethylamine and formaldehyde 16 has shown that the smallquantity of the desired base produced is accompanied by a con-siderable amount of unchanged material and a notable amount ofdi-p-phenylethylaminomethane. l7A 1 kaloicls .The lactonic nature of pilocarpine and isopilocarpine has beenconfirmed.Further, it has been shown that isomerisation ofpilocarpine occurs under the influence of traces of sodium ethoxide,proceeds more rapidly than delactonisation, does not occur inaqueous solution, and is not applicable to the salts resulting fromdelactonisation by alkali. The lactonic grouping is thereforeessential to the change, which seems comparable with that ofhyoscyamine to atropine, and therefore is considered most probablyto consist in partial racemisation of one of the two asymmetriccarbon atoms of the lactonic group.18metaPilocarpine, which is produced when pilocarpine hydro-chloride is heated for a longer time and a t a higher temperaturethan is necessary for the preparation of isopilocarpine hydrochloride,is found to differ from its generators in being optically inactive, andan extremely weak base, but very soluble in water.The compoundis therefore considered to be a betake (I).l9f (1.1 -The constitution of ricinine has been finally determined byreplacing its reactive 4-methoxyl group successively by chlorineand hydrogen. The product, ricinidine, on the basis of the earlier14 I(.H. Meyer, Bor., 1921, 54, [B], 2277; A., 1921, i, 851.16 W. KtSnig, ibid., 1923, 56, (B], 1643; A., i, 862; A. Adam, Wiseensch.Ind., 1923, 2, 2; A., i, 1129.16 A. Pictet and T. Spengler, Ber., 1911, 44, 2036; A., 1911, i, 750; H.Decker and P. Becker, Annalen, 1913, 395, 342; A,, 1913, i, 291.l7 H. Kondo and E. Ochiai, J . Pharm. SOC. Japan, 1923, 496, 313; A.,i, 837.l8 M. and M. Polonovski, Bu2l. SOC. chim., 1922, [iv], 31, 1185, 1201; A.,1923, i, 129, 130. Readers of these papers will note that in the formulaemployed, the side chain is erroneously attached in the 4- instead of in the6-position; compare F. L. Pyman, T., 1910, 97, 1810.&id., p. 134; A,, 1923, i, 130ORGANIC CHEMISTRY. 153formuls,2* might have been expected to furnish on treatment withcaust'ic alkali either 2-pyridonyl-1 -acetic acid or l-methyl-2-p yridonc -6 - carboxy lic acid. Actually, however, 1 -met hyl-2 -pyridone-3-carboxylic acid (IV) was obtained, jdentical with theproduct of the action of methyl iodide on the &silver salt of2-hydroxypyridine-3-carboxylic acid. It therefore follows thatricinidine is the corresponding nitrile (111), and that ricinine is3 - cyano -4-methoxy- 1 -methyl-2 - pyridone (11) : 21OMeThis conclusion has been confnmed by synthesis. 4-Chloro-quinolinic acid, from the oxidation of 4-chloroquinoline, was con-verted through its imide into 4-chloro-2-aminoquioline-3-carb-oxylic acid, from which the 2-hydroxy-derivative was preparedand converted into 2 : 4-dichloro-3-cyanopyridine. The 2 : 4-dimethoxy-derivative obtained from this was converted by treat-ment with methyl iodide into a product identical with naturalricinine.22 It has been shown by exactly analogous methods,both analytical and synthetic, that echinopsine is l-methyl-4-quinolone .z3Thus ricinine, echinopshe, and cytisine are pyridones, butst'rychnine is probably not, because it does not show the colourreactions which characterise these compound^.^*The inference that the base scopoline, isolated as a product ofthe acid hydrolysis of scopolamine, is not the base of which thealkaloid is the tropyl derivative 25 has been confirmed by thepreparation of the latter base, scopine, by hydrolysis with pan-creatic lipase in ammonia-ammonium chloride buffer solution. Aswould be expected, scopine is readily converted into scopoline byhcat or treatment with alkali or acid. It is more stable towardsacid than towardsAldehydes have been prepared from quinine and cinchonine20 Compare Ann. Reports, 1522, 19, 157.21 E. Spath and G. Koller, Ber., 1923, 56, [B], 880; A ., i, 594.22 Ibid., p. 2454.23 E. Spath and A. Kolbe, Monatsh., 1923, 43, 469; A., i, 479; compare24 E. Spath and G. Kollor, Zoc. cit.25 Compare Ann. Reports, 1922, 19, 160.26 R. Willstatter and E. Berner, Ber., 1923, 56, [B], 1079; A., i, 701.M. Greshoff, Rec. trav. chim., 1900, 19, 360; A., 1900, i, 338164 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.and their acetyl and benzoyl derivatives by first converting theminto ozonides.27Reference has already been made (p. 127) to the reason for adopt-ing a fundamental modification of the formulse assigned to themorphine alkaloids. The formula (I) is adopted for thebaine toexplain its hydrolysis to codeinone, and its oxidation by acidhydrogen peroxide to hydroxycodeinone, of which the formula ismost probably (11), since the ketone furnishes no osazone and,unlike j3-hydroxyketones, shows no tendency to lose the elementsof water.28As a preliminary to the further confirmation of these formulze,the molecular structures of codeinone, thebainol, and thebainonehave been shown respectively to contain the groupings *CH2*CO*,*CH,*CO*CH,*, and CH : CH- C 0 *CH,*. 29Both anhalonidine and pellotine 3O have been synthesised by theusual methods from ethyl 6-acetoxy-3 : 4-dimethox3.phenylethyl-aminoa~etate.~lThe application to corydaline of the Hofmann and the Emdemethods of degradation by exhaustive methylation has shown thelatter to be the more trustworthy in this instance. For whereas,as would be expected, trimethylamine was obtained in the lattercase only after the third treatment, in the former it was produced,alt,hough in poor yield, after the second. This is attributed topossible slight splitting up of the corydaline methiodide into baseand methyl iodide during the heating with sodium hydroxide.The methyl iodide could then combine with the base obtained bythe degradation proper and give a methiodide, which immediatelyin turn would be decomposed and yield trimethylamine.3~27 L. Seekles, Rec. trav. ohirn., 1923, 42, 69: A., i, 237.28 J. M. Gulland and R. Robinson, T., 1923, 123, 980.2* Idem, ibid., p. 998.s1 E. Spath, Monateh., 1923, 43, 477; A., i, 479.Compare Ann. Reports, 1922, 18, 162.E. Spiith and E. Mosettig, Annalen, 1923, 433, 138; A., 1924, i, 74ORGIANIO CEtEMISTRY. 165;In connexion with the question of the constitution of corydaline,=the base (111) has been synthesised, but found not to be identicalwith the racemic form of the alkaloid.34A preparation of the alkaloids from Corydalis cara, in which anunusually small amount of corydaline was present, was found tocontain, besides the alkaloids previously observed, d-tetrahydro-palmatine and a base, corypalmine, differing from the latter incontaining a free hydroxyl in place of the methoxyl group. Atthe same time, the existence of a similar relationship betweencorybulbine and corydalines5 was confirmed by conversion of theformer into the latter by methylati~n.~~The investigation 37 of the alkaloids of the Calabar bean appearsto be entering a stage a t which it may be convenient to summarisethe present position. One constituent, eserine (or physostigmine),is a laevorotatory, strongly alkaline compound, easily convertibleinto a dihydro-derivative. It is hydrolysed by sodium cthoxidein absolute alcoholic solution to methylurethane and eseroline, andmay be regenerated from the latter by treatment with methgl-carbimide a t the ordinary temperature, although a t 100" theproduct is isoeserine. Eseroline contains t2wo methylimino-groups 38and a phenolic hydroxyl group etherifiable by means of ethylp-toluenesulphonate. The ether so prepared, eserethole, whenconverted into its methiodide and treated with sodium hydroxidefurnishes, in place of the expected methine, by a reaction apparentlyakin to the conversion of quinolinium salts into quinolanols, acompound, esoline, containing the elements of an extra moleculeof water. From the last compound, two distinct methiodides(only one of which suffers degradation on treatment with alkali)are obtainable, as well as a dimethiodide. Correspondingly, if themethiodide be treated with excess of methyl iodide and sodiumethoxide, an ethoxy-derivative is obtained, which is convertedinto esoline when its aqueous suspension is boiled. Correspond-ingly, it has been independently observed that when eserethole is33 Compare Ann. Reports, 1922, 18, 163.34 E. Spiith and E. Mosettig, loc. cit.35 Compare J . Dobbie, A. Lauder, and P. Paliatseas, T., 1901, 79, 89;J. Gadamer and D. Bruns, Arch. Pharm., 1903,241, 634; A., 1904, i, 186.36 E. Spath, E. Mosettig, and 0. Trothandl, Ber., 1923, 56, [B], 875; A.,i, 593.37 M. Polonovski and others, Bull. SOC. china., 1915, [iv], 17,235,244 ; 1916,19, 2 7 ; 1915, 23, 335, 356; Compt. T W ~ , 1923, 176, 480, 1896; 177, 127;A., 1915, i, 891, 892; 1916, i, 221; 1918, i, 504, 505; 1923, i, 700, 831, 831;E. Stedman, T., 1921, 119, 891; G. Barger and E. Stedman, T., 1923, 123,758.38 J. Herzig and H. Lieb, Monatsh., 1918, 39, 285; A., 1918, i, 504156 ANNUAL REPORTS ON THE PROGRESS OF CBEMISTRY.treated with excess of methyl iodide and sodium ethoxide, adimethiodide is produced. These relationships may be representedas follows : 39NHMe*CO*O*CllHll~~NMe N&*$ HO*Cl1Hll=NMeEserine Eseroline Eserethole I Me1YIt would be inappropriate to do more than refer to the tentativesuggestions 40 in regard to constitutional formula for these com-pounds until outstanding difZiculties have been cleared up. Forexample, whilst esoline ethyl ether dimethiodide is opticallyinactive, etheserolene is stated to be hvorotatory.Geneserine is a congener of eserine, into which it passes onreduction, and furnishes analogous derivatives, geneseroline andgeneserethole, which in turn are similarly convertible into eserolineand eserethole.J. KENNER.89 The mode of representing the various compounds has been adopted fromthe paper by G. Barger and E. Stedman, loc. cit., but modified to exhibit t,lieparallelism between the results of the two sets of investigations.40 Straus, Annalen, 1913, 401, 358; M. and If. I’olonovski, Cornpt. rend.,1923, 178, 1896; Bull. 6oc. chim., 1923, [iv], 33, 970; A., i, 831, 940

ISSN:0365-6217    

DOI:10.1039/AR9232000057

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY.THE volume of work published on analytical chemistry during thepast year has exceeded even those of the years preceding the war,and, in order to make a survey of the whole field, it has beennecessary to select mainly those methods in which a new principlehas been devised or the scope of an old one extended, and to omitreferences to modifications which are of more limited application.Physicul Methods.Apart from electro-chemistry, which is dealt with in a seyaratcsection, the main advance in this branch of the subject has beenin the extension of various opttical methods to analysis.The refractive indices of selenious and selenic acids in aqueoussolution have been determined for various concentrations, and ithas been shown that a determination of this constant affords anaccurate means of estimating the two acids.1The various factors influencing the accuracy of the analysis ofmixtures of organic liquids by means of tho water interferometerhave been investigated and precautions to eliminate these andrender the method trustworthy have been devised.2A modified form of the Kleinmann nephelometer has beendescribed, in which the drawbacks pointed out by Weinberg 3have been avoided. The instrument can be used for the estim-ation of small amounts of calcium in blood, etc., with a fair degreeof accuracy? It is also useful for estimating minute quantities ofprotein.5The oxy-acetylene flame has been adapted to the spectral analysisof minerals, and although the method is not so generally applicableas the spark spectrum, it gives good results with the alkali andalkaline-earth metals, and with many heavy metals, but is lesssatisfactory with magnesium, zinc, cadmium, and mercury.6A method of quantitative spectroscopic analysis has been based011 the observation of the most sensitive rays (raies ultimes) of anH.W. Stone, J . Anter. Chef?&. SOC., 1823, 45, 29; A., ii, 175.E. Colien and H. R. Bruins, 2. p h p i o l . Chem., 1923,103, 337; A, ii, 188.A. A. Weinberg, Biocheni. Z., 1921, 125, 292; A., 1922, ii, 309.H. Kloinrnann, ibid., 1923, 137, 142; A., ii, 439.P. Rona and H. Kleirmiann, ibid., 1923, 140, 461; A., ii, 890.A. cle Grarnont, Compt. rend., 1923, 178, 1104, A., ii, 428.J 5158 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.element, and comparison, by means of photography, of the spectrumof an unknown substance with those of standard specimens ofsalts and alloys.'Errors of measurement of the mean wave-lengths of absorptionbands, due to the indefiniteness of the edges, are eliminated in acoincidence method of measurement, in which the spectroscope isso constructed that the spectra are seen side by side, but reversedin direction.Then by setting one edge of a band so that it coincideswith the same edge of the one above, the mean wave-length canbe read on the micrometer scale with a limit of error of about0.6The basis of a new method of measuring t'he colour of brownsolutions, such a6 tannin extracts, is that of measuring the depthof the liquid a t which a half, or other fraction, of the light isabsorbed a t three or four parts of the spectrum.Colour screens,which may be calibrated by comparison with standard flames, areused, and a solution of iron ammonium sulphate forms the colourstandard to which the measurements made with the colour screensare referred.gReference may also be made to a spectropbotornetric method ofidentifying different dyes by quantitative measuremeqts of theirintensity of absorption under varied conditions.lOA new polarimetric mefhod of estimating basic groups in merenttypes of compounds consists in determining the effect of the basicsubstance upon the velocity of the inversion of sucrose by hydro-chloric acid. For this purpose the relationship between the velocitycoefiticient of inversion, k, and the normality, iv, of the acid isfirst established over a wide range and expressed as an equation,in which the value of the constants is then ascertained.llFor the polarimetric estimation of malic and tartaric acidsadvantage has again been taken of the fact that uranium andmolybdenum compounds cause an increase in the optical activityof organic substances, and the relationship between the concen-tration of solutions of the acids and their optical activity has beendetermined under specified conditions.12There have been few contributions to the subject of vkcometry,but mention may be made of an apparatus by means of which1 W.F. Meggem, C. G. Kiew, and F. J. Stimson, BUZZ. Bur. StandQrda,1932, 18, 236, Sci.Paper No. 444; A., ii, 81.H. Hartridge, PTOC. Roy. SOC., 1923, [ A ] , 102, 676; A,, ii, 105.H. R. Procter, J . SOC. Chem. Ind., 1023, 42, 73; A., ii, 270.le W. C. Holmes, Ind. Eng. Chem., 1923, 15, 833; A., ii, 332.11 J. Groot, Biochem. Z., 1923, 137, 617; A., ii, 503.l2 F. Auerbach and D. Kriiger, 2. Untere. Nahr. Genwm., 1923, 46, 97;A., ii, 884ANALYTICAL CHEMISTRY. 159the viscosity and surface tension of a liquid a t high temperaturesmay be sucwssivdy ~leasured.1~Gas Analysis.Traces of nitrogen in hydrogen may conveniently be estimatedby a modification of the ordinary method of combustion overcopper oxide and measurement of the residual gas.14The use of phosphorus as an absorbent for oxygen in gas analysisobviates some of the drawbacks of alkaline pyrogallol, but itsabgorbent action is not so rapid.l5Various modifications of the method of estimating carbon mon-oxide in air by absorption with defibrinated blood have beenstudied, and an apparatus for the purpose has been devised.16The tannin reaction of Weltz with the blood which has absorbedthe carbon monoxide from the air has been developed into a quantit-ative method,17 and permanent standards for the purpose havebeen prepared.It is shown that the accuracy of the method iswithin the limits of 0.005 to 0-03 per cent. of the total volume ofcarbon monoxide in the air tested.18When estimating methane in mine gases by combustion incontact wit4 a gbwing platinum spiral, complete oxidation is notattaiaed unless the platinum i s brought to a white heat and themethaae exposed to its action for three to four minutes.l9Sulpburic acid of 87 per cent.strength has been found a suitablereagent for separating propylene from ethylene. AU the propyIene(when not present in too large excess) i s absorbed within ten minutes,but scarcely any of the ethylene.20For the analysis of gas mixtures containing methyl chloride andother compounds soluble in organic solvents, the gas is burnedwith a measured excess of oxygen in a combustion pipette overpotassium hydroxide solution, and the absorbed chloride estimated.Measurement of the oxygen consumed affords a check on theresult .21l a F. V. von Hahn, Chew. Ztg., 1923,47,402; A., ii, 379.1' R. L. Dodge, J.Amer. Chem. Soc., 1923, 43, 1688; A., ii, 653.1 5 A. Holmes, lnd. Eng. Chem., 1923, 15, 357; A., ii, 332.l6 M. Nicloux, BuU. SOC. chim., 1923, [ivJ, 38, 818; A., ii, 678.1'1 V. Andrisk, 5. Unlers. Baht-. Genw8m., 1923, 46, 43; A., ii, 876.18 R. R. Sayera, W. P. Yaat, and G. W. Jones, U.S. Bur. Mines Rept.Investigatim, 1923, No. 2486; A., ii, 789.19 J. W. Whitaker, Fuel, 1923, 2, 201; A., ii, 586.H. Tropsch and A. P. Philippovich, Brennstog-Chent., 1923, 4, 147;21 R. H. McKee and S. P. Burke, Ind. Eng. Chem., 1923, 15, 578; A.,A., ii, 509.ii, 586160 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Investigation of the rate of absorption of gaseous oxides ofnitrogen has shown that those corresponding approximately withthe formula N,03 are absorbed much more rapidly than nitrogendioxide or peroxide. Absorption with sulphuric acid is preferableto absorption with alkaline liquids for nitrous gases, since lessnitrogen in the higher state of oxidation is obtained.In the caseo€ the alkaline absorbents, secondary reactions with water orwater vapour occur.22A liquid secondary amine, such as ethylaniline, is used as anabsorbent for nitrous anhydride in a method of estimating nitricoxide by combustion with oxygen. The excess of oxygen is thenabsorbed by means of alkaline pyrogallol, and the volume of nitricoxide obtained from the contraction of volume.23Among new forms of apparatus described, mention may be madeof a modification of tjhe Hempel explosion pipette, in which leakageof gas during the explosion is prevented,24 and of a burette withtwo parallel limbs connected by means of a capillary tube.25Agricultural Analysis.The method of estimating carbon by oxidation with sulphuricacid and silver &chromate26 has been adapted to soils, and isshown to yield results in agreement with those obtained by thecupric oxide method.27 From a comparison of this sulpho-chromicmethod with the standard method of igniting the soil and weighingthe carbon dioxide formed, the conclusion is drawn that eithermethod may be used for estimating humus.An approximate ideaof the amount of humus may be obtained from an estimation ofthe chlorine in a soil.38Another method of estimating soil humus has been based uponits extractiori by means of aqueous pyridine.Combined humus issubsequently estimated by extracting the residual soil, with thesame solvent, after treatment with dilute hydrochloric a ~ i d . 2 ~A microscopical examination, with an eye-piece micrometer, ofthe fractions of soil separated from the clay by the usual mechanicaltreatment enables an estimation of the relative proportions of22 A. Sanfourche, Bull. SOC. chim., 1922, [iv], 31, 1248; A., ii, 84.23 A. Koehler and M. Rfarqueyrol, 1'6m. Poudrea, 1922,19,369; A., ii, 178.24 K. Tiddy, Qa8 World, 1923, 79, 187; A., ii, 694.25 H. J. 3%. Creighton, Trans. Noca Scotia Imt. Sci., 1919-20, 16, [2],28 Compare Ann. 12eports, 1922, 10, 172.2 7 L. J. Simon, Compt. rend., 1923, 176, 1409; A., ii, 506.28 V. Agafonoff, ibid., pp.l i 7 , 404; A., ii, 668.115; A., ii, 750.M. Picttre, ibid., p. 1329; A,, i, i36ANALY!I!ICAL CHEMISTRY. 161mineral particles and colloidal aggregates to be made by directobservation.80For the colorimetric estimation of the hydrogen-ion concen-tration in soils, a clear solution may be readily obtained by theuse of Parker's method of downward displa~ernent.~~ The resultsobtained by titrating the extract, with the use of brom-cresolpurple as indicator, agree closely with electrometric e~timabions.~~An apparatus for measuring the oxygen-supplying power of soilconsists essentially of a closed porous pot connected with a bottlecontaining alkaline pyrogallol. The pot is buried in soil understandardised conditions, and the rate of oxygen-diffusion is indicatedby the time required for the oxygen to diffuse through the wallsof the p t and change the colour of the indicator to a standardcolour.33Mention may also be made of a new form of respirometer designedto afford an accurate measurement of the oxygen consumed andcarbon dioxide produced by seeds, etc., from a total volume ofair in a, given time.34Low and irregular results may be obtained in estimating smallamounts of nitrates in soils by the phenoldisulphonic acid method,owing to retention of nitrate by filter paper. This may be pre,vented by the us& of a particular type of coarse filter-pa~er.~SThe replulfs obtained in estimating potassium and " citric-soluble '' phosphoric acid in soils and fertilisers vary considerablywith the fineness of the material, but are not appreciably affectedby ignition of the soil extract.Variations in the duration ofshaking or the volume of citric acid solution do not have muchinfluence on the phosphoric acid results.36Organic Analysis.Qualitative.-The use of perchloric acid as a general reagentenables many amines and alkaloids to be classed into two largegroups) which can be distinguished by the form and optical pro-pertiw of the microcrystalline precipitate^.^' Potassium ferro-30 W. H. Fry, J. Agric. RM., 1923, 24, 879; A., ii, 892.31 F. W. Parker, Science, 1921, 54, 438; A., 1922, i, 611.82 C. T. Gimingham, J . Agric. Sci., 1923, 13, 69; A., ii, 668.33 L. M. Hutchins and B. E. Livingstone, J . Agric. Bes., 1923.25, 133; A,34 G.T. Harrington and W. Crocker, ibid., p. 101; A., i, 424.35 C. T. Gimingham and R. H. Carter, J . Aggc. Sci., 1923, 13, 60; A.,as H. F. L. Bischoff and B. de C. Marchand, J. S. African Chem. Inat.,97 V. Cordier, blonatrh., 1923, 43, 625; A., ii, 347.i, 1166.ii, 577.1923, 6, 63; A., ii, 786.REP.-VOL. XX. 162 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.cyanide is another group reagent for many of the common alkaloids,which combine with it to form crystalline compounds of distinctiveform.36A study of Schiff's rosanihe and sulphurous acid reaction foraldehydes has shown that the violet coloration is only trustworthyas a test when the solution has a certain acidity. In the case of anumber of organic compounds which do not contain aldehydicgroups, a red coloration may appear owing to the liberation ofrosaniline.39A new test for aldehydes is based upon the gradual hydrolysisof their compounds with sodium hydrogen sulphite, with liberationof sodium hydroxide, which is indicated by a pink coloration withphenolphthalein.Conversely, formaldehyde in presence of phenol-phthalein may be used for the detection of ~ulphites.~~Another general reagent for aldehydes is benzidine, which givesdifferent colorations with different types of aldehyde^.^^Acraldelzyde reacts with phloroglucinol in ethereal solution, inpresence of water and hydrochloric acid, to form a red, aqueoussolution (or purple precipitate in presence of excess of acraldehydc).Apparently the reaction is due to the same compound whichcauses the Kreis reaction in rancid fats.42Various colour reactions for the detection of sterols have beendescribed, based on their interaction with sulphuric acid, form-aldehyde, and acetic anhydride (or acetic acid), or with aceticanhydride and nitric acid.Sterolins may be differentiated fromsterols by the different colorations which they give with thymol inthe presence of sulphuric acid. It is suggested that essentially all thecolour reactions for sterols in solution are very similar in character.43A violet coioration, resembling that given by liver oils withsulphuric is produced when a solution of cholesterol andfurfuraldehyde or o-hydrosymethylfurfuraldehyde is treated withsulphuric acid. The reaction is capable of detecting 0.1 mg.ofcholesterol. 45Of the colorations given by certain alkylglycerols (after oxidationwith bromine) with certain alkaloids and phenols, only that pro-duced by codeine (blue coloration) 46 will differentiate glycerol from38 H. I. Cole, Philippine J . Sci., 1923, 23, 97; A., ii, 703.89 I<. Josephson, Ber., 1923, 56, [BJ, 1771; A., ii, 664.40 J. Estalella, Anal. 3%. Quirn., 1922, 20, 271 ; A., ii, 98.41 P. N. van Eck, Pharm. Weekblad, 1923, 60, 1204; A., ii, 887.W. C . Powick, Ind. Eng. Chem., 1923, 15, 66; A., ii, 191.43 G. S. Whitby, Biochem. J., 1923, 17, 5; A., ii, 344.44 Compare Ann. Reports, 1922, 19, 170.45 A. Harden and R. Robison, Biochent. J., 1923, 17, 116; A., ii, 347.48 G. DenigBs, Pre'ci.-. de Chinzie analytique, 1920, 151ANALYTICAL CHEMISTRY. 163its homologues.None of the oxidation reactions of glycerol withpotassium permanganate is specific.47A characteristic reaction for oxrelic acid depends upon the factthat it gives a blue or green zone coloration with resorcinol andsulphuric acid, whereas other organic acids give yellow or redcolorations .4*The so-called pyrrole reaction (red coloration of pine shavingmoistened with hydrochloric acid and exposed to pyrrole vapour)has been shown to be due, not to resin, but probably to coniferin.It is given strongly by asparagus, which contains coniferin, but notresin .49Certain phenols give specific colorations with copper. Forexample, quinol gives a blue coloration, the intensiky of whichis proportional to the amount of copper, and a-naphthol gives aviolet coloration, which serves to distinguish it from p-na~hthol.~~Various tests for distinguishing between glutin and chondrinhave been described, such as the precipitation of the barium saltof chondroitinsulphonic acid, which is optically active ( [ c c ] ~ =Qua,iztit~tiz.e.--Aluruina lras been sbown to have several advan-tages over other substances as an absorbent for water in tbleinent8aryanalysis.52A new mctliod of combustion giixalysis depends upoii heatingthe substancc with cupric oxide in an exhaustcd silica t’ube, aridmeasuring the products of combustion.53Further applications of the use of silver dichromatc and sulphuric:acid as an oxidising agent for combustion have been described, inadditlion to its use for t,he estim:ttion of humw referred to inanotlher section of this Repo~t.5~I n estimating carbon and hydrogen in organic compounds COI) -taining arsenic and mercury, satisfactory results may bc obtairicdby a modification of Dennstedt’s method.55Various new methods of estimating halogens in organic snb-p7 R.Deltzby, Compt. rend., 1923, 176, 396; A., ii, 264.48 Muller, Bull. Assoc. Chim. Sucr., 1922, 40, 169; A., ii, 346.50 J. AIoy and A. Valdigui6, Bull. SOC. chim., 1922, 31, 1176; A.,-+- 46.5”).51E. S. Chotinski, J . Russ. Phys. Chem. SOC., 1917, 49, 149; A., ii, 444.ii, 91.31. A. Rakudn, Chem. Ztg., 1923, 47, 602; A., ii, 667.52 H. L. Fischer, H. L. Faust, and G. N. Walden, Ind. Eng. Chem., 1922,53 11.Hackspiil and G. de Heeckeren, Conapt. rend., 1923, 1’7’7, 59; A , ,64 A. J . A. Guillaumin, ibid., 1923, 176, 1063; A., ii, 432.(rs M. F a l k o ~ and G. JV, Raizies, J . Amer. C’heiri, flora> 1023, 45, 998; A,,14, 1138; A., ii, 83.ii, 578.ii, 335.a164 ANNUAL REPOBTS ON THE PROQBX€3S OF CHEMISTRY.stances have been published. In the case of certain compounds,hydrazine may be used as a reducing agent, the volume of nitrogenevolved (which depends upon the proportion of halogen) beingmeasured.56 Combustion in a current of ammonia gas can be usedfor organic halogen compounds, except those of the aromaticseries, for which a mixture of ammonia and hydrogen is re-q~ired.~’ In the case of certain volatile compounds, chlorinecan be estimated by burning the substance in a wickless lampin a current of hydrogen, igniting the vapours in oxygen, andtitrating the halogen in the products of the combustion, afterabsorption in sodium carbonate.58 A modification of this methodconsists in dissolving the substance in benzaldehyde, or a mixtureof benzaldehyde and alcohol, and burning the solution in thelamp.59FOF the gravimetric estimation of organic phosphorus, the sub-stance may be oxidised as in the Kjeldahl process, and the phos-phorus precipitated as phosphomolybdate, which is subsequentlyconverted into magnesium ammonium phosphate.60for the estimation of the acetyl group givesbetter results when an aromatic sulphonic acid is used for thehydrolysis, instead of sulphuric acid.62It has been shown that the nature and position of substituentgroup have an accelerating or retarding influence on the reactionof the nitro.groupt3 in Kjeldahl‘B process, and certain constituentgroups can be classified on this basis.63A process of reduction with ferrous sulphate and estimation ofthe unoxidised iron salt enables aliphatic nitrates to be estimatedin the presence of certain aromat<ic nitro-compounds.64Certain amines with a dissociation constant of not less than5 x 10-9 may be separated from their (preferably neutral) solutionby treatment with “ permutite,” and the principle has been adaptedto the estimation of adrenaline.65Turning to individual organic compounds, it has been shownPerkin’s method56 A.11;.Maobeth, C‘hern. News, 1922, 125, 305; A., ii, 34.57 J. Heslinga, Diss. Ddft, 1923, 1; A., ii, 782.58 J. Voigt, 2. angew. C M . , 1922, 85, 634; A., ii, 34.K. Rubke, ibid., 1923, 36, 136; A., ii, 249.6o W. Jones and AI. E. Perkins, J. BioE. Chem., 1923, 55, 343; A., ii, 432.61 A. G. Yerkin, T., 1905, 87, 107.ci2 K. Freudenberg, Annnlen, 1923, 433, 230; A., ii, 884.63 B. M. Margosches and W. Kristen [with E. Scheinost], Ber., 1923, 56,G4 W. 6. Huff and R. D. h i t c h , J . Amer. Chem. SOC., 1922, 44, 2643;65 J. C. Whitehorn, J . Biol. Ckm., 1923, 56, 761; A., ii, 798.[B], 1943; A., ii, 785.A., ii., 36ANALYTICAL CHEMISTRY. 165that formaldehyde cannot be directly est'imated by the usualmethods in presence of copper.66A useful method of estimating formic acid by titration has beenbased on the fact that one molecule of hydrogen chloride is liberatedin the reduction of mercuric chloride by a f~rmate,~' and animproved gravimetric met hod based on tlhe reduction of mercuricto mercurous chloride has been worked out.6SAn analogous method for abietic acids depends upon the reduc-tion of mercuric acetate and gravimetric estimation of themercurous a~etate.~QThe naturally-occurring d-tartaric acid may be quantitativelyprecipitated as a calcium or lead salt after the addition of anequivalent quantity of the 2-acid.70There have not been many contributions to the methods ofanalysing oils and fats, but mention may be made of a gravimetricmethod of estimating the hydroxyl and acetyl values,71 and ofthe use of pyridine sulphate dibromide for the rapid estimation ofthe iodine value.72 A new method of estimating arachidic andlignoceric acids has also been devised; it is based on the relativeinsolubility of their magnesium salts in 90 per cent.alcohol.73Investigation of the conditions under which gallotannin is pre-cipitated by gelatin has shown that the precipitation is quanfitativewhen the ratio of tannin to gelatin is not less than 2 : 1. There isan optimal hydrogen-ion concentration for the precipitation ofeach individual tannin.74A colorimetric method of estimating gallotannin and its deriv-atives has been based upon the apparently specific violet color-ation given by the pyrogallic group with a ferrous tartrate reagent.The coloration is compared with that given by a standard solutionof pyrogallol or gallic acid.In the case of mixtures of gallotanninand gallic acid, both substances are estimated together in terms ofgallic acid, the gallotannin is then precipitated by means of quininehydrochloride, and the gallic acid in the filtrate estimated as before. 756 6 M. Jakeg, Chem. Ztg., 1923, 47, 386; A., ii, 442.6 7 B. Holmberg and S. Lindberg, Ber., 1923, 56, [B], 2048; A., ii, 794.€ * Fr. Auerbach and H. Zoglin, 2. physikaZ. Chem., 1922, 103, 161; A.,6g F. Schulz and S. LEmda, BulE. SOC. chim., 1922, [iv], 31, 1353; A., ii, 96,70 A. Kiing, Ann. Chim., 1922, [ix], 18, 189; A., ii, 97.72 K. W. Rosenmund and W. Kuhnheim, 2. Untera. Nahr. Qenmsm., 1923A.W. Thomas and Chrti-Lan Yu, J . Amer. Chem. SOC., 1923, 45, 113;74 A. W. Thomas and A. Frieden, lad. ling. Chem., 1923,15,839; A., ii, 664.'I' c b A. Mitchell, Adp88, 1923, 48, 1 ; A., ii, 188.ii, 95.E. B. ELsbach, C'hem. Umckau, 1923, 30, 236; A., ii, 796.46, 164; A., ii, 886.A., ii, 189166 ANNUAL REPORTS ON TJIE PROURESS OF CHEMISTRY.The gallotlannin used as a standard for this method was practicallyfree from sugar. This was subsequently confirmed, and the factof the existence of such a tannin must necessarily affect Pischer'sconception of gallotannin as a gallloyl glucoside.76A riel.\- method of estimating reducing suga,rs by means ofFehling's solution, with the use of nicthylene-blue as an internalindicator, has been devised, and tables for mixtures of varioussugars have been calculated for use with the method.'? Theamounts of criprous oxide deposited by mixtures of sucrose andreducing sugars have also been worked out and embodied intables, 78 and a volumetric method of estimating the precipitatedcuprous oxide has bcen devised; 79 also ail electrometric methodof titrating reducing sugars.80It has been shown under what conditions aldoses are quantit-atively oxidised to their corresponding carboxylic acids by analldine solution of iodine,sl and the principle has been applied tothe estimation of lactose, dextrose, and I~vulose in variouspreparations.82The method of Willstiitter and S c h ~ d e l , ~ ~ in which dextrose isoxiclised to gluconic acid by meens of potassium iodide and sodiumhydroxide, has not been found accurate in the presence of othersugars.The iodometric msthod is also applicable to maltose in thepresence of dextrose, lzevulose, and sucrose; a period of aboutthirty-five minutes is required to oxidisc the maltose.85For the estimation of mucir, acid, a process of oxidation ivithpzrmanganate and titration of the excess of reagent with oxalicacid gives trustworthy results under specified conditions.86Most of the methods of estimating alkaloids described aremodifications of older methods.Nicotine may be accuratelyestimated by precipitation as silic~tungstate.~~Reference may also be made to a method of estimating allantoin,70 Rf. Nierenstein, Ber., 1923, 56, [B], 1876; A., i, 1109.7 7 J.If. Lane and 1;. Eynon, J. SOC. Cyhem. Ind., 1923,42, 32r; A., ii, 193.78 €1. Jessen-Hanscn, Compt. rend. Trav. Lab. Carlsberg, 1923, 16, 21 pp.;79 Ed. Lasnusse, J. Pham. Chim,, 1922, [vii], 26, 401; A., ii, 41.80 W. L. Daggett, A. W. Campbell, and J. L. Whitman, J . Amer. Chem."~oc., 1923, 45, 1043; A., ii, 346.81 I. M. Kolthoff, Pharm. T'Veekbtad, 1923, 60, 362; A., ii, 346.83 Idem, ibid., p. 394; A . , ii, 346.83 R. Willstatter and a. Schudel, Eer., 1918, 51, 780; A , , 1918, ii, '13784 G. Bruhns, Chem. Ztg., 1923, 4'9, 333; A., ii, 440.(15 F. A. Cajori, J . B i d . Chern., 1822, 54, 617; A., ii, 04.8 6 E. 0. Whittier, ,J. Amer. C J L C ~ . Soc., 1923, 45, 1391; A , , ii, 589.97 0. 31. Shedd, J . Agric. Rm., 1923, 24, 961; A , , ii, 708.A.ii, 88ANALYTICAL CHEMISTRY. 167basad on its reaction with Nessler's reagent, to yield mercurous saltsinsoluble in hydrochloric acid, and subsequent iodometric titrationof the solution.88Inorganic Analysis.Q italillr ti re .-Hexame t hylene te tramine, with am d without theaddition of potassium iodide, is a useful microchemical reagentwhich forms distinctive crystalline precipitates with the salts ofmany metals. The test is particularly sensitive in the case ofantimony and bismuth.s9Several new systematic schemes of separation of metals andacids into groups have been devised. I n one of these, the sue-cessive group reagents used are (1) magnesium nitrate with am-nonia, (2) calcium and ammonium nitrates, (3) barium nitrate,(4) mercuric nitrate, and ( 5 ) silver nitrate.gOI n another scheme acids are divided into the following eightgroups : (1) volatile with acetic acid, (2)' nitric and boric acid,not volat'ile with acetic acid, (3) precipitated by barium andcalcium acetate, (4) precipitated from ammoniacal solution bybarium acetate, (5) by lead acetate, (6) by boiling with lead acetateand ammonia, ( 7 ) by nitric acid and silver nitrate, and (8) per-chloric, chloric, and bromic acids .91 A somewhat analogousscheme has also been devised for detecting volatile acids.92The elements precipitated by hydrogen sulphide may be differ-entiated by the use of spotting tests, with appropriate reagents, onfilter-~aper.~~Peroxides and per-salts may be distinguished by their respectivebehaviour witlh an alcoholic solution of paminophenol, whichgives a blue coloration with alkali and barium peroxidcs, but nocoloration with magnesium peroxide or p e r - ~ a l t s .~ ~Among the new tests for individual substances is a biochemicalone for oxygen, depending on its forming melanin when broughtinto contact with filter-paper impregnated with worm blood andZ- p - 3 : .4-dihydroxyphenyl- a-alanine .95Isatin can he used as a microchemical reagent for silver andcuprous salt's, with which it yields characteristic crystallineprecipitates.96J. More, J . Pharm. Chim., 1923, 2'7, 209; A., ii, 348.90 H. I. Cole, Philippine J. Sci., 1923, 22, 631; A., ii, 660.L. Fernandes and U. Gatti, Gazzetta, 1923, 53, i, 108; A., ii, 429.g1 Z.Karaoglanov and M. Dimitrov, Z . anal. Chem., 1923, 63, 1 ; A., ii, 780.g2 G. Karaoglanov, ibid., 1923, 62, 217; A., ii, 250.93 F. Feigl and F. Neuber, ibid., p. 369; A , , ii, 508.9* A. Blankart, Helv. Chim. Acta, 1923, 6, 233; A., ii, 338.95 H. Schmalfuss, Ber., 1923, 56, [BJ, 1855; A., ii, 783.J. €3. Menke, Rec. trav. chim., 1923, 42, 199; A., ii, 150.163 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.A sensitive reaction for cadmium consists in adding potassiumthiocyanate and pyridine to an aqueous solution of one of its salta,when a white, crystalline salt, Cd(C6H5N),(CES),, is f0rm6cl.~~ Ananalogous compound is formed by zinc.98The chemistry of the Reinsch test has been studied, the com-position of the films ascertained, and the conditions for obtainingthe best results with arsenic, antimony, and bismuth determined.99A convenient substitute for Bettendorf’s reagent for arsenicconsists of a solution of calcium hypophosphite in hydrochloricacid; it will detect 0.1 mg.of arsenious 0xide.lNickel may be detected by the formation of a metallic mirrorwhen its solution is treated with ammonia, saturated with hydrogensulphide, and boiled.2For the microchemical differentiation of potassium and sodium,advantagfx has been taken of the difference in the crystalline formof the picrates and tartrates of the two metals.3Erratic results sometimes obtained in the brown ring test fornitrates have been found to be due to the reduction of the nitricacid being too slow. This is remedied by adding a drop of dilutehydrochloric acid prior to the sulphuric acid.4 A new ring testfor nitrates and nitrites consists in the formation of a wine-redcoloration with certain naphthol- and naphthylamine-sulphonicacids.liBy the use of silver nitrate as a reagent, it is possible to detectas little as 0-1 mg. of thiosulphate (S,03),6 and not lesR than 0.0001 g.of sulphiteA sensitive test for hydroxylamine depends upon the formationof an unstable purple coloration on treatment with yellow ammoniumsulphide and ammonia.* Another test is based upon its condensingaction on an ammt niacal solution of diacetylmonoxime, to formdimethylglyoxime, which can be readily identified by its well-known reaction with ~ o p p e r . ~97 G. Spacu, Bul. ~ O C .8ttiinte C h i , 1922, 1, 538; A,, ii, 879.** idem, dbid,, p. 348; A., ii, 690.*@ B. S. Evans, Analy8t, 1923, 48, 357; A., ii, 696.1 E. Rupp and E. Muschiol, BeT. Deut. p h u m . cfes., 1923, 33, 62; A , ,ii, 333.C. G. Vernon, Chem. Nm8, 1923, 126, 200; A,, ii, 342.3 Ed. Justin-Mueller, J . Pham. Chim., 1923, [vii], 28, 15; A., ii, 666.C. Faurholt, Ber., 1923, 56, [B], 337; A., ii, 179.5 I. G. Nixon, C hrcm. h ew8, 1923, 126. 261 ; A., ii, 432.6 0. Hackl, Chem. Ztg., 1923, 47, 210; A., ii, 250.7 Idem, ibid.. p. 466; A., ii, 505.8 W. M. Fischer, ibid., p. 401; A., ii, 431.* W. N. Hirschel and J. A. Verhooff, Chem. TYeekbZud, 1923, 20, 319; A.,ii. 677ANALYTICAL CHEMISTRY. 169Q,,antitati2Ie.-There have been several new contributions to themethods of determining hydrogen-ion concentration.Among thenew indicators described are the colourless carbinols of certaintriphenylamine dyes which form coloured ammonium bases onthe addition of acid.10The method of Al.ichaelis,ll in which one-colour indicators areused, with inorganic solutions for comparison, has been foundinaccurate, and the constants of the indicators have been redeter-mined, with the use of Clark's buffer solutions.12Brornoxylenol- blue (dibromoxylenolsulphonephthalein) is a con-veniently prepared new indicator with about the same range ofpH value as bromothyrnol-bl~e.~~A new method in acidimetry and alkalimetry has been based uponthe use of certain inorganic salts (lead and silver salts, ferric thio-cyanate) instead of a colour indicator.Excess of alkali is addedto the acid solution, which is then titrated until the metal hydroxidedi~appears.1~A hydrolytic precipitation method can be used with solutions ofcompounds of weak acids with strong bases, or vice versa. Forexample, barium chloride may be titrated in slightly acid solutionwith potassium chromate , in presence of methyl-red as indicator,the excess of chromate becoming hydrolysed and causing theliquid to become alkaline and affect the indi~at0r.l~An alkalimetric method of estimating magnesium and calcium isbased on the principle of reducing the solubility of their hydroxidesby the addition of another solvent, such as alcohol, so that theyno longer affect an appropriate indicator, such as thymolphthalein.16It has been found that malic, maleic, and fumaric acids can bereadily purified for use as standards in alkalimetry.17Among the new osidimetric methods is one for the estimation ofphosphorous acid in presence of phosphoric acid, by trzatmentwith a cold saturated aqueous solution of bromine, the excess ofwhich is afterwards removed by means of a current of air.18Tellurium dioxide is quantitatively oxidised to tellurium trioxideb30 L.Karczag and R. Bodb, Biochem. Z., 1923, 139, 342; A., ii, 694.11 Ibid., 1921, 109, 165; A., 1921, ii, 56.12 I. M. Kolthoff, Pharm. Weekblad, 1923, 60, 949; A. ii, 694.13 A. Cohen, Biochem. J., 1923, 17 535; A., ii, 779.14 K. Jellinek and P. Krebs, 2. anorg. Chem., 1923, 130, 263; A., ii, 871.16 I(.Jellinek and J. Czerwinski, ibid., p. 253; A., ii, 878.16 R. Willstatter and E. Waiclschmidt-Leitz, Ber., 1923, 56, [B] 448; A.,17 N. A.. Lange and H. Kline, J . Amer. Chem. SOC., 1922, 44, 2709; A,,ii, 258.ii. 180.18 A. Wingler, 2. anal. Chem., 1923, 62, 338; A., ii, 606.G170 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.by potassium dichromate in hydrochloric acid solution, and avolumetric method of estimating tellurium has been based onthe reaction.19Various applications of the use of bromate in Volumetric analysishave been studied. A solution of potassium bromate is notdecomposed by boiling for five minutes with 2iV-perchloric, nitric,or acetic acid, so that an excess of the reagent may be used foroxidising purposes under such conditions.20By using a mercuric salt, such as mercuric perchlorate, the reducingaction of chlorides, bromides, and iodides upon potassium bromateyields only bromide, whereas in the absence of the mercuric saltfree bromine is also formed.21For the estimation of bromate in the presence of ferric iron, aniodometric method may be used, or the bromate may be reducedwith sodium oxalate in presence of mercuric perchlorate, and theexcess of oxalate titrated with permanganate.22A new reduction method for.estimating iron consists in addinga freshly prepared emulsion of zinc sulphide to a hot solution ofthe ferric salt in sulphuric acid, and subsequently estimating tlheferrous iron.23Work on the use of amadgams as reducing agents has been con-tinued,2* and methods have been devised for their application inthe estimation of chromium and iron.25Reference may also be made to a reduction method of estimatingpersulphuric acid in the presence of hydrogen peroxide and Caro'sacid.26The new iodometric methods include one in which the reductionof ferric salts by means of iodides is accelerated by the additionof a cuprous compound, to such an extent that the liberated iodinecan be titrated immediately.The principle is also applicable tomixtures of ferric and cupric s a l t ~ . ~ 7Hyposulphites may be estimated by measuring the amount ofiodine which they liberate from a solution of potassium iodide andiodate.28 The conditions for obtaining quantitative rcsult's in thereaction between sodium hypochlorite and potassium iodide havelD V.Lenher and Ef.. F. Wakefield, J . Amer. Chm. SOC., 1923, 45, 1423;A., ii, 576.2o G. F. Smith, ibid., p. 1115; A., ii, 604.a1 Idem, ibid., p. 1417; A., ii, 673. 23 Idem, {bid., p. 1666; A,, ii, 660.23 P. F. Thompson, Proc. Australasian Inst. Mining Met., 1922, N.S.24 Compare Ann. Reports, 1922, 19, 177.26 N. Kano, J . Chem. SOC. Japan, 1923, 44, 37; A., ii, 699.2 7 F. L. Hahn and H. Windisch, ibid., p. 898; A., ii, 262.z8 8. H. Wilkea, J . SOC. Chem. Ind., 1923, 43, 360; A., ii, 698.No. 4, 343; A., ii, 791.R. Wolffenstein and V. Makow, Ber., 1923, 56, [B], 1768; A., ii, 652ANALYTICAL CHEMISTRY. 171also becn studied ,29 and applied to the estimation 01 hypochloritc.30For the iodomctric estimation of free chlorine in solutions inwhich it cannot be directly titrated, calcium carbonate is addedto the acid liquid, and the resulting gases itre led into a solutionof potassium iodide.31It has been found possible to use ferric chloride instead of iodincfor the estimation of oxidking and reducing agents, the methodbeing based on the reaction2FeC1, + Na,S,Q, = 2FeC1, + 2NaCl + Na,S,06.32Several new colorimetric methods have been described.Forexample, bismuth may be estimated by means of the orange colourof colloidal solutions of quinine iodobisillrrthate ; 33 rhodium by thecrimson coloration (dw to colloidal particles of the metal) derelop-ing in an aqueous solution of its salts after boiling with stannouschloride ; 34 and tin by means of the molybdenum blue reaction.35For the estimation of small quantities of molybdenum in tungstenadvantage has been taken of the blood-red coiour of molybdenumt h i ~ c y a n a t e .~ ~The conditions under n-hich metallic sulphides volatilise quantit-atively when ignited in a current of hydrogen sulphide have beenstudied, and the results applied to the estimation of lcad, bismuth,thallium, antimony, and tungsten; the method cannot be usedfor tin, nickel, cobalt, or m0lybdcnum.~7 A suitable reductionmethod for treating the solution before separating arsenic fromantimony and tin by distillation ol the chloride has been workedArsenic may also be accirately estimated as silver araenate,either gravimetrically or by decomposing the arsenate with nitricacid and titrating the silver.39Other new precipitants for metals of this group include sodiumcyanide for lead,40 benzoinoxime for copper,41 and phenylthio-hydantoic acid for antim011-y.~~29 I.31. Kolthoff, Rec. tmv. chim., 1922, 41, 615; A., ii, 176.30 Idem, {bid., p. 740; A., ii, 176.31 E. Kordes, 2. anal. Chem., 1923, 63, 117; A., ii, 873.32 K. Jellinek and L. Winogradoff, Z. anorg. Chem., 1023, 129,lEi; A., ii, 871.33 L. Cuny and G. Poirot, J . Pharm. China., 1923, 28, [vii], 215; A., ii, 792.34 V. N. Ivanov, J. Rus8. Phya. Chem. SOC., 1917-18, 49, 601; 50, 460;36 G. F. Huttig, Chem. Ztg., 1923, 47, 341; A., ii, 437.36 W. J. King, I n d . Eng. Cyhenz., 1923, 15, 350; A,, ii, 342.3 7 L. Moser and E. Neusser, Chem.Ztg., 1923, 47, 541, 581; A., ii, 580.K. K. Jkvinen, Z. anal. Chem., 1923, 62, 184; A., ii, 254.39 W. Eschweiler and W. Rohrs, 2. angew. Chem., 1923, 36, 464; A,, ii, 787.40 W. Herz and E, Neukirch, 2. anorg. Chem., 1923, 130, 343; A., ii, 879.4 1 F. Feigl, Ber., 1923, 56, [B], 2083; A., ii, 850.42 A. and ( W e ) A. Lassieur, Compt. rend., 1923, 176, 1221; A., ii, 438.A., ii, 439.a" 172 ANNUAL REPORTS ON THE PXOGFRESS OF CHEMISTRY.Under specified conditions ammonium phosphate can be used toseparate bismuth from lead, copper, and cadmium.43Zinc may be estimated by treatment, with thiosulphate andpyridine, ignition of the resulting compound Zn(C5NH5),(CJSS),,a.nd weighing the residual zinc oxide.44For the separation of iron and manganese a new method hasbeen based on the quaiitlitative precipitation of iron from ferricsalts by means of “ infusible white precipitate,” KH,HgCl, theresulting compound yielding ferric oxide on ignition.45Dinitrosoresorcinol precipitates cobalt quantitatively as the com-pound (C6H304N,),Co, and a method of estimating cobalt in thepresence of nickel and other metals of the iron group has beenbased on the reaction.469 new method of estimating nickel consists in precipitating itas oxalate, igniting the precipitate, and weighing the nickel oxide,or by dissolving the precipitate in sulphuric acid and titrating thesolution with permanganate.47Magnesium may be separated from the alkali metals by pre-cipitation with gucznidine or (less satisfactorily) with pi~eridine.~~New methods of estimating some of the rarer metals have beendevised.For example, germanium may be quantitatively pre-cipitated as orthogermanate ; 49 praseodymium may be estimatedby heating its oxalate in air and weighing the residue of oxide,Pr,O,, ; 50 and indium may be precipitated as sulphide under specifiedconditions, and separated from other sulphides by suitable reagents.The methods of estimating potassium by precipitation as per-chlorate and cobaltinitrite have been critically examined, andconditions for obtaining quantitative results e~tablished.~~n-Butyl alcohol has been used as a means of separating theperchlorates of potassium and sodium,53 and an analogous processhas been devised for the quantitative separation of sodium fromlithium.54A gravimetric method of estimating nitric acid has been based43 G.Luff, Chem. Ztg., 1923, 47, 133; A., ii, 263.44 G. Spacu, B d . ~ O C . #ttiinte Cluj, 1923, 1, 361 ; A., ii, 580.45 B. Solaja, C h . Ztg., 1923, 47, 557; A., ii, 583.W. R. Orndorff and M. L. Nichols, J. Amer. Chem. SOC., 1923, 45,1439;A., ii, 584.4 7 W. Laffelbein and J, Schwmz, Chm. Ztg., 1923, 47, 369; A., ii, 435.G. Hemming, 2. anorg. Chem., 1923, 130, 333; A,, ii, 878.49 J. H. Miiller, J . Amer. Ckem. SOC., 1922, 44, 2493; A., ii, 43.P. H. M.-P. Brinton and H. -A. Pagel, ibdd., 1923, 45, 1460; A., ii, 581.I. Wads and S. Ato, J. Chem. SOC. Japan, 1923, 44, 1; A., ii, 657.52 R. L. Morris, A4talyet, 1923, 48, 250; A., ii, 698.ss G. F.Smith, J . Amer. Chem. SOC., 1923, 45, 2072; A., ii, 789.64 Idem, ibid., 1922, 44, 2816; A., ii, 182ANALPTICAL CHEMISTRY. 173upon the fact that it combines with di( a-naph thy1methyl)amine toform a nitrate which is only slightly soluble in water.55Elect roc hemist ry .There has been an exceptionally large number of contributionsto the methods of electrochemical analysis. Several new types ofapparatus have been described, including one in which oxygen isexcluded from the titration vessel,56 and another in which tubuluresfor the hydrogen electrode, calomel electrode, and hydrogen inletare grouped round the burette jet.57 By the use of an oxygen orair electrode it is possible to titrate an acid or alkali in the presenceof potassium permanganate and other oxidising agents.58It is claimed that the use of a bimetallic electrode system com-posed of two dissimilar metals (for example, certain metals oralloys of the platinum group) gives sharper end-points than thoseobtained with an ordinary electrode.5gSystems comprising two similar metals are of advantage fortitrating solutions which may exist in two stages of oxidation;on the other hand, there is a small risk of over-titration.60 Theend-point in the titration of sodium sulphids with ammoniacalsilver solution is exceptionally sharp when a bimetallic electrodesystem is used.61A quinhydrone electrode may be used instead of a hydrogenelectrode for the titration of acid solutions, but is unsatisfactoryfor alkaline solutions unless air is excluded.62 An antimony olec-trode is particularly suitable as an indicator for the titration ofacids and bases, since it yields salts which are readily dissociat,edby water and forms an amphoteric hydroxide.63A method of determining the hydrogen-ion concentration ofaqueous solutions of carbon dioxide, calcium carbonate, andcalcium sulphate by electrometric t'itration with carbon dioxidegas has been devised, and the bearing of the results obtained withknown mixtures of these compounds on the corrosion of iron pipesin earth is discussed.aIt has been shown that amino-acids loehave like weak acids with-6 5 I-I.Rupe and F. Becherer, Heh. Chim. Actu, 1923,6, 674; A., ii, 577.5 8 A. J. Pelling, J . S. African Chem. last., 1923, 6, 40; A., ii, 779.6 v W.T. Bovie, J. Amer. Chem. SOC., 1923, 44, 2892; A,, ii, 175.t a N. H. Furman, ibid., 1922, 44, 2685; A., ii, 175.59 H. H. Willard and F. Fenwick, ibid., 2504; A., ii, 33.8o Idem, ibdd., p. 2516; A., ii, 33.61 Idem, ibid., 1923, 45, 645; A., ii, 332.62 I. M. Kolthoff, Rec. t~av. chim., 1923, 42, 186; A., ii, 247.63 A. Uhl and W. Kestranek, Monatsh., 1923, 44, 29; A., ii, 648.64 J. W. Shipley and I. R. McHaffie, J . SOC. Chem. lnd., 1923, 42, 311.1.;A.. ii. 649174 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.out amphoteric character when electrometrically titrated.65 Ofthe alkaloids tried, it was found that brucine, quinine, narcotine,and morphine can be estimatcd by electrometric titration withhydrochloric acid, but that caffeine is too weak a base to show asharp break in the curve.G6Turning next to the new applications of conductimetric methodsto precipitation analysis, we find that lithium sulphate can beused for the titration of barium salts and lead salts, but not ofcalcium and strontium salts; G7 and sodium chromatg can bc usedfor the titration of barium, silver, and lead.68 Silver, lead, andcopper may be accurately titrated with likhium oxalate, but mag-nesium interferes with the titration of calcium.G9Owing to the mobility of potassiurn-ions potassium ferricyanidedoes not give sharp results as a reagent, and lithium ferricyanideis preferable.It can be used for the estimation of copper, cadmium,nickel, and cobalt.70 Potassium ferrocyanide is a suitable reagentfor the estimation of lead, and for zinc in a weak ammoniacal~0lution.71 It may also be used, under specified conditions, forthe consecutive titration of zinc and lead in the same solution,72and for zinc in the presence of cadn~ium.'~A modification of the electrolytic apparatus of Sand and Hack-ford 74 for the estimation of arsenic has been devised.Leadelectrodes are used, and the procedure described enables 0.001 mg.of arsenious oxide to be detected.75Arsenic and antimony may Be estimated together provided bothare present in the tervalent condition. Subsequently, the quinque-valent antimony is electrometrically reduced by means of titanouschloride, and then estimated, as before, by means of potassiumbromate in hydrochloric acid solution.76To obtain correct results in the electrolytic deposition of anti-mony, a platinum electrode coated with mercury should be used;with platinum alone there is excessive deposition.7766 F. M. P. Wildmar and E. L. Larsson, Biochem. Z., 1923, 140, 284.W. D. Treadwell and S. Janett, Helv. Chim. Acta, 1923, 6, 734; A , ,6 7 I. M. Kolthoff, 2. anal. Chem., 1923, 62, 1; A., ii, 88.68 Idem, ibid., p. 103; A., ii, 88.69 Idem, ibid., p. 161; A., ii, 256.70 Idem, ibid., p. 214; A., ii, 256.7 1 Idem, ibid., p. 209; A., ii, 260.72 E. Muller and K. Giibler, ibid., p. 29; A., ii, 90.73 F. Miiller, 2. unorg. Chenz., 1923, 128, 125; A., ii, 879.74 H. J. S. Sand and J. E. Hackford, T., 1904, 85, 1018.7 5 G. W. Monier-Williams, Analyst, 1923, 48, 112; A., ii, 252.7 6 E.Zintl and H. Wattenberg, Ber., 1923, 56, [B], 472: A., ii, 253.77 A. Lassieur, Compt. rend., 1923, 1'77, 263; A., ii, 660.ii, 790ANALYTICAL CHEMISTRY. 175Silver nitrate may be used for the electrometric estimation ofzinc, thc solution being treated with excess of standard potassiumcyanide solution prior to the titration; silver wire is used as theindicator electrode.78 The same method is also applicable to theestimation of cobalt by means of silver nitrate.79Ferrous salts and quadrivalent vanadium salts may be succes-sively titrated electrometrically with potassium permanganate inthe same solution, the former being more vigorous reducing agentsthan the latter.s0 The method may also be used for mixturesof salts of iron, uranium, and vanadium after reduction with zincand sulphuric acid, but air must be excluded during the titrationof the vanadium.81The conditions for the electrometric oxidation of halides totheir respective cyanides by means of potassium permanganate inhydrocyanic acid solution have been determined for the mixedsalts. I n the case of iodides, oxidation to iodate by means ofalkali hypobromite, and electrolytic estimation of the excess ofreagent by means of arsenite, is more accurate than the cyanidemethod.82 Another electrometric method depends upon theliberation of the halogens and their successive separation by boilingthe s0lution.8~ Methods have also been devised for the electro-metric titra t ion of halides, cyanides, sulphides, and t hiosulphates ,with the use of a mercury electrode.84Electrometric titration with titanous chloride in acid solutionaffords an accurate means of estimating iodates, bromates,chlorates, and ferricyanides.85The same reagent is also applicable to the electrometric titrationof selenium in quantities not exceeding 0.1 mg. in cold solution.Under these conditions, tellurium is not reduced. 86Water -4 nalysis.Attention has been directed to the contamination of samples ofwater when stored in bottles of bad glass. Within a week,78 E. Miiller and A. Adam, 2. Elektrochem., 1923, 29, 49; A., ii, 260.79 E. Muller and H. Lauterbach, 2. anal. Chem., 1923, 62, 23; A., ii, 92.80 E. Muller and H. Just, 2. anorg. Chem., 1922, 1% 155; A., ii, 42.81 R.G. Gustavson and C. M. Knudson, J. Amer. Chem. Soc., 1922, 44,82 €1. H. Willard and F. Fenwick, J. Amer. Chem. SOC., 1923, 45, 623;83 G. Schay, 2. EEektrodem., 1923, 29, 123 ; A., ii, 331.84 I. M. Kolthoff and E. J. A. H. Verzyl, Rec. trav. chim., 1923, 42, 1055;s 5 W. S. Hendrixson, J . Amer. Chem. Soc., 1923, 45, 2012; A., ii, 781.S6 H. H. V’illa,rd and F. Fenwick, $bid., p. 033 ; A ., ii, 430.2756; A., ii, 185.A., ii, 331.A., ii, 873176 ANNUAL REPORTS ON THE P R O O E E ~ OF CHEMISTRY.sufficient mineral matter may be dissolved to alter the characterof the water, notably in its silica and soda content.87A rapid gasometric method of estimating the dissolved oxygenand nitrogen in water has been described, the gases being liberatedby dissolving a highly soluble substance, such as potassiumhydroxide, in the water.88A new formula has been devised for calculating the active carbondioxide ( c ) in drinking water from the total carbon dioxide ( t )in mg. per litre : c = 2 7 [ v t - dp+ 58233, a correction beingrequired where the value of t exceeds 2CO mg.89In estimating carbonates in mineral waters, it is necessary toeliminate any sulphide present, for cxample, by means of leadperoxide followed by hydrogen peroxide, and to filter the liquidafter heating it for thirty minutes at 4 5 O . 9 0 The total iodine inmineral waters containing sulphides may be rapidly estimated byoxidising organic matter and sulphides with alkaline perman-ganate, liberating the halogens with sulphuric acid, absorbing theiodine in carbon disulphide, and estimating it coIorimctrica1ly.Q~il new reagent for the detection of nitrites in water by meansof a zone test consists of a Gi per cent. solution of resorcinol in puresulphuric acid. The intensity of the coloration (pale rose tobrownish-black) a t the zone of contact enables an approximateestimation of the nitrous acid present to be made.92The yellow coloration produced by ammonium molybdate withsilica, has been used for the colorimetric estimation of silica inwater, and enables colloidal silica to be differentiated from non-colloidal silica, which is the form of usual occurrence in water.g3C. AINSWORTH MITCHELL.87 W. D. Collins and H. B. Riffenburg, Ind. Eng. Chem., 1923, 15, 48;88 H. G. Becker and W. E. Abbott, S C ~ . PTOC. ROY. ~ u b l i n SOC., 1923, 17,89 p. Lehm- and A. Reuss, 2. Unters. Nahr. Gertwm., 1923, 45, 227;90 F. Touplain and J. Dubief, Ann. FaZ&f., 1923, 16, 76; A., ii, 337.9 1 J. Dubief, ibdd., p. 80; A,, ii, 332.92 G. Rodillon, J . Pharm. Chdm., 19.22, [vii], 26, 376; A., ii, 37.93 F. Dihert and F. Wandenbulcke, Cornpt. rend., 1923, 176, 1478; A . ,A., ii, 83.249; A,, ii, 784.A., ii, 697.ii, 607

ISSN:0365-6217    

DOI:10.1039/AR9232000157

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY.THIS year it has been decided, in view of the large amount of workwhich should be reviewed, to omit that portion of the Reportwhich in previous years has been devoted to personalia and noticesof new books.A survey of the literature published during the past year leavesa reporter little choice other than to deal to a large extent with thesubjects that were reviewed at the end of 1922.It is of interest to note that the work reviewed in the followingpages includes the researches for which no fewer than four of therecently awarded Nobel Prizes were given. The 1923 Prize forMedicine was awarded to Dr. F. G . Banting and Prof. J. J. R.Macleod, of Toronto, for their researches on insulin, whilst, by ahappy choice, the complementary researches of Prof.A. V. Hilland of 0. Meyerhof on the mechanism of muscular contractionwere selected for a second joint award in 1922.The Internal Secretion of the Pancreas.In last year’s Report the discovery of the long-sought internalsecretion of the pancreas by the Canadian investigators F. G.Banting and C. H. Best was described. It is not surprising thatthe announcement of a discovery of such importance has beenfollowed by a great deal of experimental work. Indeed, the taskof reviewing the literature which has appeared during the pasttwelve months on this subject has proved to be no easy matter,particularly when it was soon apparent on perusal that muchthat has been published does not represent careful work or matureconsideration.In the fist place, chemists will naturally beinterested to learn of the progress that has been made towardsa recognition of the nature of “ insulin.” For some months afterthe discovery of insulin it was usual to prepare it by the originalmethod described by Collip.1 This method was a somewhattedious fractional precipitation by means of alcohol, and yieldeda preparation, usually referred to now as “crude insulin,” whichwas a white, hygroscopic powder. The yield varied considerably,but averaged 0.7 gram per kilo. of fresh pancreas, and its potency,measured in terms of the original Toronto unit of standardisation,J J. B i d . Chern., 1923, 46, Proc. Amer. Soc. Biol. Chm., XI,17175 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.that is, the dose required to lower the concentration of the blood-sugar of a 2-kilo.rabbit, which has fasted for sixteen to tmenty-four hours, from a normal value of 0.1 per cent. to about 0.04 percent., and to induce typical hypoglycEmic convulsions withinfour hours, was represented by a dosage of about 7 mg. Obviously,from its method of preparation, such material contained very muchthat was not the active substance, and several investigators havepublished improved metho$. Perhaps the most important ofthese practical improvements has been that advised by Dudley.2He found that “ crude insulin ” made by Collip’s original methodcontains nearly 50 per cent. of inorganic salts, and that it gavepositive reactions with such diverse tests as biuret, Millon, gly-oxylic acid, Pauly, Molisch, Selivanov, and the test for organicsulphur.Furthermore, he found that the hormone is precipitatedfrom aqueous solution by a, variety of reagents, such as uraniumacetate, phosphotnngstic acid, and, in particular, picric acid. Thecompound with the last-named substance is a lemon-yellow powder,which is only slightly soluble in water, but can readily be convertedinto a soluble hydrochloride. The “ hydrochloride ” is an almostwhite powder which is readily soluble in water. As it is not hygro-scopic, it can be kept more readily than “crude insulin,” whilstits activity, weight for weight, is approximately ten times thatof the original material. A similar method is used by Sordelli andDeulofeu.2aIt is clear that this improved method of preparation has givenus a much cleaner product than “ crude insulin,” but it is equallyobvious that we are not yet dealing with the hormone in a purestate. The “ hydrochloride ” no longer shows positive tests forthe presence of phosphorus, which is in agreement with theobservations of Doisy, Somogyi, and Shaff er,3 who prepared theirinsulin by precipitating it a t its isoelectric point, pH 5, nor doesit give a positive Selivanov test for fructose, in this respectdiffering from the preparations made by Winter and Smith 4 frompancreas and from yeast.Of the reactions mentioned above, theonly ones given to a marked degree by the “ hydrochloride ” arethe Pauly reaction for the iminazole ring, the biuret test, and thetest for organic sulphur.These are properties which would reason-ably be given by a protein derivative, and such an idea of thenature of insulin is supported by Dudley’s further observationsthat both pepsin and trypsin destroy the activity of insulin “ hydro-Biochem. J., 1923, 17, 376; A., i, 967.2a Compt. rend. SOC. Biol., 1923, 89, 743..3 J . Biol. Chem., 1923, 55, Proc. Amer. SOC. Biol. Chem., xxxi.4 Proc. Physiol. SOC., J . Phyeiol., 1923, 57, xl; A,, i, 613PI3YSIOLOQICAL CHEMISTRY. 179chloride.” These facts, together with the results of experimentswhich show that the active principle is readily destroyed by alkali,and that it is quickly adsorbed from acid solution by filtrationthrough a Berkefeld filter, although not from weakly alkalinesolutions, have led Dudley to conclude that insulin may be a verycomplex protein derivative.This view is supported by Widmark,5who has made a study of the solubilities of insulin, but his supportloses much of its value because he employed a crude preparation,and also by Witzemaiin and Li~shis.~~ The observations of Bestand Macleodg are not in agreement with this opinion, for theyfind that whereas insulin prepared from, ox or pig pancreas maygive certain protein reactions, that prepared from the skate doesnot, and furthermore, by employing phosphotungstic acid theprotein matter may be separated from insulin prepared from oxor pig pancreas without impairing its activity.Recent papers by Piper, Allen, and Murlin,’ and by Kimballand Murlin8 also contain evidence that insulin is not a proteinderivative.Bearing in mind that there is general agreement on the easewith which insulin is carried down from solution by adsorbents,it is reasonable to suppose that many of the preparations describedare adsorption complexes of insulin with complexes of a proteinnature.Its destruction by the proteoly-bic enzymes pepsin andtrypsin recorded by Dudley and others is not, however, explainedby this view.The discovery of insulin was soon followed by the commercialpreparation of this material on a large scale for therapeutic use.As is now well known, the preparation in this country was con-trolled by the Medical Research Council, and there can be nodoubt that this action, much criticised a t the time, protected thepublic from being exploited in a manner which might have hadserious consequences.The manufacture of insulin by trustworthymakers only has led to the results of its widespread clinical usebeing in general highly satisfactory. Naturally, the supply ofpawreas is a limiting factor on the output, and there have beencuriously interesting developments as a result of the search forother possible sources of insulin.J. B. Collip, one of the original team of the Toronto workers,impressed with the relation between the power of the liver to formglycogen and the pancreatic hormone, was led to suspect that5 Biochem. J., 1923, 17, 668; A , , i, 1148.5~ J . Biol. Chem., 1923, 57, 425; A., 1924, i, 108; ibid., 58, 463.6 Arner. J . Physiol., 1923, 63, 390.7 J , BioZ.Chem., 1923, 58, 321. Ibid., p. 337180 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.wherever glycogen occurs there will be found a hormone similarin i t s action to the pancreatic substance. Accordingly, he investi-gated two sources, which, if this hypothesis were correct, shouldyield such a hormone. There were, in the first place, certainlower animals such as the clam, and secondly certain yeasts andother fungi, in all of which glycogen is formed in relatively largeamounts. From the tissues of the clam (Mya arenaria) a sub-stance was prepared9 which definitely produced a fall in the con-cenfration of blood-sugar in animals, but only after a latent periodof from one to four days after injection. This result he explainedby postulating the slow.activation of an inactive precursor. Inthe same manner, Collip 10 has prepared an active substance fromyeasts, although a t first many failures were recorded. Theadministration of the material from yeast sometimes gave rise toan immediate hyperglyczemia, followed later by hypoglycemiain from five to sixty-five hours. Of even more irpportance is theobservation that the blood-sugar level. of a depancreatised dogcould be reduced by the administration of the yeast preparations.Simultaneously with Collip's announcement, a similar claim wasadvanced by Winter and Smith, working in the CambridgeLaboratory.ll Hutchinson, Smith, and Winter,l2 and Funk andCorbittlh also note a variability in the activity of preparationsmade from yeast, and the former state that micro-organisms otherthan yeast can yield substances which reduce the concentration ofsugar in the blood.Having traced an apparent association betweenglycogen and a substance resembling insulin in a, plant, yeast,Collip 13 directed his attention to the theory regarding theaction of insulin which had been advanced by Winter andSmith (compare Ann. Reports, 1922, p. 195). Collip reasonedthat if insulin is concerned in the animal organism with the con-version of a mixture of CC- and p-glucose into the more reactive7-glucose, then a similar hormone should be an essential con-stituent of any plant which breaks down dextrose. This trainof thought should lead to the logical conclusion that all livingtissues require the co-operation of such a hormone, but it inducedhim to examine the onion, as typical of a plant which oxidisesglucose and does not form starch.The onion extracts were foundto induce the same type of physiological effects in animals as didthe extracts from yeast.0 J . Biol. Chem., 1923, 55, PTOC. Amer. SOC. Biol..Chem., xxxix.10 B i d . , 1923, 56, 513; A., i, 967.11 Proc. Phjsiol Xoc., J Physiol., 1923, 57, XI; A . , i, 513.12 Biochem. J . , 1923, 17, 633, 764.1 2 ~ PTOC. SOC. Exp. Biol. Med., 1923, 20, 422.18 J. Biol. Chem., 1923, 56, 513; A,, i, 967PHYSIOLOUICAL CHEMISTRY. 181Best and Scott also record the preparation of active extractsfrom wheat, beet, and celery, whilst Collip has also used barleytops, sprouted grain, green wheat leaves, bean tops, and lettuce.That plant extracts from various sources can depress the blood-sugar level both in normal animals and in depancreatised dogswould therefore appear to be definitely established.In view ofthe fact that the effects develop much more slowly than wheninsulin is used, it is possible that the factors are not identical withthe hormone of the pancreas, and on these grounds Collip proposesfor them the name glucokinin.16 Dubin and Corbitt 16a have recentlyfurnished evidence that in such plant extracts there are presenttwo factors, one producing hyperglycaemia, and the other, whichresembles insulin, producing hypoglycEmia. By suitable meansthese two substances may be separated, and it is then found thatthe latter factor is probably identical with insulin from the pancreas.These investigators attribute the slow action of plant extractsin reducing blood-sugar on injection to t’he inhibitive effect of thesubstance causing hyperglyczmia.The therapeutic value ofplant extracts has not yet been sufficiently examined to enable anopinion to be formed, but if it should be found possible to employthem, a very big advance will have been made. In favour oftheir possible employment for human use is the fact that, althoughthe physiological effects of their administration develop moreslowly than in the case of insulin, they are maintained for a muchlonger time.In connexion with the therapeutic administration of insulin,which is by injection, it is possible that important improvementsmay follow the statement by Winter l7 that the hormone may beabsorbed from the stomach when administered by the mouth inthe form of weak alcoholic solutions, although this has not beenconfirmed by H ~ r r i s 0 n .l ~ ~Turning now to the important question of the actual significanceof insulin in relation to carbohydrate metabolism, we find that,in spite of a certain amount of somewhat rash speculation in certainquarters, steady progress is being made towards its solution. Inlast year’s Report (p. 195) reference was made to Winter andSmith’s hypothesis that the sugar in the blood of diabetics is amixture of a- and p-glucose which must be transformed into amore reactive form-possibly the ethylene oxide or y-glucose-before it can be oxidised in the organism.This hypothesis, whichhas received little or no support, has now been extended by thesel6 Nuture, 1023, 111, 571; A,, i, 728.lBa Proc. SOC. Exp. Biol. &led., 1923, 21, 16.l4 3. Metabolic Res., 1923, 3, 177.l6 J . Physiol., 1923, 58, 18.l7 Winter and Smith, Brit. Med. J., 1923, i, 711.17a Brit. Med. J., 1923, Dec. 22182 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.investigators 17, l 8 so as to allocate a r6le to insulin, although itmust frankly be admitted that the experimental evidence insupport of their conclusions is somewhat inadequate.188 Theyclaim to have shown the presence of an enzyme in the liver whichwill cause certain changes in the rotation shorn by dextrose andlawulose solutions in the presence of small amounts of insulin.These changes were not observed when boiled liver-tissue wasemployed.The view of these workers, that sugar is present innormal blood as the highly reactive 7-glucose, was referred to inlast year’s Report, and doubt was then expressed as to the adequacyof the evidence on which this theory was advanced. The workpublished during the ensuing twelve months has not caused thereporter to change his opinion. The results of Hewitt and Pryde,l9on which this theory was largely based, have been challenged byStiven and Reid 20 and by van Crefeld 20a whereas one of the formerobservers21 has himself raised strong objection not only to thetechnique employed by Winter and Smith, but also to their inter-pretations of the results.The differences that occur between theresults of estimations of sugar in blood by polarimeter and bycopper-reducing methods which first led Winter and Smith toadvance their theories have also been noted by Stepp,22 particularlyin the case of bloods from diabetics. From a study of this relationof the polarimetric value to the copper-reducing value, as theymay for convenience be termed, of diabetic blood extracts beforeand after acid hydrolysis, Winter and Smith believe they haveobtained evidence of the presence of a complex carbohydrate inthe blood in this disease.23 They also find that the injection ofinsulin into diabetics causes a breakdown of this complex carbo-hydrate.24 Furthermore, the injection of adrenalin into normalrabbits, in their opinion, changes the normal sugar of the bloodinto something resembling this complex carbohydrate present indiabetic blood.In the blood of normal animals which had receivedinjections of insulin until convulsions appeared, the same authorsclaim to have detected the presence of a dextrorotatory carbo-hydrate without copper-reducing power.26 One cannot helpexpressing regret that so much of this work would appear to havebeen published in an immature condition.The relation between the amount of sugar utilised by thela Proc. Physiol. SOC., J . Phy8iol., 1923, 57, xiii.18a See Alles and Winegarden, J . Biol. Chem., 1923, 58, 225.lo A., 1920, i, 508.2oa Ibicl., 860.22 Ergeb. Physiol., 1922, 20, 108.23 Proc.Physiol. SOC., J . fhysiol., 1923, 57, xxxi; A., i, 513.24 Brit. Med. J . , 1923, i, 711.20 Biochem. J., 1923, 17, 656; A., i, 1153.21 J. A. Hewitt, Brit. Med. J., 1923, i, 590; A., i, 973.2s Nature, 1923, 111, 810; A., i, 72PHYSIOLOGICAL CHEMISTRY. 183organism and that of insulin administered was, both from earlyexperiments on animals and from clinical trials, recognised as aquantitative one, and this is of considerable importance from thepoint of view of the physiological standardisation of insulin.McCormick, Macleod, Nobel, and O’Brien,26 as wrell as other in-vestigators, have pointed out that the amount of glycogen presentin the test animal has a distinct influence on the dose of insulinwhich is required to produce the requisite fall in concentrationof the blood-sugar amid the typical convulsions; hence the import-ance of employing as test subjects only those animals which havepreviously had their glycogen reserves depleted by twenty-fourhours’ starvation.The most natural question that came t o one’s mind when oneheard that insulin causes a diminution of the blood-sugar in theanimal organism, so that by careful regulation a diabetic can berestored to all intents and purposes to normal health, was toinquire as to the fate of the sugar that disappears.Since thediabetic may with properly regulated insulin treatment gainmarkedly in weight, and exhibit an almost normal carbohydratetolerance, it might reasonably be expected that the sugar is oxidisedalong the normal paths of metabolism.However, Dudley, Laid-law, Trevan, and Boock27 have shown by determinations of therespiratory quotient that the injection of insulin does not apparentlydirectly increase the rate of combustion of dextrose, and con-firmatory results were obtained by Kellaway and Hughes 28 in astudy of the effect of insulin administration on the respiratorymetabolism of a normal human subject. If this does not occur,then the possibility that the sugar leaving the blood goes to formglycogen a t once suggests itself. Dudley and MarrianZ9 find,however, in such animals no increase in the glycogen reserves inthe liver or the skeletal muscles. If the sugar leaves the bloodand is neither oxidised nor converted into glycogen, there is thenthe possibility to be considered that it is transformed into fat,but Dudley and Marrian could find no evidence that this occurs.McCormick, Macleod, O’Brien, and Nobel 3O believe that insulincauses what they call a “ glucose vacuum ” in the tissue-cells,which accordingly withdraw the sugar faster from the blood thanit is being formed from glycogen.Nevertheless, its fate afterabsorption by the cell is still the subject of some speculation.Dale31 believes it not improbable that as in complete pancreatic2 6 J. Phgsiol., 1923, 57, 234; A., i, 614.2 7 Proc. Pkysiol. SOC., J . Physiol., 1023, 5’9, xlvii.28 Brit. N e d . J., 1933, 1, 710; A,, i, 972.2B Biochern. J., 1923, 17, 436; A., i, 978.8o Arner. J . Phyaiol., 1923, 63, 389. 81 Lancet, 1923, 1, 992184 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.diabetes the organism cannot burn sugar, so in the state producedby excess of insulin there is the direct antithesis, and the body isliving on nothing but sugar.This explanation would appear toagree with certain of the experimental observations. Thus, thefirst effect of a large dose of insulin should be to cause a sharprise in the respiratory quotient, which actually occurs, and wouldnot necessarily be accompanied by an increase in general meta-bolism. Later, as the supply of sugar begins to run low, the mets-bolisrn should fall rapidly, until, when the blood-sugar reaches acertain level, the failing combustion of this substance would beovertaken by the metabolism of fat and protein and the respiratoryquotient would reach the values far below normal which areobtained.The Cambridge group of investigators have recordedthat the inositol content of rats is increased after convulsionscaused by insulin,32 and also that there is a rapid fall in theinorganic phosphates which persists for many hours after recoveryfrom the convulsions.33 The significance of these changes is asyet not clear, although the authors advance somewhat tentativeexplanations. The conclusion drawn from studies of the respiratoryexchange that insulin does not cause an increased oxidation ofsugar is supplemented by the observations of Eadie, Macleod, andNoble34 that the rate of glycolysis in shed blood or the excisedliver 35 is unaffected by insulin. Thalhimer and Perry,36 however,believe that the low glycolytic power of diabetic blood can beraised to a normal value by insulin administration, although theyagree that no such effect can be observed in vitro.Azuma andHartree36a could detect no influence of insulin on the heatproduction of isolated frog's muscle.Noble and Macleod37 record the interesting fact that dextroseand mannosc are the only sugars of a number tested which bringabout a disappearance of the characteristic symptoms of insulinadministration. Arabinose, xylose, sucrose, lactose, sodium lactate,glycerol, ethyl alcohol, and alkalis had no effect'.What may prove to be a discovery of the fist degree of importanceis recorded by Burn,% who finds that the subcutaneous adminis-tration of pituitary extract diminishes or abolishes the hypoglyciemiaproduced by insulin.Indeed, the convulsions associated withinsulin hypoglyczemia can be dispelled as rapidly by pituitaryextract as by dextrose. In this connexion it is interesting to recall32 Noedham, Smith, and Winter, J . Physiol., 1923, 57, lxxxii.33 Wigglesworth, Woodrow, Smith, add Winter, J. Physiol., 1923, 57, 447.34 Amer. J . Physiol., 1923, 65, 462; A., 1924, i, 113.35 Noble and Macleod, J. Physiol., 1923, 58, 33.36 J . Amer. Illed. AS^., 1923, 80, 1614. 38% Biochem. J., 1923, 17, 875.=jr Amer. J . Pliysiol., 1923, 64, 547. 88 J . P&8iol., 1923, 67, 318PHYSIOLOGICAL CHEMISTRY. 186that cases of pituitary insufficiency frequently exhibit a raisedcarbohydrate tolerance. In direct relation to these results arethose obtained by Olmsted and Logan,39 who find that decerebratecats with intact pituitary maintain a high blood-sugar level whichis not much reduced by insulin.If the pituitary is removed,insulin provokes typical convulsions. Decapitated cats may havethe blood-sugar level lowered by insulin below that a t which con-vulsions appear in normal cats without obtaining convulsions.Internal Secretions of Pituitary and Thyrold Gland.to isolatethe active principle of the pituitary gland, but, unfortunately,without success. The greater part of the uterine stimulant maybe concentrated in the material dissolved by ethyl alcohol fromthe butyl alcohol extract of the powdered g l a n d ~ . ~ l From thisfraction an active crystalline picrate was eventually isolated, butproved on purification to be the double salt of crestinhe andpotassium. The mother-liquors from the crystallisation of thissalt showed marked activity, and could be further separated intotwo fractions by means of acetone.The insoluble fraction con-sisted of a dry powder with an activity on the isolated uterusabout twelve times as great as that of hktamine, and showed asimple pressor effect on blood pressure. The constituents of thesoluble fraction, which was a deliquescent resin, showed a smalleruterine activity, and a pressor effect on blood pressure, which waspreceded by a depressor effect. Dudley believes that a t leastthree distinct active principles are present in pituitary extracts,a view which is not accepted by Abel and R o ~ i l l e r , ~ ~ who regardthe oxytocic principle as probably identical with the pressor anddiuretic principles.In a recent publication,43 the latter authorsdescribe in a preliminary manner the separation, after a longfractionation, of what they appear to regard as the active principlein the form of a tartrate. This preparation is stated to have anactivity 1,000 to 1,250 times greater than that of histamine, whilstthe doses necessary to raise the blood pressure by an appreciabledegree in cats, and to cause marked diuresis in rabbits, arerespectively 1/100 and 1/20 of a milligram. This preparation isundoubtedly highly potent, but in the light of Dudley's experience,and of the admission by Abel and Rouiller themselves that theactive principle is readily ads'orbed, and that the chemical purityAnother careful attempt has been made by DudleyAmer.J . Phyaiol., 1923, 66, 437. '' J . Phamn. E x p . Ther., 1923, 21, 103; A., i, 629.41 A., 1920, i, 344.43 Abstract of Communications to XIth Intern. Congress Physiol. Edin-J . €'ham. Exp. Ther., 1922, 20, 65.burgh, 1923156 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.of their tartrate has not yet been established, it would seem wiseto reserve judgment on this matter.The announcement by Romeis44 of the isolat#ion of the thyroidhormone may be mentioned here as recalling Kendall's isolationof thyroxin.*S Rorneis separates his material in the form of aprecipitate obtained by acidifying the products of hydrolysis ofthyroid gland after boiling with barium hydroxide solution untilthere is no response in the biuret test.The crude material thusobtained is purified by repeated dissolution in alkali and pre-cipitation with acid. Extraction of this product with acidifiedalcohol yields a fraction which is further purified by extractionand precipitation. Finally, a light brown powder with a highiodine content is obtained, which is stated to be a substanceresembling, and probably related to, Kendall's thyroxin. Althoughit shows marked physiological activity, one is led to questionwhether products prepared by such drastic methods can bear anydirect relation to the active principles of the gland. There is aregrettable tcndency to announce the separation from thyroidtissue of any sttbstmce with a higli iodine content as the isolationof the active principle.It can be recalled that not only was astructural formula advanced for Kendall's thyroxin, but also thatOsterberg claimed to have on a t least two occasions (1917, 1919)effected its s~mthesis.~6 As yet no details of this important achieve-ment have been forthcoming.Fat-soluble J7itamiw and Calcification of Cartilage.Although this subject has been dealt with a t some length inseveral previous Reports, the results achieved during the pasttwelve months are o€ such importance that they cannot well bepassed over. Perhaps the most striking publication of the yearhas been the report of the investigations on rickets in Viennaduring I 919-1922,47 in which is described the work of Dr.HariettcChick and her colleagues. This report deals with the practicalapplication on a large scale of the dietary theory of the etiologyof rickets advanced some years ago by M e l l a n b ~ , ~ ~ and the resultsdescribed therein should dispel any doubts which might remainas to the truth of Mellanby's main contentions. A most strikingfeature of this report is the preface written by Prof. C. von Pirquet,the eminent authority on nutrition, who provided Miss Chick withthe fncilities for her invcstigntion. ' He records how after closelywatching the experiments tliroughout their course he finally became44 Biochem. Z., 1922, 13, 3, 97; A , , i, 267.4 5 Ann. Reports, 1919, p. 169.4 i Medical Research Council, Special Report, No.77, 1023.4 0 I b z Z , No. 61, 1921,40 Ibid., 1919, 1920PHYSIOLOGICAL CHEMISTRY. 187convinced, not only that rickets is a disezse of nutrition, but alsot'hat a deficiency of fat-soluble vitamins in the diet is an essentialcause of the disease. It will be remembered that Mellanby tlraceda close parallel between the distribution of the organic factor whichexerted an anti-rachitic action, and that of the substance knownas vitJamin-A, although he mas careful not to assume their identity.I n 1921 McCollum, Simmonds, Shipley, and Park 49 expressed theview that the anti-rachitic substance is distinct from the vitamin-A,and in last year's Report the reporter expressed the opinion thatthese workers might possibly not have considered the mattersufficiently froin the qmntitative point of view. Lster .work byMcCollum and his co-workers, as well as by Goldblatt and Zilva,50has now provided satisfactory cvidence that the anti-rachitic andgrowth-promoting factors am distinct.Although both substancesare present in cod-liver oil, they are destroyed a t markedly differentrates by oxidation ; furthermore, certain foodstuffs, for cxample,spinach, may serve as valuable sources of one substance withoutproviding appreciable amounts of the ot,her.The newly discovered substance may provisionally be termed theanti-rachitic vitamin, as an attempt to term it vitamin-D has ledto some confusion with another recently discovered substance inyeast, for which Punk has reserved this nanie.The Vienna experi-ments again emphasim the importance of light in the preventionand cure of rickets. When last year's Report was written, it wasuncertain whether or not exposure to short wave-length radiationcould actually replace the fat-soluble vitamins in bringing aboutsatisfactory growth and bone formation. This point has nowbeen satisfactorily cleared up by the work of H ~ m e , ~ ~ and ofGoldblatt and Soa~lles,~~ who agree that the radiation mill notrender the fat-soluble vitamins dispensable, but may, however,enable an animal to economise to no small degree its supply ofthese substances, so that an animal on a diet deficient in the fat-soluble vitamins will thrive much longer if irradiated than if itwere not so treated.Very interesting too has been the claimby Huim and Henderson Smith 53 to have produced this sameeffect, not by radiating the animals themselves, but by maintainingthem in vessels containing air which had previously been irradiated.Replacing the irradiated air in the jars by ordinary air or by ozoncbcaused the effect to disappear. In attempting an cxplanatjon ofthis most curious obscrvation, one naturally thinks of ionised airor oxides of nit'rogeii as possibly being the active suhstances formed49 It., 1921, i, 757.to Lancet, 1923, ii, 647.63 Riochem. J., 1923, 17, 364.Also Amer. J . Hyg., 1921, 1, 512.6' Ibid., 13. 1318. G 2 %d., p. 1321188 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.by the radiation, but in view of the failure of Webster and Hill 54to confirm the main results of Hume and Smith, it may be well topostpone further discussion.Regarding the nature of the organic factors in cod-liver oil, nofurther work of outstanding interest has been published on the natureof the anti-rachitic substance.The vitamin-A, which is nowsupposed to be mainly concerned with the growth processes, has,however, been further investigated. K. Takahashi and Kawakami 55have described the preparation from cod-liver oil of a substancewhich they claim to be the vitamin-A in a semi-crystalline andnearly pure condition. From a close survey of the description theyhave published it would appear doubtful that they have actuallygot anything approaching a pure substance. It is stated to containonly carbon, hydrogen, and oxygen, and to resemble an aldehydein its properties.It shows the general solubilities of fatty sub-stances.Although it is generally recognised now that one or more un-identified organic factors, such as are now loosely termed thefat-soluble vitamins, play an essential part in normal calcificationof cartilage, we are entirely ignorant as to their r61e. Turning,however, to the actual mechanism of calcium deposition, we findencouraging progress to report. Until recently, the process bywhich calcium salts are deposited in cartilage to form bone hasbeen regarded very much as if it were purely a physico-chemicalproblem. Thus for a number of years Freudenberg and Gyorgy 56have investigated the influence of various conditions on the absorp-tion of calcium salts from solution by pieces of cartilage in witro.The results, whilst interesting in themselves from the point of viewof colloid chemistry, cannot be said to have advanced to anyappreciable extent our knowledge of the process of calcificationas it occurs in the body.Indeed, Watt 57 has shown that thecrystalline forms in which calcium carbonate and calcium phosphateare deposited from aqueous or colloidal solutions are dissimilarfrom the deposits in bone. A clue to this difficult problem has,however, been provided from a most unexpected quarter, and itis one which bids fair to solve many of the major difficulties. I ninvestigating the products of fermentation of sugar by yeast,Harden and Robison 58 described the presence of a hexosemono-phosphoric ester.The compound was isolated by Robison anddescribed by him in a recent paper.59 It is entirely different from54 PTOC. Physiol. SOC., J. Physiol., 1923, 57, lxxvii.6 5 J. Chem. SOC. Japan, 1923, 44, 580; A., i, 968.66 See Ann. Reports, 1921, p. 187.G 7 Riol. Hull., 1923, 44, 280; A., 1924, i, 119.6s Biochern. J., 1922, 16, 809; A., i, 86.6 * P., 1914, 30, 16PHYSIOLOGICAL CHEMISTRY. 189the compound prepared by NeubergyGO and yields calcium andbarium salts which are readily soluble in water. Robison was ledto investigate the action of enzymes on solutions of these salts,and found that in some cases the ester was hydrolysed. In suchcases the progress of the hydrolysis was shown by the depositionof sparingly soluble calcium or barium phosphate.These resultsa t once suggested to him the possibility that such a soluble calciumsalt might be tlie form in which fhe mineral could be carried toossifying cartilage, there to be broken down by an appropriateenzyme into calcium phosphate and free sugar. Experimentssoon proved that ossifying cartilage of young animals actuallypossesses the power rapidly to hydrolyse this hexosemonophosphoricacid, whereas of all other tissues the only one showing this powerto any significant degree is the kidney.The dBculties of explaining the deposition of calcium in cartilageand not in other tissues has in the past led to all sorts of suggestions,such as the specific adsorption of ions (Pfaundler 61)y whilst thefact that serum contains more calcium salts in solution than canbe carried in the form of calcium phosphate or carbonate by thesame volume of wafer has also given rise to much speculation.It must be remembered that Cushny 62 found that when serumis filtered through collodion all the crystalloids pass through exceptsome of the calcium and magnesium, and also that many investi-gators have recorded the presence in blood of a certain amountof organically-combined phosphoric acid in a form readily hydro-lysed by acids.63, 134 If it can be shown that blood contains thecalcium salt of a hexosephosphoric acid such as Robison has studied,the importance of his discoveries may indeed be far-reaching.Perhaps not unconnected with these results are the observationsthat in rickets there may be a decreased amount of calcium andphosphorus in the bl00d.65 Hess and Lundagen 66note that theremay be seasonal variations in the amounts present in children’sblood, and that minimum values are usually observed in March,when also the incidence of rickets is at its height.The values mayrapidly be brought again to normal by exposure of the child toshort wave-length radiation, or by administration of cod-liver68 As an attempt to explain the beneficial action of radiation62 Ann. Reporte, 1920, 17, 161,6o Biochem. Z., 1918, 88, 432; A., i, 423.6l Jahrb. Kinderheilk., 1904, 60, 123.63 Greenwald, J. Biol. Chern., 1916, 25, 431.64 Bloor, ibid., 1918, 36, 49.6 s Howland and Kramer, Amer.J. Dis. Child., 1921, 22, 106; A., i, 418.6 6 J . Arner. &led. AM., 1923, 79, 2210; A., i, 624.6 7 Kramer and Boone, Proc. SOC. Exp. BiOl. Med,, 1922, 20, 87.68 Steenbock, Hart, Jones, and Black, J. Riol. Ckm., 1923, 58, 59190 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.in rickets, J. H. Clark 69 records that the exposure of blood-serumto ultra-violet radiation increases t'he amount of dialysable calcium.Biological Oxidations.The gradual revelation step by step of the significance of gluta-thione 70 in relation to the mechanism of oxidations in living tissuesbecomes more fascinating with each publication from the labora-tories of Hopkins and his colleagues. Hope was expressed by thereporter last year that the constitution of the dipeptide mould soonbe established, and by the careful work of Quastel, Stewart, andTunnicliffe that has now been done.Working with rather lessthan 2 grams of material, and employing the method of condens-ation with 2 : 3 : 4trinitrotoluene used so successfully by Bargerand Tutin 72 to determine the constitution of carnosine, theseworkers found that the condensation product; yielded free cysteinebut no free glutamic acid on hydrolysis. It is therefore concludedthat the coiistitution of the reduced form of the dipeptide is repre-sented either by I or 11.rH*CH( CH,*SH)*CO,H H*CH(CH,*SH)*CO,HC0.CH(NH,)*CH2*C'€~,*C02H CO*CH2*CH2*CH(NH2)*C02H(1.) (11- 1On oxidation of glutathione with hydrogen peroxide in the presenceof a trace of iron salt no trace of succinic acid was detected, whereasafter hydrolysis of bhe oxidation product a yield of succinic acidamounting to 50 per ccnt, of the thcoretical was obtained.FromDakin's studies 011 the oxidation of a-amino-acids 73 this wouldindicate that formula I1 represents glutathione. In last year'sReport, attention was directed to the remarkable discovery of athermostable component of washed tissues which together withglutathione can form a system capable of absorbing atmosphericoxygen. Thc mechanism of this change may be represented bythe following scheme, in which X stands for the as yet unidentifiedtissue constituent,, and C-S-S-G and G-SH for the oxidisedand reduced forms of glutathione, respectively.X<g + G-S-S-G -+ X + 2G-SH2G-SH + ;02-.+ G-8-S--G + H2OThis characteristic r6le of glutathione as a transporter of hydrogenwill cease, of course, when the supply of the oxidisable component69 Amer.J . Hyg., 1923, 3, 4, 81.71 Biochern. J., 1923, 17, 586; A , , i, 1072.72 Ibid., 1918, 12, 402; A., i, 170.i 3 J . Bid. Chew&., 1985, 1, 111; 5, 410; A,, 1906, ii, 105.7o Ann. Reports, 1921, 1922PHYSIOLOGICAL CHEMISTRY. 191is exhausted. Naturally, there has been keen interest focussed onthe possible nature of the tissue component, but as yet no definiteinformation on this point is available. A clue may, however, havebeen provided by the experiments of both Meyerhof and Kopkinson the autoxidation of unsaturated fatty acids under the influenceof glutathione and similar substances.Meyerhof 74 has found thatwashed frog’s mwcle, which regains the power to absorb oxygeri inthe presence of substances containing the snlphydryl group -SHYsuch as thioglycollic acid or cysteine, may be replaced by the materialprecipitated by acetone from the alcohol-ether extract of the muscle-tissue. This a t once suggests substances of the lecithin class, anda reduction in the amount of unsaturated groupings present duringthe process farther suggests that unsaturated fatty acids (linolenic)may be concerned. Strong support for this idea is furnished bylik experiments with lecithin and by the work from the Cambridgelaboratory. 73When the system outlined in the scheme gix7e;i above ceases toabsorb oxygen, it is because all the tissue constituent X has beenoxidjsed. If, however, an emulsion of an oil containing unsaturatedfatty acids (linseed or cod-liver oil) be part of the systein, there isa greatly increased uptakc of oxygen, and, generally speaking, tlieincrease i3 proportional to the amount of fat added.Control te3;t:L;on the emulsion, alone or mixed with the tissue rcsidue, show thatit takes up oxygen at a very much slower rate. If, howcver, theoil emulsion be mixed with the dipeptide, there will be a markedoxidation of the former provided the reduced form of the catalystis present. This condition is essential because the oil has no powerto reduce the disulphide form such as is possessed by the tissuecomponent X.I n these circumstances, glutabhione acts as an agent for sxygentransport, probably, as both MeyerhoE and Eopkins think, by theintermediate formation of an unstable peroxide.This reaction mayperhaps be illustrated by such a scheme as :G-SHG-SSM-f- &lo, G-SE 0 2 G-S-Hq 11 -+ 0 ----, G-SH G-S-H’The liberated oxygen will be taken up presumably at the un-saturated linlcing of the fatt’y acids (M) present in the oil. On theother hand, if t,he tissue component X is present, the oxidation ofthe oil will proceed without the necessity of the reduced form ofglutathione being present, for it possesses the necessary power74 Pfiiiger’e Archiv, 1923, 199, 531; A . , 1024, i, 118.’s Hopkine, Gancet, 1923, i, 1251192 ANNUAL REPORTS ON THE PROURESS OP CHEMISTRY.itself to reduce the disulphide compound.It is for this reasonthat in the absence of the tissue component the oxidation of un-saturated fatty acids by the agency of glutathione ceases as soonas the dipeptide is’converted wholly into the disulphide form, butproceeds fully when the presence of the tissue components enablesthe necessary reduction of the disulphide to occur. As Hopkinshas remarked, “We see, then, that the oxidation of a substanceinvolving one type of change (let us say hydrogen transport) maycontrol the oxidation of another substance involving another typeof change (oxygen transport) ; we may recognise here an indicationof that correlation and organisation of chemical events wbich is socharacteristic of living tissues.”Dixon and Tunnicliffe 76 have carefully examined the reductionof methylene-blue by the sulphydryl grouping in glutathione,cysteine, and thioglycollic acid and show, as Strassner 77 showedfor the last-named substance, that the reaction curve resemblesthat of an aufocatalytic reduction.The active agent causing the catalysis is the disulphide formproduced by the reaction, and they present gome evidence thata more active intermediate compound of the R-SH with theR-S-R-S compounds may be formed.The reduction potentialsof cysteke and of glutathione are, however, independent of thepresence or absence of their oxidised forms.78 The uptake ofoxygen by the sulphydryl grouping of cysteine 7 9 y *O and glutathione 76is most rapid at pH 7-4, a fact which is obviously of considerablesignificance from the physiological point of view.These resultsnaturally lead us to consider the glutathione system in the lightof the views on oxidation which are associated to a large extentwith the names of Warburg and Meyerhof. The development ofthese views is traced in a most illuminating manner by Meyerhofhimself in a lecture which he has recently given.81 The essentialpoints of their beliefs are that Oxidation in vico is closely associatedwith actual structures present in the cell, and that the occurrenceof oxidation at the surface of these structures is to a considerableextent dependent on the presence of iron. Indeed Warburg con-ceives the surface of such structures as a mosaic of areas containingiron and of others free from iron.Such a conception satisfies experimental results obtained inis Proc.Roy. SOC., 1922-23, [B], 94, 266; A,, i, 416.7 7 A., 1911, ii, 57.78 Dixon and Quastel, T., 1923, 123, 2943.79 Mathews and Walker, J. Bdol. Chem., 1909, 6, 289; A., 1909, i, 289.80 Abderhalden and Wertheimer, Pfliiger’B Archiv, 1923,*19’9, 131 ; A., 1924,81 Lancet, 1923, i, 322.ii, 11PHYSIOLOGICAL CHENISTRY . 193studying the inhibition of oxidation by narcotics or by cyanides,whether in the living cells, or in simpler systems such as bloodcharcoal suspended in aqueous solutions. In general, narcoticsdepress oxidation in proportion to the degree to which, by surfacetension, they replace the substrate on the surface of the structure,whereas, in the case of cyanides, in which no relation can be tracedbetween their very powerful inhibitive effect on oxidation and theextent to which they are adsorbed by the surfaces, it is believed thatby chemical interaction the iron-containing areas are inactivated.82, 83Certainly these views are strongly supported by Warburg’sexperiments on the oxidation of cystine at charcoal surfaces,sPMeyerhof 85 has now suggested that tho inhibitive effect ofhydrocyanic acid on the autoxidation which occurs in the presenceof substances containing the sulphydryl group is due to the inactiv-ation of traces of metals, and he has been able to show that theautoxidation of thioglycollic acid in presence of traces of coppermay be inhibited by the formation of complex compounds of copperand cyanogen when cyanides are present.This is not in agreement with the conclusions of Abderhalden andWertheimer,s6 who found that oxidation of cysteine takes placein the absence of iron, although its presenoe accelerates the change.Furthermore, these authors state that cyanides depress the oxidationin the absence of iron.It is probable, however, in considering thesystem formed by glutathione in conjunction with the heat-stablepreparation from washed muscle that some progress will be achievedby testing the application of the views of Warburg.In the light of the now popular idea that sugars before oxidationor metabolism are converted into compounds with phosphoricacid, it is interesting to note that Meyerhof and Weber 87 haveascertained that dextrose is not appreciably oxidised a t the surfaceof blood charcoal suspended in an a’queous solution of the sugar,but that hexoscphosphate is slowly but surely changed.E’ructosewas unaffected, and lactic acid only very slightly oxidised. Theoxidation of amino-acids under similar conditions 88 has beenexamined by Ellinger and Land~berger,~~ who in general agree withWarburg’s main ideas. Baur has found that glycine in aqueous82 Natumiss., 1923, 11, 159.83 Biochem. Z., 1923, 136, 266; A., i, 501.84 Ibid., 1921, 119, 134; Pfliiger’s -4rchiv, 1923, 200, 203.a6 Pfluger’s krchiv, 1923, 288, 1.86 Ibid., 1923, 198, 122; A., 1924, i, 11.8 7 Biochem. Z., 1923, 135, 558; A., ii, 317.Sa Warburg, A., 1921, i, 230; 1922, i, 190.89 2. phy8iol.Chem., 1822, 123, 246, 264; A., i, 73,00 Helv. Chim. Acta, 1922, 6, 825; A., i, 97.REP.-VOL. ZIX. 194 ANXUAL REPORTS ON THE PROGRESS OF CHEMISTRY.solution is hydrolysed a t the surface of charcoal in the absence ofair. The reaction probably occurs according to the equationNH,*CH,*CO,H + H,O + OH*CH2*C02NHa,but attempts to separate glycollic acid were unsuccessful.The hypothesis advanced by Hopkins (p. 191) that glutathionemay act as an oxygen transporter by the intermediate formationof a loose type of peroxide recalls the generally accepted conceptionsof the so-called “ oxidase ” system as propounded by Bach andChodat in 1903. These were that there is a substance, probablyan enzyme (oxygenase), which can unite with molecular oxygen toform a peroxide, which is then broken down by the action of asecond enzyme (peroxydase) with the liberation of active oxygen.If Hopkins is justified in his speculation, it is possible to viewglutathione as an oxygenase, but as one which is not an enzymeand which does not need the co-operation of a peroxydase to effectoxygen transpork.Gallagher 91 has examined the mechanism ofoxidation in plants, and has shown that there is no definite evidencethat the substances, oxygenases, which form intermediate peroxidesin plant juices exposed to air are enzymes, as Bach and Chodatheld, and that it appears that they are autoxidisable substances.A substance of this nature isolated from fresh potato tubers wasfound to bear a close relation to the lipins.The view expressedby Onslow 92 that the constituents of plant juices which formorganic peroxides are of the nature of catechol is not supported,and it is shown that the darkening of such juices is due to theaction of tyrosinase on tyrosine. It is very encouraging to catcha glimpse already of the manner in which one day the new theoriesconcerning oxidation in the tissues may be linked up with the oldertheories in which peroxides formed so important a part, and whichstill rest on the sound foundation of Dakin’s classic work.e3The Chemistry of Huscular Contraction.Although Professor Barger reviewed this subject in the A n n dHeports for 1921, it is obvious from a perusal of the literature thatmany important advances have been made during the interveningyears.It must be said, however, that most of the new facts areconcerned with the thermodynamical aspect of the problem, ratherthan with purely chemical matter, in which field there is not muchnew to report.The general position of our knowledge of this subject has recently91 Biochern. J., 1923, 1’4, 516; L4.7 i, 1159.92 Ibid., 1910, 13, 1 ; 1020, 14, 635.93 “ Oxidation and Reduction in the Aiiimal Uody,” 2nd edu., London,1922PHYS~OLOGTCAL CHZMIS’IRY. 195been made clear by a valuable summary by Hill and Meyerh~f.~~Both experiments on isolated muscle and on man have proved thatthe production of lactic acid in muscle contraction is very sudden.Thus, violent exercise lasting only ten seconds may produce inan athlete an oxygen ‘‘ debt ” corresponding to the oxidative removalof no fewer than 30 grams of lactic acid, or 0.1 per cent.of theactive muscles.95 Obviously the sudden liberation of so much acidis a serious call on the neutrality-regulating mechanism of thebody, and there has been considerable speculation as to the natureof the means employed to readjust promptly the normal reaction ofthe tissues. Meyerhof 96 has shown Ohat the available salts,bicarbonate, and phosphates could not under the conditions possiblyfurnish the necessary basic radicals, and has suggested that themuscle possesses in certain of its colloidal constituents large reservesof far more effective buffers than the alkaline salts of the tissuefluids. Hartree and Hill have recently shownQ7 that this hypo-thesis may actually provide a closer agreement between the observedheaf liberated during contraction and relaxat,ion, and the calculatedvalue, since it provides for a greater heat of neutralisation of thelactic acid produced.In this paper further evidence is broughtforward to show that the proteins of blood, in particular the sodiumor potassium salt of hzmoglobin, may act as effective buffers inpreventing a marked rise of hydrogen-ion concentration. Probablythe proteins of the plasma can also act in this capacity, butto a much less extent, as Milroy has in opposition to theview held by Ba~liss.~* The isolation from living muscle of analkaline protein buffer capable of functionating in such an efficientmanner when lactic acid is produced will be awaited with interest.Hartree and Hill give in their paper the following “balancesheet,’’ which represents a summary up to date of their viewsregarding the distribution of heat production in the various phasesof the cycle of the isometric contraction of frog’s muscle.Phase.2‘otuL unal;robic ........................Total initial ...........................Total delayed anaerobic ............Total oxidative .....................Initial (contraction) ..................Initial (relaxation) ..................Oxidative delayed ..................liela tivc.1-251-00-252.50.60-41.5Absolute,. per gram oflactic acid.3 702967474017811s44494 Erg&.Phy8ioZ., 1923, 22, 300.9 5 Hill and Lupton, Quart.J. M d . , 1923, 135; A., i, 977.Q6 Pfliiger’a Archiv, 1922, 195, 22; A., i, 268.O1 Ibid., 1919, 53, 162.J . Phg8iOZ., 1923, 58, 125. s7a Ibid., 1923, 57, 253.K 196 AK;BUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The initial anaerobic heat can, as Slaterg9 has just shown, besatisfactorily accounted for by the production of lactic acid fromglycogen. Employing the accepted value for the heat of combustionof glycogen,l it appeared that the calculated heat given out by theproduction of one gram of lactic acid from Slycogeil, and the sub-sequent neutralisation by the alkaline salt of a protein, wouldaccount for the initial heat, but leave the delayed anaErobic heatentirely unaccounted for. This, and other considerations, led to aredetermination of the heat of combustion of glycogen, with theresult that Stohmann and Schmidt's value has been replaced bythe value of 3874 cals.per gram for the hydrated product(CGH,O,,H,O),. This value is nearly 100 cals. higher than thatpreviously accepted. Slater concludes, on the basis of the followingscheme, that it is possible, using this new figure, to explain theactual heat measurements on muscle entirely on chemical grounds.(u) Glycogen -+ lactic acid.( b ) Lactic acid and contractile mechanism produce mechai:icalContraction,response.Previously Hartrcc and Hill had directed attention to ihcirinability t o account satisfactorily for the delayed anaerobic heatproduced. This heat appears to be about 0.25 of the initial heat,and its rate of evolution is unaffected by temperature.In accord-ance with the above scheme, Slater has produced evidence that i tmay represent t'he replacement of the intcrmcdiate and temporarybuff ering of the lactic acid with bicarbonate and disodiurn phosphateby the more efficient buffering with proteins. Such a complctechange would require a further 119 cals., and as only 74 are actuallyevolved it is assumed that the change proceeds only to about60 per cent. completion. The independence of this heat productionon temperature is explained by Slater on the grounds that thccontrolling factor in the velocity of reaction is the physical one ofthe rate of diffusion of the acid phosphate and carbonic acid ion..through the muscle-tissue.From the figures which Hartree and Hill have advanced i t isapparent that between 1 part in 4.7 parts and 1.part in 6 parts ofthe lactic acid removed is oxidised, the remainder being retainedas glycogen. Hill, Long, and Lupton,2 using the retention ofcarbon dioxide as a measiire of lactic acid removal, and the oxygenDo J . Physiol., 1923, 57, 163.1 Stohmann and Schmidt, J. pr. L'hem.. 189-l. [ii], 50 3s;.Froc. Physid. SOL, J . Physid., 1923, 57, xivPHYSTOLOQICAL CHEMISTRY. 197used in recovery as a measure of the lactic acid oxidised, foundthe ratio between lactic acid removed and lactic acid oxidisedafter exercise in man to be 4.2; a value much the same as thatgiven by experiments on frog’s muscle. In later experiments, inwhich the lactic acid was determined directly instead of by theindirect method of determining the retention of carbon dioxide,Long and Lupton3 obtained values ranging from 4-96 to 9.10 witha mean of 7.5.From these values they regard the efficiency ofremoval as being greater in man than in the case of the frog’smuscle, but too much significance cannot be placed on thesediffercnces. Lesser 4 states, however, that the observations ofMeyerhof 5 on the disappearance of glycogen from, and the form-ation of lactic acid in, exercised muscle cannot be applied to thewhole animal. Lesser finds, in contrast to Meyerhof’s records,t h s t in the winter, during anoxybiosis, 40 pcr cent. of the totalloss of glycogen in frogs occurs in the liver, whereas in summerunder the same conditions only 16 per cent.is so lost. Duringrestitution, the resynthesis of glycogen in the muscle is independentof the season, but during winter if is in part masked by the con-current diminution of liver glycogen.As remarked abovc, the past year’s work does not record anyimportant advance in the purely chemical study of intermediatecarbohydrate metabolism in the muscle. Laquer and Meyer findthat fresh frog’s muscle produces lactic acid more readily fromglycogen than from a numbcr of other carbohydrates tested ;1 2 vulose, starch, dextrose, and mannose follow in order of decreasinglactic acid yield, whilst no acid was produced from galactose,sorbose, sucrose, ma1 tose, -diamylose, tetra-amylose, and inulin.The mechanism by which part of the lactic acid is oxidised duringthe recovery process is still obscure, but Hirsch claims to havedetected acetaldehyde as an intermediate product.Not unrelated to the production of lactic acid from carbohydratein muscle are the observations recorded by Anrep and Cannan *on thc concentrations of lactic acid in the blood in experimentalarllralEmia and acidzmia.It will be remembered that Macleodmid his collaborators showed that administration of alkali maycause an increase of lactic acid in the blood and urine, an increaseof glycoIysis in blood, and a decrease in blood-sugar concentration.Proc. PhysioZ. SOC., J . Physiol., 1923, 57, Isvii.Biochem. Z., 1923, 140, 577; A . , i, 1154.Pftiiger’s Arcluiv, 1920, 185, 20.Z. physiol. Chem., 1923, 124, 211; A., i, 268.J.Physiol., 1923, 58, 244.Amer. J . Physiol., 1917, 42, 193, 460; 1918, 47, 180.’ B~OC~CWL. Z., 1922, 134, 415; A., i, 415198 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Moreover, Macleod 10 also recorded some experiments on lactic acidin anoxaemia. As Anrep and Cannan point out, the interpretationof the results is complicated by the fact that in t,hese experimentsthe anoxaemia was accompanied by a lack of carbon dioxide.Employing a technique providing adequate control on this point,Anrep and Cannan report that the concentration of lactic acidrises when the alkalinity of the blood is increased, and falls againwhen the reaction moves towards acidity. The concentrationof lactic acid in the blood would seem to be primarily dependenton the reaction of the blood rather than on the tension of oxygenor carbon dioxide.The mechanism of the removal of lactic acidfrom the blood, and in part also its appearance in the blood, isresident in the tissues. The authors view this mechanism asanother line of defence by which the organism can protect itselfagainst excessive changes in the reaction of the blood.8pecific Bacterial Substances.Some few years ago it was shown by Dochez and Avery l1 thata substance is present in cultures of pneumococci grown in fluidmedia which precipitates specifically in anti-pneutnococcus serumof the homologous type.The presence of this soluble substance is best demonstratedduring the initial period of rapid growth of the organisms in culture,and can also be detected in the blood and urine both of experi-mentally infected animals and of human patients suffering fromlobar pneumonia.The substance is not destroyed by boiling. Itis readily precipitated from aqueous solution by acetone, alcohol,ether, or colloidal iron, and does not pass through a dialysingmembrane, whilst the serological reactions are not affected bydigestion by trypsin. Naturally, the authors regarded such asubstance as an ideal starting point for a study of the relationbetween bacterial specificity and chemical constitution. RecentlyZinsser and Parker l2 have described the preparation from filteredalkaline extracts of various pulverised bacteria, amongst thempneumococci, of substances which appear to be free from coagul-able protein, which they term " residual antigens." These sub-stances show specific precipitation with homologous antisera,and are regarded by their discoverers as being related to the sub-stance described by Dochez and Avery. Zinsser and Parker were,however, unable to produoe anti-bodies by injecting their " residualantigens " into animals. Heidelberger and Avery l3 now describethe preparation of the specific Substance from cultures of pneumo-l 1 J . Exper. Med., 1917, 26, 477.l3 Ibid., 1922, 38, 73.lo Amer. J . Physioz., 1921, 55, 18-3.12 Ibid., 1933, 37, 275PHYSIOLOGICAL CHEMISTRY. 199cocci, and a method by which the crude material may be con-siderably purified so as to concentrate its specific properties. Bythe method outlined, it is possible to obtain about 1 gram of materialfrom 75 litres of broth culture, and the preparation is a colourless,varnish-like mass.As remarked before, this product is unaffected by heating a t100”. Furthermore the method of preparation eliminates allsubstances precipitable by phosphotungstic acid or giving a biurettest. No claim is made that the final product is a chemical entity,but the remarkably interesting fact is established that it consistsvery largely of a polysaccharide yielding glucose on hydrolysis.Whilst our general knowledge of the properties of “ active prin-ciples ” naturally leads us to think of such a product as an “ adsorp-tion complex,’’ the fact that its specific activity increases as puri-fication raises the carbohydrate content of the material suggeststhat the polysaccharide may actually be the soluble specific sub-stance. Attempts to stimulate anti-body production by theimmunisation of animals with the purified substance yielded negativeresults. It is interesting to note that this substance is chemicallyanalogous to the bacterial ‘‘ gum ” described by other investi-gators,l4 and which is apparently derived from the capsule. Ina later paper, Avery and HeidelbergerI5 present evidence thatin the cell of pneumococcus there may be at least two distinctsubstances which are intimately concerned with its biologic speci-ficity. One of these is the specific soluble substance describedabove, whilst the second is a protein fraction which they haveisolated by precipitation from extracts of pneumococci by aceticacid. This material appears to consist of nucleoprotein andmucoid, and to exhibit species specificity rather than the typespecificity shown by the carbohydrate preparation.J. C. DRUMMOND.14 KramBr, Centr. Bakt., 1922, 8’4, 401, and earIier Iiterature.1 5 J . Exper. Med., 1923, 38, 81

ISSN:0365-6217    

DOI:10.1039/AR9232000177

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

AGRICULTURAL CHEMISTRY AND VEGETABLEPHYSIOLOGY.IN this Report the general arrangement of subject matter is thegame as that adopted last year, following the more or less logicalsequence of : the soil and soil phenonema per se; the influence of@oil and related factors on plant growth; the biochemistry of theliving plant ; the constituents of the plant.Unfortunately, the amount of material calling for commentunder these headings has proved to be so large that it has not beenpossible this year to devote any space to enzyme action and thebiochemistry of micro-organisms (apart from soil micro-organisms).A discussion of the very considerable amount of work which has beencarried out in these fields of the subject during the past year or twowould swell this Report to prohibitive dimensions.In any case,the subject is at present developing rapidly, and it is better to deferfor another year a critical discussion of the position, by whichtime it will probably be easier to pick out the main advances fromthe large mass of experimental facts.As in former years, this Report should be read in conjunctionwith that to the Society of Chemical Industry on “ Soils andFertilisers.” In the latter Report an attempt has been made todeal with all the more technical aspects of the subject, including t,hechemistry, analysis, and agricultural applications of fertilisers, andlaboratory methods for the examination and analysis of soils,leaving for this Report a consideration of the more theoreticalaspects of the subject.T h e S o i l .Xoil Colloids.Modern work on soils is tending more and more to take specialaccount of the colloidal matter in soils and its influence on t>heirproperties.The weathering of ininerals and the chemical denudation of soilshave hitherto been considered almost entirely from the point ofview of the removal of the products of weathering in true solution,and the accumulation of insoluble colloidal alumino-silicates in theresidue.Whitney,l however, has pointed out the possibility thatchemical erosion is not a selective process, that is to say, that inthe breaking down of silicates to a point a t which, say, potassium200M. MThitney, Science, 1922, 56, 216; A., i, 80AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 201goes into true solution, silica, alumina, and iron may also go intocolloidal solution in the same proportion as they bear to the potassiumcontent of the original material. Further investigations will benecessary to decide this point.The amount of potassium broughtinto solution from finely ground (200-mesh) orthoclase by watertreatment was found by Haley to be considerable; the potash sodissolved was readily available to buckwheat plants in sand cultures.The constitution of the inorganic colloids, known as the clay orthe " colloidal clay," in the soil has been a subject of considerablespeculation. The view was formerly held that zeolites existed inthe soil, but for lack of satisfactory evidence this idea is now generallydiscounted, although it still crops up from time to time, as in thecase of a paper by Scurti,3 who seeks to explain certain soil propertiesin terms of the properties of the natural ,zeolites. Although theexistence in the soil of actual zeolites as such has not been proved,recent work shows quite clearly that in such phenomena as absorptionand basic exchange there is evidence for the existence in the soiI ofcolloids with reactive acidic groupings, which may be regarded asanalogous to zeolites in many ways.This aspect of the subject isdiscussed more fully on pp. 204-207.The colloidal material extracted from a heavy clay soil has beenexamined by B~-adfield.~ The analyses of the material indicatedthat the natural colloid might be composed' of the completelybroken down products of weathering, that is, colloidal silica, alumina,and ferric hydroxide, but on comparison of the natural colloid witha synthetic mixture of these three colloidal materials, it was foundthat the two behaved quite differently with regard to cataphoresis,buffer action, and towards electrolytes.The inorganic colloid ofthe soil evidently consists mainly of a complex, readily decom-posable alumino-silicate .The effect of the soil colloids on the physical properties of the soil iswell illustrated by the work of Haines 5 and of Hardy on theshrinkage of soils 6n drying. The latter worker interprets his resultson the assumption that the colloidal gel coating around the soilparticles possesses a reticulate structure; at the point of saturationthe hydrogel contains water in two phases, one of water absorbedin the walls of the gel and the other filling the vesicles of the gel.'The shrinkage of soils and clays on drying is supposed to be dueD.E. Haley, Soil Sci., 1923, 15, 167; A., i, 888.F. Scurti, Ann. Chim. Appl., 1923, 13, 161; A., i, 1047.R. BradfkId, Missouri Agr. Exp. Sta. Research Bulletin, 60, 1023.W. B. Haines, J . Agric. Sci., 1923, 13, 296. 6 F. Hardy, ibid., p. 243.7 See also Wilsdon, Mem. Dept. Agri. India, Chem. Xer., 1921, 6, 3, whohas advanced similar views with regard to the structure of the colloidalmaterial in the soil.H202 ANNUAL REPORTS ON TEE PROGRESS OF CHEMISTRY.solely to loss of vesicular water. Hardy has also applied the samehypothesis to a study of the maximum water-retaining capacityand certain other soil moisture constants.8 He urges the importanceof recognising the specificity of soil colloidal material, as illustratedby the marked difference in physical behaviour between clay soilscontaining hydrophilous siliceous colloids which swell greatly whenwetted, and lateritic soils the colloid of which consists mainly ofalumina and ferric oxide hydrogels, which do not exhibit markedswelling on wetting.E.A. Fisher has published some interesting and suggestive paperson the evaporation of water from soil, clay, and other material^.^Using the elegant experimental method originally devised by Keen, lohe has studied the characteristic curvature which is exhibited bythe curve for the rate of evaporation of moisture from soils.Thisourvature was ascribed by Keen, and by Fisher in his earlier papers,to the shrinkage of the colloid as it dried, with a resultant diminutionof evaporating surface. It has now been found, however, that ballclay, which also exhibits shrinkage on drying, does not give anevaporation curve with the characteristic curvature shown by thatfor soil, and it is concluded that this particular type of curvature ischaracteristic of the evaporation curves of such materials as soilwhich are mixtures of colloidal and non-colloidal substances, andthat it is due to the simultaneous evaporation of imbibitional waterheld by the colloid and of interstitial water wedges between the soilgrains. The former water evaporates at a practically constant rate,whilst the latter evaporates a t a rapidly diminishing rate, curvaturein the evaporation curve resulting.Fisher’s “ imbibitional ” waterevidently corresponds to what is termed “ vesicular ” water byWilsdon and Hardy.The flocculation of colloidal clay has been studied by Bradfield,llwho finds that flocculation is brought about by many common acidsa t about the same hydrogen-ion concentration.The absorption of electrolytes by soils and the part played bythe soil colloids in this process are being extensively studied in theBureau of Soils of the U.S. Department of Agriculture. It hasbeen shown that, except for the most highly micaceous soils, inwhich the non-colloidal absorption might reach 10-20 per cent.ofthe whole soil absorption, less than 5 per cent. of the total absorptionof the soil is due to the non-colloidal part.12 Absorption by non-F. Hardy, J . Agric. Sci., 1923, 13, 340.E; A. Fisher, Proc. Roy. SOC., 1923, [A], 103, 139, 664; J . Agric. Sci.,1923, 18, 121.lo B. A. Keen, J . Agric. Sci., 1914, 6, 456.l1 R. Bradfield, J . Amer. Chem. SOC., 1923, 46, 1243; A., ii, 470.l2 M. S. Anderson, W. H. Fry, P. L. Gile, H. E. Middleton, and W. 0.Robinson, U.S. Dept. Agr. Bull., 1922, 1122, 1-20; A , , i, 283AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 203colloidal constituents should therefore not seriously affect absorptionmethods for estimating the amount of colloids in soil. In the samelaboratory, the absorption of electrolytes by silica, alumina, andferric hydroxide gels is being studied with regard to their bearingon the properties of soils,13 but in view of the results of Bradfield(see p.201) it is evident that the application of the results to theinterpretation of soil phenomena must be carried out with caution.The absorption of phosphates by the soil probably depends onsomewhat different factors from those governing the absorption ofbases. Fraps 14 has studied the influence of various factors on theprocess. His results appear to indicate that iron and aluminiumoxides have a more important effect than lime on the fixation.The organic matter of the soil is also of importance. Auten l5 hasfound considerable amounts of phosphorus in the soil in organiccombination, not in the form of nucleic acid, phytin, lecithin, orpyrimidine nucleotides, but apparently in an amphoteric organiccomplex, in combination with calcium and magnesium, or otherbases.The chemical properties of the inorgarhic colloids of the soil have animportant bearing on the phenomena of absorption, basic exchange,and acidity in soils.The colloidal coating on the surface of themineral soil particles must be supposed to consist largely of a gelcomposed of complex aluminosilicic acids, containing reactive acidgroupings which are saturated to a greater or less degree by bases.Some time ago Gans (now known as Ganssen) put forward thehypothesis that it was possible to deduce, from the molecularproportion of silica, alumina, and bases in the colloidal clay of thesod, the solubility of the nutrient materials in, and the manurialneeds of the soil.According to his view, if the molecular ratioSiO, : A1,0, : bases (CaO, MgO, K,O, Na,O) is 3 or more : 1 : 1, thesoil is absorptively saturated or neutral, an active exchange of thebases takes place between the salts in the soil solution and thecolloidal clay, and the soil is fertile. If, however, the ratio is 3 ormore : 1 : less than 1, the soil is acid and the salts in the soil solutionarc decomposed with absorption of the kation; and the soil is nolonger fertile.16 A number of heavy clay soils have been inves-tigated from this point of view by Tacke and Arnd,17 who found thatl3 R. C. Wiley and N. E. Gbrdon, Soil Sci., 1922, 14, 441; A., i, 524;E. B.Starkey and N. E. Gordon, ibid., 449; A., i, 523; D. C. Lichtenwalner,A. L. FIenner, and N. E. Gordon, ibid., 1923, 15, 157; A., i, 888.G. S. Fraps, Texas Agr. Expt. Sta. Bull., 1922, No. 304; A., i, 1167See also G. Leoncini and F. A. Rogai, Agr. Ituliana, 1922, 45, Nos. 4-6,109; A., i, 1167. l5 J. T. Auten, Soil Sci., 1923, 16, 281; A., i, 176.l6 See R. Ganssen (Gans), 2. PfEanz. Dihg, 1923, 11, A , 370, wheroreferences to his earlier papers are also given.l7 B. Tacke and T. Arnd, Internat. Mitt. Bodenkunde, 1923,13, 6.IF* 20.1 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.t’he known manurial needs of these soils could not be correlated withthe molecular ratio of SiQ, : Al,O, : bases in the above manner.We can, however, leave the question of the molecular compositionof the alumino-silicic complex for the time being, and pass on to aconsideration of the chemical properties of that complex as a whole.The affinity for kations which finds expression in the phenomena ofsoil acidity, basic exchange, and absorption may be regarded as achemical affinity due to acidic groupings in the colloid.It is possiblefrom this point of view to interpret most of the above phenomena onthe basis of chemical reactions under stoicheiometrical relationshipsand subject to the laws of mass action, due regard being paid to t,heimplications of the fact that one of the reactive ions forms part ofa colloidal phase, which is thus akin to a colloidal electrolyte.There is, in fact, in modern views a swinging back towards the ideasof the presence in soils of reactive silicates, as originally advancedby Way,l* with the important difference that the colloidal natureof those silicates is also taken into account.This may perhaps beregarded as a logical outcome of modern views as to the nature ofthe forces involved in interfacial phenomena ; improved knowledgeof the nature of molecular forces is tending to sweep away the olderideas as to the sharpness of the distinction between so-called physicaladsorptions and chemical reactions.Bradfield l9 has found that the same amount of a suspeiision of anacid colloidal clay was required to neutralise equivalent quantitiesof calcium or sodium hydroxide, using electrometric and con-ductometric methods of determining the end-point. The cohduc-tivity curves, which were of the type usually obtained in titratinga strong base with a weak acid, exhibited definite breaks, indicatingthe neutralisation of definite acids, which in 1 per cent.solutionshad concentrations ranging, for four different clays, from 0.0027to 0.0037N. It is therefore concluded that the reaction betweenacid colloidal clays and strong bases is an ordinary neutralisationand that recourse to a theory of (physical) adsorption is unnecessary.It is now definitely established that, when a soil is treated with asolution of a neutral salt, the interchange of kations between thesolution and the reactive colloids of the soil takes place accordingto stoicheiometric laws, so that the amount of the kation of theneutral salt that disappears from the solution is chemically equivalentt o the amount of the kations that leave the colloid and appear inthe solution.Moreover, the amount of the absorbed * ion, and ofl8 J. T. Way, J . Roy. Agric. SOC. Eng., 1850, 11, 313; 1852, 13, 123.la R. Bradfield, J. Amr. Chem. SOC., 1923, 45, 2669.MI The word cc absorbed ” is used here and in the following discussion merelyas a convenient method of referring to the bases hold by the soil colloids in thefashion indicated aboveAGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 205the replaced ions, at equilibrium, is an exponential function of theequilibrium concentration of the replacing ion in the solution, thesereactions conforming to the general type of Freundlich’s absorptioncurves and equations.If, however, the soil is continually treatedwith fresh portions of the original neutral salt solution, the equili-brium is continually disturbed, and ultimately the whole of theoriginally absorbed kations will be removed from the soil. Thisforms the basis of the method developed by Hissink 2o for fhe deter-mination of the replaceable bases in the soil, which seems likely toprove of considerable value in the study of the fertility and fertiliserrequirements of soils.It is obvious from the above relationships that when the soil istreated with a solutlion of a neutral salt, the soil colloids undergo achange which is rcciprocal to that of the solution. Thus when theoriginal concentration of the neutral salt solution is greater thanthat which would be in equilibrium with the kations absorbed bythe soil colloids, the decrease in concentration of the kation of theneutral salt in the solution is accompanied by an increase in theconcentration of that kation in the colloidal phase.When thereaction is carried to an end by continual treatment with theoriginal salt solution, the colloidal phase will then be saturated withthe kations of the neutral salt. By the application of these viewsto the special case of the action of sodium salts on soils, considerablelight is thrown on the genesis of sodium carbonate in “ alkali ” soils,and on the processes operative in the conversion of a saline soil intoan “ alkali ” soil. I n a normal fertile soil containing a sufficiencyof lime, the colloidal phase contains a large proportion of calcium-ions, and the resulting complex appears to be a stable gel.Ontreatment with sodium salts, the absorbed calcium is replaced to ztgreat extent by sodium. In the presence of excess of sodium salts,this sodium-clay complex is stable, but on removal of the excess ofsodium salts by washing, the sodium-clay complex readily hydrolyseswith the production of sodium hydroxide, which is rapidly convertedinto sodium carbonate by the carbon dioxide in the soil atmosphere.Although work somewhat along these lines was carried out in Franceas long ago as 1888 by MondBsir,21 priority in the detailed develop-ment of these views must be given to Gedroiz, whose work has beenrather overlooked by most soil investigators owing to its having beenpublished only in Later, D~minicis,~~ Pre~cott,~3a and2O See Ann.Rep. Appl. Chem. (SOC. Chem. Ind.), 1921, 6, 415; also SoilSci., 1923, 15, 269; A., i, 992.21 P. de Mondesir, Compt. rend., 1888, 160, 459.22 K. K. Gedroiz,Zhur.Opit. Agron., 1912,13,363; 1914,15,181; 1016, $7,472,23 A. de Dominicis, Staz. Sper. Agr. Ital., 1918, 41, 103.33% J. A. Yrescott, Cairo rSci. J., 1922, lo, 68206 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Hissink 24 put forward very similar ideas, the latter worker havingapplied them in a suggestive manner to the soil problems arisingin the reclamation of land from the sea in Holland. More recently,in California, Cummins and Kelley 25 have made a special study ofthe formation of sodium carbonate in soils, with special reference tothe " black alkali" soils which are of only too common occurrencein that and other parts of the United States.They even succeededin converting an acid soil into an alkaline one by treatment withsodium chloride followed by washing with water. The position iswell summarised by these authors in the following quotation fromtheir paper :" By essentially chemical processes, probably due to differencesin their respective electrolytic solution potentials, sodium hasbeen shown to replace a part of the calcium from the soil silicatesreadily and rapidly. When the concentration of sodium in solutioni s high and the calcium set free can be readily removed, a relativelyhigh degree of saturation with sodium may occur.The physicalproperties of the new sodium silicate combinations are diflerentfrom those of the original calcium-silicate compounds, and are sopronounced as to alter profoundly the characteristics of the entiresoil mass.The sodium ' absorbates,' 80 called, are much less stable thanthe corresponding calcium compounds. They are probably colloidalin nature, but this has not been established and is not a necessarymsumption for an explanation of their behaviour. Their importantproperty is that of slowly hydrolysing in the absence of strongelectrolytes. Hydrolytic equilibrium is not rapidly established innature because the hydroxyl-ions resulting from hydrolysis arereadily removed by the CO, in the soil atmosphere.This favoursthe decomposition of the ' absorbates ' and the development ofalkalinity. Calcium carbonate may also favour the removal of thehydroxyl-ions ." The other product of the hydrolysis, the silicate complex,shows a tendency to be present in a colloidal state. This, as iswell recognised, may be an important factor favouring slowhydrolysis. Furthermore, reactions between the soluble hydrolyticproducts and the colloid probably favour a high degree of dispersionand account for the marked change in the physical properties of thesoil. These striking changes in the physical properties of the soilswere always observed associated or coincident with the develop-ment of alkalinity, and constitute one of the most important aspects24 L O C .cit. (20).26 A. B. Cummins and W. P. Kelley, Univ. Calif. Publications, Techn.Paper, No. 3, 1923. See also W. P. Kelley and E. E. Thomas, ibid., No. 1,1923; W. P. Kelley and A, B, Cumrnins, Soil Sci., 1921, 11, 139AQRICULTUBAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 207of the phenomenon. The characteristic hardness and imperme-ability of many alkaline soils may be ascribed to the presence ofsodium ‘ absorbates,’ or the products of their hydrolysis.“Lessons may be drawn from these studies as to the propertreatment of saline soils. Leaching alone may be expected tolower the concentration of soluble salts, but in some cases, a t least,a deterioration of the land may be expected, partly to offset thisadvantage.In such cases some means must be provided to preventthe hydrolysis of the sodium ‘ absorbates ’ with their attendantdeflocculation.“Any means of preventing hydrolysis during and after theremoval of the soluble salts,such as the addition of soluble aluminium,ferrous and ferric salts, acids and organic matter, may be expectedto be beneficial. There may be some objection to the use of someof these substances, however, since the soil may be left in an un-favourable condition for crop growth. Moreover, none of thesematerials can correct the fundamental mischief caused by the originalsodium salts, i.e., they cannot restore the calcium to its originalposition in the active soil silicates. The importance of calcium inthe silicate-complexes of the soil in maintaining a desirablephysical and chemical medium for plant growth can hardly be over-emphasised. Soluble calcium salts should not, therefore, beignored in the practical reclamation of saline lands.”26Reference may also be made to a paper by Ssokolowski 27 inwhich the importance of the replaceable calcium in the colloidalsilicates of the soil, and the association of the latter with humicsubstances, are emphasised ; also to an interesting discussion byHager 28 in which special attention is given to the relative influenceof the absorbed calcinm- and sodium-ions on the flocculation of soilcolloids and the physical condition of the soil.Soil acidity, in connexion with which so much work has been donein the past few years, may also be regarded in some of its phases asa function of the reactivity of the colloidal silicate complex in thesoil, on the lines first developed by Daikuhara 29 and developed byRice 30 and many subsequent workers .31 The almost universalpresence of soluble compounds of iron and aluminium, and sometimesof manganese, in acid soils is now a generally accepted fact, whichforms the basis of the well-known and widely adopted Comber test 3a26 In this connexion, see also F.S. Harris, M. D. Thomas, and D. W. Pitt-man, J . Agric. Res., 1923, 24, 317.2 7 A. N. Ssokolowski, Internat. Mitt. Bodenkunde, 1923, 13, 81.2 8 G. Hager, 2. Pflanz. Dung., 1923, 2, A , 292; A., i, 1047.2o G. Daikuhara, Bull. Imp. Central Agric. Expt. Sta. Tokio, 1914, 2, 1.a0 F. E.Rice, J. Physical Chem., 1916, 20, 214.31 See Ann. Rep., 1916, 13, 224; 1918, 15, 177; 1920, 1’9, 178; 1922,32 See Ann. Rep. Appl. Chem. (SOC. Chern. Ind.), 1923, 8.19, 213208 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.for sour soils. In an acid, or, as Ramann termed it, an “ absorp-tively unsaturated ” it may be supposed that the affinities ofthe reactive groups of the colloidal silicates are only satisfied to aminor extent by absorbed basic ions (for example, Ca”), the bulkof the absorbed ions being those of hydrogen. The exchange whichoccurs when such a soil is treated with a neutral salt may be supposedto result either in the primary liberation of hydrogen-ions, solubleiron and aluminium salts then appearing as a secondary effect dueto the action of the acid on the aluminosilicate, or the iron andaluminium compounds may be liberated actually by direct exchangewith the neutral salt.Until we have a much more precise knowledge of the chemicalnature of the reactive silicates in the soil, it is not possible to decideas to the exact mechanism of the reaction.In practice, the im-portant point is the undoubted fact that soluble iron and aluminiumcompounds occur in acid soils. Most of the investigations on soilacidity, the results of which have been published in the past year,deal with this aspect of the subject ; 34 attention may also be directedto Mukherjee’s hypothesis regarding the nature of soil acidity,35which is somewhat similar to the views formerly put forward byOddn to account for similar phenomena in peat.36 Willis hasstudied certain North Carolina soils which are very rich in organicmatter (“ muck ” soils), and is of the opinion that the acidity ofthese soils is due to nitric acid produced by vigorous nitrification.37The influence of soil reaction on plant growth is discussed on p.218.The Soil Solution.Attention was directed in last year’s Report 38 to the doubtwhich exists as to whether it is possible to isolate, from a soil wellsupplied with colloidal matter, a solution of which the compositionreally corresponds to that of the soil solution in situ. These con-siderations do not apply so strongly to relatively coarse soils contain-ing little clay. Working on soils of this type and using the Parkerdisplacement method39 with the addition of positive air pressureon the displacing liquid, Burd and Martin40 have obtained resultsconfirming the results of Parker, in that successive portions of thedisplaced fluid were of constant composition and conductivity.33 E.Ramann, “ Bodenkunde ” (Berlin, Parey), 1911, p. 242.34 T. Okazawa, Rilcwagaku Kenkyujo Iho, 1923, 2, 189; A., ii, 693; P. S.Burgess, SoiE Sci., 1923, 15, 131, 407; A,, i, 1047; W. T. McGeorge, ibid.,16, 195; A., i, 1275; H. Liesegang, Landw. Vew-Stat., 1922, 99, 191.96 J. N. Mukherjee, Nature, 1922, 110, 732; A., i, 79.36 S. Odh, KoEZ. Chern. Beihefte, 11, Ileft 3-9 (Die Huminsawen), p. 141.3 7 L. G. Willis, N . Carolina Agr. Exp. Eta. Technical Bull., No. 24, 1923.38 Ann. Rep., 1922, 19, 211.39 F.W. Parker, SoiE Sci., 1921, 12, 209; A., i, 914.40 J. S. Burd and J. C. Martin, J . Agric. Sci., 1923, 13, 265AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 209They also found an inverse proportionality between the totalmoisture content of the soil and the concentration of the displacedsolution as indicated by specific electrical resistance. Moreover,when the solution displaced by water from a given mass of soil wasitself used as a displacing agent on another portion of the same soil,the newly displaced solution had the same concentration of elec-trolytes as the displacing solution. This is taken as showing thatthe displaced solution corresponds in composition to the soil solutionin situ. These investigators also carried out a comparison of thecomposition of soil-water extracts with that of the “ soil solution ’’displaced from the soil a t different water contents. From thiscomparison, it appears probable, (1) that the concentration of certainions, notably chlorine, nitrate, and calcium, in the soil solution insitu varies inversely as the moisture content, that is to say, the wholeof the chlorine and nitrate exists in the soil in a state of solution,together with an equivalent amount of calcium; (2) that theconcentration of phosphate in the soil solution in situ is constant forvarying moisture contents of the soil, representing a saturation value.This value, however, varies widely from soil to soil; (3) that theconcentration of potassium in the soil solution in situ is higher in asoil with a low moisture content than in the same soil with a highermoisture content, but not proportionally so.This fact appears toindicate an equilibrium between the potash in the liquid and solidphases, conforming to the general type of Freundlich’s absorptionequations.Tulaikov and Kuzmin 41 have described a method of expressingsolution from the soil by the use of mechanical pressure combinedwith suction. Using the older pressure method of Ramann and VanZyl, Groh 42 has studied the concentration of calcium in the expressedsolution, and the influence of season and crops on the results obtained.The Humic Matter of the Soil.Eller and his co-workers have carried out an interesting investig-ation of the properties of the artificial “ humic acids ” produced bythe oxidation of phenols43 in comparison with those produced bythe action of dilute acids on carbohydrates, and with natural humicacids.44 He advances strong evidence in support of his view thatthe latter substances are closely related to those produced fromphenols, and distinct from those produced from carbohydrates.The arguments advanced earlier by Eller against the presence of4 1 N.M. Tulaikov and M. S. Kuzmin, Soil Sci., 1923, 15, 235; A., i, 992.42 A. W. Groh, Int. Mitt. Bodenkunde, 1923, 13, 107.43 Compare Ann. Rep., 1922, 19, 204.44 W. Eller, Annalen, 1923, 431, 133; A., i, 542; W. Eller, H. Meyer,and H. Saenger, ibid., p. 162; A., i, 543; W. Eller, E. Herdieckerhoff, andH. Saenger, ibid., p.177 ; A., i, 544. See also P. Stamberger, Naturprodukte,1923, 108; A., i, 1006210 ANNUAL REPORTS ON THE PROGRESB OF CHEMISTRY.furan nuclei in humic acid are, however,.not accepted as valid byMarcu~son.~~ Fuchs46 is of the opinion that natural humic acidcontains both furan and phenol nuclei; he alsQ concludes, from thefact that it can be methylated in alkaline solutions without beingprecipitated, that it contains both phenolic hydroxyl and carboxylgroups. Fischer and Schrader's hypothesis, which regards ligninas the parent substance of humic acid,*' is somewhat supported bythe work of Pictet and Gaulis48 on the vacuum distillation oflignin.All these conflicting views as to the nature of humic acid are moreor less reconciled by an interesting sugges-tion by S c h r a ~ t h , ~ ~ who regards the funda-mental unit of lignin as consisting of theannexed nucleus, which besides containing0 1 .-------------.--..--- _ _ three phenolic hydroxyl groups (in the\/%/\/'cH2 keto-form) also contains, as shown by theI / I d dotted lines, three w-hydroxymethyl furfuralnuc1ei.m This is no more than a workinghypothesis at present, but its further : co'*.* CH,O ( p LI ' * * ~ J 9/\><\,/'\,poH2%,-development will be awaited with intere~t.~lBiochemical Changes in the Soil.The Nitrogen Cycle.-An interesting study of various phases of thenitrogen cycle-nitrogen fixation, nitrification, losses of nitrogen-and of biological activity as measured by the evolution of carbondioxide, in an acid soil in Assam, has been published by Meggitt.62The effect of various climatic and soil factors on these processes,and on the nitrogen economy of the soil, under tropical conditionsis well brought out.The fixation of nitrogen by Axotobacter has been investigated byHunter,53 Gainey,54 Johnson and L i ~ m a n , ~ ~ V O ~ C U , ~ ~ and Truf€aut45 J.Marcusson, 2. angew. Chem., 1923, 36, 42; compare A , , 1921, ii, 690;1922, i, 437 ; 1923, i, 353.46 W. Fuchs, Naturprodukte, 1923, 98; A., i, 1006.47 H. Fischer and H. Schrader, Brenmtofl-Chem., 1921, 2, 3.48 A. Pictet and M. Gaulis, Helv. Chim. Acta, 1923, 6, 627; A., i, 758.49 W. Schrauth, Brennetoff-Chem., 1923, 4, 161; gl., ii, 502.60 C. F. Beckley, J . Agric. Sci., 1921, 11, 66; A., i, 227.51 For a fuller discussion of the nature of the humification process and of62 A.A. Meggitt, Mem. Dept. Agr. India, Chem. Ser., 1923, i, 31.53 0. W. Hunter, J . Agric. Res., 1923, 23, 665; 24, 263; A., i, 985;54 P. L. Gainey, ibid., 24,185 ; A., i, 881 ; P. L. Gainey and H. W. Batchelor,6 5 H. W. Johnson and C . B. Lipman, Univ. Califwnia Pub. Agr. Sci.,66 J. Voicu, Co7rvpt. rend., 1923, 176, 1421; A., i, 735.its relation to coal formation, see H. J. Page, FueZ, 1923, August, p. 232.ibid., 1923, 23, 825.ibid., p. 759; P. L. Gainey, ibid., p. 289, 907; A . , i, 1166.1922, 4, 397 ; A., i, 633AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 21 1and Bezs~onoff.~~ Hunter found that growth was increased byGration, and that the protein content of the cells wits thereby almosttrebled. In continuation of earlier work, Gainey has shown thatsoils with a hydrogen-ion concentration greater than that corre-sponding to pH 6.0 cannot support the growth of Azotobacter, andthat the most favourable reaction for nit$rogen fixation is pH 6.5,although Johnson and Lipman 55 placed this value between pH 7.0and 8.0.These investigators found, however, that between pE6-2 and 8.8 there was but little variation in the amounts of nitrogenfixed, but that outside this range slight changes in pH caused anabrupt decrease in fixation. Voicu has shown that humus has amarked stimulating effect on the fixation of nitrogen by Azotobacter,whilst Truffaut and Bezssonoff find that the development of thisorganism and also that of BaciZZus TruJfuuti, both aerobic organisms,are most favoured by concentrations of sugar of the order of 0-1per cent.rather than by higher concentrations, the converse beingtrue of the corresponding anaerobic bacilli.as a result of which he claimed to have shownthat green alga were able to assimilate atmospheric nitrogen in thepresence of nitrates, has been critically repeated by Bristol andPage 59 a t Rothamsted. These investigators entirely failed toobtain evidence of any fixation of nitrogen by green algae, althoughthe conditions of the experiment were as nearly as possible identicalwith those used by Wann. Moreover, they showed that the methodsof analysis used by Wann were faulty, and that it was possible toexplain the whole of the apparent fixation in Wann’s results asdue to analytical errors.Whilst still admitting the possibility thatgreen alga might fix atmospheric nitrogen: they point out that thereis still no conclusive evidence in favour of the occurrence of thisaction. The function of the green alga in the soil must thereforebe sought in some other direction.Nasir 80 has obtained evidence that the fixation of nitrogen byAzotobacter in liquid or sand cultures is stimulated by the presenceof soil protozoa.Unlike nitrogen fixation and nitrification, the process of ammoni-fication is not brought about by a specific organism or group oforganisms, but by a large number of different species of bacteriaand also by fungi. Abbott 61 has isolated twenty-eight species offungi, representing twelve genera, from five Iowa soils.With twoexceptions all the species showed vigorous ammonifying power.The work of57 G. Truffaut and N. Bezssonoff, ibid., 1923, 177, 649; A., i, 1268.5 8 F. B. Wann, Amer. J . Bot., 1922, 8, 1.50 (Miss) B. M. Bristol and H. J. Page, Ann. Appl. Biol., 1923, 10, 378.60 S. M. Nasir, Ann. Appl. Biol., 1923, 10, 122.61 E. V. Abbott,-Soil-Sd., 1923, 16, 207; A., i, 1167212 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Soil moulds are very tolerant of acid conditions, as illustrated bythe work of Johnson,62 so that they probably play an importantpart in ammonification in sour soils. Waksman G3 has studied theammonifying power of various soils in solution and in the soil itself ;he concludes that owing to the variety of the organisms concerned,and to the fact that the process is influenced by so many otherfactors, ammonification in solution or in soil cannot be used as anindex of soil fertility, From a study of the nitrifying power ofvarious soils, however, the same investigator 64 concludes that thispower is in general an indication of the productivity of the soil.The mechanism of the bact'erial nitrification process, wherebyammonia is oxidised f i s t to nitrous and then to nitric acid, has upto now resisted all attempts a t its elucidation.The existence of anextracellular ammonia-oxidising enzyme or " nitroxidase," wherebythe organism is supposed to convert ammonia into nitrous acid, hasnever been demonstrated.Bonazzi,65 however, has now carriedout a suggestive investigation using a pure culture of an active formof Nitrosococcus, in which he has shown (1) that the ratio O / N ,where 0 is the quantity of oxygen absorbed by the culture, and Nis the quantity of nitrogen nitrified, both expressed as gram-atoms,is equal to 3, which is in accordance with the symbolisation of theprocess as NH, + 3 0 --+ HNO, + H,O; (2) that iron, which isknown to be essential to the action, is reduced from the ferric to theferrous state, in active cultures ; (3) that in faintly alkaline solutionhydrogen peroxide is able to oxidise ammonium salts to nitrites ;(4) that although no evidence can be obtained for the existence ofeither a peroxide or a peroxydase in the culture liquid itself, a culturecontaining active Nitros?coccus or even the dead bacterial cells,killed and washed by treatment with acetone and ether, canunder alkaline conditions catalyse the decomposition of hydrogenperoxide, but this property is lost after heating, On the basis ofthese results, Bonazzi formulates the following hypothesis : ironexists in the bacterial cell in the ferrous state, in which form it actsas an oxygen carrier owing to its ready conversion into ferrous oxideperoxide ; accepting Bach and Chodat's conception of oxydaseaction, it is concluded that the iron by its mechanism of auto-oxidation fulfils the functions of the peroxide, whilst the breakdownof this peroxide with liberation of " active '' oxygen is accomplishedby a mechanism inherent in the cell itself-an intracellular per-oxydase.The evidence is a t present rather circumstantial, but thehypothesis is an attractive one, and will no doubt serve as a valuablestimulus to further work.H. W. Johnson, Iowa Agr. Sta. Research Bull., 76, 1923.63 S. A. Waksman, Soil Sci., 1923, 15, 49.64 Idem, ibid., 16, 55. 6 6 A. Bonazzi, J . Bact., 1923, 8, 343AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 213The autotrophic character of the nitrifying organisms in liquidcultures, whereby they derive their carbon from carbon dioxide,with the aid of the energy liberated in the oxidation of ammonia,is an important factor in the process. The bearing of this factor onthe gaseous exchange of the organism does not appear to have beenconsidered by Bonazzi, although it would appear probable that apart of the oxygen utilised for the conversion of ammonia intonitrate would be derived from that liberated from the carbon dioxidein its assimilation by the organism.This oxygen would be so tosay “ internal,” and would not figure on the gaseous exchange. I nview, however, of the fact that the ratio of ammonia nitrogenoxidised to carbon assimilated was found by Winogradsky to be ofthe order of 35,66 this factor would not seriously affect the validityof the conclusions Bonazzi drew from the value found by him forthe ratio O/N in the gaseous exchange; it might even account forthe slight defect of the experimental value (2.89 0.08) from thetheoretical value of 3.0.The nitrate content of the soil a t any time is the resultant oftwo opposing sets of factors, one set being concerned with the pro-duction of nitrate, and the other with its removal.It is well knownthat the soil shows a seasonal fluctuation in its nitrate content,maxima occurring in the spring and autumn, and minima in winterand summer. Schoiibrunn 67 concludes from the results of aninvestigation into this question that these seasonal fluctuations areconditioned solely by seasonal changes in the environmentalfactors such as soil temperature, rainfall, and so on, and that thereis no inhereizt periodicity in these processes. Schonbrunn’s work andconclusions have been, however, strongly assailed by Lohnis 68 who,whilst admitting the influence of environmental factors, is of theopinion that there is some evidence also for an inherent seasonalperiodicity in the activity of the organisms themselves.Other factors that influence the credit side of the nitrogen balancesheet are the reaction of the soil and the content of salts.Meekand Lipman 69 have shown that the nitrifying organisms are particu-larly resistant to hydroxyl-ions, surviving in a medium of pH 13,and remaining active in a medium of p a 11. Among various sodiumsalts tested, sodium sulphate was not nearly so toxic as sodiumchloride or sodium carbonate.On the debit side of the nitrogen balance sheet there is a varietyof factors operative. I n addition to actual losses of nitrogen fromG G S. Winogradsky, Ann.Inst. Pasteur, 1890, 4, 213, 257.67 B. Schonbrunn, Zentr. Bakt. Par., 1922, 56, ii, 546; from Chem. Zentr.,8 8 F. Lohnis, Zentr. Bakt. Par., 1923, 58, ii, 207; from Chem. Zentr.,6v C. S. Meek and C. B. Lipman, J . Ben. Physiol., 1922, 6, 196; A,, i, 74.1923, I, 1606; A,, i, 1167.1923, I, 1606; A., i, 1167214 ANNUAL REPORTS ON THE PROGRBSS OF CHEMISTRY.the soil, such as those due to absorption by plants and to drainage,and to denitrifying organisms 70 and other processes which give riseto gaseous nitrogen, various biological processes result in the con-version of soluble nitrogen (nitrates) in the soil into insoluble formsnot immediately available for plant growth. This conversion occurspre-eminently when organic matter of low nitrogen content is addedto the soil, as illustrated by the effect of straw, which is confirmedby the results of Sievers.?l This type of action is regarded byLyon, Bizzell, and Wilson 72 as the cause of the well-known effectof growing plants in depressing nitrate accumulation in the soil toan extent greater than that accounted for by their own absorptionof nitrate; this effect has sometimes been regarded in the past as anindication of a depressing effect of the gmwing plant on nitrateformation, but the above investigators advance evidence in favourof the view that the organic matter derived from the roots of growingplants is often of low nitrogen content, and thus favourable to theaction of nitrate-consuming soil organisms, and that the variationin the depressive effect of different plants on nitrate accumulationmay be correlated with the variations in the nitrogen content of theorganic matter derived from their roots.In other words, the effectof the growing plant is not one of inhibition of nitrate production,but one of the stimulation of nitrate consumption, by soil organisms.The well-known effect of the growth of grass around fruit, trees, indepressing the vitality and yield of the trees, on which Pickeringdid so much work 73 has been studied by Lyon, Heinicke, andWilson,74 whose results appear to show that this effect also is due,a t least in part, to the biological conversion of nitrate into insolublenitrogen compounds in the soil in the manner just discussed, resultingin nitrogen starvation of the tree.It must be emphasised that processes of this type do not depletethe soil as a whole of nitrogen, but only of available nitrogen.Theyfigure in the nitrogen balance sheet as a transfer to capital accountrather than as an actual expenditure.The Sulphur Cycle.-The oxidation of sulphur to sulphuric acid inthe soil by specific autotrophic bacteria, which has been extensivelystudied by J. G. Lipman and his co-workers a t New Jersey,75 still70 See, for example, C. Lumia, Annali Chem. Appl., 1923, 7, 155.71 F. J. Sievers, Washington Agric. Expt. Sta. Bull., 1922, 167, 45; A.,'* T. L. Lyon, J. A. Bizzell, and B. D. Wilson, J . Amer. SOC. Agron., 1923,73 S. U. Pickering and the Duke of Bedford, Reports of Woburn Expt.74 T. H.Lyon, A. J. Heinicke, and B. D. Wilson, Corndl Univ. Agri. Expt.7 5 See Ann. Rep., 1922, 19, 209.i, 1048.15, 457.Fruit Farm, 3rd Report, 1903; 13th Report, 1911; 14th Report, 1914.&a. Memoir 63, 1923.See also J. A. Bizzell, ibid., 1922, 14, 320; A., i, 522AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 215provokes a considerable amount of research.76 Waksman andStarkey 77 have studied the growth and respiration of Sulphornonasthio-oxidans. They find that in the oxidation of sulphur and ofsodium thiosulphate the ratio of sulphur oxidised and carbon dioxidereduced is 31.8 and 64-2, respectively. Lipman and Waksman 78have also described an analogous group of autotrophic bacteria whichoxidise selenium to selenic acid.Phosphates have been shown to be liberated from nucleo-proteinsand their breakdown products by various soil bacteria (nucleo-b a ~ t e r ) .~ ~Partial Xteri1isation.-Broadly speaking, the effect of partialsterilisation on the soil is the resultant of four main groups of factors,thus :(1) The removal of factors inimical to the growth of bacteria.(2) The direct liberation of plant food from the soil by the actionof the partial sterilising agent.(3) The direct stimulation of the growth of certain groups ofbacteria by the feeding effect on them of the sterilising agent itself(for example, phenol).(4) The removal of factors inimical to plant growth (for example,plant disease organisms).Waksman has carried out a series of investigations 80 with a viewto the elucidation of the relative importance of these factors.Heconcludes from his results that the part played by the soil fungi ismore important than is generally realised; he ascribes the limit-ation of bacterial numbers in untreated soil largely to the competitionfor nutrient material between the fungi and the bacteria. The soilfungi are very greatly reduced in numbers on partial sterilisation,and the bacteria are thus, in his view, enabled to multiply to muchgreater numbers when free from the competitive action of thefungi. He considers that although protozoa may limif; bacterialdevelopment in abnormal soils such as greenhouse soils, such aninhibition is improbable in ordinary soils. Against this, however,must be reckoned the fact that Cutler, Cruup, and Sandon *l wereable to demonstrate the inverse relationship between the number of'13 See, for example, H.0. Brown, J. Amer. SOC. Agron., 1923, 15, 350.See also Ann. Rep. Appl. Chem. (Soc. Chem. Ind.), 1923, 8, where the practicalapplications are discussed.7 7 S. A. Waksman and R. L. Starkey, J . Qen. Physiol., 1923, 5, 285; A.,i, 273.J. G. Lipman and S. A. Waksman, Science, 1923, 67, 60; A., i, 735.Om A. Koch and A. Oelsner, Biochem. Z., 1922, 134, 76; A., i, 422.*O S. A. Waksman and R. L. Starkey, Soil Sci., 1923, 16, 137, 247, 343;81 See Ann. Rep., 1922, 19, 218.A., i, 1167216 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.protozoa and bacteria in a field soil; further, Cutler 82 has nowshown that the same phenomenon can be demonstrated by the in-oculation of sterilised field soil with bacteria alone and with a mixtureof bacteria and protozoa.Where bacteria alone were used, thenumbers remained high, but when protozoa were also added, thenumbers of bacteria fell very considerably. From these facts itwould appear that protozoa cannot be left out of account as a factorlimiting bacterial numbers in field soils.Baldwin 83 has studied the effect of crude petroleum on the soilmicro-flora, and on ammonification and nitrification.Other Soil Constituents.Griffiths-Jones 84 has found that t'he titanium content of Nilesilt is from 1.3-2-5 per cent. Wester 85 has studied the manganesecontent of some Duttch soils, which varied from a trace up to 120 mg.per 100 grams of dried soil.Generally the more fertile soils werericher in manganese than the less fertile.Kunz-Krause 86 has described the occurrence of a greyish-bluecoloration on arable soil near Dresden. This he ascribes to thepresence of blue basic ferric ferrous phosphate (vivianite) formedfrom colourless ferrous phosphate by oxidation in air.Iron and manganese, together with humic substances, wouldappear to be the agents chiefly responsible for the power of soils todecompose hydrogen peroxide, the effect of bacteria and of enzymesbeing less important. 87T h e Soil as a Medium for Plant Growth.So far in this Report we have dealt with soil processes and pro-perties, per se, mainly without reference to the plant. The influenceof soil and associated factors on the growing plant will next beconsidered.The concentration of the soil solution has an important effect onplant growth.This has been studied by T u l a i k o ~ . ~ ~ There isan optimum value for plant growth, and an increase above thisoptimum caused delayed germination of seeds and weakened growthof seedlings ; it also caused in his experiments on cereals an increasednitrogen content of the crop and a greater hardness of the grain.The characteristic hardness of wheat from Russia and the arida2 D. W. Cutler, Ann. Appl. Biol., 1923, 10.83 I. L. Baldwin, Soil Sci., 1922, 14, 465.E. Griffiths-Jones, Anulyst, 1923, 48, 320.a5 D. H. Wester, Phurrn. Weekblad, 1923, 60, 446; A., i, 640. See also86 H. Kunz-Krause, Ber. Deut. pharm.Ges., 1923, 83, 20; A., ii, 325.8' S. Osugi, Ber. Ohara Inst. Landw. Forsch., 1922, 2, 197; A,, i, 524.*@ N. M. Tulaikov, Soil Sci., 1923, 16, 229;; A., i, 992.Internat. Mitt. Bodenkunde, 1923, 13, 1AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 217regions of the United States is regarded by this investigator as dueto the high osmotic pressure of the soil solution in those areas.Shive 90 has studied the inter-relation between the osmotic pressureof the soil solution and the ratio of the various ions (‘‘ physiologicalbalance”) with regard to their effect on the yield. The mostfavourable physiological balance is about the same for appreciablevariations in total concentration. Variations of the latter type arejust as important as changes in the physiological balance, from thepoint of view of crop yield; the effect of unfavourable moistureconditions cannot be counteracted by altering the physiologicalbalance by special fertiliser treatment.glA special case of the influence of the ratio of the different basesin the soil on plant growth is the so-called “ potash lime law ” ofEhrenberg,92 according to which the amount of potash taken up bythe plant is reduced by treatment with lime, so that in soils whichare poor in potash liming may depress the crop.Fischerg3 hasstudied this phenomenon in pot experiments with various crops ;in general, his results confirm Ehrenberg’s conclusions.It is commonly supposed that sodium can replace potassium to acertain extent in plants, seeing that in soils which are potash starved,manuring with sodium salts usually gives bigger yields than when it isomitted.This may be partly due to liberation of potash fron thesoil by basic exchange (see p. 204), but this does not appear toexplain the whole effect. Sodium chloride seems to have a beneficialeffect on some leguminous crops ; in the case of lucerne this has beendemonstrated by Lomanitz 94 in water culture, where basic exchangephenomena are excluded, whilst a somewhat analogous result is thatobtained with red clover by Emerson and Barton,95 who found thatthe potassium of kainit, which contains a large excess of sodiumchloride, was more readily absorbed than that of high grade chlorideor sulphate of potash. Marschhaupt 96 found, however, that in thecase of turnips the potash content fell with increasing quantity ofsodium in the soil, and vice versa.Sodium chloride is usuallysupposed to have a favourable effect on the development of sugarbeet--a plant of maritime origin-but Meyer 97 could find no9O J. W. Shive, ibid., 1922, 14, 391; A., i, 283.91 For other work on similar lines, see A. L. Bakko and L.. W. Erdman,Amer. J . Bot., 1923, 10, 18; New Mexico Agr. Expt. Sta. Ann. Rep., 1921,24 ; A., i, 1048.S2 P. Ehrenberg, Landw. Jahrb., 1919, 54, 4.93 W. Fischer, ibid., 1923, 58, 1. 94 S. Lomanitz, Soil Sci., 1923, 16, 183.g5 P. Emerson and J. Barton, J. Amer. SOC. Agron., 1922, 14, 182; A.,96 J. G. Marschhaupt, Versl. Landbouwk. Onclers. Rijklundbouwproefstat.,9 7 D. Meyer, 2.P/lunz. Dung., 1923, 2, B, 44G.i, 522.Sept., 1923218 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.evidence for such an effect in his experiments. In all work ofthis sort the type of soil and the species of plant have such animportant influence on the result that the conflicting results oftenobtained by different investigators are not a t all surprising.The relation of the hydrogen-ion concentration of the soil to plantgrowth is a complex one. Although there can be no question of thedirect toxic effect of an excessive concentration of hydrogen- orhydroxyl-i~ns,~~ opinions differ with regard to the nature of thetoxicity in cases where that concentration is not excessive, althoughstill appreciable. The effect may still be a direct one, as supposedby O l ~ e n , ~ ~ the concentration of hydrogen- or hydroxyl-ions in-fluencing the absorption of nutrient salts by the plant root, or itmay be due to secondary effects, owing to the correlation of the soilreaction with the concentration of nutrient or toxic substances inthe soil solution. This latter alternative is illustrated by the vieworiginally advanced by Hartwell and Pember,l who suggested thatthe toxicity of acid soils was due to the soluble aluminium theycontained.This view is gaining ground, especially in the UnitedStates,2 iron and manganese being included in the same category asaluminium. Although the concentration of soluble iron in a soursoil may thus be so high as to be toxic, in an alkaline soil the positionmay be reversed, and the iron may be rendered so insoluble thatchlorosis occurs in the plant.This is shown by the work of Willisand Carrero? Barnettc and Shive? and Jones and S h i ~ e , ~ in whichis also illustrated the important difference between a " physio-logically alkaline " fertiliser like nitrate of soda, which leaves analkaline residue in the soil and thus tends to cause chlorosis, and a" physiologically acid " fertiliser like sulphate of ammonia, whichdoes not cause chlorosis, but which, if used continually in absenceof lime, sets up excessively acid conditions. Reference may alsobe made to the use of physiologically acid fertilisers in conjunotionwith insoluble phosphates a8 a means of improving the availabilityof the latter.GSee, for example, 0.C. Bryan, Soil Sci., 1923,15, 376.O9 C. Olsen, Compt. rend. Trav. Lab. CUd8beTg, 1923, 15, 1; A., i, 522.See also A. P. Kelley, Soil Sci., 1923, 16, 41.Hartwell and Pember, Soil Sci., 1914, 6, 259. * J. W. Kelly, J . Agric. Res., 1923, 23, 223; R. H. Cam and P. H. Brewer,Id. Eng. Chem., 1923, 15, 634; A,, i, 1275; A. W. Blai and A. L. Prince,Soil Sci,, 1923, 15, 109; P. L. GiIe, J . Arner. SOC. Agron., 1923, 15, 305.3 L. G. Willis and J. 0. Carrero, J. Agric. Bee., 1923, 24, 621.R. M. Barnette and J. W. Shive, Soil Sci., 1923,. 15, 413.L. H. Jones and J. W. Shive, Ann. Bot., 1923, 37, 355; A., i, 1043.For other workon the question of soil reaction, see A. Gehring and F. Sander, 2. Pflanz.Diing., 1923, 11, B, 299; F. Munter, ibid., p.289.6 See Ann. Rep. Appl. Chem. (SOC. Chem. Ind.), 1923, 8AQR,ICULTURAL CHEMISTRY AND VEQETABLB PHYSIOLOQP. 219Atkins 7 has brought forward evidence that the influence of soilacidity in causing the flowers of the hydrangea to become blue mayalso be due to the increased availability of the iron in such a soil,the iron taken up by the plant giving a blue complex with theanthocyanin flower pigment.A sufficient supply of oxygen to the plant root is known to benecessary for healthy growth. The rate at which oxygen can reachthe root through the soil depends on the physical condition of thesoil and its moisture content. Hutchins and Livingstone * havedescribed an apparatus for measuring the oxygen-supplying powerof the soil, based on diffusion into a porous cylinder buried in thesoil, the oxgyen being continually swept out of the cylinder by aninert gas, and passed through alkaline pyrogallol.Stirnulctnts and Toxic Agents.-In the case of certain elements onecannot a t present discriminate between the alternative possibilitiesof their acting as true plant nutrients, or as stimulants, the latterterm being used merely in the sense of indicating that the cause ofthe stimulating effect of the element in question is unknown.Additional support for the view that silica is of value to theplant 9 is afforded by the results of Schollenberger.10 Boron haslong been known to exert a toxic effect on plants above a certainconcentration ; 11 as a result of recent work a t Rothamsted, however,Miss Warrington l2 has demonstrated that small amounts of boronare not merely stimulating, but essential for the development ofthe broad bean and certain other leguminous plants, when grown inwater culture.The results are very striking : very marked responseis observed at concentrations of boric acid ranging from I : 25,000to as low a9 1 : 12,500,000. The same results are not usuallyobtained in soil cultures owing to the common occurrence of boronin most ordinary soils. For other crops, such as barley, there is noevidence that boron is necessary.There is already evidence that manganese is of value to the plant,in minimal concentration^,^^ although in higher concentrations it isharmful. This is supported by the results of McHargue,I4 whofinds that leguminous plants are specially responsive, and of Picadoand Vi~ente.1~ According to Rippel,16 the toxic effect of higher7 W.R. G. Atkins, Sci. Proc. Roy. Dubl. SOC., 1923, 17, 201; A., i, 1162.@ L. M. Hutchins and B. E. Livingstone, J . Agric. Res., 1923, 25, 133 ;A., ii, 66.See Ann. Rep., 1922, 19, 215.lo C. J. Schollenberger, Soil Sci., 1922, 14, 347.l1 See, e.g., J. J. Skinner and F. E. Allison, J . Agric. Rm., 1923, 23, 433.l2 K. Warington, Ann. Bot., 1923, 37, 629; A,, i, 1274.l3 See W. E. Brenchley, Ann. Bot., 1910, 24, 521.l 4 J. S. McHargue, J . Agric. Res., 1923, 24, 781; A., i, 1160.l6 A. Rippel, Be'ochern. Z., 1923, 140, 316; A., i, 1160.E. Picado and E. Vicente, Ann. Inst. Pasteur, 1923,37, 891; A., i, 1276220 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.concentrations of manganese is due to iron chlorosis , the manganeseapparently influencing, not the intake of iron, but its availabilityafter absorption by the plant.The assimilation by the broad beanof lead, which is toxic in concentrations of NjlO or above, has beenstudied by Hevesy 17 by a method depending on the admixture withthe lead salt of a radioactive isotope (thorium B), the amount oflead taken up being estimated by measuring the radioactive intensityof the ash.report the result of pot experiments from whichit appears that the growth of mustard, peas, and lucerne was stimu-lated by the addition to the soil of titanium in the form of sodiumtitanate or titanocitrate.Hexamethylenetetramine is a nutrient €or the broad bean in smalldoses, but in higher concentrations than 0.3 gram per litre it is toxic.19In the soil it is readily broken down into ammonia by soilNgmec and K&3T’he Chemistry of t h e Living P l a n t .Carbon Assimi1ntioia.-The formation of formaldehyde fromcarbon dioxide solutions by the action of sunlight in presence ofcolloidal oxides of uranium or ferric iron, as observed by Moore.andWebster 21 and conflrmed by Baly, Heilbron, and Barker,22 couldnot be detected by Baur and Rebmann.23 Similarly, Spoehr 24could not repeat Baly, Heilbron, and Barker’s observation of theaction of ultra-violet light in causing the formation of formaldehydefrom carbon dioxide in aqueous solution.The latter investigators ,however; have repeated their earlier work with the same results asbefore, and they suggest that Spoehr’s failure may have been dueto deterioration of the quartz mercury lamp employed.25Maquenne z6 has put forward a theory of chlorophyllic photo-synthesis which is supposed to get over the difficulty that the presenceof formaldehyde in plants has never been indubitably proved.Histheory depends on the assumption of a combination of carbon dioxide1 7 G. Hovesy, Biochem,. J., 1923, 17, 439; A., i, 11GO.A. Namec and V. KSB, Biochenz. Z., 1923, 140, 583; A . , i, 1161.1 9 E. Nicolas and G. Nicolas, Compt. rend., 1922, 175, 836; 176, 40420 E. Blanch, ’CV. Geilrnann, and F. Giesecke, J . Landto., 1922, 70, 2212 1 B. Moore and T. A. Webster, Proc Boy.SOC., 2913, [B), 87,163; A . , 1913,22 T., 1921, 119, 1025.z3 E. Baur and A. Rebmann, Helv. Chim. Acta, 1922, 5, 828; A., i, 91.24 H. A. Spoehr, J . Amer. Chem. SOC., 1923, 45, 1184; A., ii, 452.25 E. C. C. Baly, I. M. Heilbron, and W. F. Barker, Nature, 1923, 112, 328.26 L. Maquenne, Cornpt. rend., 1923, 177, 853; A., i, 1272.A., i, 77, 427.A . , i, 171.i, 1303AGRICULTURAL CHEMISTRY AXD VEGETABLE PHYSIOLOGY. 221with the magnesium atoms in the chlorophyll molecule ; the resultingcomplex is assumed to undergo isomeric change, followed by loss ofoxygen, polymerisation, and the splitting off of carbohydrate. Oneessential difference between this view and that of Baly and hisco-workers is that, according to the former, the polymerisation ofthe formaldehyde units is supposed to occur inside the chlorophyllcomplex, whereas Baly's view is that, although the carbon dioxidecombines with the chlorophyll, and is photocatalytically reduced toformaldehyde in virtue of that combination, the formaldehyde itselfis liberated in an active form (as H-C-OH) which immediatelypolymerises.Thunberg 27* has advanced another explanation of the mode offormation of formaldehyde; he supposes that the first action is thedecomposition of water by sunlight to give hydrogen peroxide andhydrogen.These then react with carbon dioxide to give methylencglycol, thus : GO, + H, + H,02 = H,CO, + 0,, and the methyleneglycol loses water to give formaldehyde. There is not a t presentsufficient experimental evidence available to enable the relativemerits of these rival hypotheses to be tested.The energetics of the reactions postulated by Thunberg have beendiscussed by Weigert,28 whilst Warburg and Negelein 29 haveinvestigated the influence of wavc-length on thc energy change ofcarbon dioxide assimilation in presence of chlorophyll.Bose 30 has shown that the photosynthetic activity of the aquaticplant Igydrilla verticillatn was very greatly increased by nitric acidin concentrations between 1 in 1O1O and 1 in 3 x lo9, Similarincreases were obtained by the application of dilute solutlions ofthyroid gland cxtract and of formaldehyde, the latter substanceproducing a marked effect in a concentration of 1 in lo9.Sabali-tschka 31 has described experiments from which it appears that thenasturtium and the water weed Elodea canadensis can fixformaldehyde and polymerise it to carbohydrate even in the absenceof light.Spoehr and McGee32 have published an account of a lengthyinvestigation on the inter-relation between photosynthesis andrespiration, from which they conclude that photosynthesis may be adual or coupled reaction.The original must be referred to for details.2 7 T. Thunberg, 2. plvysikal. Chem., 1923, 106, 308; R., i, 1271.2 * F. Weigert, ibid., p. 313; A., i, 1271.29 0. Warburg and E. Negelein, ibitl., p. 131 ; A., ii, 718.30 J. C. Bose, Nature, 1923, 112, 95; A., i, 1043. See also E. and G.31 T. Sabalitschka, 2. angew. Chew., 1922, 35, 684; A . , i, 76.32 H. A. Spoehr and J.M. McGee, C'arnegis I n s t . Pub., 1923, 325, 1; A,,Nicolas, Compt. rend., 1322, 175, 1437.i, 888222 ANNUAL REPORTS ON THE PROQRElSS OF CHEMISTRY.Mitscherlich has published a suggestive paper on the principlesunderlying the use of atmospheres artificially enriched with carbondioxide as a means of obtaining increased yields of plants.%Synthesis and Translocation of Complex Carbon and Nitrogen Com-pounds.-In continuation of their work on the photocatalytic forma-tion of nitrogen c0mpounds,3~ Baly and his co-workers 35 have nowstudied the action of activated formaldehyde on ammonia, both byexposing to ultra-violet light a solution of carbon dioxide in ammoniaand by the use of daylight and a solution of carbon dioxide inammoniacal cupric carbonate, the coloured copper-ammoniumcomplex acting as the photocatalytic energy transformer.Theyobtained in this way solutions from which they isolated methyl-amine, pyridine, and piperidine, and an alkaloidal base which theyclaim to have identified with coniine by chemical and physiologicaltests. These results have, however, been challenged by Snow andStone,36 who, whilst not denying the possibility of the photocatalyticformation of the. nitrogen compounds isolated by Baly, adduceevidence that they may have been the result of secondary reactionsduring the operations used for working up the solutions, and thatthe identification of the coniine-like alkaloid was not conclusive.Baudisch, whose work on the interaction of nitrites with activatedformaldehyde to give f ormhydroxamic acid, methylamine, andamino-acids, etc., was confirmed by Baly and his co-w0rkers,3~ hasstudied the mechanism of the reduction of nitrates t o nitrites,38 inwhich he claims to show that iron plays an essential part.Prianischnikov39 has further developed his earlier theories onthe nitrogen metabolism of plants.Asparagine is held to perform thesame function in plant metabohm as urea in animal metabolism. Inseedling plants receiving $mmonium salts, the amount of asparagineformed depends on the amount of carbohydrate available. Amino-acids and proteins are supposed to be formed from asparagine inpresence of carbohydrates, and the process is held to be reversible,so that in absence of carbohydrates degradation of protein toasparagine or glutamine and fhally to ammonia occurs.Similarviews are advanced by S m i r n ~ v . ~ ~ Roberts41 has shown, in theFor a discussionof the practical aspects of this question, see Ann. Rep. Appl. Chem. (SOC.Chem. Ind.), 1923, 8. 34 See Ann. Rep., 1922, 19, 220.33 E. A. Mitscherlich, 2. Pflanz. Diing., 1923, 2, A , 211.as E. C. C. Baly, I. M. Heilbron, and H. J. Stern, T., 1923, 123, 185.3~3 0. W. Snow and J. F. S. Stone, T., 1923, 123, 1609.8’ See Ann. Rep., 1922, 19, 220.8 8 0. Baudisch, Science, 1923, 57, 451; A., ii, 816.8s D. N. Prianischnikov, Landw. Versuchs-i?tat., 1922, 99, 267 ; A., i, 425 ;Ber. Deut. bot. Ges., 1922, 40, 242; A., i, 273.( 0 A. I. Smirnov, Biochem. Z., 1923, 13’4, 1; A., i, 636.4 1 R.H. Roberts, Proc. Amer. SOG. Hort. Sci., 1921, 143; fnom Ph’yE$Ol.Abstr., 1923, 8, 107; A., i, 884AGRIUULTUBAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 223case of apple trees, that carbohydrates decrease with an increase innitrogen content and vice versa. Chibnal42 concludes from areview of the literature that the withdrawal of nitrogen from theleaves of the plant occurs a t night. The movement of nitrogenand of carbohydrates in the wheat plant during growth andripening has been studied by Olsen 43 and by Colin and B e l ~ a l , ~ ~respectively.In 1920, Parker and Truog advanced the hypothesis that thereis an intimate relationship between the r62a of calcium andnitrogen in plant nutrition.45 They supposed that the synthesis ofprotein in plants involves the production of by-product organic acidswhich are neutralised and precipitated by calcium, so that the amountof calcium taken up is directly related to the amount of proteinformed in the plant.They instanced the case of leguminous plantswhich are high in calcium content as well as in nitrogen. Thishypothesis has now been tested by Newton.46 His results do notsupport it, since in water cultures the intake of calcium by suchplants as barley and peas was not proportional to the nitrogencontent. They explain the high calcium content of leguminousplants when grown on soil as due to the much larger amounts ofcarbon dioxide evolved by the roots of such plants, in comparisonwith non-legumes, this resulting in an increase in the solubility ofcalcium in the soil and thus in an increased calcium intake whichdoes not necessarily bear any relation to the nitrogen content.Although these arguments are not entirely conclusive, they renderfurther work necessary before Parker and Truog's hypothesia canbe accepted.Werner *' has directed attention to the presence of urease in theroot nodules of various leguminous plants, whilst Beijerinck 48has shown that urease is produced more profusely by pure culturesof Bacterium radicicob than by nodules.49 These results may haveanimportant bearing on the process of nitrogen fixation by the noduleorganism.Miss Semmens 50 has demonstrated a curious effect of plane-polarised light on the hydrolysis of starch in the mustard seed andalso of starch grains when acted on by diastase in vitro.Iljin5142 A. C . ChibnaI1, Ann. Bot., 1923, 37, 511; A., i, 1045.43 G. A. Olsen, J. Agric. Rm., 1923, 24, 939; A,, i, 1164.44 H. Colin and H. Belval, Compt. rend., 1922, 175, 1441; A,, i, 282.45 F. W. Parker and E. Truog, SoiZ Sci., 1920, 10, 49.4 6 J. D. Newton, ibid., 1923, 15, 181.4 7 E. A. Werner, Nature, 1923, 112, 202; A., i, 1046.4 8 M. W. Beijerinck, ibid., p. 439; A., i, 1157.49 See also H. E. Armstroag, Nature, 1923, 112, 620; A,, i, 1275.50 E. S. Semmens, Chemistry and Industry, 1923, 42, 954; A., ii, 718.61 W. S. Iljin, Biochern. Z., 1922, 132, 494, 611, 626; A., i, 172224 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.has studied the effect of various kations and anions on the hydrolysisand synthesis of starch in vegetable cells, and the antagonism betweenions in this process.Germination.-Baker and Hulton 52 and also Loibl 53 have dis-cussed the nature of the chemical changes involved in the mobilis-ittion of carbohydrate and nitrogen reserves in the germination ofcereal grains.Tamhane 54 has made a similar study of the germin-ation of safflower seed. Bach and Oparin 55 have investigated therate at which the content of respiratory and hydrolytic enzymesrises during the germination of wheat and sunflower seeds.From an investigation of the mobilisation of mineral substancesand nitrogen during the sprouting of shoots of Xumbucus ~aigru,Rippel 66 concludes that the potassium, phosphate, and nitrogenare strongly mobilised, magnesium and soda to a lesser extent, andcalcium, sulphur, and chlorine scarcely at all.Re.spiration.-Apparatus for the study of gaseous exchangeduring the respiration of plants and seeds has been described byFernandes 57 and by Harrington and Cr0cker.5~ Using theapparatus of the latter investigators, Harrington has studied therespiration of apple seeds under different condition^.^^ At theordinary temperature, the respiratory quotient corresponds tocomplete oxidation of fats or only slight increase in sugars; withadvancing germination the respiratory quotient becomes low,indicating the rapid transformation of fats and accumulation ofsugars.In series of papers 6o the effects of lactic acid, chloroform,hydrogen peroxide, ferric sulphate, and various other salts onrespiration have been investigated.It is concluded that lacticacid is not an intermediate substance in the metabolism of wheatseedlings, Analogies are also drawn between the effect of chloro-form on plant respiration and on the oxidation of organic acids byhydrogen peroxide and ferrous sulphate.62 J. L. Baker and H. F. E. Hulton, J . Inst. Brewing, 1923, 29, 824.53 H. Loibl, Z . ges. Brauwesen, 1923, 46, 30, 37, 45, 53, 61, 69; fromChem. Zentr., 1923, 111, 396; A., i, 1270.6 1 V. A. Tamhane, Mem. Dept. Agric. India, 1923, 6, 223; A., i, 883.65 A. Bach and A. Oparin, Biochem. Z., 1922, 134, 183; A., i, 425.66 A. Rippel, ibid., 1923, 135, 518; A., i, 521.6 7 D. S. Fernandes, Proc. K . Akad. Wetensch. Ameterdam, 1923, 26, 408;6 8 G.T. Hnrrington and W. Crocker, J . AgTic. Res., 1923, 23, 101; A.,59 G. T . Harrington, ibid., p. 117; A . , i, 421.60 E. 32. Smith, Arner. J . Eot., 1922, 9, 307; A . , i, 1270; G. B. Ray, J ,Gen. PliysioE., 1923, 5, 4G9, 611, 623; A., i, 520, 882; C. J. Lyon, ibid,, 1921.8, 458; A,, i, 1270.A., i, 1270.i, 424A~B;L~LTORAL CEEMISTRY AND VEQETABLE PEY SIOLOQY. 225Stoklasa 61 has studied the depression of the respiration of youngpine trees by sulphur dioxide.The loss of carbohydrate from grain during ripening has beenmeasured by McGinnis and Taylor 62 by the amount of carbondioxide evolved during respiration. The loss, which is con.siderable, reaches its maximum just before the drying off of the grain,when the moisture content is about 40 per cent.Osmotic Pheitornena : Permeability and the Absorption of Ions byPhnt Cdls.-In continuation of earlier work, Raber 63 has studiedthe mutual effects of ions on their penetration into cells of Laminaria,on the basis of which he attempts to explain by one general theory,based on a consideration of the charge on the membrane, the varioustypee of antagonism met with.Osterhout64 and Hoagland and Daviss5 have confirmed thefindhge of earlier investigations, that the fresh-water alga, NiteEZa,contains most of the inorganic elements of its cell sap in a dis-sociated form, and that these plant cells are able to cause the move-ment of ions from a solution of lower concentration to one of higherconcentration.Seeing that this process necessitates that the plantmugt do work in absorbing ions from dilute solutions, Hoagland andDavis 66 have studied the influence of light, as a source of energy,on the process, and they have shown that this absorption of ionsagaiast the concentration gradient is in fact favoured by illumin-ation.It is concluded that light supplies the energy necessary forthe transference of ions from a dilute solution into the more con-centrated cell sap. They have also demonstrated that even inextremely dilute solutions one ion can markedly influence the absorp-tion of another, as instanced by the depressing effect of chlorine-ions on the absorption of nitrate-ions. Osterhout has suggestedthat effects of antagonism may be relatively unimportant in verydilute solutions. According to this investigator antagonism isdefined as follows : " When toxic substances act as antidotes toeach other, this action is called antagonism." 67 According to thisdefinition, it would not be strictly correct to describe the above61 J.Stoklasa, (with J. Sebor, V. Zdobnickf, and V. Nekola), Biochem.Z., 1923, 136. 306; A., i, 621.63 F. W. McGinnis and G. S. Taylor, J . Agric. Res., 1923, 24, 1041; A.,i, 1164.6s 0. L. Raber, Proc. Nat. Acud. Sci., 1017, 3, 682; from Physiol. Abstr.,1923, 8, 315; A., i, 1274; The Botan. Gazette, 1923, 75, 298; from Physiol.Abatr., 1923, 8, 314; A., i, 1273.64 W. J. V. Osterhout, J . a n . Physiol., 1922, 5, 226; A., i, 76.65 D. R. Hortglsnd and A. R. Davie, ibid., 1923, 6, 629; A., i, 882.86 Idem, ibid., 1923, 6, 47; A., i, 1272.67 W.J. V. Osterhout, Soknce, 1916, 44, 318.REP.-VOL. XX. 226 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.observations made by Hoagland and Davis as antagonism, but fromthe point of view of nutrition and the general metabolism of theplant the latter phenomena are also of very great interest,.and theirinterpretation provides a fruitful field of research for the plantphysiologist .68The nature of the membrane must be taken into account in allinvestigations of this sort, and in this connexion the recent work ofLoeb with regard to ion-protein relations is probably significant,especially with regard to the marked influence of hydrogen-ionconcentration on permeability.On the basis of experiments on the absorption of water and aciddyes by potato tissue, Robbins advances the hypothesis that anampholyte, possibly a protein, plays the chief part in these processes,and that its isoelectric point is in the vicinity of pH 6.0.The bearingof this hypothesis on theories of permeability of the plasma membraneis discussed.P l a n t Constituents and Products.Inorganic Constituents.-McHargue 7O has found that themanganese content of the seeds of grasses and cereals is roughlyequal to that of iron, but in leguminous plants there is far more ironthan manganese. Schmidt and his co-workers have developed amethod for the removal of incrustive substances fro? plant tissues,depending on the use of 6 per cent. aqueous chloride dioxidesolution.'1 According to Freundler, Laurent, and Mhager, iodinemay be regarded as of importance in Laminaria in connexion withthe storage of reserve energy material.71"Organic Plant Products.-In this section the occurrence of organicsubstances in plants, and their constitution, are considered only sofar as they appear likely to give an insight into their mode of forma-tion in the plant. For references to the large number of papers dealingsolely with the occurrence of plant products, the index to thcJournal should be consulted, whilst work on the constitution ofplant products is dealt with in the Reports on Organic Chemistry.Carbohydrates.-Ling and Nanji 72 have made an important6 8 Other papers on permeability : S . PrBt, Biochem.Z., 1923,136,366; A., i,636; M . M. Brooks, Proc. Soc. Exp. Biol. Med., 1922, 20, 39, 384; U.S. PublicHealth Reports, 1923, 1449, 1470 ; A., i, 1273 ; W. Seifriz, Ann. Bot., 1923, 37,489; A., i, 1043. See also Newton, loc. cit.W . J. Robins, Amer. J . Bot., 1923, 10, 412.' 0 J. S. McHargue, J . Agric. Res., 1923, 23, 395; A . , i, 635.71 E. Schmidt and A. Mierster, Ber., 1923, 58, [B], 1438; E. Schmidt,E. Geisler, P. Arndt, and F. Ihlow, ibid., p. 23 ; A., i, 274.P. Freundler, (Mlle) Laurent, and (Mlle) MBnager, Bull. SOC. chirn.,1922, [iv], 31, 1341; A., i, 276.?* A. R. Ling and D. R. Nanji, T., 1923, 128, 2666AGRIUULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 227contribution to the problem of the constitution of starch, which isreferred to here owing to its important bearing on many plantproblems, although its discussion is outside the scope of this Report.Ling has also applied his method for the estimation of starch, topotatoes.73 Verhulst, Peterson, and Fred 74 suggest, from anexamination of the maize plant, tha6 pentosans are produced fromstarch.Tutin 75 advances evidence against the existence of " pro-topectin," which thus, in his opinion, cannot be the cause of thehardness of unripe fruit. Buston and Schryver 76 have isolated anew triose from cabbage leaves, to which they assign the constitutionOH*CH,-CH( OH)*O*CH,*OH ; they discuss the possible relation ofthis substance to anthocyanin formation.Pigrneizia.-Wlodek 77 has studied the influence of light and offertilisers on the chlorophyll coefficient (ratio of chlorophyll a tochlorophyll b) in the potato, sugar beet, and in Iris gerrnanica.Itis interesting to note that the coefficient falls, corresponding to anincrease in chlorophyll b, which is richer in oxygen than chlorophylla, during daylight, that is, during a time when, owing to photo-synthesis, oxygen is being liberated ; at night, when oxygen is beingused up by respiration, the proportion of chlorophyll b falls, thatof chlorophyll a, with less oxygen, rises. Lack of potassiumtends to diminish the amount of chlorophyll 6, and to iiicreascthat of chlorophyll a, whilst lack of nitrogen has the reverseeffect.Noack 78 has shown that the equilibrium in green plants betweenfiavonols and their reduction products, the anthocyanins, is normallyon the sidc of flavonol.If, howcver, assimilation is inhibited byinjury to the chloroplasts or otherwisc, anthocyanin is formed fromflavonols.AZkaZoids.-Annet and Bose 79 have fouiicl that the meconic acidcontent of Indian opium is roughly equivalent to that of the totalalkaloids present; they conclude that the latter exist in the latex73 A. R. Ling and W. J. Price, J. Inst. Brewing, 1923, 29, 732; A., 1922,ii, 879; 1923, ii, 702. Other papers on the subject are by Franz Tenipus,Naturprodukte, 1923, 52; G. I?. Walton and Mayne, R. Coe, J. Agric. Res.,1923, 12, 995; A., ii, 688.74 J. H. Verhulst, W. H. Peterson, and E. E. Fred, J. Agric. Res., 1923, 23,655; A., i, 638.76 F. Tutin, Biochem. J., 1923, 17, 510; A., i, 1162.'6 H.W. Buston and S. B. Schryver, ibicl., p. 470; A., i, 1062.7 7 J. Wlodek, Bull. Acad. polonuise Sci. let., Glasse Sci. Math. Nut., 1920,7 8 K. Noack, 2. Bot., 1922, 14, 1; from Chem. Zenty., 1923, I, 964; A., i,79 H. E. Annett end M. M. Bose, Mern. Dept. dgric. India, 1922, 6, 215;[B], 19; 1921, [B], 143; A., i, 1160, 1161.037. .A., i2 358.I228 ANNUAX REPORTS ON THE PROGRESS OF oHlEMIS!l?R~.wholly as meconates, the sulphates present being those ofmineral bases.Plant Enzymes.-Without here dealing with the more generalquestion of the mode of action of plant enzymes, papers publishedduring the year on their occurrence in plants may be referred to.Ling and Nanji so have demonstrated the presence of maltase, notonly in malt, whether green or kilned, but also in ungerminatedbarley, although in this case the enzyme is insoluble and its presencecan be demonstrated only by employing the ground barley instead ofan extract. As maltase is destroyed by alcohol, it is not presentin diastase preparations obtained by the addition of alcohol toaqueous extracts of malt.Sjoberg 81 found a very marked increase in amylase contentof seeds during ripening; he has also noted that the amylaseactivity of plants is usually greatest in the young leaves. Oparin 82states that increased partial pressure of oxygen is without effect onthe formation of enzymes during the germination of wheat grains,with the exception of oxygenase, which is inhibited. Conversely,replacement of oxygen by an inert gas such as hydrogen is inimicalto all the enzymes except oxygenase.Goris and Costy 83 have studied the distribution of urease * intwelve species of fungi. In all cases, the hymenium contained thegreatest proportion of the enzyme. Kato * claims to have shownthat urease consists of two constituents, one stable and the otherlabile to heat.According to Palladin and ManskajaB5 peroxydase occurs inplant cells not only in ths cell sap, but also associated with theprotoplast. Gallager 86 has demonstrated the presence in thepotato of an autoxidisable substance which appears to be akin tolecithin, and is concluded to be the so-called oxygenase of thepotato. In this connexion, it is interesting to note that Raper andWormall have shown that the acceleration of potato tyrosinaseby the addition of boiled potato juice is due, not to the inorganicconstituents, but to some organic activator. Annet 88 has found80 L4. R. Ling and D. R. Nariji, Biochem. J., 1923, 17, 593; A., i, 1162.Seo also L. Maquenne, Compt. rend., 1923, 176, 804; A., i, 442.81 K. Sjiiberg, Bz'ochem. Z., 1922, 133, 218; A., i, 275.s2 A. Oparin, ibid., 184, 190; A., i, 425.83 A. Goris and P. Costy, Compt. rend., 1922, 175, 998; 1923, 178, 412;84 N. KatB, Biochem. Z., 1923, 136, 498; 138, 352; A., i, 622, 1034.* j W. Palladin and (Frl.) S. Manskajrt, Biochem. Z., 1923, 135, 142; A.,8 6 1'. H. Gallagher, Biochem. J., 1923, 17, 615; A., i, 1159.8' H. S. Raper and A. Wormall, Ibia., p. 454; A., i, 1146.8 a H. E. Annett, ibid., 1922, 16, 763; A,, i, 281.A., 1922, i, 1220; A., i, 171, 405.i, 427AGRIUULTURAL CHEMISTRY AND VEGETABLE PHpsIoLouY. 229an oxydase in the latex of the Indian opium poppy, and suggeststhat the loss of morphine in dry opium powder on storage may bedue to the action of oxidising enzymes.Nemec and Duchon 89 have brought forward further evidence insupport of their view that the vitality of seeds is correlated withtheir catalase activity.Vitamins. -Coward 90 has further studied the factors controllingthe formation of vitamin-A in green plants. She finds t'hat lightis essential, but not ultra-violet light; the formation of thevitamin occurs in artificial light as well as in daylight. Thepresence of carbon dioxide and of oxygen in the surroundingatmosphere, of chlorophyll in the plant, and of more than traces ofcalcium in the nutrient solution, does not appear to be necessary,but the process is inhibited by chloroform. H. J. PAGE.89 A. N&mec and F. Duchon, A'nn. Sci. Agron., 1923, 40, 121.@O K. H. Coward, Biochem. J., 1923, 17, 134; A., i, 521

ISSN:0365-6217    

DOI:10.1039/AR9232000200

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

CRYSTALLOGRAPHY.THE scientific study of crystals and minerals has always been asubject which contributed to and borrowed from many neigh-bowing sciences, and perhaps the credit and debit have for a longtime nearly balanced. But in the last decade, owing to the intro-duction of the method of X-rays, crystallography has made suchrapid strides and assumed such outstanding importance that itscontributions to allied sciences are undoubtedly beginning to out -weigh its debt. The last few years have witnessed the practicalconfirmation of the theoretical basis of crystallography, and, fromthis point of view, the year 1923 is noteworthy in having broughtforward a large mass of useful evidence which has definitely madefor solid progress. The science has now attained a position fromwhich it can speak with authority.Structure Theory.Thirty years ago, the geometrical theory of crystallography foundits final expression, and the labours of Fedorov, Schoenfiies, andBarlow had succeeded in establishing that there are 230 types ofhomogeneous Structure to which the ultimate structural detailsof crystals must conform.Twenty more years elapsed before thereappeared a method capable of putting this purely geometricaltheory to the practical test. Naturally, the first workers in theX-ray an&lysis of crystals were physicists. These pioneers werewise in refraining from plunging deeply into a theory and nomen-clature which are nothing if not confusing to the uninitiated, andthe first results gave the relative positions of the atoms and mole-cules in simple terms familiar to all.This procedure was un-doubtedly the safest plan. It was this simple statement of resultsin terms of positions of atoms and molecules which showed thattheoretical crystallographers mere on the right track and whichindicated that the geometrjcal theory could be adopted unreservedly.The work of Fedorov, Schoenflies, and Barlow has been justified,and it is satisfactory to know that there is at hand a completetheory, tested and confirmed again and again, which can be usedfearlessly and yet in perfect harmony with a rapidly developingtechnique.In its essentials, the geometrical theory of crystallography treatsof systems of operations whereby infinite systems of points may23CRYSTALLOGRAPHY .231be brought to coincidence. From the physical point of view,these points, in the most general case, are simply correspondingpoints of asymmetric bodies with definite relative positions andorientations. Of the structure of the ultimate asymmetric bodiesthe theory takes no cognisance, and, of course, it is unaffectedby the substitution of a body of n-fold symmetry for n-asymmetricbodies of suitable positions and orientations.As was pointed out last year by Sir Wm. Bragg and G. Shearer,2it seems that Nature, for these structural bodies, has made useof the substance, if not always the form, of the individual chemicalmolecules. There is nothing in the theory against the use ofpolymerides of chemical molecules, but experiment has shown that,in the case of organic and non-ionised substances in general, thesimple chemical molecules are the ultimate structural bodies.Thecombination of this fact with the theory of space-groups leads a tonce to a knowledge of the symmetry of the molecule in thecrystalline state. This is a natural consequeiice of the fact thatthe theory is unaffected by the replacement of n-asymmetriobodies of suitable positions and orientations by another body ofn-fold symmetry. T. V. Barker3 has pointed out that E. vonFedorov in 1912 made similar proposals, and acknowledgment isdue to both for this. The definite advance is the recognition ofthe nature of the structural bodies to which the rules can beapplied, for, in reality, the latter have existed for thirty years,and are contained implicitly in the work of Fedorov, Schoenflies,and Barlow.The rule that the symmetry number of the molecules is obtainedby dividing the symmetry number of the class by the numberof molecules per (true) unit cell requires modification when weconsider the case of ionised molecules. There is little doubt thatsimple chemical molecules go to build up crystals, but often ina crystal, just as in a solution, it is impossible to associate anydefinite atomic group with the chemical molecule, for the simplereason that the features of the ionised solution are preserved inwhat we may call the ionised crystal.There is an equilibriumdistribution of positive and negative ions, and, as far as we cansee a t prescnt, the ordinary chemical forces are indistinguishablefrom the cohesive forces.It is impossible to describe any definiteion 5s belonging to another of opposite sign. In such circum-stances, it is clear that the unmodified rule does not apply, andit is necessary to fall back on the fundamental concept of thetheory of space-groups, that of systems of coincidence movements1 T., 1922, 121, 2'766. 2 Proc. Physical SOC., 1923, 35, (ii), Feb.4 2. Kryst. Min., 1912, 52, 22, Nature, 1923, 111, 632232 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.or symmetry operations. For instance, in a case like that ofczesium chloride, in which there is a czesium atom a t each cornerof a, cube and a chlorine atom in the middle, there is the substanceof one chemical molecule per cell and the whole structure has(probably) full cubic (48-fold) syrnmetry.We cannot point t o adefinite chemical molecule, and even if we could, it would clearlypossess less than the 48-fold symmetry which the rule demands.But yet the complete structure extended indefinitely is obviouslysubject to one (Oh’) of the 48-fold systems of coincidence oper-ations as defined by the theory of space-groups. The symmetryin this case cannot be approached from a less restricted point ofview. The ultimate structural body to which the rule now appliesis a positive ion surrounded by its shell of eight negative ions,or a negative ion surrounded by its shell of eight positive ions.We cannot in fairness consider anything smaller because of theimpossibility of stating definitely to which of the eight negativeions the included positive ion belongs.When considered fromthis point of view, the case is analogous to that of organic molecules.has analysed st largenumber of crystals is more convenient for the discussion of thosecrystals in which the chemical molecule is indistinguishable, sinceit is the analytical expression of the theory of space-groups.Wyckoff uses the co-ordinates of the equivalent points of thesystem, so specialised that certain sets coincide on elements ofsymmetry. By this means the number of equivalent points,starting from the most general case, is reduced step by step, where-upon it is found that for each number of equivalent points altern-ative cases present themselves.For details of this method, whichis largely used in America, reference should be made to Wyckoff’sbook and to various papers published in American scientificjournals. A simple example will here suffice, C.,’, the simplesttype of monoclinic domatic crystal. Two asymmetric bodieswhich are the reflections of each other are required to producethis symmetry. If, however, it were found that the unit cellcontained one molecule of a compound AB, it would not neoessazilyfollow that the AB molecule was symmetrical about a plane (asthe unmodified rule would suggest); for when we reduce, bycoincidence in a symmetry plane, the two equivalent points of thegroup C,’ to one equivalent point, two cases are derived, (a) inwhich AB lies in planes parallel to the symmetry plane (OlO),and ( b ) in which A lies in planes (010) while B lies in planes haH.way between the A-planes. This, in its simplest form, is theThe method by which R.W. G . Wyckoff“ The Analytical Expression of the Results of the Theory of Spaoe-Groups.”-Carnegie Inst. of Washington, Oct., 1922CBPSTALLOGRAPHY. 233method used by Wyckoff and his followers. It is the completeanalytical expression of the geometrical theory of crystallography.T. V. Barker 6 and J. W. Evans 7 have raised objections to theconsiderations put forward last year by Sir Wm. Bragg * andG. Shearer? but, when viewed from the point of view of the theory,the rules suggested cannot be refuted. On the other hand, Barker’scontention that the symmetry of the molecule does not necessarilyreveal itself in the symmetry of the structure must be consideredif only with a view to remove all misunderstanding. It has neverbeen claimed that the symmetry of a molecule in a crystal isidentical with the symmetry of that molecule in solution or inthe free state.Probably the latter symmetry is the greater ofthe two, but, in any case, a simple example of dimorphism likethat of calcite and aragonite shows that molecular symmetry iP,by no means unchangeable. In calcite, the carbonate group issymmetrical about a triad axis, whereas in aragonite it is not,Nevertheless, it must be remembered that it requires very littledistortion of a molecule to destroy its symmetry, and that it isnot at all likely that the act of crystallisation involves great dis-tortion.We must accordingly believe that, although the chemicalmolecule is not necessarily identical with the crystal molecule, itis not very far removed from it.The molecule as it exists in the crystal is part of the structure,and, by the theory of space-groups, its symmetry in the crystul ispart of the symmetry of the structure. This much is perfectlyclear, when there is no misunderstanding as to what is meant bythe symmetry in the crystal. The symmetry of the molecule inthe crystal is a property which is perceived only indirectly, thatis, Vice the symmetry of the structure as a, whole. It is merelythe symmetry of the immediate environment of the molecule, or,in other words, the symmetry of the points of contact with itsneighbours.Whether this can be considered as extending rightdown into the heart of the molecule is another question. In thecase of crystals of elements, diamond, for instance, it is not likelythat it extends any deeper than the outer shell of electrons, butsince it is probable that chemical molecules are built up from atomsby the agency of these outer electrons, it is difEcult to believethat a crystal molecule with symmetrically arranged environmentmay yet be completely asymmetric in the body of the molecule.Such a thing is not impossible, of course, but, physically speakhg,it appears highly improbable.Recently there have appeared several papers discussing thePTOC. Phyeical Soc., 1923, 85, (ii), Feb.Nature, 1923, 111, 632; 112, 96.T., 1922, 321, 2766.‘I Ibid., 1923, 111, 740.I234 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.question as to whether the criteria which have hitherto beenaccepted in crystallography are really safe guides to the truesymmetry of the structure.These criteria are such properties asfacial development, etched figures, piezo- and pyro-electric effects,etc., and before the advent of X-ray analysis a crystal was assignedto one of the thirty-two classes on the strength of such evidencealone. And there is no doubt that in the great majority of casesthe conclusion is correct. But now that so many crystal structureshave been analysed more or less completely, discrepancies havebeen found. In some cases, the symmetry of the structure asdeduced from X-ray analysis is different from that obtained fromthe ordinary crystallographic data.Cases in point are potassiumchloride and ammonium chloride, both of which have hithertobeen described as cubic holoaxial (class 29). The structure ofpotassium chloride is definitely known and to all appearances itis cubic holosymmetric (class 32), while, although the structure ofammonium chloride is not known with absolute certainty, thismuch is quite clear, that it belongs to one of the cubic classes whichare symmetrical about pkanes as well as axes, probably the hexakistetrahedral class, or if not that, then the holosymmetric class.An interesting paper on the subject has been contributed byE. T. Wherry,lO and the case of ammonium chloride has beendiscussed by R.W. G . Wyckoff.ll Apparently another exampleis afforded by CaS20,,6H,0,12 which has always been supposedto belong to the anorthic asymmetric class (1). The unit cell ofthis crystal contains two molecules which, by analogy with otheranorthic crystals and organic crystals in general, are the inversionsof each other, that is, the crystal really belongs to the anorthic pin-akoidal class (2). This conclusion is not absolutely certain, as it isbased on the hypothesis that single molecules are used instead ofpolymerides (a rule which has been found to hold in all othercases examined), but it must be allowed that the X-ray evidence isstrongly against the original crystallographic conclusion. We canget out of the difficulty in the case of potassium chloride byassuming that both the potassium- and the chlorine-ions possessonly cubic holoaxial symmetry, and for CaS,03,6H20 we can saythat a two-molecule polymeride has been used, but the case ofammonium chloride is not so easily dismissed and at present nosolution of the problem is forthcoming. T.V. Barker l3 haswritten at some length to protest against this tendency to ignorecrystallographic evidence, but he confesses his inability to explainthe divergence of ammonium chloride. For the rest, he suggests10 Amer. J. Science, Sept., 1022.1) W. T. Astbury, Nature, 1923, 112, 63.11 Ibid., 1922, [v], 4, 469.Ibin'd., p. 602CRYSTALLOGRAPHY. 235that the periodicity in the crystal structure that is revealed byX-rays is not necessarily the true periodicity of the structure,since (sic) it is generally accepted that the outer electrons do notappreciably scatfer the X-rays.There is no denying that whatBarker suggests may be true, but, as Sir Wm. Bragg l4 stated in hisreply, we must not forget that in diamond at least, the conclusionis that the outer electrons do scatter the rays, or how else can weexplain the observed tetrahedral symmetry of the atom? Suchevidence points to the fact that X-rays do detect the true periodicityand that for an explanation of the anomaly of ammonium chlorideand other crystals (diamond itself is one) we must look in otherdirections. The reason may be that the surface conditions ofcrystals are not always the same as those holding within the body,but for want of a more definite answer, the question for the presentmust be left subjudice.It has been mentioned above that the early workers in crystalanalysis by X-rays did not make use of the nomenclature of thetheory of space-groups. This procedure has been condemned byR.W. G. Wyckoff 15 in his " Survey of Existing Crystal StructureData," and unjust statements have been made. These have beenanswered elsewhere.16 Wyckoff has also published a paper con-demning the hypothesis of constant atomic radii,17 but here againit must be maintained that in the original paper on atomic radii l8110 such rigid. doctrine was ever advanced. It was pointed outthat there is an approximate additive law which may be helpfulin the study of complex structures, and that the curve obtainedby plotting the " radii " characteristic of the atoms resemblesLothar Meyer's curve of atomic volumes and is susceptible of aready explanation in terms of the Eewis-Langmuir theory ofchemical combination.Although characteristic numbers werecalculated for most of the elements, strict observance of thesewas never advocated. Indeed, it is not at all likely that the sameatom in different environment will occupy precisely the samespace. Wyckoff has recalculated the " atomic radii," startingfrom diff erent points, and he naturally finds large discrepancies.To quote from his paper, " these data conform t o the rule that inisomorphous crystals composed of only two kinds of atoms theinteratomic distances have additive properties which can beillustrated through a summing up of 'atomic radii.' The data,also show that for compounds of different crystal structures in1* W.T. Astbury, Nuture, 1923,112, 618.l5 J . Franklin Inst., 1923, 195, 183, 349, 531.la Sir W. H. Bragg, ibid., 1923, 196, 675.17 Proc. Nat. Acad. Sci., 1923, 9, 2, 33.l8 W. L. Bmgg, Phil. Mag., 1920, [vi], 40, 169.I" 236 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.which atomic environments are different, the interatomic distanceslikewise are unlike. Where the changes of environment arerelatively small, this change in interatomic distance may be almostnegligible; in other cases, it amounts to several tenths of anAngstrom unit.This is no doubt a correct conclusion, but when we rememberthat the real difficulty of crystal analysis begins where space-group theory ends and that we are far from being able to interpretcorrectly the various intensities of reflection, the good points ofthe hypothesis of constant atomic radii may not be so lightlydiscarded. In organic crystals especially is it useful (see below),for there is much evidence to show that 1.5 A.U.is nearly alwaysa good working value for the “ atomic diameter ” of carbon, and,in fact, in chain-compounds the influence of hydrogen appearsnegligible. Long rows of successive carbon atoms conform in aremarkable manner with the carbon “diameter ” found fromdiamond. T. W. Richards l9 has contributed a theoretical paperon the subject of atomic radii.Like Wyckoff, he points out theinaccuracy of the hypothesis of constant atomic radii, since atomsare subject to different “internal pressures” (defined as thepressures due t o the forces of affinity), in different chemical com-binations, and their dimensions depend on this and on the com-pressibilities of the elements concerned.An interesting paper on a related subject, that of structure andisomorphism in crystals, has been contributed by Wyckoff to theAmerican Mineralogist.20 He states that ‘‘ no general and exactst’atement of the connexion between isomorphism and atomicarrangement can be made at the present time.” The discussionarose out of two recent papers on isomorphismYz1* 22 and it isfortunate that this has happened, since a summary of the con-clusions to be drawn from crystal analyis is a welcome additionto the study of the subject.Isomorphous crystals wilI not ingeneral have identical crystal structures, for even in the simplecases so far examined the variable parameters which describe theatomic positions have not been found to have identical values.H. S. Washington and Wyckoff suggest the use of the term‘‘ homeotaxial ” for orystals which are chemically alike, with thesame type of atomic arrangements, and in which the respectivedistributions of atoms are so nearly similar that they are iso-morphous in the usual sense. Examples of such homeotaxial1s Wash. Nut. Acad. Sci., 1923, 9, 73; J . Amer. Chem. SOC., 1923, 45, 422.20 1923, $, May.21 E. T. Wherry, Arner. MGneraZo&t, 1923, 8, 1.z2 F.Zambonini p. S. Washington], ibid., p. 81; Rend. Accad. Lime;,1922, 31, 295CRYSTALLOGRAPHY. 237crystals are pyrites and hauerite, but not zinc blende and galena.All homeotaxid crystals are isomorphous in its widest sense, butwe cannot say that all isomorphous crystals are homeotaxial.We do not a t present know enough about the atomic arrangementsin complicated crystals to justify a generalisation as to how f a rwe may depart from compIete identity and yet retain isomorphism.By choosing for discussion such favourable cases as are offeredby the alkali and alkaline-earth metals, we have overlooked thenumerous cases of atomic replacement which should be possible,but have not been found. The following table (taken fromWyckoff's paper) will bring home how m c u l t it is a t the presenttime to prophesy in advance of experiment anything about prob-able atomic arrangements.TABLE I.Nacl NH,Cl Cubic ZnS ZnOgrouping.groupmg. grouping. groupmg. 8 LiX NaX CSCI CUClK x RbX CsBr CuBrCsF CSI CUI ZnSTlCl ZnS ZnONH,ClM O 2'NH,BrCaS MnScfo NiO pgr[X represents any of the halogen atoms.]There is much evidence to show that neither homeotaxis norisomorphism is determined primarily by the atomic 'sizes. Crystalswith such widely different molecular volumes as lithium fluorideand casium fluoride are completely homeotaxial, as are also thepotassium and caesium alums. And besides, as Wyckoff points out,if the atomic sizes be the basic criterion in a solid solution of albiteand anorthite, why does not a similar replacement (that of Na andSi for Ca and Al) hold in the case of the cubic garnets ? Yet evenalthough the sums of the valencies also balance, no cubic garnetsof this eort are found.Although no doubt isomorphous replace-ment is unlikely if the respective sizes of the atoms involved in thesubstitution are not very similar, the results of crystal analysisdo not justify the idea that this is the principal determining factorin such replacements.Xtructure of Alloys and Metals.Early in the present year E. C. Bain23 gave an account of anX-ray examination of a large number of alloys. He investigatedsolid solutions of tin, zinc, manganese, and aluminium in copper,cadmium and zinc in silver, and tungsten, molybdenum, chromium,a3 Ohem.and Met. Eng,, Jan. 3rd and loth, 1923238 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.and manganese in iron. The investigations of Rain and of hisco-workers have the merit of being largely pioneer work with respectto the particular cases examined and as such are worthy of specialconsideration, in spite of the fact that the results cannot be acceptedwithout reserve. Bain’s results in these two papers suffer from thedefect-a serious one to metallurgists-that results are givenwith insufficient detail or without statement of experimental con-ditions. Furthermore, they cannot always claim to be in goodagreement with confirmed thermal and microscopical investigations.Some of the work has already been repeated more satisfactorilyelsewhere (see below), but the details of the remainder will besummarised. Cu-Zn :-Thirty per cent.Zn changes edge of face-centred Cu from 3-60 B.U. to 3-68 B.U. (a-brass). The ranges ofthe brasses in these experiments do not correspond accuratelywith the ranges given by thermal and microscopical investigations.The brasses have been examined thoroughly by Owen and Preston(below). Cu-Xn :-Five per cent of Sn atoms expands the sideof Cu from 3-60 to 3.655, which is less than would be expected froma consideration of the respective atomic volumes. Cu-AZ :-18.8per cent. A1 stretches Cu from 3 . 0 to 3-633, again less than expect-ation. (These alloys have been studied in detail by Owen andPreston.) Cu-Mn :-33& per cent.Mn stretches Cu from 3-60 to3.615 : usually described as completely miscible, but not so accord-ing to Bain’s results. Ag-Cd :-Ag saturated with Cd increasesside by 1-1 per cent. (less than expected). Ag-Zn :-The edge isin this case decreased from 4.06 to 4.005 A.U. (more than wouldbe expected). Fe-Cr :-No measurable distortion, as would beexpected. W-Ye and Mo-Fe :-Both form compounds (WFe andMoFe) of a hexagonal type not yet elucidated. Fe dissolves alittle W or Mo without measurable change, whilst very little, ifany, Fe can be dissolved by W or Mo without the formation of thecompound. Fe-Mn :-Up to 30 per cent. Mn preserves the body-centred Fe, up to 60 per cent. the face-centred Fe. Above 60 percent, gives (unknown) Mn lattice distorted by Fe.Fe-Ni :-Con-tains two types, (a) Ni dissolved in body-centred Fe and (b) Fedissolved in face-centred Ni. These exist side by side over a greatrange. According to X-rays, it is not quite true that Fe and Niare miscible in all proportions. Cu-Au, Cu-Ni, Au-Ag are trulymiscible (face-centred cubes). No-W :-Similar to Ag-Au exceptthat it is body-centred.From the above. results Bain draws the conclusion that whenlarge and small atoms pack in a common lattice, they pack moreclosely than would be expected, whilst unlike atoms of about thesame size do not show attraction or compression to any extentCRYSTALLOGRAPHY. 239Bain also claims, in a very few cases, to have obtained conclusiveevidence of the existence of binary structures in which the atomicarrangement is not at random but really symmetrical, for example,25 A : 76 B can give, according to Bain, besides the lines of theface-centred cube, the lines of the simple cube also.This evidenceis offered in support of the chemical and electro-chemical workof Tammann, which demands for explanation the existence of suchstructures.More recently than Bain's work, an account has been given,with abundant detail, of a careful X-ray investigation of variousalloys carried out by E. A. Owen and G . D. Preston24 at theNational Physical Laboratory. These workers used the Braggionisation spectrometer after the manner described in an earlierpaper.25 Their results, in the cases examined, con@m the " sub-stitutional '' hypothesis of alloy structure advanced by W.Rosen-hain,26 that is, t'hey show that solid solutions of a metal B in ametal A are built on the same space-lattice as crystals of pure A,with the difference that a certain number of atoms of A are replacedby atoms of B. The substitution of B atoms for A atoms is accom-panied by a slight distortion of the A lattice in the neighbourhoodof the B atoms, to an extent depending on t'he relative sizes of thetwo atoms. An alternative hypothesis is that the B atoms arereceived into the interstices between the A atoms (the work ofWestgren and Phragmen indicates such a structure for steel), butin the cases examined by Owen and Preston this is certainlyinapplicable. From the distortion and density changes, whenthese are not inappreciable, it is easy to decide between the twohypotheses.AZ-Cu Alloys rich in Cu :--Alloys containing 2, 4, 6, and 8 percent.by weight of A1 were examined. For 8 per cent. Al, the cubeside of Cu increases from 3.60 to 3.65 B.U., and the results indicateclearly that the solution is of the substitutional type. AZ-CuAlloys rich in AZ :-In these there is no appreciable lattice distor-tion, and no decision can be made between the two hypotheses.Al-Cu AZZoy containing 30 per cent. Cu by weight :-It is shownthat this eutectic alloy consists of CuAI, and a substance which isindistinguishable from pure Al, but which may be an Al-Cu alloyrich in Al (see above). Structure of the compound CuAZ, :-Theunit cell is shown to be tetragonal with a = 4.28 B.U.andc = 2.40 A.U. The Cu-atoms lie at the corners of the cell and theAl-atoms at the centres of the side faces. Note that in this arrange-ment both A1 centres and Cu centres are separated by 2.40 A.U.,26 Proc. Roy. SOC., 1921, [A], 99, 196.The work will now be summarised.24 Proc. Physical Soc., 1923, 36, 14, 49. 25 Idem, ibid., 1923, 35, 101240 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.a distance which is smaller than the '' atomic diameters " given bythe pure metals (2.86 B.U. for A1 and 2.54 B.U. for Cu). Xtructureof CuAl :-This compound is apparently obtained from the face-centred A1 lattice with such distortion that it becomes a rhomb ofside 3.89 B.U. (as against 4.05 for Al) and axial angle 94.6". Itappears to be face-centred with two molecules of CuAl per cell,with (3) planes composed alternately of Cu and A1 atoms.Notethat such a structure resembles the type postulated by Tammann.&-Hg Alloys:-Eight per cent. Mg by weight distorts the A1lattice from side 4.05 to 4-10 A.U., and the results agree with thesubstitutional hypothesis. With 92 per cent. by weight of Mg,the spectrum corresponds to the close-packed hexagonal lattice ofMg ( a = 3.17 A.U. and c = 5.17 b.U.), the side being decrertsedto 3.15 B.U. and the height increased to 5.23 A.U. Cu-Ni Alloys :-The Ni produces a small contraction of the Cu lattice, and theresults (as also those of Al-Mg alloys) axe in agreement with thesubstitution theory.Cu-Zn Alloys containing up to 38.7 per cent. Zn by weight :-!?%mealloys gave spectra characteristic of the face-centred cubic structureof Cu.38.7 per cent. Zn increases the side of Cu from 3.60 A.U.to 3.696 A.U., and the results agree with the substitutional theory.Cu-Zn AWoy containing 48.5 per cent. Zn :-This alloy lies in theregion of the p-brasses, with a centred-cubic structure of side2.960 B.U. The structures of the @ a d @' phases are identical, andthe them1 eflect which occurs at 470" is not accompanied by a breakingup of the p-constituent into a mixture of a and y. Cu-Zn Alloycontaining 67-2 per cent. Zn :-This alloy lies in the region of they-brasses. It is apparently built on a rhombohedra1 lattice ofside 4.136 B.U. and axial ratio 0.6495. Cu-Zn allot^ conhining80-1 per cent. Zn :-This specimen of c-brasB corresponded to aclose-packed hexagonal arrangement of side 2.71 8 W.U.and axialratio 1.585, derived from that of pure Zn (a = 2.670 and c =The above careful X-ray study of the various brasses is in agree-ment with the constitutional diagram of Shepherd as modified byDesch and Hudson. It should be noticed that the thermal pheno-menon in the p-brasses is similar to the change from E- to @-iron,that is, there is no change in crystal structure. The atomic volumecurve consists very approximately of two straight lines meeting inthe region of the y-brass. In this region there is the maximumdistortion from the straight line joining the atomic volumes ofcopper and zinc. Thus the atomic volume curve corresponds tothe fact, which has been known for some time, that the hardnessof the brasses increases from the copper end t o the region of y-brass4-97 B.U.)CRYSTALLOGRAPHY. 241and then diminishes as we proceed to the zinc end of the series.Along one limb of the curve the crystal structure of the alloysfollows the rhombohedra1 arrangement, and along the other theclose-packed hexagonal arrangement.Various HeusZer AZEoys have been examined by J.F. T. Young,27who has suggested that these alloys are solid solutions of man-ganese-aluminium in copper, and that the magnetic effects areassociated, not with molecular or atomic groupings, but with thevalency electrons.K. Becker and F. Ebert 28 also have examined by X-rays certainmetals, metallic compounds, alloys, and mixed crystals.If a isthe side of the unit cube, they obtain the following results :-Ta,a = 3.32 B.U.; Cu2Zn,, a = 4.01 A.U.; mixed crystals of 96.3per cent. Mg,Al, and 3.7 per cent. Al, a = 4.80 A.U. ; NiA1, a = 2-82A.U. ; Cu,Al, a = 3-47 A.U. ; Ni,W, a = 3-68 A.U. Tantalumis body-centred cubic and thallium face-centred tetragonrtl (a ==4-75 i$.U., c = 5.40 A.U.). It is essential that the X-ray study ofalloys should be carried out in the closest association with thermal,microscopical, and other studies.A system analogous to that of the alloys, the system formed byhydrogen occluded in palladium, has also been examined this yearby means of X-rays. Mituo Yamada29 found only a continuousdisplacement of the palladium lines by the occluded hydrogen, andooncluded that no actual compound was formed, but only a solidsolution.In the May lecture delivered to the Institute of Metals, W.Rosen-hain 31 put forward certain general considerations arising out ofthe work of Owen and Preston. As mentioned above, this work isdefinitely in favour of the substitutional theory of alloy structure,and Rosenhain points out how it follows from this and the con-oeption of a limiting atomic displacement in the lattice that greatdistortion is associated with low solubility and increased hardness.Similarly, it is the hard metals, for example, iron, nickel, cobalt,manganese, chromium, tungsten, and molybdenum, which formlong series of solid solutions, since in them, because of their hardness,the distortion is not localised and the limiting parameter is notoverstepped.In the soft metals, lead and tin, practically no solidsolutions are formed. In a precisely analogous manner, the dis-tortion existing in solid solutions, because it aids or opposes thebreak-up of a lattice by heat, lowers or raises the freezing pointand causes that temperature difference which is observed betweenL. W. McKeehan 3O has drawn similar conclusions.2 1 Phil. Mag., 1923, [vi], 46, 291.29 Phil. Mag., 1923, [vi], 45, 241.31 Inst, of Metals, 13th May Lecture, 1923,28 Z. Physik, 1923, 16, 165.so Physical Rev., 1923, [ii], 21, 334242 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.the beginning and the end of freezing and melting of alloys. Rosen-hain also mentions the large heat absorption that occurs whenmetals are made amorphous by stress, and shows that metals, andcrystala in general, which are plastic should (as they do) exhibitthe phenomenon of diffusion.Electrical conductivity and '' super-conductivity" also are dealt with from the same point of view.The irregularities in the rows of atoms decrease the conductivityand temperature coefficients of alloys as compared with those ofthe pure metals : similarly for elastic-hysteresis and fatigue.A brief mention must now be made of this year's BakerianLecture to the Royal Society.32 The subject of distortion andslip-planes in metals and crystals in general is of extreme interestto the mathematician, crystallographer, and metallurgist alike,but the lecture is too mathematical to lend itself to abstraction.Prof.G. I. Taylor and Miss C. F. Elam discuss the distortion ofan aluminium crystal under tensile stress and show from a study ofthe surface slip-lines that the planes of slip are parallel to theface (111). Prof. A. W. Porter33 has pointed out that the phe-nomenon was observed ten years ago by Baker and Rndrade,who showed that sodium and potassium cylinders when stretchedcontracted laterally so as to lead to an approximately ellipticalsection, and when they broke they did so at a chisel edge. Thesurfaces were marked with a double set of slip-lines. H. Mark andM. PolAnyi 34 have also been studying the phenomenon by the aidof X-rays. Last year they examined zinc crystals and now findanalogous results for white tin.According to these authors, whitetin crystallises in the ditetragonal bipyramidal class, space-groupDqh19. The unit cell is body-centred and its horizontal axes aretaken a t 45" to the crystallographic axes. Its dimensions area = 5434 A.U., c = 3.15 A.U. There are four atoms in the cell, theco-ordinates of which are (000), (0 a/2 c/4), (u/2 o 3c/4), (a12 a12 c / 2 ) .Slipping was found to take place parallel to the (110) and (100)planes, the former occurring the more frequently.Xtructure of Long-chain Compounds.The X-ray investigation of long-chain organic compounds hasbeen one of the most interesting and important researches of theyear. It supplements and confirms the more indirect but highlyingenious work of Langmuir, Adam, and others on the dimensionsof unimolecular films, and justifies hypotheses which have beenheld by chemists for a long time.The fist observation of a longspacing (43.5 A.U. from sodium oleate) was made by De Broglie92 Proc. Roy. SOC., 1923, [A], 102, 643. Nature, 1923, 111, 362.34 2. Phy8ik, 1923, 18, 75PLATE 1.[To face Annual Reports, p . 243.CRYSTALLOQRAPHY. 243and FriedeL35 Soon after, S. H. Piper and E. N. Grindley 36made some systematic measurements of the X-ray reflections tobe obtained from sodium laurate (ten CH, groups), myristate(twelve CH, groups), and palmitate (fourteen CH, groups). Thesethree salts, examined in the form of curds, gave wide spacings of33.5, 38.5, and 43.5 K.U., respectively, together with two othersmaller spacings of 4.22, 4.18, 4.15 and 4.88, 4.9, 4.9 d.U., respec-tively.The interesting fact is thus revealed that, whilst the smallspacings remain fairly constant, the long spacing increases by5 B.U. per CH, group. From these results the authors concludethat, in order to harmonise with the work of Langmuir and ofAdam, we must assume two molecules, end to end. The effectiveincrease of length per CH, group would then be 1-26 B.U., and thechain would be made up of a zig-zag arrangement of carbon atomslinked together at the tetrahedral angle. The authors also concludethat their observations accord with the " smectic condition "described by Friede1,37 that is, the structures are not reallycrystalline.The most complete and satisfactory X-ray examination of theseelongated molecules has been carried out, independently of Piperand Grindley, by A.Muller and G. Shearer. In a paper by theformer 38 are described the observations which are summarised 'inTable I1 and beautifully reproduced in Plate I. The increase perCH, group is approximately constant and equal to 2.0 A.U., whilstthe existence of the two small spacings, d, and d3, suggests thatthe unit cell is a long prism which has the same cross-section forall the substances in question.TABLE 11.Acid. M. p. N. 4, 4. 4.Capric - 10 23-2 - -Myristic ......... 14 32.2 4.12 3-72............Lauric ............ 43-44' 12 27.0 4.11 3.68Palmitic ......... 62.5' 16 34.7 4.08 3.65Stearic ............69-69.5' 18 38.7 4.05 3.62Behenic ......... 80.5' 22 47.8 4-10 3.66the chemical formula.M. p. denotes melting point and N the total number of carbon atoms inThe investigation is continued and discussed in two furtherpapers delivered to the Chemical Society. Shearer 39 examinedcertain long-chain esters and aromatic compounds. The data forthese are given in Table 111.Behenic acid is not reproduced in the plate.36 Compt. rend., 1923, 176, 738.313 Proc. Physical Xoc., 1923, 35, 269.31 *4np. Phy8ique, Nov., 1922.38 l'., 1923, 123, 2043.39 Ibid., p. 3152244 ANNUAL REPORTS ON !I'HE PROGRESS OF CHEMISTRY.Substance.Methyl pahitate . . .Ethyl 9 , ...Octyl ...Cetyl 9 , ... 99Methyl stearate . . . . . .Ethyl , , . . . . . .Octadecylbenzene .. .pHexadecylpheno1.. .p-Octsdecylphenol . . .TABLE 111.Formula. dl.Cl 5H3, *CO.O*CH3 22.0C16H3,.CO*O*C2H6 23.2C15H3,.C0.0C8H17 30.4C16H3,*CO*O*C16H33 40.4Cl7H3,*CO.O*CH3 24.0C17H36*C0.0*CzH6 25.2C16H38*CBH4-OH 46.5 cl ,H3,.C 6H,.0H 51.31 8H37'C6H6 49.2d2.4-074-074.164.054.074.14 -d3-3.723-673-723.693-743.69 -These results indicate a uniform increase of 1-22 A.U. on theester side of the molecule as compared with the increase 2.0 A.U.found by Miiller for the fatty acids. In the third (joint) paper 40are given the following supplementary results (Table IV), andthe conclusions to be drawn from the whole are discussed.Substance.Undecylic acidPentsdecylic ,)Mmgaric ,,Oleic # YElaidic Y,Emcic Y,Brassidic ,,i8001ei0 9 ,TABLE IV.F0ITUUla.4. d2. ...... Cl lH2202 24.7 -...... C16H3002 36.2 4.00 ...... C17H8402 3 8.2 4-05. . . C18H3403 48.3 4.03...... CZ!2H4202 46.3 4-22 ...... C2sH4202 59.9 4.25...... C18H3402 36.2 ( 4 ) -...... C18Ha408 35.9 -4. -3.763.773-653.723.72--These conclusions are of fundamental importance to chemists,and may be stated briefly as follows.The authors argue that these long-chain compounds form realcrystals which are all built up after a similar fashion, with thelength of the molecule lying approximately perpendicular to thecleavage flakes. These latter generally lie parallel to the surfaceon which they crystallise out. What we may provisionally callthe unit cell is a long, narrow prism of height d, and side dimensionsd, and d,.Such a cell would show only one large spacing, all therest being small. In some of the compounds d, represents tholength of a single molecule (the case of one molecule per cell, or,a t least, one molecule between successive cleavage planes), and inothers the Iength of two molecules, end to end and pointing inopposite directions (two molecules per cell). Thus Cl, and d3 areapproximately constant, because they represent the width of thechains, whilst d, varies in two observed ways : (a) an increase of%0/2 = 1.0 B.U. per CH, group; (b) an increase of 1.22 A.U. perCH, group: (u) is exemplified by the fatty acids and other corn-pounds containing two molecules per cell, whilst (b) is exemplified bythe ester side of long-chain esters containing one molecule per cell.40 A.Muller and G. Shearer, T., 1923,125, 3156CRYST.4lXOGIlUPHY. 245The authors now consider the question, What are the possibletypes of carbon chains, given that the linking is always at thetetrahedral angle (that is, 109"28', as observed in diamond), andthat the continued addition of a limited number of atoms to thechain always results in a uniform increase in the length of thechain 1 There are several chains which satisfy these conditions.The three simplest are shown in Figs. 1, 2, and 3.In Fig. 1 the atoms are all in one plane, and the increase perFIG. 1. FIG. 2.carbon atom, given that the carbon "FIG. 3.diameter " is 1.5 A.U., is1-22 A.U. The chain in Fig.2 is a spiral, of which the period isthree atoms. It is like the spiral of silicon atoms in quartz, andthe increase per carbon atom is 1.12 A.U. In Fig. 3 the period isfour atoms and the increase is 2.0 B.U. for two carbon atoms, eachset of four atoms lying in a plane, but successive sets not necessarilyco-planar. The chains in Figs. 1 and 3 are exemplified by theerjters and fatty acids, respectively.The above remarks outline the chief features of this new advancein chemical crystallography, but there are several other interestingpoints, such as the nature of '' double bonds " and of cis- an246 ANNUAL REPORTS ON THE PBOGRESS OF CHEMISTRY.trans-isomerism, considered in the papers mentioned,reference should be made to the original discussion.For theseStructure of Inorganic Crystals.In the following summary, all points of peculiar interest, espe-cially chemical, will be indicated where need arises, and the bearingof the results on current theory briefly discussed.Hydraxine Dihydrochloride, N2H,,2HC1.41-This salt crystallisesin the same class arid subgroup (Th6) as iron pyrites. There arefour molecules per cell and the side of the unit cube is 7.89 A.U.The structure is also analogous to that of the nitrates of the alkalineearths, the centres of the hydrazine groups (N,H,++) replacing thecentres of the metals a t the corners and face-centres of the cube,and the chlorine atoms replacing the nitrate groups.In aqueoussolution, the salt presumably ionises to doubly-charged (N,H,)groups and negative chlorine-ions .Apparently the distancebetween nitrogen and chlorine centres is 3.14 A.U., and betweentwo chlorine centres 3.96 B.U. These results are at variance withthe hypothesis of constant atomic radii.The Alums, R’R”’(SO,),, 12H,Q .42-Eacrlier X-ray examination 43of this series of double salts assigned to them the space-group Th2,but this recent investigation has decided in favour of Th6 (the ironpyrites class and group). The dimensions and the number ofmolecules per cell (four) are the same, and no attempt has beenmade completely to locate the atoms. There are, however, certaingeneral conclusions to be drawn from these latest results. (1) Allfour of the oxygen atoms of the sulphate group cannot be exactlyalike.Three of the oxygen atoms must be alike, but differentfrom the fourth. (2) The twelve water molecules fall into twogroups of six each. (3) The hydrogen atoms of the ammoniumgroups in the ammonium alum present an interesting difficulty.The only arrangement which satisfies symmetry considerationsmakes all five of the atoms of the ammonium group lie on a straightline, a triad axis of the crystal, and such a grouping is not chemicallyplausible. As a possible way out of this difficulty, Wyckoff suggeststhat the hydrogen atoms need not have a symmetry which conformsto that of the crystals as a whole and yet, because of the few electronsinvolved, be still in agreement with X-ray and optical data. Sucha hypothesis must be approached warily; more examples arenecessary before a decision can be arrived at.Wyckoff quotesthe case of the alums as a particularly good example of the futilityof unaided spectrometric investigation.4 1 R. W. G. Wyckoff, Arner. J. Sci., 1923, 6, 16.42 Idem, ibid., p. 209; 2. Krist., 1923, 57, 696.4a L. Vegard and H. Schjeldemp, Ann. Phy&, 1917, 64, 146CRYSTALLOQRAPHY. 247Cubical Arsenious and Antimonious Oxides, As406 and Sb406.44-The interest attaching to the determination of the structure ofthese two compounds has been greatly enhanced by the almostsimultaneous discovery of the structure of basic glucinum acetate.45All three are built on the “ diamond structure,” space-group Oh7.The molecules preserve their identity in the crystal and possess the%-fold symmetry of the regular tetrahedron.We must thereforeconsider the arsenic and antimony atoms as associated with thefour corners of a regular tetrahedron and the oxygen atoms withthe six edges of the same tetrahedron. The sides of the unit cubescontaining eight molecules are 11-06 A.U. for As,06 and 11.14 B.U.for Sb40,. The shortest distance between arsenic and oxygen atomsis 2.01 A.U., and between antimony and oxygen atoms 2-22 &TJ.Quartz, Si0,.46-This crystal has been again investigated thisyear, but by the powder method, The author confirms the hex-agonal lattice found by Bragg 47 and concludes that the moleculesare obtuse-angled isosceles triangles, having an angle a t the siliconatom centre of 115” 14’, and a distance between the silicon andoxygen atoms of 1.631 A.U.The molecules are said to lie com-pletely in the basal planes of the three interpenetrating hexagonallattices, but such a conclusion is difficult to accept when we considerthe intensities of the different orders of reflection from the basalplane. Sir Wm. Bragg has recently considered the questionanew and a discussion is given in “ X-Rays and Crystal Structure’’(new edition, now in the press). If all the atoms lie in successivebasal planes, as McKeehan suggests, we should expect a more orless “ normal” falling-off of intensities in the successive orders ofreflection from the basal plane, but actually experiment shows thatthe second order is abnormally large.Cinnabar, HgS.48-This crystal belongs to the same crystal classas quartz, but is much more optically active.The author con-cludes that it belongs to Type (23-24) of Sohncke, with c = 9.51A.U. and u = 4.15 B.U. The reflections from the basal plane(second order greater than first) indicate that planes of mercuryand sulphur alternate, but no definite decision as to the atomicpositions can yet be made.Molybdenite, MoS,.~’-T~~ hexagonal cell of this structure con-tains two molecules, whilst c = 12-30 A.U. and c / a = 3.90. The44 R. M. Bozorth, J. Amer. Clzem. SOC., 1923, 45, 1621.45 Sir Mr. H. Bragg and G. T. Morgan, Proc. Roy. Xoc., 1923, [ A ] , 104, 437.46 L. TV. McKeehan, PhysicaE Rev., 1923, 21, 503.4 7 W. H. and W. L. Bragg, “ X-Rays and Crystal Structure,” old edition,48 C.Mauguin, Cornpt. re@., 1923, 176, 1483.48 R. G. Dickinson and L. Peuling, J . Amer. Chem. SOC., 1923, 45, 1466.p. 163248 ANNUAL REPORTS ON THE PkOG$iESS OF CHEMISTRY.8truCtWe is derivable from Deh4 aa well as from D3h4, Dg8, CG2,ahd DN2, which means that if the atoms can be considered as pointsor spheres, the symmetry is hexagonal holohedral. The co-ordinatesof the molybdenum atoms are (4, 8, 4) and (6, Q, $), while those ofthe sulphur atoms are (&, 8, u), (5, 9, G), (8, 3, Q - t ~ ) , and (f, 3,5 + u), where u = 0.621 &0.004. Each sulphur atom is equidistantfrom three molybdenum atoms, and each molybdenum is a t thecentre of a triangular prism of sulphur atoms. The molybdenumatom8 are distant 2.41 rt: 0.06 A.U. from the nearest sulphuratoms,which is in good agreement with W.L. Bragg’s “atomic radii.”The perfect basal cleavage is apparently connected with therelatively great distance between the sulphur atoms.Tin Tetraiodide.m-This crystal also belongs to the pyrites classand group, Th6. There are eight molecules in the unit cube, theside of which is 12.23 A.U. Crystallographically, one of the iodineatoms is different from the other three, but this fact probably hasno chemical significance, since all four are arranged tetrahedrallyaround the tin atoms. Apparently the distance from tin to iodinecentres is 2.63 B.U., but that between the nearest iodine atomsis 4-21 B.U., which is the same as in the structure of cadmiumiodide. The structure must be considered as molecular.Thiscrystal has been examined by other workers who, althoughuncertain of the space-group, draw similar conclusions regardingthe atomic arrangement.Potassium Hydrogen Fluoride. 52-There are four molecules in a,cell which is 5.67 x 5-67 x 6-81 B.U. It is tetragonal and may bederived from Dqh18, DzdlO, or D49. The structure may be regardedhs an ammonium chloride arrangement of potassium atoms 4 andfluorine dumb-bells, the two atoms in each dumb-bell lying in aplane perpendicular to the tetrad axis. There are two possiblepositions for the hydrogen atoms, one of which is in the middle ofthe fluorine dumb-bell, making a negative (HF,) ion.Sodium Ch2orate.-The structure of this compound has givenrise to a great deal of discussion, and much conflicting evidenceand argument have been put forward.Apparently L. VBgard 53condemns the work of Kolkmeijer, Bijvoef, and Karssen,= but thethree last-named are supported by R. G . Dickinson and E. A.Goodhue 55 and by W. Kiby,66 whilst G. Wulff 57 has deduced yetR. G. Dickinson, J . Amer. Chem. SOC., 1923, 45, 958.H. Mark and K. Weissenberg, 2. Physik, 1923, 16, 1.62 R. M. Bozorth, J . Amer. Chem. Soc., 1923, 45, 2128.63 2. Physik, 1922, 12, 289; 1923, 18, 379.64 K . Akad. Wetensch. Amsterdam, 1921, 23, 644.6 5 J . Amer. Chem. Soc., 1921, 43, 2046.5 7 2. Krist., 1922, 57, 190.66 2. Physik, 1923, 7, 213CRYSTALLOGIRAPHY. 249another structure. The crux of the matter is that we do not yetknow enough about the scattering of X-rays to settle the questionhally.58 In all the work on sodium chlorate to date, there areinvolved certain unverifiable and perhaps unwarranted assump-tions.Silicon .S9-All samples tested gave spectra conforming to the“ diamond structure.” The side of the elementary cube is 5.4204 &0.00016 A.U.The different chemical activities of varieties ofsilica are due solely to differences in the ratio of surface to ma88 ofthe specimen.Xulphides of Magnesium, Calcium, Strontium, and Barium,MgS,CaS,SrS,BaS.6*-These all conform to the “ rock-salt struc-ture.”Calcite, CaC0,.6~-A critical discussion of the interpretation ofthe experimental results. The conclusions afford a new con-firnation of W. L. Bragg’s hypothesis.Alkali Halides.62-By the powder method, preciaion measure-ments have been made of twenty alkali halides.The dimensionsand densities together with probable error are given in the paper.Natural and Synthetic Oxides of Uranium, Thorium, and Ceri~m.6~-Pitchblende, broggerite, cleveite, thorianite, and the oxides ofuranium, thorium, and cerium have been examined by the powderand Laue methods. The dioxides are isomorphous and seem toconform to the “fluorspar structure.” The cube sides are 6-47,5.61, and 5.41 B.U., respectively. The structure of manoso-urrtnic oxide, U308, is irregular, and uranio oxide was obtainedonly in the amorphous form. The minerals thorianite (5-57 B.U.),broggerite (5.47j B.U.), and cleveite (5.47 B.U.) correspond withisomorphous mixtures of the three oxides and lead peroxide.Theground lattice of all these minerals is uranous oxide, and if issupposed that the excess of oxygen corresponding with uranicoxide is present in solid solution. Broggerite in which the uraniumis partly transformed into lead retains the original lattice arrange-ment.Silver iodide, e t ~ . ~ ~ - - B y the powder method the author k c i s thatsilver chlonde and bromide are of the rock-salt type with sidesThe results are tabulated in the paper.68 A. Karssen, Rec. trav. chim., 1923, 42, 904.69 H. Kiistner and H. Remy, Physikal. Z., 1923, 24, 25.B o S. Holgersson, Z . anorg. Chem., 1923, 126, 179.81 C. Meuguin, Compt. rend., 1923, 176, 1331.6p W. P. Davey, Physical Rev., 1923, [ii], 21, 143.88 V. M. Goldschmidt and L.Thomassen, v~easkufssebkapct8 Skriftcr.64 R. B, Wdsey, Phil. Mag., 1923, [viJ, 40, 487.Mat. Nuturv. Klusse, 1923, 5; from Chem. Zentr., 1923, i, 1149250 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.5.540 and 5.768 B.U., respectively. Silver iodide ia cubic of thezinc sulphide type, side 6.493 kU., and hexagonal of the zincoxide type with a = 4.593 A.U. and c / a = 1.633. Metallic silveris face-centred cubic with side 4.078 B.U. The question of thestructure of silver iodide 64 is particularly interesting, and Wyckoff,in his " Survey of Existing Crystal Structure Data," has madesome strong (but possibly unjust) comment's on the subject.Wyckoff and others maintain that silver iodide is purely hexagonalat the ordinary temperature and cubic at temperatures above146", whilst Wilsey and Davey 65 claim that the lines of the cubicstructure are observed in many samples at the ordinary temperature.In spite of Wyckoff's criticism, the conclusions of the two last-named workers are perhaps not unreasonable.Lithium HaZides.'j6-The author finds that anhydrous lithiumchloride, bromide, and iodide are of the rock-salt type. Thedimensions are given.The monohydrate of lithium chloride is ofthe czesium chloride type.Iron Carbide, J-c'e,C.67-The author finds a rhombic lattice, a =4.481 A.U., b = 5.034 A.U., c = 6.708 A.U. The forms of cementiteshown in the iron-carbon thermal diagram are not distinguishableby their lattice structure, and data taken above 210" show that themagnetic transformation is not associated with a change in the typeof lattice .Vitreous Carbon.68-This hard, lustrous, crystalline form of carbonis said to give a spectrum containing both graphite and diamondlines.It is dense (d, 2-07) and very pure and can be prepared withk hardness greater than that of carborundum. Its electrical con-ductivity is low.Lithium and Lithium Nydri~le.~~-This investigation is particularlyinteresting as an attempt to locate the electrons in the two simplestcrystal structures. Lithium is found to be centred-cubic withside 3-50 B.U. A lattice of stationary electrons does not explainthe results, and it is thought possible that the valency electronrotates round the nucleus or describes an orbit between the lithium-ions, in planes perpendicular to the trigonal axes, the radius in thelatter case being larger than about one-fifth of the distance betweenthe two ions (one-quantum orbits suffice). Lithium hydride isalso cubic with four molecules per cell of side 4.10 A.U. Thereappear t o be two possible structures, both analogous to sodium6 6 W.P. Davey, Physical Rev., 1922, 19, 218.6 6 H. Ott, Physikal. Z., 1923, 24, 209.6 7 F. Wever, Mitt. Kaiser Wilh.-Inst. Eiaenforsch., 1922, 4, 67; from Chcm.68 K. A. Hofmann and C. Riichling, Ber., 1923, 56, [B], 2071.6@ S. 3T. Bijvoet, Rec. trav. chim., 1923, 42, 859.Zentr,, 1923, iii, 187CRYSTALLOGRAPHY. 251chloride : (1) in which atoms with radii of approximately the 8ameorder of magnitude as those calculated by Bohr for the free atomsare placed a t the lattice points; (2) with positive lithium-ions andnegative hydrogen-ions at the lattice points, the electrons rotatinground the nucleus in paths the planes of which are perpendicularto the trigonal axes.Thus in lithium hydride there is a possibilityof a heteropolar binding, whilst in lithium itself the binding isprobably homopolar.Hexagonal Zinc fiulphide and Nickel Arsenide.70-In these twohexagonal structures there are two molecules per cell. For ZnS,a = 3.80 and c = 6-23 B.U., whilst for NiAs a = 3.57 and c = 5.10A.U. For both crystals two possible structures accord with theexperimental results. These are given by the following co-ordinates.1. Zn: (0, o o), ($, 3, *); S : (0, o,p), (8, 4, p - i). 2. Zn (or S) :(0, 0, o), (8, $, 8 ) ; S (or Zn) : (+, -3, p ) , (9, 8, p - 4).For ZnS,the former arrangement is the more probable, where p &, whilstfor NiAs the latter is favoured, where p N 2. If we accept thesevalues of the parameters, the " atomic radii " are in good agreementwith the values calculated from other crystals.Calcium Thiosulphde Hexahydrate, CaS,0,,6H,0.71-This crystalhas hitherto been regarded as perhaps a unique example of thetriclinic asymmetric class (l), but there are two molecules in thefundamental cell. It thus seems likely, from analogy with othercomplex structures, that the two molecules are inverse to eachother, and the crystal is after all only one of the many examplesof the triclinic pinakoidal class ( 2 ) .Structure of Organic Crystals.He~arnethylenetetrari?~e,~~ C,H,,N,.-The authors conclude thattheir data accord with a body-centred cube of edge 7.02 A.U., inwhich there are two like molecules of C,H1,N4 / T --\ of tetrahedral symmetry.Both the carbonCH2 YH2 L'CH2 atoms and the nitrogen atoms are equivalent,a, 1 among themselves, and this fact is broughtN" 'HZ ' = 2 \ ~ out by the structural formula annexed. Twonitrogen atoms arc about 1.44 A.U. from eachcarbon atom, and a t least approximateJy in thedirections of two vertices of a tetrahedron.Anlkrac~,ne.~~-The structure of this crystal is exactly analogousto that of naphthalene, monoclinic prismatic, with two moleciiles%H/ '17O G. Aminoff, 2. Krist., 1923, 58, xi, 203.7 1 W. T. Astbury, Nature, 1923, 112, 53.72 R.C. Dickinson and A. I,. Raymond, J. Amer. Glzeni. ~ o c . , 1023, 45,73 TT. H. Rragg, Proc. Physical SOC., 1923, 35, 167.22262 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.per cell. The major length of the molecule lies along the c-axis,and the difference in the lengths of this axis in the two cases is2.5 A.U., which corresponds exactly with the width of the benzenering. The calculated density, 1.255, also agrees with an experi-mental determination. The molecular symmetry of naphthaleneand of anthracene in the crystalline state is centro-symmetry only.Anhydrous Racemic A~id.'~-The crystallographic cell is not thetrue fundamental cell, since it is associated with a half-molecule ofd- and a half-molecule of Z-tartaric acid, that is, alternate cornersof the (001) face are occupied by active molecules of the samesort, There is no evidence from the X-ray examination thaf.racemic acid exists as an independent inactive doublet of molecularweight 300.The chemical molecule in racemic acid is substantiallyof the same shape and dimensions as the molecule in active tartaricacid, but a small contraction in the length of the molecule and theabsence of a certain cleavage appear to be associated with smallchanges in physical properties which accompany the formationof racemic acid from its active components. The disappearance ofthe distortion of the hydroxyl groups of tartaric acid favours thehypothesis of the anomalous optical properties of the active acid.An explanation is given of the multiple twinning and irregulargrowth of anhydrous racemic acid.Urm.75-The authors have shown that the structure of thisinteresting substance can be determined independently of crystal-lographic and chemical characteristics, since there is only onespace-group and one atomic arrangement which are compatible withthe X-ray results. It is tetragonal scalenohedral, space-groupDzd3, with a = 5.63 A.U.and c = 4.70 A.U. There are two mole-cules per cell, which means that each molecule possesses the sym-metry C,,, that is, two mutually perpendicular planes intersectingin a diad axis. The distance between the centres of two adjacentmolecules lies between 3.98 and 4-62 B.U.PeniberythritoZ.76-The structure of this compound, more interest-ing still than that of urea, has been elucidated by the s8me authors.It is ditetragonal pyramidal, with a = 6-16 A.U.and c = 8.76 A.U.It i a body-centred, contains two molecules of C,H1204, and belongsto the space-group C42. But the most striking conclusion is thatthe symmetry of the molecule is C4a, that is, four planes of symmetryinclined a t 45" to each other and intersecting in a tetrad axis. Thissymmetry must be shared by the central carbon atom, about whichthe four substitution groups (*CH,*OH) are structurally equivalent74 W. T. Astbury, Proc. Roy. SOC., 1923, [A], 104, 219.'16 H. Mark and K. Weissenberg, 2. Physik, 1923, 16, 1.Idem, ibid., J923, 17, 301CRYSTALLOGRAPHY. 253and lie in the hemimorphic plan= of symmetry.This importantresult means that the valkncy bonds of the central carbon atomare not arranged tetrahedrally, but point towards the four cornersof a square.Basic Olucinum Acetate and Propion~te.?~--The structure of thebasic acetate, Gl,O(CO,*CH,),, has been already mentioned. It ishighly interesting and important chemically, but the results of thecrystal analysis are no less fascinating. The crystal is built, likearsenious oxide, on the “ diamond structure,” space-group Oh7,that is, in each unit cube there are eight molecules each possessingthe symmetry of a regular tetrahedron. The side of the unit cubeis 15.72 A.U. The outstanding fetiture of these observations isthe conclusion with regard to the molecular symmetry. Basicglucinum acetate is extremely stable and is associated with remark-able chemical and physical properties.It is a co-ordination com-pound built round a unique central oxygen atom. The fourglucinum atoms are grouped tetrahedrally round this central oxygenatom, whilst the six acetate groups span the six edges of the tetra-hedron. Such an arrangement is capable of simple interpretationin terms of the electronic theory of valenoy, but it must beremembered that the molecule possesses the 24-fold symmetryof a regular tetrahedron, that is, the acetate groups which spankhe dgm must each be symmetrical about a plane. Consequerltly,the ordinary structural formula does not apply t o them. Theoriginal difference between hydroxyl and carboxyl oxygens has beensmoothed out by the presence of a plane of symmetry.The o---co-ordinated acetate group must be looked upon as CH3-Cq0----.Some as yet unpublished observations 78 on the symmetry of theacetylacetones lead to similar conclusions. Basic glucinum pro-pionate has been shown to belong to the monoclinic system, withtwo molecules per cell (which is probably monoclinic prismatic).The molecule is either centre-symmetrical or nearly so. Beyondthis, nothing can be concluded with certainty.Star~h.~~-The author claims that starch is built on a tetragonallattice, 5 ~ 9 4 ~ x 5-05 A.U., with one group, C,HI0O5, in such a cell.This result is approached with caution, since the number andquality of the spectral lines obtained from starch are both some-what inadequate.Various Cmpounds.80-The authors have made by the X-raymethod measurements of the cells of various organic substances.7 7 Sir W.H. Bragg and G. T. Morgan, Proc. Roy. SOC., 1923, [A], 104, 487.’ 8 W. T. Astbury.8o K. Becker and H. Rose, 2. Physik, 1923, 14, 309.79 0. L. Sponsler, J. Gen. Phgaiol., l923, 6, -767254 AISNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Abnormal Reflection of X-Ray~.~l g2A series of papers, dating from May, 1922, have appeared on thesubject of the reflection by a crystal of X-rays characteristic ofthe elements in it. The authors, using an ionisation spectrometerand the “ white ” radiation from a tungsten target, claim that inaddition to the ordinary reflections which are observed on Lauephotographs, they have observed certain abnormal reflections ofrays characteristic of the elements constituting the crystal examined.For instance, when examining potassium iodide crystals, they claimto have observed the iodine lines besides the usual tungsten lines.The values of the wave-lengths producing these abnormal refiec-tions were obtained by determining the critical voltages belowwhich the reflections did not occur and combining these resultswith the quantum relation.Some of these reflections appear toobey Bragg’s law, whilst others do not, but by the aid of thosethat do obey the law the authors state that they have found thespacings of the atoms giving rise to the characteristic rays. Thusthey have put forward structures for the polyhalides KI,, CsI,,CsIBr,, and CsICI,.For CaI,, it is stated that the spacing of theiodine atoms is one-quarter that of the caesium atoms, and thattherefore the crystal unit is a, rectangular parallelepiped wit-hcaesium atoms a t the corners and iodine atoms at the centre andequidistant along t’he body-diagonal. The results for the otherpolyhalides are similar, the heaviest halogen being at the centreof the body-diagonal. The halogen atoms constitute a singly-acting group just as they do in the formation of complex ions insolution. The stability of the polyhalides is apparently directlyproportional to the atomic volumes of the metals.No one else seems to have been able to detect the effect describedby Clark and Duane, and it must be confessed that their inter-pretation is not as yet generally accepted.The effect should beeasily noticeable on Laue photographs, but Wyckoff 83 has failedto detect any trace of it. If it is a true effect, it is highly importantand marks a new advance in the development of crystal analysis.Nothing is more desirable than to be able to detect the periodicityof individual atoms. When we can do that, the science will bealmost complete.Miscellaneous Papers,Cohesion and Molecular Forces.-At the recent meeting of theBritish Association a t Liverpool a joint discussion on cohesion and8 1 G. I,. Clark and W. Duane, Proc. Nut. Acad. Sci., 1922, 8, 90; 1923, 9,117, 131.82 Idem, J. Optical Boc. Amer., 1923, 7, 455.8% Amer. J. Sci., 1923, [v], 6, 277CRYSTALLOGRAPHY. 255inoleuular forces was held.The discussion was opened by SirWm. Bragg, who examined the question from the point of view ofthe results of X-ray analysis. The point he emphasised was thatit appears to be necessary to say that the very strong forces betweenatom and atom, molecule and molecule, are limited in their effectiverange of action to distances much smaller than we have hithertosupposed. It seems nearer the truth to think that the exact adjust-ment in crystal structure is brought about, not by forces betweenpoints representing the molecules, but by the close association ofcertain points of one molecule with certain points of the next, thatis to say, in considering the binding of the individual molecules ofEL solid, the analogy of the electrostatic attraction of two chargedspheres is imperfect. Rather should it be replaced by that of twomembers of a girder structure adjusted until the rivets can bedropped into the holes provided for them. A significant example ofthis process is afforded by the long-chain compounds describedabove.In them, the forces associated with the ends of the moleculeappear to be without effect on the atomic arrangement of the middleof the molecule. Dr. Rosenhain, who followed, discussed theproblem of alloys and pure metals from tho point of view of theconsiderations already set out above, whilst Dr. A. A. Grifiith askedthat physicists should study thoroughly the collapse of space-lattices under shearing stress. Prof. Lindemann declared that theassumptions of previous speakers with regard to bonds were prem-ature, and Sir Oliver Lodge added the h a 1 touch by sayiiig thatwe do not yet know why, when we raise one end OI a stick from atable, the rest of the stick also comes up,In diamond,each carbon is surrounded tetrahedrally by four electron-pairs,but in graphite thc alternative arrangement must hold, that is,there must be an electron pair between the nearest atoms in adjacentlayers and a sextet oE electrons around the centre of each hexagon.Such an arrangement accounts for the tightening of the hexagonsand their wider distance apart and also for physical and crystallo-graphic properties.Huggins rejects Hull's structure for graphite,but suggests an alternative hexagonal structure. But this pointis immaterial; the chief point is the existence of the hexagon firstsuggested by Korner in 1874.Applying the valency theory to this,we get a sextet in the centre, an'electron-pair joining carbon t ohydrogen, and an electron pair a t each of the hexagon corners. Ifunits of this type are close-packed side by side, they form a layer inwhich the molecular boundaries are no longer distinguis ha ble.Structure of Benzene, ekS4-A tlheoretical paper.84 M. L. Huggins, J . Anier. Chenz. Soc., 1923, 45, 264; &4mer. Aso. Ad%?.&cia, Aw. 5t,h, 1921256 ANNUAL REPORTS ON TEE PROGRESS OF CHENISTRY.Removing the hydrogen atoms and plaoing layer upon layer in sucha way as to produce C-C bonds where C-H bonds had beengives one or other of two possible graphite structures : (a) modifiedDebye-Scherrer structure, ( b ) Huggin’s hexagonal structure.Nowamume that crystals of benzene, etc., are formed of close-packedlayers of hexagons. Then, for example for quinol, p = 1-33,a/c = 1/0-6680 and mol. vol. (7) = 136.54. If the distance betweenthe layers is c and there are n molecules per cell, volume of unitcell == nc x 15-84 (area of ring) = n V . Therefore c = 8-61,u = 12.8 = 6 x 2.15. By this method and extensions of it,Huggins has deduced the ring dimensions from eleven compounds,and they all agree closely with the graphite dimensions. More-over, he explicitly states the limitations of the method. In certaincases, the molecular, atomic, and electronic arrangements aredetermined.Electronic Structure of the SpineZs.8s-The interatomic distancesare calculated and the conclusion is drawn that the empiricalformula R”R”’204 is the only one which correctly represents thestructure in the crystalline state.Crystal Cleavage and Structure.s6-The following rules governingcrystal cleavage are presented : (1) Cleavage tends to occur so as toleave the two new crystal surfayes electrically neutral.(2) Weakerbonds will be broken in preference to the stronger bonds. (3)If all bonds are equally strong, cleavage will occur between thcplanes connected by the fewerst bonds per unit area. These rulesare used to explain satisfactorily the observed cleavage in diamond,sphalerite (ZnS), wurtzite (ZnS), sodium chloride, iron pyrites,calcite, aragonite, graphite, antimony, and bismuth.Isomorphism in the Organo-metallic Xeries.8 7-A study of thetemperatures of fusion and solidification of binary mixtures ofoxides and sulphides of triphenyl-phosphine, -arsine, and- stibine.The results indicate that if in a pair of organo-metallic compoundsthe asymmetry of the central atoms is increased by the additionof oxygen in one and of sulphur in the other, the tendency t o isodi-morphism is increased.If, on the other hand, the central atomsare saturated by the same element, oxygen or sulphur, the tendencyto isomorphism is increased.Structure of Halides from Compressibility. 88-A theoretical paper.Calculations,’ based on Sir J. J. Thornson’s hypothesis, are made ofthe compressibilities of various cubic halogen salts ; values areobtained which me in good agreement with the experimental values85 M.L. Huggins, Physical Rev., 1923, 21, 509.8 8 Idem, Amer. J . Xci., 1923, 5, 303.8 7 P. Pascal, Bull. SOC. ch+n., 1923, [iv], 33, 170.a8 Ida Woodward, Phil. Mag., 1923, [vi], 45, 882CRYSTALLOGRAPHY. 257of Richards and Jones. In addition, the specific photoelectriceffect and the specific inductive-capacity for the sodium and potassiumsalts are calculated with the aid of W. L. Bragg's atomic diameters.Refraction and Absorption of Light by Zinc Blende.89-Thesequantities were measured for temperatures ranging from - 80"to 700" and for wave-lengths between 400 and 800p. The resultsindicate that in the visible spectrum the dispersion is normal andattributable principally to an oscillator with a frequency in theultra-violet .Optical Activity of Sodium Chlorate and Sodium Bromate.*-Atheoretical paper. The author uses Born's theory of crystal latticesto deduce expressions for the optical rotatory powers.Observedand calculated values for sodium bromate agree well for wave-lengths between 4 and 8 x 10-5 cm., but for sodium chlorate thecalculated values are approximately only one-half of the experi-mental values. This result indicates the necessity for considerablealteration of the lattice model used in developing the theory, possiblyeffected by a displacement of the centre of mass of the electrons, aprocedure possible only with VBgard's model.Rotatory Dispersion.gl-1n this paper it is shown that opticalactivity depends on the presence of an axially symmetrical sys'temof a t least four coupled electrons, which may be carried either bya single atom or by several atoms of the molecule.An activemolecule may contain more than one of such electron systems, andconsequently the rotatory dispersion may exhibit an abnormalcharacter. Besides the rotatory dispersion, the Cotton effect,absorption, and circular dichroism are discussed. The rotatorydispersion of a large number of heavy-metal complex derivativesand organic substances has been investigated and the resultshave been considered from the point of view of spectroscopic,photo c hemic a1 , and s t ereoc hemical data.The Structure of Thin Films.92-Although not belonging to thesubject of crystallography proper, these papers should be read inconnexion with the X-ray investigation of long-chain compoundsdescribed above.Dimensions of Molecules, Atoms, and Ions.93-A critical r&umd ofthe literature on this subject and a discussion of the relative accuracyof the different methods of determining molecular dimensions-viscosity, critical data, X-ray analysis, measurement in liquids,diamagnetism, optical measurements.Much smaller dimensions8s Maria Mell, 2. Physik, 1923, 16, 244.80 C. Hermann, ibid., p. 103.91 I. Lifschitz, 2. physikal. Chem., 1923, 105, 27.92 N. K. Adam, Proc. Roy. SOC., 1923, [AJ, 103, 676, 687.93 K. F. Herzfeld, Jahrb. Radioaktiv. Electronik, 1923, 19, 259.REPe-VOL. XX. 258 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.are obtained for molecular dimensions in the gaseous than in thecrystalline state, and this is ascribed to the occurrence of phaserelationships between the electron orbits in the latter case whichconsiderably increase the repulsive forces.Paramagnetism at Low Temperatures.94-A complete investigationis given of the susceptibilities, down to the lowest temperature obtain-able with liquid hydrogen, of the anhydrous sulphates, the hepta-hydrated sulphates, and the ammonium double sulphates of cobalt,nickel, and ferrous iron, all in the powder form ; and of two completecrystals, cobalt ammonium sulphate and nickel sulphate hepta-hydrate.The last-named are the only data yet available of theprincipal susceptibilities of crystals at the lowest temperatures.In all the cases examined, the susceptibilities follow the Weiss Law,x(T +, A) = C a t higher temperatures, but various deviations arefound a t the lowest temperatures.For the complete crystals, theCurie constant is the same for each of the three principal suscepti-bilities, and these increase more rapidly with fall of temperaturethan is given by the Weiss Law, which is obeyed a t higher tempera-tures. There does not seem to be an intimate connexion betweenthe “magnetic dilution ” of a substance and the A of the WeksLaw, but the connexion between A and the spacings of the para-magnetic atoms has been used to construct a hypothetical space-lattice for the nickel atoms of the sulphate heptahydrate.Apparently,this suggested lattice is in agreement with an X-ray powder photo-graphy and it would be interesting to have the structure workedout thoroughly. The above low-temperature investigations areextended in a subsequent paper 95 to cobalt potassium sulphate,cobalt rubidium sulphate, and manganese ammonium sulphate.Uniwersal Interferometer and Vave-length Tor~~rneter.~~-Fordetails of these ingenious instruments reference should be made tothe original papers.Thermal Conductivity of Bismuth Crystal~.~7-This quantity hasbeen determined for directions parallel and perpendicular to thetrigonal axis. The values at 18” in C.G.S. units are : (a) Parallelto trigonal axis, 0.0159, ( b ) perpendicular to trigonal axis, 0.0221.Ratio = 1.39.A new “ plate ” apparatus has been developedwhich makes it possible to measure thermal conductivities as highits 0.02 C.G.S. unit with the accuracy of about 1 per cent., usingspecimens 2 cm. by 1 cm. and about 1 or 2 mm. in thickness.Rotatory Polarisation in an Orthorhombic Crystal exhibiting Crossed94 L. C. Jackson, Phil. Trans., 1923, [A], 224, 1.9 5 L. C. Jackson and H. K. Onnes, Proc. Roy. Soc., 1923, [A], 104, 671.96 A. E. H. Tutton, ibid., pp. 47, 62.9 7 G. W. C. Kaye and J. K. Roberts, ibid., p. 98CRYSTALLOGRAPHY. 259Axial Dispersion.g*-Crystals of triphenylbismuthine dichloride(orthorhombic holoaxial, a : b : c = 0.774 : 1 : 0.409) are uniaxialfor green light of wave-length 510 ,up a t 17’. They exhibit thephenomenon of crossed axial dispersion, and a section perpendicularto the acute bisectrix does not extinguish between crossed nicols,but transmits light of a bright green colour.Similar phenomena areshown by potassium sodium tartrate. A salt of one part of sodiumpotassium tartrate and two parts of sodium ammonium tartrate isuniaxial in the green, whilst a salt of equal proportions is uniaxialin the blue. These highly interesting observations of opticalactivity in biaxial crystals lead us finally to one of the most importantoptical researches in recent times :-Rotatory Polarisation in Crystals, especially Biaxial Crystals egg-L. Longchambon has shown that in reality the number of activecrystals is considerable. The majority of crystals in which thedissymmetry is structural and all those in which it is molecular havebeen found to be optically active.The author has devised a specialarrangement whereby an extremely parallel beam of monochromaticlight can be produced. He has shown that very little deviation fromparallelism is sufficient to mask the rotatory polarisation of crystals,but with the new system the most feeble effects have been observedand measured. The crystals examined include lead, barium, andstrontium formates, nickel and zinc heptahydrated sulphates,magnesium chromate, ammonium oxalate, iodic acid, hydrazinesulphate, sodium arsenat’e, and lithium sulphate. The only excep-tions are the-cubic nitrates of lead, barium, and strontium, butsince in Wyckoff’s “ Survey ” these substances are described asbelonging to the pyrites class, this result is not to be wondered at.On seven chosen examples, it has.also been shown that the rotatorydispersion has exactly the same value whether the substance isliquid, dissolved, or crystalline. From these results, Longchambonproposes two generalisations, (1) that the rotatory dispersion isindependent of the direction of observation; (2) that the rotatorypower due to structure, if it exists in these crystals, has the samerotatory dispersion as the chemical molecules which constitute thecrystal.New Books, Etc.An English edition of Rinne’s “ Das feinbauliche Wesen derMaterie nach dem Vorbilde der Kristalle ” (translated by W. S.Stiles) has been published by Messrs. Methuen.In June there appeared “ Kristalle und Rontgenstrahlen ” fromthe pen of Dr. P. P. Ewald (Berlin : Julius Springer, pp. viii + 327).Ewald has always been one of the foremost in the ranks of crystal-s8 G. Greenwood, Min. Mag., 1923, 20, 123.0u J . Phyeique, 1922, [iii), 6, 156s. K260 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.analysts, and a first-hand discussion of the subject from such itmaster is extremely welcome. The book deals with both crystal-structure and X-rays, and the science is developed step by step insuch a way as to give a thorough and comprehensive account of theprogress from the discovery of Laue to the present time. Thevarious methods of attacking the problem are carefully described andmany interesting chemical and physical points considered from thenew point of view. At the end are a number of Notes on mofedifficult and specialised branches, and a very complete list of paperson crystals analysed and related physical topics.One of the founders of the structure-theory, Prof. Schoenflies,has rewritten his epoch-making work “ Krystallsysteme undKrystallstruktur.” The new edition (“ Theorie der Kristallstruktur.Ein Lehrbuch,” Berlin (Borntraeger), 1923, xii + 555 pp., 257 figs.,lSs.), is largely unaltered, but it is adapted for the benefit of moderncrystal-analysts, and the subject is viewed in the light of recentresearches. But the subject must always remain to a large extentmathematical, and, on account of this, this new edition from the penof one of the pioneers of the science is specially recommended tothe mathematical crystallographer. For the object for which it isintended it is invaluable.“ A Survey of Existing Crystal Structure Data,’’ by R. W. G.Wyckoff,l is a very useful addition to the literature of the subject.A new edition of “ X-Rays and Crystal-Structure ” by W. H. andW. L. Bragg is now in the press.Volume I11 of ‘‘ Mindralogie de Madagascar ” (A. Lacroix, Paris,SOC. d’6ditions gdogr. 1923, viii + 450 pp. 4”, 8 pls., geol. map,28 text figs.) has appeared, and this handsome topographical miner-alogy is now complete.A very cheap (Is.) second edition of the ‘‘ Guide to the collectionof gemstones in the Museum of Practical Geology” (W. F. P.McLintock, London, 1923, iv + 80 pp., 24 figs.) has been publishedon much the same lines as the first edition. A fifth edition of‘‘ Grundriss der Kristallographie ’’ [G. Linck, Jena (G. Fischer),1923, x + 293 pp., 3 col. pls., 521 text figs.], has also appeared.This Report cannot be better concluded khan by reference to thelatest edition of the Zeitschrij’t fiir KristalZographie,2 prepared speciallyin honour of the eightieth birthday of the foremost crystallographerof our time, Professor P. H. v. Groth. Contributions from theleading crystallographers and mineralogists of the world have beenlaid at his feet, and the volume is at once a valuable addition toscientific literature and a fitting tribute to a brilliant genius and anotable personality. W. T. ASTBURY.W. H. BRAGG.1 J . Frankl, Inst., 1923, 195, 183, 349, 531. * 2. Krist., 23 June, 1923

ISSN:0365-6217    

DOI:10.1039/AR9232000230

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY.Distribution of Chemical Elements in the Earth’s Crust.A TABULATED compilation of 8,611 chemical analyses of igneousrocks published between the years 1884 and 1913 has been givenby H. S. Washingt0n.l From a selection of 5,159 of the moretrustworthy of these analyses, F. W. Clarke and H. S. Washington 2have calculated the average composition of the rocks of variouscountries and regions, but these being arbitrary political divisionsonly small accidental variations are shown. Their new averagefor all igneous rocks is quoted in part under I. Including alsosedimentary rocks (shale estimated a t 4.00 per cent., sandstone0.75 per cent., and limestone 0.25 per cent.) in a lithosphere tenmiles in thickness, and also the hydrosphere and atmosphere, theirestimate of the average chemical composition of the accessibleportions of the earth is given under I1 :0.Si . Al. Fe. Ca. Na. K. Mg.I. 46-41 27.58 8.08 5.08 3.61 2.83 2.58 2.0911. 49.19 25.71 7:50 4.68 3.37 2.61 2.38 1.94H. Ti. c1. P. C. Mn.I. 0.129 0.720 0.096 0.157 0-051 0-12411. 0-87 0.648 0.228 0.142 0.139 0.108The fourteen elements listed under I1 total 99.517 per cent., andthe eighteen others separately estimated range from sulphur0.093 per cent. to boron 0.001 per cent.Speculations as to the composition of the interior of the earthcan only be based on a comparison of the observed densities ofsuperficial rocks (mean 2-77) and that of the earth as a whole(viz., 5.55). H. S. Wa~hington,~ in a paper on “ The Chemistryof the Earth’s Crust,” distinguishes “ petrogenio ” elements of lowatomic weight characteristic of igneous rocks, and “ metallogenic ”elements of higher atomic weight.He assumes that the core of theearth is made up of heavier metallogenic elements (platinum, etc .)either free or as arsenides, tellurides, etc. ; and that between thecore and the silicate crust there is a zone of nickel-iron. V. M.1 Prof. Paper U.S. Geol. Survey, 1917, No. 99, 1201 pp.9 Proc. Nat. Acad. Sci., 1922, 8, 108.8 J . Franktin In&, 1920, 190, 757.26262 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Goldschmidt * supposes that under the influence of gravity theinterior of the earth has separated into four well-marked zones :(1) a core of heavy metals, chiefly nickel-iron, and represented bymeteoric irons; (2) a zone of metallic oxides and sulphides, repre-sented in meteorites by troilite and chromite nodules; (3) a zoneof dense silicates, called the eclogite shell; and (4) a thin outershell of lighter silicates.The chemical elements proper to thesezones and to the atmosphere he places in four main groups : (1)" siderophil " elements (Fe, Ni, Co, P, C, Mo, Pt, Ir, etc.) ; (2)" chalcophil " elements (S, Se, Te, Fe, Cu, Zn, Pb, As, Sb, Bi, Ag,Au, Hg, Pd, etc.) ; (3) " lithophil " elements of silicate fusions(0, Si, Ti, F, C1, Al, Ce, Na, K, G1, Mg, Ca, V, etc.) ; (4) " atmophil "elements (H, N, He, A, etc.). Seismologists have deduced thepresence in the earth of three zones with the thicknesses and densitiesstated below, the middle layer with a density of 5.6 having acalculated thickness of 1,400 kilometres.These three zones arecompared by G. Tammann with the slag, sulphide, and metallayers in a crucible. Arranging the metals in relative order fromelectro-positive to electro-negative, he points out that those morepositive than iron are the ones that are abundant in the silicatecrust, whilst thoso more negative than iron include the preciousmetals and mould be expected to be more abundant in the metalzone. The composition deduced for the three zones is as follows :Thickness Den-in h. sity. Composition.SilicateSulphideMetalliccrust . . . 0-1500 2.9 l(A1,O,,Fo,O,,FeO,CaO,RlgOyK,O,Na,O),l &SiO,layer ... 1500-2900 5.6 FeS; Fe,P; FeO; Fe; SiO,core ...2900-6370 9.6 Fe 88% ; Ni 8% ; (Fe, S, P) 3% ; preciousmetals 1%P. N. Chirvinsky 6 compares the hypothetical zones of a pyrogenicglobe with the progressive series : igneous rocks, meteoric stones,pallasites, and meteoric irons. Treating these as pseudo-elements,he calculates from the means of numerous analyses their equivaJentatomic weights, which divided by densities gives a constant. Thisis held t o be a consequence of Avogadro's law when the differentzones were in a gaseous state. He also adds " terrium " or primordialmatter, representing the average for the whole earth. From aVidewkaps. SkTifter, Krktiania, 1922, No. 11, and 1923, No. 3; Z.Elektrochem., 1922, 28, 411.2. anorg. Chem., 1923, 131, 96.6 Izv.Don. Polytech. Inst., Ncwocherkaask, 1915, 4, 76; 1918, 6, suppl.;1919, 7, 94; 1923, 8, 6 s ; Bull. Acad. Sci. Petrograd, 1917, 11, 387; [illin..Mag. (Abstr.), 1923, 2, 82-85, 157.MINERALOGICAL CHEMISTRY. 263comparative study of meteorites and igneous rocks he attempts toevolve a system of “ cosmochemistry.”Equivalent At. wt.Pseudo-element. composition. At. wt. d. d.“ Crustaterrium ” ...... RSiOs 204G 2.806 7.327“ Chondriurn ” ............ R,SiO, + RSiOa 24-36 3.4 7.165“ Pallasium ” ............ R,SiO; + 3R 30.90 4.66 6.63‘‘ Siderium ’’ ............ R 55.72 7-693 7.243“ Terrium ” ............... - 39-98 5.5 7.269Another suggestion touching a possible change in chemicalelements during geological time has been made by J. Joly7 inconnexion with his examination of the pleochroic haloes surroundingminute crystals of radioactive minerals enclosed in biotite.Measure-ments of the thorium-haloes correspond exactly with the theoreticaldimensions, but in the uranium-haloes, although the outer featuresare in good agreement with the calculated values, both the secondand first rings appear to be displaced outwards. The explanationsuggested is that the range of the or-rays, which attend the &ststages of the radioactive change of uranium, has diminished ingeological time-an effect which might be due to the existence ofuranium atoms derived from some antecedent element possessingdifferent radioactive properties from the uranium of the presenttime. A new type of halo, seen as minute, colourless or bleachedspherical spots in a biotite from Sweden, is believed to be due tonuclei of a radioactive substance containing an element emittinga-rays of very low velocity.This element, although possiblyidentical with yttrium, is perhaps new, and it is provisionally named“ hibernium.” 8Returning to more practical considerations concerning thedistribution of chemical elements in the accessible portions ofthe earth’s crust, where during geological time there has been aconstant re-sorting of material, it has long been recognised thatcertain elements are associated with certain types of rock, forexample, tin with granite, platinum with olivine-rocks, and thatcertain groups of elements usually go together. This is enlargedon in the papers of H.S. Washington and V. M. Goldschmidt quotedabove, and an instructive diagram (Fig. 1) has been given byR. H. Rasta1l.QAlthough the distribution of the elements appears to be quitecapricious, yet there is promise that the study of the differentiationof rock-magmas and the segregation of ore-deposits will in time leadPhil. Trana., 1917, [ A ] , 217, 51.J. Joly, Proc. Roy. Soc., 1923, [A], 102, 682. ’ “ The Geology of the Metalliferous Deposits,” Cambridge, 1923264 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.to some guiding principles. P. Niggli’s recent text-books lo containmuch suggestive material on the paragenesis of minerals, and W.Lindgren l1 writes on the “ Concentration and Circulation of the Ele-ments from the Standpoint of Economic Geology.” J.W. Gregory,12in his lecture before this Society on “ Ore Deposits in relation toGeographical Distribution,” suggested the occurrence of localuprisings of the metal-rich barysphere along continental marginsa t different periods of mountain-building. He pointed out thatthe more volatile mercury l3 ores are limited to regions of the laterAlpine mountain-building, that tin ores are exposed in the earlierno. 1.N i co Ti Sncu Th Ce Y CU A u AgGenealogical tree showing connexion of metals with igneous rocks.(After R. H. Rastall, 1923.)and more denuded Hercynian system of mountain-folding, whilstthe most productive gold-quartz lodes are of still deeper-seatedorigin and only exposed in the oldest rocks.Dealing with the geographical distribution of minerals as com-meroial sources of supply of crude material, a valuable series ofpamphlets is now being issued by the Imperial Mineral ResourcesBureau,14 in which are given particdars of the mode and place oflo “ Lehrbuch der Mineralogie,” Berlin, 1920; “ Gesteins- wid Mineral-l1 Econ.CTeot., 1923, 18, 419.Is It is a noteworthy fact that no mercury-bearing mineral has ever beenfound in the British Isles.l4 “ The Mineral Industry of the British Empire and Foreign Countries,War period 1913-19,” and ssecond series of “ Statistics, 1919-21, ’ London,provinzen,” Berlin, 1923.T., 1922, 121, 750.192 1-24MINERALOGICAL CHEMISTRY. 265occurrence and statistics of production, together with detailedbibliographies. Each part (some sixty having already been issued)deals with a particular metal or mineral or group of minerals ofeconomic importance ; for example, Antimony, Cobalt, Tungsten,Vanadium, Asbestos, Graphite, Monazite, etc. Much informationrespecting the distribution of minerals is buried in the pages ofbooks and papers on topographical mineralogy, and often this isof more than mere local interest.A notable work of this type isA. Lacroix’s “ Minbralogie de Madagascar ” (Paris, 1922-23)recently issued as three large quarto volumes. Detailed descriptionsof the characters and modes of occurrence, together with manychemical analyses, are given of some 200 mineral-species that havebeen recorded from Madagascar. The chapters on petrologyinclude more than 450 new chemical analyses of rocks; and specialattention is directed to the pegmatites, which carry a variety ofrare-earth and radioactive minerals, these being compared indetail with similar occurrences in other parts of the world.Mentionmay also be made of P. P. Pilipenko’s work on the minerals andore-deposits of the Altai M0~ntains.l~ Descriptions and analysesare given of numerous metalliferous and other minerals. Of 713occurrences, details are known as to the country-rock for 582; ofthese 4.6 per cent. are in granite, 2.6 per cent. in greenstone, 18.4per cent. in quartz-porphyry, and 74.4 per cent. in sedimentary(mostly Devonian) rocks. They are, however, always in theneighbourhood of granite masses. Three main zones in depth aredistinguished on chemical grounds : (1) The ochre or oxy-zone,this being further sub-divided downwards into (a) hydrate zone,( b ) carbonate zone, and (c) sulphate zone.(2) The sooty-ore orsulphoxy-zone, with the secondary monosulphides Cu,S and Ag,S .(3) The primary sulphide or sulpho-zone. In the order of decreas-ing solubility the sulphides are : pyrites-sphalerite-chalcocite-galen+argentite ; and of these the more difficultly soluble sulphidesof silver, lead, bismuth, and copper were accumulated in the upperportion of the sulpho-zone. In the sulphoxy- and oxy-zones, theminerals are sharply differentiated according to their degree ofsolubility. Thermochemically, almost all the minerals areexothermic ; minerals with low heat of formation are characteristicof the sulpho-zone, whilst those with greater heat of formationbelong mainly to the upper zones.Constitution of Silicates.The key to the constitution of mineral silicates still remains tobe discovered, and until then no satisfactory classification of this1915, 63, 763 pp.16 “Mineralogy of the Western Altai” (Russ.) Izv.Imp. Tomb. Univ.,[Mi?%. Mag. (Abetr.), 1923, 2, 109.1K 266 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.complex group of minerals can be expected. A useful outline hasbeen given in T. M. Lowry’s “Inorganic Chemistry” (London,1922). J. Jakob has devised a long series of constitutioiialformulae based on Werner’s co-ordination theory. For example,he writes the formuh of enstatite, regarded as a trisilico-hexaoxy-silicate, and orthoclase, as a hexasilico-tetraoxy-silicato-salt,respectively, as follows : [ Si( 0 0 oSio)JMg4(Fe) and [A1(Si04Si02Si0,),]~23This is rejected by B.Gossner,l’ who works out on paper anequally fantastic scheme. Here the composition is expressed bythe combination, analogous to double salts, of certain simplemolecules, for example :Anorthite ............ SiO,Ca,[SiO,,AI,O,].Grossularite ......... [ Si03Ca,[Si0,,Al,0,]],Si04Ca,.Natrolite ............ [ Si03Na,,[Si0,,Al,03]],Si0,,2H20.or Si03Na,,[2Si0,,A102H,A103H3].Important experimental work bearing on this problem has beendone for several years past in the Geophysical Laboratory of theCarnegie Institution at Washington. Although, primarily, thiswork was undertaken from rather another point of view, namely,to determine the conditions of formation of the various rock-forming minerals in igneous rocks.The composition of the productsobtained in the synthetic experiments is expressed by the iso-m orp hous mixing of end -m em ber s , these end -mem ber s beingdefinite compounds and their composition expressed by more orless complex groups of oxides. Any deviation from such a com-position has usually been explained by the adventitious solidsolution or adsorption to a limited extent of some other oxides orgroups of oxides in the main mixture. As an example of this workmay be cited the system Ca0-Mg0-A1,03-Si0,, which wascommenced in 1906 with the investigation of the calcium andmagnesium metasilicates, wollastonite and pseudo-wollastonite,enstatite and clinoenstatite.The several binary and ternarysystems of this group were separately examined, and they have beenalready referred to in these Reports with the exception of the lastpublished,l8 namely, the system Ca0-MgO-SiO,. The thermalrelations of numerous fusions of known composition were investig-l6 Helv. Chim. Acta, 1920, 3, 669; A., 1920, ii, 754; 2. Krkt., 1921, 58,295.l7 Centr. Min., 1921, 513; 1922, 129, 193, 600, 625; A., 1921, ii, 649.la J. B Fergueon and H. E. Merwin, Amer. J . Sci., 1919, [iv], 48, 81 ; A.,1919, ii, 401MINERALOGICAL CHEMISTRY. 267ated in detail, and the crystallised or glassy products examinedwith the petrographical microscope. The stability fields of thevarious compounds have been determined. It has been found thatin many cases these compounds exist as more than one crystallinemodification over different ranges of temperature ; for example,four forms of calcium orthosilicate (2Ca0,Si02) were recognised.Continuous series of mixed crystals, solid solutions with more orless limited degrees of miscibility, and various eutectics wereFIG.2.Compounds of the system Ca0-BIg0-A1,08-Si0, plotted on a tetrahedron(shown in plan).determined. An enormous mass of useful data has been accumu-lated. Here it is only possible to indicalie the compounds thatwere observed under the conditions of the experiments. This maybe done most concisely by means of a diagram (Fig. 2). Here, onthe surface of the tetrahedron, the six edges represent the sixpossible binary systems, and the faces the four ternary systems,whilst the interior would represent the quaternary systemCa0-Mg0-A1,03-Si0, itself.On the base of the tetrahedron,representing the system Ca0-Mg0-A120,, no compounds occur(nor do any in the binary system CaO-MgO). The three otherK" 268 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.equilateral triangles meeting in the Si0,-apex and representing theother ternary systems are of course foreshortened in the diagram.Partial systems lying within the tetrahedron that have been in-vestigated, and mentioned in previous Reports, are diopside-anorthite, forsterite-anorthite, and hkermanite-gehlenite. Hereno definite compounds have been recorded, but between Lkermaniteand gehlenite there is a complete series of mixed crystals.In these experiments, the pure materials in known proportionswere subjected to dry fusion at very high temperatures (from about1,000" up to 3,800", the melting point of magnesia).The con-ditions are thus not quite the same as those occurring in nature inthe processes of rock formation. Here the element of time is ofimportance, whilst the presence of even small amounts of waterunder pressure must exert a profound influence. The diagramtherefore tells only a part of the story, and it must not be takento represent all the possible compounds or combinations of the fouroxides. Several of the compounds shown have not been found innature ; on the other hand, some common minerals (for example, theamphiboles) are not represented. The compound 3Ca0,A1,03,3Si0,,well known as garnet (grossularite), is represented in the diagramby two tetragonal forms, one of which is near to sarcolite; and2Mg0,2Al,03,5Si0, shows some resemblances to cordierite.In addition to the systems mentioned above, some other series ofsilicate fusions have been investigated in the Geophysical Laboratorya t Washington.One of these deals with the complex melilite groupof tetragonal minerals.lg Tests were made on more than a hundredmixtures in various proportions of the compounds 2Ca0,Mg0,2Si02(gkermanite), 2Ca0,A1,03,Si02 (gehlenite), 3Ca0,A1,03,3Si0,(equivalent to grossularite), 3Ca0,Pe,0,,3Si02 (equivalent toandradite), 3Na,0,A1,03,3Si0, (" lagoriolite," known only as anartificial preparation), and9(3Ca0,A120,,3Si0,) + 1 ( 3Na,O,Al,O3,3SiO2)(sarcolite).akermanite is optically uniaxial with positive signand refractive indices wNa 1.632 and cNa 1.639, whilst gehlenite isoptically negative with wNa 1.669 and cNa 1.658. These two com-pounds form a complete series of mixed crystals in which the opticalconstants change gradually with the change in composition. Crystalsof a certain intermediate composition (near 50 per cent. of eachcomponent) are optically isotropic for one or other colour of light.Mixed crystals are also common in other pairs of the compoundsenumerated above and in mixtures of three or more of them,alfhough in some cases - the miscibility is not complete. Thevarious products correspond more or less closely with the naturalA.F. Buddington, Arner. J . Sci., 1922, [v], 3, 35; A.,ii, 155MINERALOGICAL CHEMISTRY. 269minerals gehlenite, Lkermnnite, melilite, humboldtilite, and sarcolite,the analyses of which are interpreted as mixtures of the moleculesstated above. These tetragonal substances are also well known asconstituents of the slags from iron furnaces; and gliermanite longsince found in slags has only recently been recognised in volcanicrocks. The crystals present the appearance of regular cubes, owingto the equal development of a tetragonal prism with the basalplanes; and they are interesting optically on account of theiranomalous double refraction. The composition of some slagcrystals recently investigated has been interpreted in quite anothermanner.20 They are regarded as polysilicates, R",Si20,, with somealumina present in solid solution, and the name " justite '' has beenapplied to the group.Detailed determinations were made of theoptical constants of these crystals. ,Silicates of strontium and barium have been investigated in theGeophysical Laboratory.21 In the system SrO-SiO,, besidesstrontium oxide (cubic with perfect cubical cleavages) and formsof silica (tridymite and cristobalite) there are the metasilicate(SrSiO,) and orthosilicate (Sr,Si04). The metasilicate formshexagonal crystals which are hemimorphic and twinned on the base,and are optically uniaxial and positive. It forms, however, acomplete series of mixed crystals with the monoclinic pseudo-wolla-stonite (a-CaSiO,), so that it is suggested that the crystals are reallypseudo-hexagonal and monoclinic.The system BaO-SiO, givesseveral compounds, namely, 2BaO,SiO, (granular), BaO,SiO,(orthorhombic), 2Ba0,3Si02, and Ba0,2Si02, the last two beingboth orthorhombic and forming a complete series of mixed crystals.Whilst the system CaSi0,-SrSiO, gives the series of mixed crystalsmentioned above, the system CaSi0,-BaSiO, gives the doublecompound Ba0,2Ca0,3Si02. With MgSiO,, no compoundsanalogous to diopside are formed. Artificial strontium felspar,Sr0,A1,03,2Si0,, analogous to anorthite, is probably triclinic ;whilst BaO,Al20,,2Si0, is monoclinic, corresponding with themineral celsian. Different results ,have, however, been obtainedfor barium alumino-silicate by A.S. Ginzberg.Z2 The thermaldiagram of the system CaA1,Si208-BaA1,Si,08 shows the meltingpoint of anorthite a t 1,400", and of the barium compound at about1,640", a eutectic point a t 1,323" with 50 per cent. of each com-ponent, and mixed crystals limited to 20 per cent. of BaAI2Si2OsiThe optic axial angle 2V diminishes from 80" for anorthite to 6820 I<. Hofmann-Degen, Sitzungsber Heidelberger Akad. Wiss., 1919, Abt. A,Abh. 14.21 P. Eskola, Amer. J . Sci., 1922, [v], 4, 331; A., 1922, ii, 849.22 Collection of Scientific Papers dedicated to F. Y . Levinson-Lessing,Yetrograd, 1915. [&fin. fMag. (Abet?'.), 1923, 2, 153.270 ANNUAL EEPORTS ON THE PROGRESS OF CHEMISTRY.in the mixed crystals richest in barium, but the optical orientationis only slightly affected.Excess of BaAl,Si,O, crystallises out ashexagonal plates, which are optically uniaxial and positive, corre-sponding with nepheline. Fused mixtures of orthoclase andBaAl,Si,O, crystallise wit,h difficulty, but with 15 per cent. KAlSi,O,uniaxial crystals resembling the pure barium-nepheline wereobtained. The compound BaA1,Si,08 therefore exists in threeforms, namely, the hexagonal barium-nepheline, in mixed tricliniccrystals with anorthite, and as the monoclinic celsian (also preparedartificially by P. Eskola). This is analogous t o the correspondingsodium compound, Na,Al,Si,O,, which exists as the hexagonalsoda-nepheline below 1,248" and as the triclinic felspar carnegieiteup to the melting point 1,526'; although here the correspondingmonoclinic form is not known..In this connexion, mention may be made of the interestingobservations of G.W. Morey and N. L. BowenZ3 on the meltingpoint of potash-felspar. Previous observers had fomd the naturalmineral to melt very sluggishly near 1,200". Pure artificially-prepared orthoclase, after being maintained at this temperaturefor a week, presented the appearance of a glass, but when examinedmicroscopically it showed skeletal optically-isotropic crystalsembedded in a glass. At 1,400" the characteristic forms of leucitecrystals were developed. The conclusion is drawn that potash-felspar (KAlSi30,) has an incongruent melting point between1,170" and 1,530", due to the breaking down of the material intocrystallised leucite and liquid, and that it is to be regarded as abinary compound in the system leucite-silica (KAlSi,O,SiO,).The same phenomenon was observed in experiments with naturalorthoclases, but here the temperature limits vary with the impuritiespresent.The constitution of the various members of the zeolite group hasbeen discussed a t length by G. Tschermak,2* and several newanalyses are given.He finds that the ratio A1 : R" + R', is in allcases 2 : 1, and that all zeolites can be represented by the formuhH2,CaA12Si,0w+,,4 and H2,Na2A12Si,02,*+,+4. These contain agroup, CaA1,Si,08 or Na2A12Si208, equivalent to anorthite andsoda-nepheline (or carnegieite), respectively, which is regarded as anucleus (" Kern ") and written Kc or Kn (also Kb and Ks for thecorresponding barium and strontium nuclei). The various zeolitesare regarded as compounds of one or other of these nuclei with asilicic acid, combined water, and water of crystallisation, which arez3 Anzer.J. Sci., 1922, [v], 5, 1; A,, 1922, ii, 577.24 8itzungsber. Akad. T v i S S . Wien, 1917, Abt. I, 126, 641-6OG; 1918,Abt. I, 127, 177-289; A,, 1921, ii, 703MINERALOGICAL CHEMISTRY. 27 1supposed to form a network enclosing the nucleus. Such a structureis regarded as offering an explanation of the variation of the opticalcharacters of the zeolites with loss or gain of water, the variousadsorption phenomena, and the ease with which the bases may bereplaced.For example, natrolite is written as an orthosilicatewith SiH4 in combination, namely, SiH4Kn = H4Na2A12Si30,,.Chabazite as a disilicate in combination with polysilicic acids(Si,H,, Si4H,, Si,H,, or SiH,) and water, namely, Si2H4Kc0,H4,Zaq=H,,CaAl,Si,O,,; and gmelinite the same with Kn in place of Kc.(For further details see the abstract.)Lengthy discussions have taken place as to the part played bywater in zeolites.25 The experiments of some authors suggest thatdehydration and rehydration proceed in steps, corresponding t o aseries of definite hydrates, whilst other authors maintain that theprocess is continuous. A detailed account of Nova Scotian 26 zeolitelocalities includes many new analyses and dehydration curves.A book by V. Iskyul on “Experimental Investigations in theProvince of the Chemical Constitution of the Silicates.TheChlorites” has been published in Russian (Petrograd, 1917,310 pp.).27This deals more especially with the group of the chlorites, but it alsoincludes several other minerals-olivine, serpentine, garnet, amphi-bole, and pyroxene-which, by reason of their association in natureas alteration products, are usually regarded as having some bearingon the constitution of the chlorites. In the experiments, theminerals, both before and after ignition, are digested in 2.14 per cent.hydrochloric acid solution on the water-bath for two hours. Thesilica passing into solution is estimated, and also the precipitatedsilica that is extracted by sodium carbonate solution.The ratioof these two values is taken as the solubility of silicic acid in themineral. This is plotted against the volume of the solvent expressedin C.C. per gram of the mineral altered (the former as ordinates andthe latter as abscissae), and the resulting curve is called the silicasolubility curve. A large number of complete analyses are alsogiven of the minerals employed in the experiments. Minerals ofthe olivine group behave as orthosilicates; but after ignition thosecontaining iron yield some metasilicate : Fe2Si04 + 0 + Fe20, +SiO, and Mg2Si0, + SiU,+ 2MgSi0,. The serpentine minerals25 G. Stoklossa, Jahrb. Min., Bed.-Bd., 1918, 42, 1; F. Rime, Ber. Sachs.Akad. Wiss., 1920, 72, 12; 0. Weigel, Sitzungsber. OM. Naturwiss. Marburg,1920,48; K.H. Scheumrtnn, Ber. Sachs. Akad. Wim, 1921,73, 3 ; A. Beutell,Cedr. Min., 1921, 694, 721; 0. Weigel, ibid., 1922, 164, 201. [Min. Mag.(Abstr.), 1923, 2, 57.126 T. L. Walker and A. L. Parsons, Uniu. Toronto Studiiea, Geol. Ser., 1922,14, 13.27 Min. Mag. (Abstr.), 1924, 2, 207272 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.are metasilicates ; but whilst compact serpentine and chrysotitebehave like the pyroxenes (enstatite), the antigorite variety reactslike the amphiboles (anthophyllite) . On ignition, serpentine givesH,Mg,Si,O, + H20 + Mg2Si04 + MgSiO,. In the amphiboles andpyroxenes the solubility curves are approximately straight lines,but the silica solubility of the former is about twice that of thelatter. Since the bulk composition is the same for both, the differ-ence in behaviour may be due to polymerism or isomerism of the(R”SiO,), molecule.The solubility curves of silica in the chloritesare of three types : (1) lying very close to the abscisss, as in penninite(H22R13”R4/”Si8046):ll tabergite (H20R12”R41”Si8044), and rhodo-chrome (H18R11”R4 Si,O,); (2) the curve at first rising slowly,but much steeper in its later course, as in leuchtenbergite andclinochlore (both H30R1,”Rs’”Si10064) ; and (3) lying close to theordinates, as in prochlorite (H24R14/’R8’%8054) and corundo-phyllite ( ~ 2 0 ~ l l ” ~ 8 ” ~ ~ i 6 ~ 4 5 ) . With increasing silica-content, asshown by the bulk-analyses of the chlorites, there is diminishingsilica solubility. The experiments rather support Vernadsky’stheory that the chlorites are salts, and complex compounds of thesesalts, of the acids A12Si2+m0,+2m-n(OH)2n.Some comparative experiments have been made by E.Norin 28on the dissociation of the hydrous alumino-silicates, prehnite(H,0,2Ca0,A120,,3Si02), zoisite (orthorhombicand epidote (monoclinic H20,4Ca0,3A1,0,,6Si0,, with some ironreplacing aluminium and calcium), in which the small percentage ofwater is expelled only a t high temperatures. The finely powderedmaterials were heated for one hour at various definite temperaturesand then boiled for twenty minutes in a 7 per cent. solution ofhydrochloric acid. Lime, alumina, and ferric iron were estimatedin the solution, and the separated silica extracted with a 5 per cent.soda solution. Prehnite is partly soluble in this strength of acid.before ignition, and after ignition the amount dissolved is proportionalto the water that has been expelled ; finally it is completely soluble.I n all cases, the amounts of lime, alumina, and silica dissolved arein the same ratio as in the original mineral. Zoisite is only slightlyattacked before ignition. With loss of water a molecular changetakes place and the material then passes into solution. Epidotealso shows a progressive molecular change with the gradual loss ofwater between 940” and 1,100”. Here the alumino-silicate and theferri-silicate dissociate independently of each other, suggesting thatin one and the same silicate molecule ferric oxide does not iso-morphously replace alumina.H,0,4Ca0,3A1,0,,6Si02),28 China J .Sci. and Arts, 1923, 1, 390. [Mh. Mag. (Abstr.), 1924,2,215.MINERALOGICAL CHEMISTRY. 273The alumino-silicate nucleus, H2A12Si,08, evidently present inmany silicates, is very stable, and it persists from the rock-formingminerals into many of their weathering products. By chemicalmeans it can be broken down only by strong acids or at a hightemperature. As pointed out by V. I. Vernad~ki,2~ it can, however,be broken down by certain organisms. That diatoms are able toextract silica from clay suspended in water has been long known,and the same action has given rise to the presence of free aluminiumhydroxide in tlhe Russian black-earths. A culture of bacteria anddiatoms from pools near Kiev, when added to water free from silicabut containing suspended kaolin, extracted silica for their growthwith at the same time separation of free aluminium hydroxide.A somewhat analogous case is that shown in the extraction ofpotash from micas by growing plants. Comparative experiments 30with peas and oats grown in water or pure quartz-sand and suppliedwith the necessary soluble inorganic salts, but in one set with thepotash supplied as finely powdered biotite (K,O 7-44 per cent.) orsericite (K20 5.14 per cent.), gave a more luxuriant growth withthe micas, especially biotite, than with a soluble potash salt.Withthe decomposition of the biotite an alkaline reaction is produced.In this connexion, a long series of experiments has been made on theamount of potash extracted from various micas by prolonged actionof acids (hydrochloric, citric, carbonic) and salt solutions.31Some light on the constitution of silicates may be expected from acorrelation of the various physical characters with variations inchemical composition in isomorphous series.It is necessary,however, that all the data 32 should be actually determined on thesame sample of material-and not, as is often done, to quote aportion of the data from the literature for similar material from thesame locality. The regular variation of the optical constants of theplagioclase felspars (albite, NaAlSi,O,, to morthite, CaAl,Si,O,) is,of course, well known, and in fact the composition of plagioclasesin rock-sections is always deduced from their optical properties.Carefully determined data connecting the optical constants(refractive indices and optic axial angle) with the chemical com-position are gradually being accumulated for some other groups ofminerals.But usually the case is complicated by the presence ofseveral variable components in the isomorphous mixture. For29 Compt. rend., 1922, 175, 450; A., i, 1096.30 B. H. Cranner, Norges Geol. Unders., 1922, No. 114.31 V. M. Goldschmidt and E. Johnson, Norges Geol. Unders., 1922, No. 108.32 Such data are collected and tabulated in the “ Tables annuelles de con-stantes et donndes numdriques,” vol. 4, for 1913-16 (Paris, 1921-22).The mineralogy chapter is issued a.s a reprint ‘‘Donnee8 numdriques decristallographie et de rnin6ralogie.” by L.J. Spencer (Paris, 1923)274 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.example, in the olivine group 33 a first rough division must be madeinto the three series forsterite-fayalite, forsterite-tephroite, andtephroite-fayalite, and in the scapolite 34 and other groups thereare several components. In the clinozoisite-epidote group, withincreasing ferric iron the optic axial angle 2V measured over thenegative bisectrix decreases, and the refractive index p increases,whilst the dispersion 2VD - WE is irregular. To explain thesevariations, F. Zambonini35 has suggested that there are here twoseries of mixed crystals-a normal and an abnormal series. Writingthe formula of clinozoisite as Ca2A1,(A10H)(Bi0,),, he points outthat the replacement of Al, or AI(OH), or both, by iron would givethree series of stereoisomeric mixed crystals, which would beexpected to differ in their physical characters.Similarly, the iso-morphous replacement of calcium in apatite by, say, lead might giveeither 3Ca3(P0,),,(Ca,Pb)C1, or 3(Ca,Pb),(PO4),, CaCI,. This is itsuggestion that may bear fruit.The method of tetrahedral plotting, as illustrated above in Fig. 2,was extensively employed by H. E. Boeke 36 [1881--19181, andsincecontinued by his pupil W. Eitel,37 for plotting the constituent oxidesof mixed crystals. Large numbers of analyses of rock-formingminerals were collected from the literature and re-calculated asmolecular percentages. For example, 336 analyses of hornblendeare treated as representatives of the four-component systems,Si0,-CaO-( Mg,Fe)O-(AI,Fe),O, (aluminous hornblendes) andSi0,-RO-R,03-R,O (alkali-hornblendes), and the amounts of theseoxides are plotted, in each case, from the four corners of a tetra-hedron.A point inside the tetrahedron then represents the com-position shown by each analysis, and its position is recorded by theco-ordinates of orthogonal projections on three rectangular planes.It is found that the analyses fall into certain groups and clusters.Five-component systems are plotted in four dimensions, and itseven-component system is plotted on a “ six-dimensional heptatope.”Much paper is filled and the reader is left bewildered.Artijicial Reproduction of Minerals.Since the publication of P.N. Chirvinsky’s Reproductionartificielle de min6raux au xixe sikcle ’’ (par P. Tchirwinsky, Kieff,83 H. Magnusson, Geol. Fo’r. FGrh., 1918, 40, 601; A., 1920, ii, 261.34 N. Sundius, Bull. Geol. Inst. Uniu. Upsulu, 1919, 16, 96; A., 1920, ii,35 Atti (Rend.) R. Accad. Lincei, 1921, [v], 30, (2), 80, 117, 162, 203.36 A., 1916, ii, 570.37 Jahrb. illin., Be&-Bd., 1918, 42, 173, 223; 1922, 47, 201; see also ibid.,260.1921,44, 369; 1921,45,275; 1922,45,311; 2. Krist., 1921,56, 526MINERALOGICAL CHEMISTRY. 2751303-1306; in Russian) no systematic account of this subject hasbeen given. P. Niggli has summarised the recent literature bearingon the synthesis of polymorphous minerals 38 and also that dealingwith some dry silicate f~sions.~Q He concluded that the productionof the different modifications of the same chemical substance dependsin most cases on variations in temperature rather than in pressure.Much work has now been done on the synthesis of numerous minerals,and there is material for a good book on the subject.Here only afew salient and recently published points can be touched upon.The important experimental work done a t the GeophysicalLaboratory of the Carnegie Institution a t Washington has dealtmainly with the dry fusion of silicate systems, which have beenreferred to above. Here mention may be made of some hydro-thermal experiments. G . W. Morey and C. N. Fenner 40 havestudied the system H20-K2Si03-Si02 over a temperature range from200" to 1,000", and various potassium silicates have been determined,although none of them are known as minerals. By the addition ofalumina and experimenting with the system ~O-A1,03-Si0,-H,0W. J.Muller and J. G. Koenigsberger *l obtained more interestingresults. The materials, sometimes with the addition of carbondioxide, were heated in a bomb for several hours or days a t 100" to440". The bomb contained a filtering device by means of which itwas possible to collect cryst'als that had separated from the clearliquid. These were formed in only small amount and includezeolites, orthoclase, pectolite, quartz, and calcite. In the solidmaterial a t the bottom of the bomb there was found, in addition tothe minerals just mentioned, also leucite, nepheline, and pyrophyllite.The zeolites include analcite, a micaceous zeolite related to gyrolite,and several new potassium zeolites ; they commence to form belowloo", and are stable up to about 300".Orthoclase is formed at 360"and with increasing temperature takes the place of leucite. In thepresence of an excess of carbon dioxide at, 310" only quartz is stable.The system Fe,03-SO,-H,O has been studied by E. Posnjak andH. E. Merwin 42 also in the Geophysical Laboratory. Ferric sulphatewith various proportions of sulphuric acid and water was heated insealed tubes for some days or months at 50" to 200". In additionto iron hydroxides, nine sulphates were isolated and determinedcrystallographically and optically. Some of the products are stableonly in contact with solutions of certain concentrations, temperatures,38 Fortschr.Min. Kriat. Petr., 1916, 5, 131.40 J. Arner. Chem. SOC., 1917, 39, 1173; A., 1917, ii, 370.4 1 2. anorg. Chem., 1918, 104, 1;42 J. Amer. Chem. SOC., 1922, 44, 1965; A:, 1922, ii, 772.30 Ibid., 1920, 6, 35.A., 1918, ii, 402; J. G. Koenigsbergera.nd W. J. Miiller, Jahrb. Min., Be&?.-Bd. 1921, 44, 402; A., 1921, ii, 459276 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.or pressures. But of the whole series so prepared only two wereidentified with known minerals, namely, orthorhombicidentical with copiapite, and orthorhombic Fe20,,4S0,,9H,0,identical with rhomboclase. On the other hand, several crystallisedand well-defined ferric sulphates met with in nature were notobtained.Evidently nature has devised some other method, andvery likely more than one, of dealing with the system Fe,O3-SO3-H,O.Experiments on the constitution and genesis of the natural ferricsulphates have been made by R. Scharizer since 1898, and hisresults described in a long series of papers. For the orthorhombicrhomb~clase,~~ he writes the formula as (FeOH),(HSO,), + 6H,O.Over concentrated sulphuric acid it loses 6H,O; and at 128" itpasses into (FeOH),(HSO,),, then Fe(SO,)(HSO,), and finallyFe,(SO,),. The compound (FeOH),(HSO,), is deposited onlyfrom strongly acid solutions (containing a t least 66.53 per cent.H2S04) ; its crystals are pseudo-rhombohedral, consisting of threeor six monoclinic individuals twinned together. The hexagonalmetavoltine 44 has often been prepared artifically, although it is rareas a, mineral.It is a salt of ferri-sulphuric acid, H,[(SO,),(PeOH),],in which only part of the hydrogen is replaced by potassium; thewater of crystallisation is variable with a maximum of 5H,O, andtwo other definite hydrates appear to exist. Several well-crystallisedsulphates found in ancient ( '1 Roman) workings in the Rio Tintopyritic deposits have been described and analysed. In the samepaper, H. F. Collins 45 records the results of numerous experimentson the crystallisation of mixed solutions of copper and ferroussulphates in various proportions. In the monoclinic series ofmixed crystals, (Fe,Cu)S0,,7H20 (pisanite), it was found that themaximum amount of copper that can be taken up is 14-65 per cent.(= 65.95 per cent.CuS0,,7H20) ; whilst in the triclinic series,(Cu,Fe)S0,,5H20 (chalcanthite), the maximum amount of iron isonly 0.84 per cent. (= 3.65 per cent. FeS04,5H,0).Various forms of calcium carbonate have been prepared by M.Copi~arow.~6 At a temperature of 305" and pressure of 24 atmo-spheres he obtained calcite as a granular, crystalline aggregate,coherent enough to take a good polish and closely resemblingmarblea47 At a lower temperature (1-5") from solution feathery2Fe20,,5SO,, 17H,O,43 2. Krist., 1921, 56, 353. 44 R. Scharizer, ibid., 1923, 58, 420.4 5 Min. Mag., 1923, 20, 32; A., ii, 776.47 This recalls the early experiments of Sir James Hall, which were com-menced in 1790, and of which a good account has recently been given byJ.S. Flett in an address, " Experimental Geology," at the British Association(Report for 1921, 1922, 56).46 T., 1923, 123, 785MINERALOGICAL CHEMISTRY. 277crystals of hydrocalcite were formed. These are stated to have thecomposition CaC0,,5Hz0, and to become opaque through loss ofwater a t 17-18'. They are no doubt identical with the mineralhydroconite, which was re-described in 1907 under the name lublinitewith the same composition, CaC0,,5H20. Better crystals, 1 cm. inlength, have been obtained by J. E. Mackenzie 48 by the action ofcarbon dioxide on " sugar-lime " solution a t 2". In this case, thecomposition is given as CaCO,,GH,O. The clear crystals commenceto lose water a t 5", changing into calcite; and dilatometric experi-ments do not indicate the existence of any intermediate hydrate.The latter result confirms that of Johnston, Merwin, and William-who also found only one hydrate, CaC0,,6Hz0, the crystalsof which are monoclinic.The mode of formation of dolomite in nature has been muchdiscussed and many attempts have been made to prepare it arti-ficially. All attempts a t the ordinary temperature and pressurehave failed. Successful results have recently been obtained byA.E. Mitchell 5O in a special apparatus devised for working underpressures of carbon dioxide up to 20 atmospheres a t a temperatureof 25'. From mixed solutions of calcite and nesquehonite(MgCO,,SH,O) well-defined rhombohedra with the physical charactersof dolomite were obtained.Dissociation of Carbonates.In connexion with the use of dolomite as a refractory materialit has often been assumed that when heated the material firstbreaks down into magnesium oxide and calcium carbonate. Thiswould imply either that dolomite is not a definite compound,CaMg(CO,),, or that such a compound splits up into CaCO, andMgCO, before any evolution of carbon dioxide takes place.Recentexperiments do not, however, confirm this. C. S. Garnett,51 heatingdolomite in a current of air a t the ordinary pressure, determined theloss of carbon dioxide a t various temperatures, and these plottedagainst one another give a continuous curve. The dissociation isslow between 500" and 675', and is complete at 898". As soon asdissociation had commenced, free calcium oxide was found t o bepresent.Grecian magnesite (MgCO,) under the same conditionsshowed vigorous dissociation from 540" with completion below 660".Artificially prepared magnesium carbonate (" magnesia alba ") iscompletely decomposed at about 430". A. E. Mitchel152 has4 a T., 1923, 123, 2409.40 Amer. J. Sci., 1916, [iv], 41, 473 ; A., 1916, ii, 433.T., 1923, 123, 1887.61 Min. Mag., 1923, 20, 54; A,, ii, 763. 62 T., 1923, 123, 1065278 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.determined the dissociation pressures of magnesite, dolomite, andcalcite, which plotted against the temperatures give continuouscurves with dolomite (695 mm. at S32") intermediate betweenmagnesite (760 mm. a t 756") and calcite (761 mm.at 896"). F. H.Smyth and L. H. ad am^,^^ in a, study of the system CaO-CO,,have determined the behaviour of calcite up to 1,390" and 1,000atmospheres. The curve is a continuous one (for log p , the dissocia-tion pressure, against 1/T a straight line) up to 1,240" and 30,000 mm.marking the eutectic point CaO-CaCO,. The melting point ofcalcium carbonate, which persists as calcite, is about 1,339' .at779,000 mm. pressure. No evidence was obtained of an inversionfrom calcite into " ct-CaCO, " a t 970" as recorded by H. E. Boeke(1912) and by Johnston, Merwin, and Williamson.49 In this con-nexion it may be mentioned that calcite is now generally recognisedby petrologists as a primary constituent of certain types of igneousrocks; and W. C. Brergger 54 has applied the name carbonatit,es tomagmatic carbonate rocks.Pseudomorphs and Alteration of Minerals.Minerals, although usually more stable than other substances,are constantly, through long periods of time, undergoing changes inthe earth's crust.From a close study of their mutual associationsand alterations much information of a chemical nature may begained. The only books dealing specially with these matters arethose of J. F. A. Breithaupt, "Die Paragenesis der Mineralien"(1849), and J. R. Blum, " Die Pseudomorphosen des Mineralreichs "(1843, with four supplements to 1879). The study of these importantsubjects was since then long neglected, but now a revival is settingin. A suggestive little pamphlet by W. Maucher, " Die Bildungsreiheder Mineralien " (Freiberg, 1914), dealt with the order of depositionof the various minerals in metalliferous veins ; and J.Koenigsberger s5has recorded in minute detail the associations, paragenesis, andhabit of the crystals of minerals found in rock-crevices in Alpineregions. Many isolated facts are recorded in petrographical papers,and in the numerous recent papers on the metallographic method ofexamining opaque ores on polished surf aces. Various pseudomorphshave been described by H. Laubmann.66P. P. Pilipenko in his Mineralogy of the Altai Mts., quoted above,15has made a detailed study of the pseudomorphs met with in thedifferent zones of the mineral veins. I n the sulpho-zone 31 minerals53 J . Amer. Chem. Soc., 1923, 45, 1167; A., ii, 490.ca Videnskaps, Skrifter, Kristiania, 1921, No.9 (for 1920).66 Abh. Akad. Wisu. Miinchen, 1917-19,28, Nos. 10-12.6 6 Jahrb. Min,, 1921, i, 15; 1921, ii, 35; 1922, i, 1RIINERALOaICAL CHEMISTRY. 379have given rise to 112 pseudomorphs ; in the sulphoxy-zone 17minerals gave 29 pseudomorphs; and in the oxy-zone 42 mineralsgave 116 pseudomorphs. According to their tendency to formpseudomorphs, the minerals are divided as inactive (giving nopseudomorphs), slightly active (giving 1 or 2 pseudomorphs), andactive (giving more than 2). In t.he sulpho-zone, the numbers ofsuch minerals are 14, 15, and 16, respectively; in the sulphoxy-zone, 5, 15, and 2 ; and in the oxy-zone, 9,29, and 13. The inactiveminerals of the sulpho-zone include mainly sulphides of Bi, Sb, AS,sulpho-salts (with Bi, Sb, As) of Cu, Pb, Ag, and tellurium anduranium compounds.Simple sulphides are more active, in theincreasing order : cinnabar and galena, chalcopyrite and sphalerite,pyrites and marcasite. Similarly, for gangue-minerals : barytes,fluorite, silica, carbonates. In the oxy-zone the order of increasingactivity runs : smithsonite, cerussite, malachite, quartz and itsvarieties, pyrolusite, psilomelane, goethite and limonite, that is,in the order Zn, Pb, Cu, Si, Mn, Fe. Inactive or slightly activeminerals in the oxy-zone are compounds of Bi, Cr, As, U, Mo, V, P.In each zone, the pseudomorphs are formed mainly at the expenseof minerals in the same zone, a few from minerals belonging to thezone below, but none from minerals of a higher zone.The formationof pseudomorphs thus, as a rule, takes a definite course : for example,galena + anglesite + cerussite ; sphalerite -+ hemimorphite -+smithsonite ; and pyrites + jarosite + limonite.An interesting series of mineral changes has been described fromthe Mendip Hills in Somerset.57 Little work has been done on theminerals of this ancient mining district, and the only analysispreviously made is that by Berzelius in 1823, when he establishedthe species mendipite. This mineral had, however, been foundlong before, and is mentioned in John Woodward’s “ Catalogue ofEnglish Fossils ” (1728) ; he says : 58 ‘( . . . Its whole Appearance islike that of a Spar, and nothing like Lead appears, tho’ it be veryrich of that Metal.. . .” The mendipite is found as nodulesembedded in manganese oxide, the latter being much intermixedwith calcite and occurring in limestone. It is usually more or lesscompletely altered to carbonates, this change having evidentlybeen brought about by the action of water containing calciumhydrogen carbonate in solution, and the chlorine removed as calcium67 L. J. Spencer, with analyses by E. D. Mountain, Min. Mag., 1923, 20,67; A., ii, 774.68 The specimen so described, together with several others from the MendipHills, is still preserved in the Woodwardian Collection at Cambridge. Wood-ward’s Catalogue also records the results of some of his experiments made on“ Bodyee digg’d up out of the Bowels of the Earth,” Some of the specimenswere given to him by his contemporary, Sir Isaac Newton280 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.chloride. The first step in the change was to hydroceru~site,~~and not, as might have been expected, to the chloro-carbonatephosgenite (PbCO,,PbCl,) .Analyses of the pure hydrocerussiteshow, however, the presence of a small amount of chlorine isomor-phously replacing hydroxyl, thus suggesting the existence of acompound 2PbCO,,PbCl,. With further alteration the hydro-cerussite changes to cerussite, and some distinct pseudomorphs ofcerussite after rhombohedra1 crystals of hydrocerussite have beenfound. The nodules of mendipite thus come t o be surrounded byzones of alteration products as represented diagrammatically inPig.3, the changes having proceeded in the direction :Mendipito -+ Hydrocerussite + Cerussite( 2PbO,PbCl,) (2 PbCO,,Pb( OH),) (PbCOdFIG. 3.Diagram to represent the aIteration products of Menclipite andChloroxiphite.Occasionally embedded in the mendipite are green, monoclinicblades of a new mineral, chloroxiphite, an oxychloride of lead andcopper. In the alteration zone, this is represented by a compactgranular mixture of malachite with hydrocerussite or cerussite, andpseudomorphous forms are sometimes shown (Fig. 3). As a lateralteration by interaction with the surrounding manganese dioxide,the mineral crednerite (CuO,Mn,O,) was developed as fan-shapedaggregates of black scales on the surface of the nodules. Still later,Hydrocerussite, hitherto found very sparingly as a mineral, is identicalwith " white lead " (cencssa), and its formula, was based on analyses made ofthe artificial product.Large crystals in the Woodwardian Collection werementioned in 1728 aa : " They appear like Talc; but are very ponderous, anddoubtless hold Lead.MINERALOGICAL CHEMSTRY. 281the crednerite gave rise again to malachite, which in this secondgeneration is developed as silky tufts or as small, clear prisms. Thisseries of changes may be represented as follows :Pyrolusite (MnO,) + Chloroxiphite -+ Hydrocerussite + Malachite I f Cerussite + Crednerite(2 P bO, Pb( OH),,CuCl,) (BPbCO,,Pb( OH),) (CuCO,,Cu( OH),) (PbCOB) ( CuO,Mn,O,)Malachite 11. +A second type of alteration is suggested by the presence of pseudo-morphs of diaboleite (another new oxychloride of lead and copperas sky-blue, tetragonal crystals) after chloroxiphite, namely :Chloroxiphite -+ Diaboleite + Hydrocemsite(2PbO,Pb( OH),,CuCl,) (2P b( OH),,CuCl,) (2PbC03,Pb(OH),)The diaboleite is a more stable form and still persists in the cerussitezone.As to the origin of the mendipite itself, which appears to bereally foreign to the deposit of manganese ore, it is suggested thatlumps of galena derived from veins in the Carboniferous Limestonewere deposited with the Dolomitic Conglomerate (a beach depositsurrounding the limestone hill), and that by the action of sea-waterthe lead sulphide was converted into oxychloride.X-Ray Examination of Ninerals.When X-ray methods were introduced, the crystals .first examinedwere those of simple minerals, and the early quantitative dataobtained by the Braggs formed the basis of later work.Morerecently, the method has been extended to the examination ofcrystals of complex carbon compounds, and also to the structure ofthe atom itself. The positions of the spots and bands on thephotographic films are evidently often open to more than oneinterpretation, and afford ample scope for speculation andcontroversy.Two applications, however, of the X-ray methods may perhapscome to be of practical use in the determination of minerals; theseare :(1) X-ray qualitative (and quantitative) spectrum-analysis.(2) Recognition of mineral-species in intimate mixtures.The first of these depends on the known X-ray spectra of theelements.63 I n A.Hadding's 64 apparatus a few grains or powderof the mineral to be tested are placed on the copper or iron anti-63 D. Coster, Chem. News, 1923,127, A., ii, 648.64 " De Rontgenkristallografkka apparaterna och deras anviindning,"Lund, 1921 ; H a d . Ingen. V'etensk. Akad. Stockholm, 1922, no. 11 ; 2. anorg.Chem., 1922, 122, 195; A., 1922, ii, 780282 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.cathode of the X-ray vacuum-tube and bombarded at a tension of30,000 to 40,000 volts. The X-ray tube is constructed entirelyof metal (except for the insulating parts) and is provided with awindow of aluminium-foil opposite the anticathode. The spectro-graph is a small disk-shaped box with a slit a t the side and carryinga crystal plate mounted on a central axis; at the circumferenceis a photographic film.The rays emitted by the elements presentin the mineral are analysed by the crystal grating of known dimen-sions (such as rock-salt), and their wave-lengths are given by thewell-known equation nh = 2d sin 8. The spectra show only few,easily recognisable lines, and their intensities indicate roughly theamount present of each element. In fluocerite Hadding detected,in addition to cerium and yttrium earths, the element with atomicnumber 61 ; and in cassiterite he detected germani~m.~s Usingit modification of Hadding's spectrograph in which the rock-saltcrystal is turned by clockwork, V. M. Goldschmidt and L.ThomassenG6recognised the presence of element 72 (hafnium) together withzirconium in malacon and alvite from Norway. The formula ofalvite they write as (Zr,72,Th)O2,SiO,.D. Coster 63 has estimatedabout 5 per cent. of hafnium in a zirconium mineral from the Urals,and about 2 per cent. in one from Brazil.In Siegbahn's 67 apparatus a Iong-surface anticathode gives adivergent sheaf of rays of about 40" angle through the aluminiumwindow of the metal X-ray vacuum-tube. Close to the slit is afixed crystal plate which reflects the rays on to a photographicfilm. Between the angles 10" and 50" a calcite plate (with2d = 6.060 A,) will reflect wave-lengths 1.0 to 4.6 A., and a gypsumplate (with 2d = 15.15 a.) provides for wave-lengths 2.6-11-6 A.This embraces all the elements from sodium to uranium which arecharted for the two crystal plates.The simple spectra yieldedby the small amount of substance placed on the anticathode arelaid alongside the charts and the characteristic lines are quicklyidentified.A second application of X-ray methods that has been suggestedis for the recognition of the minerals present in intimate mixtures,such as fine-grained rocks, ores, clays, soils, etc. The materialis examined by the powder method, using monochromatic rays oflcnown wave-length, and the spectrum is compared with a standardset of spectra obtained under the game conditions with knownminerals. By this method A. Hadding 68 has recognised the presence6 5 A. Hadding, 2. anorg. Chem., 1922,123, 171; A., 1922, ii, 855.6 6 Norsk GeoE.Tidsskrift, 1923, 7, 61 ; A., ii, 174.6 7 31. Seigbahn, A. E. Lindh, and N. Stensson, 2. Phyeik, 1921, 4, 61 ; A.,6 8 2. Ei'rist., 1923, 58, 108.1921, ii, 344MINERALOQICAL CHEMISTRY. 283of quartz, muscovite, and kaolinite in various clays. His attemptsto apply the method for the discrimination of the felspars in rockswere, however, without S U G C ~ S S . ~ ~New Minerals.Hasty work for the sake of priority unfortunately leads to thepublication of many ill-defined species. Many papers, here aselsewhere, instead of helping in .the advancement of science, are onlyan encumbrance and swell the overwhelming flood of scientificliterature, which threatens to defeat its own ends and adds to thecongestion of libraries. Editors as well as authors have still torealise that it is quality rather than quantity that will have apermanent value. In this place it is not possible to give a full listof so-called new minerals,70 and a critical selection must be made.A few earlier more distinctive species are also included to fill the gapin these Reports between 1913 and 1922.A heavy crop of radioactive minerals recorded from the recently-discovered deposits of uranium ore in the Katanga district of theBelgian Congo includes the new names becquerelite, chinkolobwite,71curite, dewindtite, kasolite, pars0nsite,7~ schoepite,73 soddite, andstasite.Some of these were referred to in the last Report, and twoof the more certain are listed below. They all represent secondaryalteration products (uranates, phosphates, silicates, and carbonates)of pitchblende, and they occur minutely crystallised and intimatelyintermingled. It is evident that the analyses have not always beenmade on ideally pure material, nor is it certain that the optical andother physical characters have in all cases been determined on thesame kind of material as that used for analysis.A krochordite,'* basic arsenate of manganese and magnesium,Mn,As,0,,MnOH,&lgOH,5H20, found as reddish-brown, wart-likeaggregates in manganese ore at Lgngban, Sweden.The opticalcharacters suggest monoclinic symmetry.Ambuto~rinite,7~ basic carbonate of strontium and cerium metals,5SrC0,,4( Ce,La,Di),( GO,),, (Ce,La,Di),O,, occurring as colourlessgrains (orthorhombic) with celestite, monazite, etc ., as a constituentof a crystalline limestone (marble) at Ambatoarina, Madagascar.69 Lunch Univ. Arsskrift, 1921, 17, No.6.so Dictionary lists of new mineral names are given by L. J. Spencer aB the71 A. Schoep, Bull. SOC. Belge Gdol., 1923, 33, 87; Bull. SOC. Chim. Belg.,72 A. Schoep, Compt. rend., 1923, 176, 171; A., ii, 174.73 T. L. Walker, Arner. Min., 1923, 8, 67.74 G. Flink, Geod. F6r. FGrh., 1922, 44, 573.75 A. Lacroix, Bull. SOC. franc. Min., 1916, 38 (for 19151, 265; A., 1916,end of each volume of tho Miiteralogieal Magazine.1023, 32, 345; A., ii, 870.ii, 569284 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Argentoja~osite,7~ a variety of jarosite containing silver (19 percent .) in place of potassium, Ag,[Fe( OH),],( SO,),, and analogousto the lead-bearing plumbojarosite.It forms a mass of minute,yellow to brown, hexagonal and optically uniaxial scales, and hasbeen found at Dividend, Utah, in sufficient quantity to be used asan ore of silver. Apart from the very doubtful record of silvercarbonate (" selbite ") by C. J. Selb in 1794 and the oxychloridesof the percylite-boleite group, this is the only silver mineral containingoxygen.A ~ m n g i t e , ~ ~ manganese arsenite, Mn,(AsO,),, as black, rhombo-hedral crystals from Lhngban, Sweden. Arsenates are frequent asminerah, but arsenites are uncommon.C~rnseZZite,~~ hydrated magnesium borate, Mg,B,O,,H,O, formingwhite, fibrous masses intermixed with chrysotile and dolomite inserpentine from British Columbia.The optical characters indicateorthorhombic symmetry.ChZoro~iphite,~~ a lead copper oxychloride, 2PbO7PbC1,,Cu(OH), ,occurring sparingly as green, bladed crystals (hence the name)embedded in mendipite [2PbO,PbCl,] from the Mendip Hills,Somerset. The crystals are monoclinic and in many of theircharacters show a resemblance to epidote.Cornetite, a basic copper phosphate, 2Cu,(P04),,7Cu( OH),, orperhaps Cu,( PO$,,3Cu( OH),, as minute, peacock-blue, orthorhombiccrystals. It was fist described by G. Ceshro 8O in 1912 as a coppercobalt phosphate from Katanga, and was later named cornetite.81More recently it was found in a neighbouring district in NorthernRhodesia,*2 analysis of this material giving the above formula withthe absence of cobalt.A re-examination s3 of the Katanga materialshowed the presence of cobalt only as an impurity, and not inthe pure crystals. Lastly, G. Ce~Bro,~* writing the formula as(CuOH),PO,, points out that this compound is dimorphous, beingorthorhombic with optic axial angle 2E = 55" in cornetite, andmonoclinic with 2E = 95" in pseudomalachite.76 W. T. Schaller, J . Wmhington Acad. Sci., 1923, 13, 233, named argento-Also, in July, independently named7 7 G. Aminoff and R. Mauzelius, Geol. F6r. Fdrh., 1920, 42, 301; A., 1921,78 H. V. Ellsworth and E. Poitevin, Trans. Roy. SOC. Canada, 1921, [iii],7s L. J. Spencer, Min. Mag., 1923, 20, 67; A,, ii, 774.80 Ann. SOC. Btol. Belg., 1912, 39, Bull. 241 ; A., 1920, ii, 441.81 H. Buttgenbach, " Les Mineraux et les Roches," LiBge, 1916, 452.82 A.Hutchinson and A, M. Macgregor, Min. Mag., 1321, 19, 225; A . ,88 A. Schoep, Min. Mag., 1922, 19, 301 ; A., 1922, ii, 219.84 Ann, Soc.-Bkol. Belg., 1922, 45, Bull. 102.jsrosite in a preliminary note in June.argentojarosite by C . A. Schempp, Amer. J . Sci., 1923, [v], 6, 73; A., ii, 503.ii, 269.15, sect. W , 1; A,, 1922, ii, 304.1921, ii, 701M1NERALOaICA.L CHEMISTRY. 285Creedite,ss hydrated calcium aluminium fluoride and sulphate,2CaF2,2A1(P,OH),,CaSO4,2H2O, as white radiating masses ofmonoclinic crystals with fluorite near Creede in Colorado. It hasbeen further studied by W. F. Foshag,86 who writes the formula3CaF2,A1( OH,P),S04,2H,0.C~rite,~' hydrated lead uranate, 2Pb0,5U0,,4H20, occurring withkasolite as orange-yellow, acicular crystals in Katanga.Theneedles give straight optical extinction with positive elongation.Di~boleite,'~ lead copper oxychloride, 2Pb( OH),,CuCI,, orPb(OH),,PbCI,,Cu( OH),,found sparingly with choroxiphite embeddedin mendipite from the Mendip Hills, Somerset. The minute, sky-blue crystals are te.tragona1 with characters similar to those ofminerals of the percylite-boleite group [near Pb( OH),,CuCl,, andsometimes containing also silver], but, as shown on analysis by E. I).Mountain, with different molecular ratios and much higher density(6.412, against 4.77-5-25).Dixenite,88 manganese arsenite and silicate,(MnoH)2Mn3(Si0,)(As0,)2,as rhombohedra1 scales in hzematite a t Langban, Sweden.Theblack scales are red by transmitted light. The combination ofarsenite with silicate is unusual.Pir~nemanite,~~ lead chloro-arsenite, 3Pb3(As03),,PbC1,, orPb,Cl(AsO,),, as black, hexagonal prisms [a : c = 1 : 0.68801 onhematite iron-ore a t Lhngban, Sweden. It resembles mimetite inits general characters, but it is a chloroarsenite rather than a chloro-arsenate.Germanite,9° a massive, dark reddish-grey mineral containing6.20 per cent. of germanium, together with copper and iron assulphides. It occurs in some quantity intimately intermixed withzinciferous tennantite at Tsumeb, South-West Africa.Hewettite,gl hydrated calcium vanadate, Ca0,3V,05,9H,0, orCaH2V,O1,,8H,O, forming mahogany-red, silky aggregates oforthorhombic needles, and occurring as an oxidation product ofpatronite at Minasragra, Peru.An isomeric form, also ortho-rhombic, but Mering in its behaviour during dehydration, is calledmetahewettite. The latter is found as a dark-red, powdery impreg-nation in sandstone in Colorado and Utah.8 5 E. S. Larsen and R. C. Wells, Proc. Nat. Acad. Sci., 1916, 2, 360.8 6 Proc. US. Nut. Mus., 1921, 59, 419.8 7 A. Schoep, Compt. Tend., 1921,173, 1186; A., 1922, ii, 77.8 8 G. Flink, Geol. P6r. P6rh., 1920, 42, 436; A., 1921, ii, 268.89 G. Aminoff, Qeol. F ~ T . B'Brh., 1923, 45, 160.9O 0. Pufahl, Metall u. Em, 1922, 19, 324.91 w. F. Hillebrand, H. E. Merwin, and F. E. Wright, Proc. Amer. Phil.SOC., 1914, 8, 33; 2. Kryst. Min., 1914, 54, 209; A., 1915, ii, 271286 ANNUAL REFORTS ON THE PROGRESS OF CHEMISTRY.I n y ~ i t e , ~ ~ hydrated calcium borate, Ca2B6011,13H,0, found aslarge, colourless, monoclinic crystals in the borate deposits of InyoCo., California, and later in the gypsum mines a t Hillsborough, NewB r u n s ~ i c k .~ ~ Pseudomorphs of meyerhoff erite [Ca,B60,,,7H20]and colemanite 94 [Ca2B6O,,,5H20] after inyoite, evidently producedby the arid climate, are commonly found in California.K~soZite,~~ hydrated uranium lead silicate, 3U03,3Pb0,3Si0,,4H,0,as radiating groups of ochre-yellow, monoclinic crystals fromKasolo, Katanga, Belgian Congo. Further crystallographic andoptical data are given by H. Buttgenbach.96KcLtoptrite,g? manganese, aluminium, etc., silico-antimonate,14 (Mn,Mg ,Fe) 0 , 2 ( A1,Fe),03, Sb205 ,2SiO,, f ound as tabular ,monocliniccrystals with magnetite iron-ore at Nordmark, Sweden.It isblack with a brilliant metallic lustre and perfect micaceous cleavage.The brittle cleavage flakes are red and strongly pleochroic. It ispossibly identical with the incompletely described hematostibiite.a highly acidic fluosilicate, Na4(A1F),Si,0,,, as colourless,hexagonal prisms in alkali-pegmatite from Greenland.Margarosc~nite,9~ lead calcium metasilicate, PbCa2( SiO,),, formingcolourless, platy masses with perfect pearly cleavage, from FranklinFurnace, New Jersey. It was afterwards found in some quantityas snow-white columnar masses weighing up to 1 kilo. and as anorthiccrystals at LPngban, Sweden.lMeyerho#erite,2 hydrated calcium borate, Ca2B6O,,,7H,O,occurring as colourless, triclinic crystals or as a white, fibrousalteration product of inyoite (4.v.) from California.Minasrugrite,3 hydrated vanadium sulphate, V,04,3S0,,16H,0,or V202H,(S0,),,15H,0. It is abundant at Minasragra, Peru, asan alteration product of the patronite ore, and it grows as a blueefflorescence on museum specimens of patronite. It is readily92 W. T. Schaller, J. Washington Acad. Sci., 1914, 4, 355; Bdl. U.S. Geol.93 E. Poitevin and H. V. Ellsworth, Bull. Geol. Survey, Canada, 1921, 32.9a A. F. Rogers, Amer. Min., 1919, 4, 135.95 A. Schoep, Cornpt. rend., 1921, 173, 1476; A., 1922, ii, 155.0 6 BuU. A&. roy. Eelg., 1922, 573.9 7 G. Flink, Geol. PBr. FGrh., 1917, 39, 426; A., 1919, ii, 112.98 0.€3. B~ggild, Medd. om Grqhland, 1915, 51, 427; 2. Kryst. Min., 1920,55, 425; A., 1917, ii, 147.98 W E. Ford and W. M. Bradley, Amer. J . Sci., 1916, [iv], 42, 159; A.,1916, ii, 532.1 G. Flink, Ged. FGr. FGrh., 1917, 39, 438; A,, 1917, ii, 112.2 W. T. Schaller, J. Washington Acad. Sci., 1914, 4, 355; Bull. U.S. Geol.9 W. T. Schaller, J. Washington Acad. Sci., 1916, 5, 7; 1917, 7, 501; A.,Survey, 1916, 610, 35; A., 1916, ii, 628.Survey, 1916, 610, 35; A., 1916, ii, 628.1917, ii, 575MINERALOGICAL CHEMISTRY. 287soluble in cold water. The optical characters suggest monoclinicor triclinic symmetry.Pascoite,91 hydrated calcium vanadate, 2Ca0,3V20,, 11 ( ? )H20,occurring as an orange-yellow powdery efflorescence on vanadiumores a t Minasragra, Peru.magnesium, calcium, potassium, and aluminium,3R,P20,,2A10HS0,,9H,0,forming colourless or pale green, monoclinic crystals with a perfectmicaceous cleavage, and occurring with various other phosphatesPhosphophyZZite,4 hydrated sulphato-phosphate of ferrous iron,in pegmatite at Hagendorf, Bavaria.Pyr~belonite,~ hydrated lead manganese vanadate,4Pb0,7Mn0,2VZO ,,3H20,found as fire-red, needle-shaped, orthorhombic crystals in manganeseore at L%ngban, Sweden.Xeurlesite,G hydrated sodium borosilicate, NaB(SiO,),,H,O,occurring as small, white spherules of radiating fibres (probablymonoclinic) in clay at Searles Lake, California.Spence~ite,~ hydrated basic zinc phosphate,Zn,(BO,),,Zn(OH),,3H,0,forming pearly-white, scaly cleavage-masses and small monocliniccrystals.It was found in some abundance as large stalactites ina cavern near Salmo, British Columbia, and most of the materialwas sent to the smelter before its nature was recognised. Thedehydration curve 8 shows that three-fourths of the water is lostbetween 100" and 135", giving a product corresponding chemicallybut not optically with tarbuttite [Zn,(PO,),,Zn( OH),].Trevorite,v nickel ferric-iron oxide or nickel ferrafe, NiFe204,presumably belonging t o the spinel group. It is found as a massive,black and opaque, strongly magnetic mineral in the Transvaal.It has been regarded as a doubtful species, but a re-examinationby T. L. Walker 10 proves the material to be homogeneous..Trigonite,a lead manganese hydrogen arsenite, Pb3MnH(As0,),,' H.Laubmann and H. Steinmetz, Z. Kryst. Min., 1920, 55, 566; A . ,1920, ii, 697.G. Flink, Ceol. Pdr. FGrh., 1919, 41, 433; A., 1920, ii, 442.E. S. Larsen and W. 13. Hicks, J . Wmhington Acad. Sci., 1914, 4, 397;Anzer. J . Sci., 1914, [iv], 38, 437; A., 1914, ii, 851.T. L. Walker, Min. Mag., 1916, 18, 76; A., 1916, ii, 629. A. H. Phillips,Amer. J. Sci., 1916, [iv], 42, 215; A., 1916, ii, 569. T. L. Walker, J. Washing-ton Acad. Sci., 1917, 7, 45G; Univ. Toronto Studiea, Geol. s~., 1918, 10, 6 ;A., 1919, ii, 71.T. L. Walker and A. L. Parsons, Univ. Toronto Studies, Ceol. Ser,, 1921,12, 58. * A. F. Crosse, J . Chem. Met. SOC. 8. Africa, 1921, 21, 12G.lo Univ. Toronto Studies, QeoL Ser., 1923, 16, 53288 ANNUAL REPORTS ON TEE PROGRESS OF CHEMISTRY.as sulphur-yellow crystals with the form of triangular wedges andof domatic-monoclinic symmetry.It is found with native lead indolomite at Langban, Sweden.Tungstenite,lf tungsten sulphide, WS,, forming feathery flakesresembling molybdenite [MoS,] or graphite in appearance andoccurring in a compact ore from Ukah.UEtrabasite,12 an ultrabasic sulpho-salt, Sb,Ag,,Pb,,Ge,S,,, con-taining 2.20 per cent. of germanium. The orthorhombic crystals.are black with metallic lustre and came from Freiberg, Saxony.'The material had been found in an old English collection ofminerals.Vauxite,13 hydrated ferrous-iron aluminium phosphate,4Fe0,2A1,0,,3P,05,24H,0 + 3H,O,occurring as sky-blue, triclinic plates with wavellite and tin orefrom Bolivia.Associated with it is paravauxite, with nearly thesame composition, namely, 5Fe0,4A.l,0,,5P,0,,26H20 + 2 IH,O,which forms colourless, triclinic prisms.ViZlamaninite,14 a disulphide, (Cu,Ni,Co,Fe)S,, containing alsosome selenium (1-5 per cent.), occurring abundantly as small, black,cubic crystals and as nodular aggregates in crystalline dolomitenear Villamanin, Spain. E. Thomson l5 from a microscopicalexamination of polished surfaces suggests that it is a mixture oftwo undetermined minerals, but the original material was definitelycrystallised .WeinschenEite,16 hydrated phosphate of rare-earths,(Er,Y)P0,,2H,O,found as spherules and tufts of silky-white needles on limoniticiron-ore near Amberg, Bavaria. The name weinschenkite l 7 hasalso recently been applied to a variety of hornblende.Mention may here be made of three natnrally-occurring crystallisedcarbon compounds to which mineralogical names have recentlybeen applied :Pkcgstaflte l 8 = terpin hydrate, C1&€2,0,,H,0, as colourless,11 R.C. Wells and B. S. Butler, J . Washingtom Acad. Sci., 1917, 7, 696;12 V. Rosickjr and J. &t6rba-B6hm, Rozpr. 6mkS Akad., 1916, 25, no. 45;13 S . G. Gordon, PTOC. Acad. Nat. Sci. Philadelphia, 1923, 75, 261; A.,1 4 W. R. Schoeller and A. R. Powell, Min. Mag., 1920, 19, 14; A., 1920,l5 Unity. Toronto Studies, Geol. Ser., 1921, 12, 39.16 H. Laubmenn in F. Henrich, Ber., 1922, 55 B, 3013; A., 1922, ii, 860.1 7 G. Murgoci, Compt. rend., 1922, 175, 428.18 F.N. Guild, Arner. Min., 1920, 5, 169, 1921, 6, 133; A., 1921, ii, 61,A., 1918, ii, 46.2. Kryst. Min., 1920, 55, 430; A., 192Q,ii, 696.ii, 646.ii, 256.1922, ii, 76MINERALOGICAL CHEMISTRY. 289orthorhombic crystals found with resin in the radial cracks of pine-tree logs that had been buried for at least 500 years near Flagstaffin Arizona.HoeZite l9= anthraquinone, C,,H,O,, as delicate needles formed,together with sulphur and sal-ammoniac, by the burning of a coalBeam in Spitsbergen.SimoneZZite,20 C,,H,,, as a white, crystalline (orthorhombic)encrustation on lignite from Tuscany.Sme Recent Books of Reference.Fedorov’s long-delayed “ Tables of the Crystal Kingdom ” 21 hasa t last appeared, being dated 1920, but only recently has a copyreached this country. Some account of this work has already beengiven by T.V. Barker in these Reports as long ago as 1913 (10,247; 11, 248). It is issued by the Russian Academy of Sciencesand forms a quarto volume of 1,124 pages with an atlas of 213 plates.The crystallographic constants that have been determined for allknown crystallised substances , including minerals , are systematicallytabulated according to a special plan devised by the author. Bymeasuring on the goniometer the angles included between thefaces of an unknown crystal and reducing the results to the Fedorovelements, it is possible to identify the substance (in case it has beenpreviously determined crystallographically) by reference to thetables. Such a method of crystallo-chemical analysis is practicablewhen only a small amount of material is available for determination,and the material is not thereby damaged or destroyed.Fedorov’smethods are somewhat difficult to follow and are not generallyknown; but here we have a ndtable first attempt to reduce to someorder the enormous and tangled mass of published crystallographicdata. T. V. Barker z2 has estimated the number of crystallisedsubstances dealt with in the work at 7,400, for 600 of which, however,the elements are not sufficiently precise, leaving 6,800 that havebeen completely determined. The percentages of these representedin the various systems are : cubic 7, tetragonal 5, hexagonal 3,rhombohedra1 4, orthorhombic 23, monoclinic 46, anorthic 12 percent.This total corresponds approximately with the number ofcrystalliscd substances, about 7,350, dealt with in P. Groth’s well-10 I. Oftedal, “ Resultater av de Norske Stntsunderstattede Spitsbergen-ckspeditioner ” (Videnskapsselsl’capet, Kristiania), 1922, 1, no. 3.2o G. Boeris, Rend. Accad. Sci. I s f . Bologna, 1919, 23, 87. R. Ciusa andA. Galizzi, Gazzetta, 1921, 51, (i), 55; A., 1921, ii, 343.*l E. von Fedorow, unter htitwirkung von D. Artemiev, Th. Barker, B.Orelkin, und W. Sokolow, “ Das Krystallreich; Tabellen zur krystallo-chemischen Analyse,” iklf2m. Acad. Sci. Russie, [viii], 36, Petrograd, 1920.22 Note on E. S. Fedorov in Min. Mag. (Abstr.), 1923, 2, 100.REP.-VOL. XX. 290 ANNUAL REPORTS ON TIIE PROGRESS OF CHEMISTRY.known “ Chemische Krystallogrephie ” (5 vols., Leipzig, 1906-1919), where a chemical arrangement is adopted.Another large crystallographic work of reference is Victor Gold-Schmidt’s “ Atlas der Krystallformen ” (Heidelberg, 1913-1923),comprising nine volumes of text and plates, in all eighteen quartovolumes.Here only minerals are taken into account, these beingarranged alphabetically according to species. The idea has been tocollect from the literature all published geometrical figures of crystals.For example, 2,692 figures of calcite crystals, 855 of quartz, and 691of pyrites have been brought together for comparison and reference.In all, there are about 1,600 plates showing about 30,000 figures-atruly German production. In the text are tabulated the symbolsand indices used by different authors for the several crystal-formsof each species.Detailed references are given to the literature,from which also long lists of errata have been collected. We fearthat some a t least of these errata have been caused by the confusionintroduced by Goldschmidt himself into crystallographic. notation.He has even thought it necessary to change the letters, indices, andaxes of reference of calcite, and in his different works two distinctsystems are made use of (distinguished as “ GI” and “ G, ”). Surelythe old-fashioned and well-established r( 100) of Miller or r( 1011) ofDana is quite good enough to express the cleavage-form of calcite.The selection of an orientation and parameters for a crystal is inany case more or less arbitrary, and, unless the original describeris proved to be quite wrong, nothing is gained (only confusion) byintroducing a change.The alphabet of perhaps all languages isfaulty, and t o devise an entirely new set of hieroglyphs and systemof phonetics would no doubt be a fine-piece of work-but of doubtfulutility. With the new Fedorov and Goldschmidt systems ofnotation, the old LBvy system still adhered to by French authors,and the various modifications of Schoenflies’s notation for thecrystal-classes and space-groups, it is becoming increasingly difficultto compare and correlate the work of different authors. And whenan author omits to state which system he is using and what are hisaxes of reference (a matter so obvious to himself) his work is simplyuseless.The result is chaos, and until some international agreementcan be come to little real advance can be expected in crystallography.The logical and concise Millerian system of notation has beensystematically adopted in the standard works of Dana, Groth, andHintz, and will undoubtedly prevail.A detailed and systematic tabulation of the chief optical constantsof minerals has been given by E. S. Lar~en.2~ These are put into23 “ The Alicroscopic Determination of the Monopaque Minerals,” Bull.U.S. GwZ. Survey, 1921, No. 679AMINERALOGICAL CREMISTRY. 29 1the form of determinative tables, and so afford a useful means for theidentification of non-opaque minerals from such characters as canreadily be determined with fragments under the microscope. Thismethod is thus analogous to that of Fedorov mentioned above, butusing the optical constants instead of the crystallographic (morpho-logical) constants. One table gives the mean refractive index for along list of minerals ranging from ice 1.309 to stibnite 4.303. Inother tables, the minerals are grouped under the main headings,optically isotropic, uniaxial negative, biaxial positive, etc . , thearrangement in each group being according to the value o€ therefractive index. The tablcs also state the optical orientation, sizeof the optic axial angle, density, hardness, and much other usefulinformation. About 950 rnineral-species are listed. New data aregiven for more than 500 species, for many of which no optical datawere previously available. Details are given of the useful and rapidmethod of determining the refractive indices of minute fragmentsby immersing them in a series of liquids of known refractive index.24For ordinary use, methylene iodide sets the limit at 1-74; but thiscan be raised to 1.87 by dissolving in it sulphur and iodides of tin,arsenic, and antimony. Piperine containing dissolved arsenicand antimony iodides gives at -100” a liquid of refractive index upto 2-10 ; fusions of sulphur and selenium up to 2.716 ; and fusionsof selenium and arsenic selcnide up to 3.17. Tables on the samelines as those of Larsen, but much less extensive, have been compiledby W. H. Fry 25 for a series of inorganic salts.C. Hintze’s well-known and indispensable “ Handbuch dcrMineralogie,” which was commenced in 1889, is still some distancefrom completion. Since his death in 1916, the work has been carriedon under the editorship of G. Linck with the help of various contri-butors, but not with the same thoroughness and accuracy as it wasdone by Hintze himself. A number (Lieferung 19) issued in 1921starts a new pagination for division 4 of volume 1, and commencesthe borates, aluminates, ferrates, arsenites, and antimonites. Nos. 20and 21 (1922-1923) carry on with the description of the phosphates,columbates, etc. Vol. 2, dealing with the silicates and titanates,was issued during 1,889-1897. C. Doelter’s “ Handbuch derMineralchemie,” commenced in 1912, has now completed fivesectional volumes. The latest part received, No. 9 of Vol. 3, issuedin 1922, deals with mercury and commences the “ elements of the24 A recent modification of the immersion method makes use of the dis-persion, the wave-length of light at which there is exact matching beingdetermined with a monochromatic illurninator (H. E. Merwin, J. Amer. Chem.SOC., 1922, 44, 1970; S. Tsuboi, Min. Mag., 1923, 2Q, 108; A., ii, 777).25 “ Tables for the microscopic identification of inorganic salts,” U.X. Dept.Agric. Bull., 1922, No. 1108.L 292 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.third vertical series,” namely, boron, etc. P. Groth and K.Mieleitner’s “ Mineralogische Tabellen ” (Miinchen and Berlin,1921), which is really a new edition in a smaller and handier formof Groth’s well-known “ Tabellarische Ubersicht der Mineralien,”gives a systematic classification of minerals with their chemicalformula, crystal-class and axial ratios. Attention has already beendrawn to the “ Tables de Constantes ” (p. 273).L. J. SPENCER

ISSN:0365-6217    

DOI:10.1039/AR9232000261

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

INDEX O F AUTHORS’ NAMESAbbott, E. V., 211.Abbott, W. E., 176.Abderhalden, E., 192, 193.Abel, 185.Aboulenc, J., 89.Ackerman, I., 142.Adani, A., 152, 175.Adam, N. K., 22, 257.Adams, L. H., 278.Adams, R., 119.Aeschlimann, J. A., 140, 141,Agafonoff, V., 160.Akermann, A., 16.Allen, 179.Alles, 182.Allison, F. E., 219.Allsop, F., 61, 128.Aloy, J., 163.Aminoff, G., 251, 284, 285.Ammann, H., 137, 138.Anderson, E., 92.Anderson, M. S., 203.Andrews, M. R., 53.Andriska, V., 159.Annett, H. E., 227, 228.Anrep, 197, 198.Armstrong, E. F., 41.Arnd, T., 203.Arndt, F., 130, 132.Arndt, P., 226.Arseneev, A. A., 49.Artemiev, D., 289.Asahina, Y., 93.Asmus, R., 74.Astbury, W. T., 234, 235, 251, 252,Aston, F. W., 34.Atkins, W.R. G., 219.Ato, S., 172.Attwood, A. J., 103.Auerbach, F., 158, 165.Augestad-Jensen, H., 135.Auten, J. T., 203.Auwers, K. von, 69, 87, 93.Avery, 198, 199.Azuma, 184.253.Bach, A., 212, 224.Backeberg, 0. D., 66.Badische Anilin- & Soda-Fabrik, 62.Bailey, (Miss) D., 3.Bailey, J. H., 65.Bailleul, G., 51.Bain, E. C., 237.Bains, L., 72, 166.Baker, H. B., 33, 52.Baker, J. L., 224.Baker, J. W., 103.Bakke, A. L., 217.Balareff, D., 63.Baldwin, I. A., 216.Ball, T. R., 13.Baly, E. C. C., 220, 222.Bardet, J., 46.Bargellini, G., 145, 149.Barger, G., 155, 156, 190, 194.Barker, T. V., 231, 233, 234, 289.Barker, W. F., 220.Barlow, 230.Barnes, H., 132.Barnett, E. de B., 90, 121, 122,Barnette, R. M., 218.Barratt, S., 7.Barton, J., 217.Baskerville, 40.Bassett, H., 52.Bates, H.€I., 61.Baudisch, O., 222.Baur, E., 65, 86, 193, 220.Baxtor, G. P., 30.Bayliss, (Sir) W. M., 195.Beaber, N. J., 93.Becheror, F., 173.Becker, H. G., 176.Becker, K., 241, 253.Becker, P., 152.Beckley, C. F., 210.Beckmann, E., 115.Bedford, Duke of, 214.Beijerinck, M. W., 223.Belval, H., 223.Benoist, (Mlle) S., 84.Bently, W. J., 37.Bergman, A. G., 38.Bergmann, M., 78, 79.Bergstrom, F. W., 47, 48.Berkenheim, A. M., 59.Berl, E., 64.Berlingozzi, S., 149.Berner, E., 153.Bert, L., 76, 124.29294 INDEX OF AUTHORS’ NAMES.Berthoud, A., 61.Bertrand, G., 84.Best, 179, 181.Beutell, A., 271.Bezssonoff, N., 211.Bidwell, C. C., 44.Bielenberg, W., 135.Bielisch, F., 130.Bijvoet, S.M., 248, 250.Biltz, H., 129, 133, 14s.Biltz, W., 48, 55.Birch, S. F., 73, 111.Birckenbach, L., 29, 30, 32.Birk, E., 55.Bischoff, H. F. L., 1G1.Bizzell, J. A., 214.Bjerrum, N., 12, 62.Black, 189.Blagden, J. W., 93.Blai, A. W., 218.Blanchard, K. C., 86.Blanchetihre, A., 76.Blanck, E., 220.Blankart, A., 167.Bloor, 189.Blum, J. R., 278.Blum, (Miss) O., 136.Bobrov, P., 64.Bode, (Miss) H., 132.Bodb, R., 169.Boeseken, J., 28, 76.Boeke, H. E., 274, 278.Boeree, A. R., 65.Boeris, G., 289.Bogert, 31. T., 136, 142.Beggild, 0. B., 286.Bohr, N., 9, 26, 28.Bolliger, A., 139.Bonazzi, A,, 212, 213.Bone, W. A., 20, 21.Roock, 183.Boone, 189.Borsche, W,, 96.Bose, J. C., 221.Bose, M.N., 227.Boswell, M. C., 61.Bovie, W. T., 173.Bowden, R. C., 25.Bowen, N. L., 270.Bozorth, R. M., 247, 248.Bradfield, R., 201, 202, 203, 204.Bradley, W. M., 286.Brady, 0. L., 94, 119.Bragg, (Sir) W. H., 231, 233, 235,247, 251, 253, 255, 260.Bragg, W. L., 235, 247, 260.Braham, J. M., 85.Braley, S. A., 13.Brand, K., 130.Braun, J. von, 75, 87, 89, 133, 134,138, 149, 150.Brauner, B., 46.* Bougault, 95.Braunholtz, W. T. X., 141, 151.Brauns, D. H., 76.Brautlecht,.C. A., 86.Bredt-Savelsberg, M., 91, 103.Breithaupt, J. F. A., 278.Brenchley, W. E., 219.Brenner, A., 40.Brewer, P. H., 218.Brinton, P. H. M.-P., 172.Bristol, (Miss) B. M., 211.Britton, H. T. S., 37, 43.Brodersen, K., 147.Bragger, W. C., 278.Broglie, M.de, 92, 242.Brooks, M. M., 226.Brose, W., 92.Brown, H. O., 215.Bruhns, G., 166.Bruins, H. R., 157.Brukl, A., 48.Brunel, R. F., 63.Bruns, D., 155.Bruylants, P., 31, 88.Bryan, 0. C., 218.Buddington, A. F., 268.Budnikov, P. P., 49.Bullock, J. E., 119.Burd, J. S., 208.Burg, J. H. N. van der, 59.Burgess, H., 27.Burgess, P. S., 208.Burke, S. P., 159.Burn, 184.Burns, R. M., 41.Burton, H., 120.Burton, W., 227.Bury, C. R., 33.Bury, F. W., 144.Butler, B. S., 288.Butler, C., 97.Butler, J. A. V., 51.Buttgenback, H., 284, 286.Cabrera, J., 46.Cajori, F. A., 166.Calderaro, E., 75.Calingaert, G., 58.Campbell, A. N., 54.Campbell, A. W., 1GG.Campbell, N. R., 29.Cannan, 197, 198.Canneri, G., 37.Carli, F.de, 39.Carobbi, G., 40.Cam, R. H., 218.Carrero, J. O., 218.Carter, S. R., 51, 55.Catlett, 40.Centner, K., 148.CesBro, G., 284.Challenor, W. A. P., 70, 112.Chattaway, F. D., 66, 87.Chavanne, G., 68INDEX OF AUTHORS’ NAMES. 295Chemische Fabrik vorm. Weiler-terMew, 144.Cherbuliez, 8., 94.Chibnall, A. C., 223.Chick, H., 186.Chirvinsky, P. N., 262, 274.Chodat, 104, 212.Chotinski, E. S., 163.Christiansen, J. A., 19.Christie, G. H., 119, 120.Chuchrikovn, (Rllle) A. M., 103.Ciurlo, A., 85.Ciusa, R., 289.Claisen, L., 59, 96.Clark, G. L., 29, 252.Clark, J. H., 190.Clark, L., 140, 141.Clarke, F. W., 261.Claus, L., 52.Clayson, D. H. F., 82.Clendinnen, F. IV. J . , 54.Coe, M. R., 227.Coehn, A,, 33.Cohen, A,, 169.Cohen, E., 157.Cole, H.I., 162, 167.Colin, H., 223.Collins, H. F., 2;G.(:ollins, W. D., 176.Collip, J. B., 177, 179, 180, IS1.Compton, K. T., 1, 4.Consortium fur Elektrochemische In-Cook, J. W., 90, 121.Copisarom, M., 37, 276.Corbitt, 180, 181.Cordier, V., 161.Coster, D., 9, 28, 45, 46, 281, 252.Costy, P., 228.Coward, I<. H., 229.Cox, E. H., 78.Craig, W. M., 30.Cramer, M., 78.Cranner, B. H., 273.Crefeld, van, 182.Creighton, H. J. M., 36, 1GO.Crocker, W., 161, 224.Crommelin, C. A., 34.Crosse, A. F., 2S7.Crowther, 96.Cruup, 215.Cummins, A. B., 206.Cuny, L., 171.Curtis, W. E., 8.Cutler, D. W., 215, 216.Cutter, J. O., 17.Cuttica, V., 40, 55.Czerwinski, J., 169.dustrie, 64.Cushy, 189.Daggett, WT.L., 166.Daikuhara, G., 207.Dakin, H. D., 92, 190, 194.Dale, 183.Damiens, A., 58.D’Andrimont, It., 57.Dannenberg, 96.Danner, P. S., 14.Darby, E. H., 13.Dauvillier, A., 45, 46.Davey, W. P., 249, 250.Davies, (Miss) A. C., 2, 3.navies, G. R., 94.Davies, W., 95.Davis, A. R., 225.Davis, T. L., 86.Dawson, L. E., 9s.Debye, P., 10.Decker, II., 162.Dede, L., 49.Dehnert, H., 124.Delaby, R., 163.Deming, H. G., 34.Demjanov, N. J., 102, 110.Dengin, E. F., 88.DBniges, G., 162.Dennis, L. M., 43, 44, 45.Deulofeu, 178.Dickinson, R. G., 247, 248, 251.Dickson, T. W., 10.Diels, O., 129.Dienert, F., 176.Dik, H. \V. J., 8.Dimitrov, M., 1G7.Dimroth, O., 90.Dingemanse, (Miss) E., 14G.Dixon, A.E., 37.Dixon, H. B., 20, 21.Dixon, M., 192.Dobbie, J., 155.Dochez, 198.Dodge, R. L., 159.Doelter, C., 291.Doisy, 178.Dojarenko, ill., 102, 110.Dominicis, A. de, 205.Dondeyne, J., 31.Donnan, F. G., 21.Dorabialski, A., 80.Dornier, O., 139.Doser, A., 56.Driscoll, E. P., 90.Drossbach, O., 51.Duane, W., 29, 254.Dubief, J., 176.Dubin, 181.Duchon, I.”., 229.Dudley, 178, 183, 185.Duffendack, 0. S., 2.Dunnicliff, H. B., 35.Durrant, It. G., 52.Dushman, S., 19.Dutt, S., 139.Eadie, 184.I 296 INDEX OF AUTHORS’ NAMES.Eberman, N. F., 86.Ebert, F., 241.Ebert, G., 148.Eck, P. N. van, 162.Eder, J. M., 40.Edge, S. R. H., 141..Ehrenberg, P., 217.Ehringhaus, A., 25.Eisenlohr, F., 15.Eitel, W., 274.Elam, (Miss) C.F., 212.Eller, W., 209.Ellinger, 193.Ellsworth, H. V., 284, 286.Elsbach, E. B., 165.Emerson, P., 217.Emmert, B., 148.Engeland, R., 143.Engelbertz, P., 87.Erckelens, E. van, 39.Erdman, L. W., 217.Eschweiler, W., 171.Eskole, P., 269, 270.Estalella, J., 162.Evans, B. S., 168.Evans, J. W., 233.Evlampiev, V. V., 65.Ewald, 9.Ewald, P. P., 259.Eynon, L., 166.Falkov, IN., 163.Farmer, E. H., 70, 102, 112.Faurholt, C., 168.Faust, H. L., 163.Fedorov, E. S. von, 230, 231, 289.Fehse, W., 41.Feigl, F., 167, 171.Feist, 108.Feldman, A., 22.Fenner, C. N., 275.Fenwick, F., 173, 175.Ferguson, J. B., 266.Fernandes, D. S., 224.Fernandes, L., 167.Fertig, G. J., 30.Fichter, F., 50.Fierz-David, H. E., 97.Fischer, E., 93.Fischer, F., 57.Fischer, H., 64, 136, 137, 138, 139,Fischer, H.L., 163.Fischer, W., 217.Fischer, W. M., 168.Fisher, E. A., 202.Flenner, A. L., 203.Flett, J. S., 276.Flink, G., 283, 285, 286, 287.Foerster, F., 51.Ford, W. E., 286.Foshag, W. F., 285.210.?oulk, C. W., 53.Francesconi, L., SS.Franck, J., 3.Tranklin, E. C., 85.?raps, G. S., 203.?red, 2. B., 227.Freudenberg, K., 76, 164, 188.Treund, M., 126.i’reundler, P., 226.Friedel, 243.‘rieden, A., 165.Friend, J. A. N., 54.Fries, K., 142.Fritzmann, E., 85.Fromm, E., 130.Fry, W. H., 161, 202, 291.Fuchs, W., 84, 210.Funk, 180.Furman, N. €I., 173.2adamer, J., 156.%,;bier, I<., 174.Jainey, P. L., 210, 211.Zalizzi, A., 289.Jallagher, P.I€., 194, 228.Jallo, F., 40.Jandelrnan, A, 120.3anssen, R., 203.Garnett, C. S., 277.Garrison, A., 13.Zatti, U., 167.Zaulis, M., 210.Gedroiz, K. K., 205.Gehrcke, E., 7.Gehring, A., 218.Geilmann, W., 220.Geisler, E., 226.Giachery, U., 49.Gibson, G. P., 95.Gibson, W. H., 24.Giesecke, F., 220.Gilbert, L. F., 53.Gilchrist, H. S., 79.Gile, P. L., 202.Gilman, H., 93.Gimingham, C. T., 161.Ginzberg, A. S., 269.Glockler, G., 2.Gmelin, W., 149.Goebel, W. F., 86.Goens, E., 19.Goes, E. C., 58.Goldblatt, 187.Goldschmidt, V. I$., 46, 249, 262,273, 282, 290.Goldstein, K., 84.Gomberg, M., 54, 121.Goodhue, E. A., 248.Goos, O., 126.Gordon, E., 203.Gordon, N. E., 203.Gordon, 8. G., 288INDEX OF ABU!~I-IORS’ NAMES.297Goris, A,, 228.GOSS, F. R., 72, 107.Gossner, B., 266.Granacher, C., 144.Graham, H., 48.Gramont, A. de, 157.Greenwald, 189.Greenwood, G., 259.Gregory, J. W., 264.Griffith, A. A., 255.Griffiths-Jones, E., 216.Grigoriev, A., 39.Grindley, E. N., 243.Groh, A. W., 209.Groot, J., 158.Groth, B., 140.Groth, P. H. v., 260, 292.Grubb, A. C., 34.Gruneisen, E., 19..Guild, F. N., 288.Guillaumin, A. J. A., 79, 163.Gulland, J. M., 127, 154.Gustavson, R. G., 175.Guyer, A., 99.Gyiirgy, 188.RI3HHHHHHHElHHHHHHHHHHHHHHHI3HHHHHHHI3Hnhckford, J. E., 174.hckl, O., 168.:ackspill, L., 163.:adding, A., 281, 282.Iahle, H., 123.Iager, G., 207.:ahn, E., 89.:ahn, F.L., 170.hhn, F. V. von, 159.:ahn, O., 49.lakes, W. B., 201.Ialey, D. E., 201.:all, C. H., 48.:all, (Sir) J., 276.:all, J. L., 13.:all, L., 17.:all, T., 18.Lamer, (Miss) F. M., 151.lammick, D. L., 65, 150.[ance, F. E., 44, 45.[ansen, H. M., 46.[ansen, W., 139.:antzsch, A., 139.[axden, A., lG2, 188.larding, T. S., 76.[ardy, F., 201, 202.[arington, C. R., 92.[arkins, W. D., 22.[arries, C., 101.[arrington, G. T., 161, 224.[arris, F. S., 207.[arris, S., 94.[arrison, 18 1.:art, 189.[artley, H., 61.[artley, W. N., 9.Hartree, 184, 195, 196.Hartridge, H., 19, 158.qartshorne, N. H., 55.Hartwell, 218.Hatschek, E., 25.Haward, W. A., 20.Haworth, R. D., 95.Haworth, W. N., 77, 79, 80, 81, 83.Heeckeren, G.de, 163.Heidelberger, 198, 199.Heilbron, I. N., 132, 220, 222.Heinicke, A. J., 214.Heiss, H., 124.Helferich, B., 78, 120.Heller, G., 139.Hemming, G., 172.Hendriclm, B. C., 34.Hendrixson, W. S., 175.Henke, T. A., 38.Henkel, G., 51.Henrich, F., 288.Hentschel, 68.Herdieckerhoff, E., 209.Hermann, C., 267.Hermans, P. H., 76.Herrara, P. P., 136.Hem, W., 171.Herzfeld, K. F., 257.Herzig, J., 155.Heslinga, J., 164.Hess, 189.Hetherington, H. C., 85.Hevesy, G., 45, 46, 47, 220.Hewitt, 182.Heyrovsky, J., 14.Hicks, W. B., 287.Hicks, W. M., 3.Higginbotham, L., 73.Hildebrand, J. H., 14.Hilditch, T. P., 41.Hill, 188, 195, 196.Hillebrand, W. F., 285.Hilton, F. A., 30.Hingst, G., 147.Hintze, C., 291.Hirsch, 197,Hirschel, W.N., 168.Hirst, E. L., 77, 81, 83, 85.Hissink, 205, 206.Hjalmar, E., 9.Hoagland, D. R., 225.Hochwalt, C. A., 58.Hochster Farbwerke, 138.Honigschmid, O., 29, 30, 32.Hoff, J., 147.Hofmann, J., 86.Hofmann, K. A., 41, 250.Hofmann-Degen, K., 269.Holde, D., 69.Holgersson, S., 249.Holleman, A. F., 95.Hollingsworth, M., 53.Holmberg, B., 140, 165.L* 298 INDEX OF AUTHORS’ NAMES.Holmes, A., 159.Holmes, W. C., 158.Hopkins, 191, 194.Horst, C., 134.Horton, F., 2, 3.Howard & Sons, Ltd., 98.Howell, I,. B., 75.Howell, 0. R., 55.Howland, 189.Hoylc, G., 57.Huckel, E., 10.Hiittig, G. F., 48, 171.Huff, W. J., 164.Huggins, AT. L., 255, 25G.Hughes, 6, 183.Hulett, G. A., 41.Hulton, H.I?. El., 224.Hume, 187, 188.Hunter, H., 15, 16, 18.Hunter, L., 74.Hunter, AT.. A., 35.Hunter, 0. W., 210, 211.Hunter, W. H., 93.Hurd, C. de W., 68.I-Iutchins, L. RI., 161, 219.Hutchinson, 180.Iiutcliinson, A,, 234.Ihlow, F., 226.Iljin, W. S., 223.hiker, A., 43.Ingold, C. K., 72, 103, 107, 111, 112,113, 116, 128.Ipatiev, W., 38.Irvine, J. C., 77, 78, 85.Isaikin, F. M., 38.Iskyul, V., 271.Ivanov, V. N., 171.Iwata, S., 145.Jackson, L. C., 258.Jacobs, (Miss) L. M., 24.Jacobson, R. A., 92.Janecke, E., 38.Jarvinen, K. K., 171.Jake& M., 97, 165.Jakob, J., 266.James, C. W., 120.Jander, G., 49.Janett, S., 174.Jantzen, V. T., 46.Jellinek, K., 169, 171.Jenny, E., 50.Jessen-Hansen, H., 1GG.Johnson, E., 273.Johnson, E. B., 43.Johnson, H.W., 210, 211, 212.Johnson, It. C!., 7.Johnston, J., 277, 278.Jolly, V. G., 55.Joly, J., 263.Jones, 189.Jones, A., 35.Jones, G. W., 159.Jones, J. H., 35.Jones, L. H., 218.Jones, W., 164.Jong, H. G. B. de, 25.Josephson, K., 162.Jost, H., 96.Joyner, It. A., 47.Just, H., 175.Justh, R., 58.Justin-Mueller, E., 1GS.Kaascht, E., 53.liallenberg, S., 140.Kannenstine, F. M., 3.KanB, N., 170.Karaoglanov, G., 167.Karaoglanov, Z., 167.Iiarczag, L., 169.Karrer, P., 84.Karssen, A., 2 9 , 249.KAA, V., 220.Kastranck, W., 173.KatB, N., 228.Kawakami, K., 67, 188.Kaye, G. W. C., 258.Keen, B. A., 202.Kehrmann, F., 53.Kellaway, 183.Keller, K. T., 118.Kolley, W.P., 206.Kelly, J. W., 218.Kendali, E. C., 186.Kendall, J., 11.Kenner, J., 61, 119, 120, 128.Kenyon, J., 17, 18.Kessler, E., 126.Kiby, W., 248.Kiel, F., 104.Kieser, E., 26.Kiess, C. G., 158.Kiliani, H., 76.Kimball, 179.Kimura, M., 7.King, H., 143.King, H. S., 46.King, W. J., 171.Kipping, 3’. S., 125.Kirpal, A., 148.Kishner, N., 101.Kliinliardt, F., 91.Kleiner, S., 57.Kleinmann, €I., 157.Kline, H., 169.Kling, A., 163.Klosgen, G., 104.Knipping, P., 3.Knoevenagel, E., 126.budson, C. M., 175.Koch, A,, 215INDEX OF AUTHORS’ NAMES. 299Kocour, C., 66.Koehler, A, 160.Kohler, W., 139.Konig, W., 148, 149, 152.Koenigsberger, J. G., 275, 278.Koppen-Kastrop, P., 149.Kohler, E. P., 127.Kolbe, A., 153.Kolkmeijer, 248.Koller, G., 153.Kolligs, H., 93.Kolthoff, I.M., 166, 169, 171, 173,Komatsu, S., 89.Kon, G. A. R., 73, 111.Kondo, H., 152.Kondyrev, N. V., 61.Konrad, E., 41.Kopetschni, E., 90.Mordes, E., 171.Kostanecki, St. v., 132.Kramer, 189.Kramers, H. A., 19.Krannich, W., 138.Kratzer, A., 8.Kraus, C. A., 13, 75.Krebs, P., 169.Kremers, F., 69.Kremers, H. C., 40.Kremers, R. E., 9s.Kreussler, V. von, 6.Kristen, W., 164.Krollpfeiffer, F., 103, 132.Kruger, D., 158.Kuster, W., 137.Kustner, H., 240.Kuhn, R., 80.Kuhnhenn, W., 91, lG5.Kunz, A,, 76.Kunz-Krause, H., 216.Kurnakov, N., 30.Kuroda, (Bliss) C., 105.KUSS, E., 29, 39.Buzmin, M. S., 200.174, 175.Laclimann, A., 92, 118.Lacroix, A., 263, 283.Laidlaw, 183.Landa, S., 165.Landsberger, 193..Lanfear, E.W., 106.Lange, F., 51.Lange, N. A., 169.Langenbeck, W., 143.Lapworth, A., 68, 73, 95.Laquer, 107.Larsen, E. S., 285, 287, 290.Larsson, E. L., 174.Lasausse, E., 166.Lassieur, A,, 171, 174.Lassieur, (Mme) A., 171.Leu, E., 7,Laubmann, H., 278, 287.Lauder, A,, 155.Laue, H., 166.Laurent, (Mlle), 22G.Lauterbach, H., 175.Lea, C., 49.Lehmann, P., 156.Leibowitz, J., 67.Leitch, R. D., 164.Leitz, E. W., 169.Lemberg, R., 129, 133, 145.Lemke, G., 75, 138.Lenher, V., 170.Leoncini, G., 203.Leonhardt, IT., 130.Lesch, W., 91.Lesser, 197.Levene, P. A., 76.Levi, G. R., 53.Levy, (Mlle) J., 116, 133.Lewis, G. N., 33.Lewis, W. C. McC., 19.Lichtenwalner, D.C., 203.Lieb, H.,. 155.Liebl, Fr., 117.Liosche, O., 115.Liesegang, I-I., 208.Lifschitz, I., 257.Lindberg, S., 165.Lindemann, H., 124, 255.Lindgren, W., 264.Lindh, -4. E., 282.Ling, A. R., 82, 86, 22G, 227, 22s.Linnell, W. H., 77, 79.Lipman, C. B., 210, 211, 213.Lipman, J. G., 214, 215.Lipp, A., 103.Lipp, P., 103.Livens, G. H., 17.Livingstone, B. E., 161, 219.Livshis, 179.Lodge, (Sir) O., 255.Loeb, 226.Loffelbein, W., 172.Lohnis, F., 213.Logan, 185.Loibl, H., 224.Lomanitz, S., 217.Lombard, V., 34.Long, 196, 197.Longchamhon, L., 259.Losana, L., 3G, 37.Lowry, T. &I., 16, 17, 26, 27, 28, 29,59, 266.Luchini, R., 3 7 .Luckow, C., 74.Luff, G., 172.Lumia, C., 214.Lundagen, 189.Lupton, 195, 196, 197.T,yman, T., 3.Lyon, C.J., 224.Lyon, T. L., 214300 INDEX OF AUTHORS' NAMES.Maag, W., 137.Mmss, O., 63.McBain, J. W., 25.Macbeth, A. K., 48, 79, 164.McCollum, 187.McCombie, H., 87, 96.McCormick, 183.McGee, J. M., 221.McGeorge, W. T., 208.McGinnis, F. W., 225.Macgregor, A. M., 284.McHaffic, I. R., 173.McHargue, J. S., 219, 226.McHugh, G. P., 119.Msckay, J., 79.McKee, J. L., 37.McKee, R. H., 159.McKeehan, L. W., 35, 241, 247.McKelvy, E. C., 47.Mackenzie, J. E., 277.McKeown, A. C., 19.Macleod, 179, 183, 184, 197, 198.McNicol, R. A., 17.McRae, J. A., 73.McVicker, W. H., 9.Magnusson, H., 274.Mahal, A., 144.Makow, V., 170.Mannich, C., 92.Manskaja, (Frl.) S., 228.Mansuri, 6. A., 45.Maquenne, L., 82, 220.Marcelin, A,, 22.Marchal, G., 36.Marchand, B.de C., 161.Marckwald, W., 48.Marcusson, J., 210.Mardles, E. W. J., 24, 25.Margosches, B. M., 164.Mark, H., 242, 248, 252.Marqueyrol, M., 160.Marrian, 183.Marschhaupt, J. G., 217.Marsh, J. K., 9.Marshall, A. L., 33.Martin, J. C., 208.Martinet, J. L., 139.Marvel, C. A., 75.Mason, F. A., 122.Mathews, 192.Mathews, M. A., 122.Maucher, W., 278.Mauguin, C., 247, 249.Maurer, H., 137.Mauzelius, R., 284.Mayer, F., 103, 134.Mazzetti, C., 39.Meek, C. S., 213.Meerwein, H., 104, 115.Meggers, W. F., 158.Meggitt, A. A., 210.Meisenheimer, J., 126, 140.Mell, M., 257.Mellanby, 1 S6.Mellet, R., 53.Mhager, (Mlle), 226.Mcnlre, J. B., 167.Menzies, A.W. C., 7, 33.Menzies, R. C., 61.Mereshkowsky, B. K., 75.Merton, T. R., 7.Merwin, H. E., 266, 275, 277, 2T8,285, 291.Messinger, 05.Meyer, D., 217.Meyer, F., 51.Meyer, G. M., 7G.Meyer, H., 209.Meyer, J., 127.Meyer, K. H., 152.Meyer, P., 197.Neyerhof, 191, 192, 198, 195, 197.Michaelis, 169.Michailovitsch, V., 49.Middleton, I€. E., 2U2.Midgley, T., jun., 58.Miekeley, A., 78.Mieleitner, K., 292.Mierster, A., 226.Miller, W. von, 150.Mills. W. H.. 140. 141, 151. I , . Milroy, 195.Mingazzini, M., 127.Mitchell, A. D., 49.Mitchell, A. E., 33, 277.Mitchell, C. A., 165.Mitchell, J. G., 79.Mitscherlich, E. A., 222.Mohr, 54.Moldaenke, K., 133.MondBsir, P. de, 205.Monier-Williams, G. W.,Montagne, P. J., 90.Montmollin, G.de, 132.Montmollin, M. de, 132.Moog, K., 79.Moore, B., 220.More. J.. 167.74.More$, G. W., 270, 275.Morgan, G. T., 66, 94, 142, 247, 253.Morris, R. L., 172.Morrison, D. If., 63.Morton, R. A., 132.Moser, L., 171.Nosettig, E., 154, 155.Mountain, E. D., 279, 285.Miiller, A., 69, 243, 244.Miiller, E., 36, 174, 175.Miiller, F., 174.Miiller, J. H., 172.Miiller, W. J., 275.Mukherjee, J. N., 208.Mullsly, J. M., 61.Muller, 163.Mumford, S. A., 53.Mumm, O., 147INDEX OF AuTIfORS’ NAMES. 301Murch, W. O., 143.Murgoci, G., 285.Murlin, 179.Muschiol, E., 168.Nuzaffar, (Sheikh) D., 31.Nagel, W., 101.Nakamura, G., 7.Nakamura, M., 145.Nametkin, 8. S., 103.Nanji, D. R., 82, 86, 226, 228.Nasir, S. M., 211.Nekola, V., 225.Needham, 184.Negelein, E., 221.Nelken, (Miss) A., 138.Nelson, E.K., 9s.NBmec, A., 220, 229.Nernst, W., 27, 29.Neuber, F., 167.Neuberg, C., 189.Neukirch, E., 171.Neumann, F., 43.Neusser, E., 171.Ncwitt, D. M., 20.Newman, F. H., 8.Newton, J. D., 223, 226.Nichols, M. I., 152.Nicloux, M . , 159.Nicolas, E., 220, 221.Nicolas, G., 220, 221.Nierenstein, M., 166.Nieuwland, J. A., 65.Niggli, P., 264, 275.Nishida, D., 121.Nitze, E., 129.Nixon, I. G., 168.Noack, K., 227.Nobel, 183, 184.NOCZZU, R., 89.Nolin, E., 372.Norris, W. S. G. P., 53, 111.Norrish, R. G. W., 50, 59.Noyes, A. A., 6.Noyes, W. A., 62, 86.O’Brien, 183.Ochiai, E., 152.Oddo, G., 49, 75.Odkn, S., 208.Oelsner, A., 215.Oftedal, I., 289.Ogburn, S.C., 55.Okazawa, T., 208.Oldham, J. W. H., 78.Olmstea,d, P. S., 2.Olmsted, 155.Olsen, C., 215.Olsen, G. A., 223.Olson, A. R., 2.Onnes, H. K., 258.Onslow, 194.Opttrin, A., 224, 228.Ordkhov, A. P., 93, 115.Orelkin, B., 112, 289.Orndorff, W. R., 172.Osterberg, 186.Osterhout, W. J. V., 225.Osugi, S., 216.Ott, H., 250.Owen, E. A., 239.Paetzold, H., 145.Page, H. J., 210, 211.Pagel, H. A., 172.Paliatseas, P., 155.Palladin, W., 228.Pandya, K. C., 107.Park, 187.Parker, F. W., 161, 198, 208, 233.Parsons, A. L., 271, 287.Pascal, P., 37, 45, 256.Patterson, J. C., 77, 85.Pauling, L., 247.Pauly, H., 93.Payman, W., 20.Pelling, A. J., 173.Pember, 218.Perkin, A. G., 122, 124, 164.Perkin, W.H., 05, 105, 122, 131.Perkins, M . E., 164.Perry, 184.Peskov, N. P., 25.Peterson, W. H., 227.Petrenko-Kritschenko, P. I., 120.Petzold, A., 150.Pfaundler, 189.Philippson, M., 10.Phillippovich, A. P., 159.Phillips, A. H., 287.Picado, E., 219.Pickard, R. H., 15, 16, 17, 18.Pickering, S. U., 214.Pictet, A., 152, 210.Piettre, M., 160.Piggott, H. A., 111, 128.Pilipenko, P. P., 265, 278.Piloty, O., 137, 138.Piper, S. H., 179, 243.Pirani, M., 41.Pisbor, K., 139.Pittman, D. TV., 207.Plant, S. G. P., 131.Poirot, G., 171.Poitevin, E., 284, 286.Polanyi, M., 242.Polonovski, Max, 152, 155, 156.Polonovski, Michel, 152, 156.Ponomarev, I. F., 39.Ponzio, G., 142.Popelier, J., 62.Porter, A. W., 242.Posner, T., 135302 INDEX OF AUTHORS' NAMES.Posnjak, E., 2T5.Powell, A.R., 288.Powick, W. C., 162.PrAt, S., 266.Pratt, D. D., 144.Prescott, J. A., 205.Preston, G. D., 239.Prianischnikov, D. N., 222.Price, W. J., 227.Prince, A. L., 218.Pringsheim, H., 67, 84.Procter, H. R., 158.Pryde, J., 77, 182.Pschenicyn, N. K., 56.Puetter, K. F., 40.Pufahl, O., 285.Pummerer, R., 86.Purves, C. B., 77.Putochin, N. J., 138.Putzeys, P., 32.Pyl, G., 135.Pyman, F. L., 142, 143, 152.Quastel, J. €I., 190, 192.Raber, 0. L., 225.Riider, M. G., 45.Raiziss, G. W., 163.Rskuzin, M. A., 49, 163.Ramann, E., 208.Ramsay, IV., 67.Rankine, A. O., 50.Raper, H. S., 228.Raschig, F., 47.Rastall, R. H., 263, 264.Rau, M. G., 99.Ray, G.B., 224.Raymond, A. L., 251.Reade, T. H., 87.Rebmann, A., 65, 220.Reeves, H. G., 66.Reich, R., 125.Reichert, J. R., 65.Reid, 182.Reiter, E., 148.Remy, H., 249.Reuss, A., 176.Revesey, G., 91.Rice, F. E., 207.Rice, J., 19.Richards, T. W., 30, 32, 236.Richter, F., 96.Rideal, E. K., 26, 60.Riding, R. W., 36.Riffenburg, H. B., 176.Rinne, F., 271.Rippel, A., 219, 224.Roberts, H. M., 33.Roberts, J. K., 258.Roberts, R. H., 222.Robins, W. J., 226.Robinson, G. M., 87.Robinson, R., 8", 95, 127, 144, 154.Robinson, W. O., 202.Robison, R., 162, 188.Rodebush, W. H., 47.Rodillon, G., 176.Rochling, C., 41, 280.Rohrs, W., 171.Rogai, F. A., 203.Rogers, A. F., 286.Romburgh, R. van, 59.Romeis, 186.Rona, P., 157.Rose, H., 253.Rosenhain, W., 239, 241, 255.Rosenmund, K.W., 89, 01, 105.Rosicky, V., 288.Roth, F., 59.Rothweiler, F., 136.Rouche, H., 94.Roughton, F. J. W., 19.Rouiller, 185.Roylo, F. A., 97.Rozycki, A., 132.Rubenstein, L., 95.Riibke, K., 164.Riiggli, P., 139.Ruell, D. A., 81.Ruff, O., 43.Ruggeri, G., 142.Rupe, H., 16, 173.Rupp, E., 168.Russe, A., '78.Ruzicka, L., 100, 101, 117, 127.Sabalitschka, T., 221.Saenger, H., 209.Saha, M. N., 5.Salathe, A., 47.Sand, H. J. S., 10, 174.Sander, F., 21 8.Sandon, 215.Sands, J. E., 125.Sanfouche, A., 160.Sarasin, J., 134.Sayers, R. It., 169.Scarf, F., 18.Schiifer, J., 115.Schlifer, W., 103.Schaller, W. T., 284, 286.Scharizer, R., 276.Schay, C., 175.Schedler, J.A., 07.Scheibe, G., 150.Scheinost, E., 164.Schempp, C. A., 284.Schenck, R., 43.Scheuing, G., 118.Scheumann, K. H., 271.Schjelderup, H., 246.Schleede, A, 74.Schlcnk, W., 136MDEX OF AUTHORS’ NAMES. 303Schlesinger, IT. I., 47.Schlubach, H. H., 58, 79.Schmalfuss, H., 167.Schmalz, K., 84.Schmidt, 196.Schmidt, E., 74, 226.Schmidt, J,, 37, 120.Schneider, R. P., 13.Schneider, W., 129, 132.Schoch, E., 104.Schhberg, A., 118, 136.Schonbrunn, B., 213.Schoeller, W. R., 288.Schoenflies, 230, 260.Schoep, A., 283, 284, 285, 286.Scholl, R., 123, 124.Schollenberger, C. J., 219.Schorigin, P., 91.Schrader, H., 210.Schrauth, W., 210.Schroeter, G., 146.Schryver, S. B., 82, 227.Schubert, M.. 136, 138.Schudel, G., 166.Schurmann, W., 104.Schutze, M., 126, 140.Schultheiss, A., 149, 150.Schultze, H., 132.Schulz, F., 166.Schumacher, R., 74.Schwarz, J., li2.Schwarz, R., 40, 41.Schweizer, R., 90.Scott, 181.Scripture, E.W., 30.Scurti, F., 201.Sebor, J., 225.Seekles, L., 154.Seelen, K. von, 140.Seeley, E. A, 112.Seidel, W., 51.Seidler, C., 146.Seifriz, W., 226.Seitz, F., 88.Seka, R., 130.Relb, C. J., 284.Solle, H., 18.Semmens, (Miss) J3. S., 323.Semon, W. L., 4’7.Semp, H., 124.Senderens, J. B., 62, 89.Sewell, NT, G., 122.Shaffer, 178.Shaw, B. D., 67.Shearer, G., 69, 231, 233, 243, 241,Shedd, 0. &I., 16G.Shibats, K., 145.Shilov, E. A., 49.Shipley, J. W., 173, 187.Shive, J. W., 217, 218.Sidgwiclr, N.V., 26, 29.Siegbahn, M., 282.Severs, F. J., 214.Silberstein, L., 8.Simmonds, 187.Simon, A,, 49.Simon, L. J., 65, 79, 160.Simonsen, J. L., 99.Singh, B., 72, 106.Sjoberg, K., 228.Skinner, J. J., 219.Slater, 196.Smeykal, K., 137.Smirnov, A. I., 222.Smith, 178, 180, 181, 182, 184, 188,Smith, C. J., 50.Smith, E. P., 224.Smith, G. F., 53, 170, 172.Smith, G. M., 13.Smith, H., 187.Smith, J. D. M., 27, 29.Smits, A., 33.Smyth, F. H., 278.Snow, 0. W., 86, 222.Soames, 187.Society of Chemical Industry in Basle,135, 144.Sokolov, W., 289.Solaja, B., 172.Somieski, C., 41, 42.Somogyi, 178.Sosman, R. B., 42.Souther, B. L., 127.Spacu, G., 168, 172.Spath, E., 183, 154, 155.Speidel, P. E., 120.Spencer, L. J., 273, 279, 283, 284.Spengler, T., 152.Speyor, E., 133.Spiers, C.H., 26.Spoehr, H. A., 65, 220, 221.Sponsler, 0. L., 253.Rsolrolowski, A. N., 207.Stamberger, P., 209.Stamm, G., 103.Starkey, E. B., 203.Starkey, R. L., 215.Starynkevitsch, A., 38.Stedman, E., 155, 156.Steenbock, 189.Steinheil, M., 32.Steinkopf, W., 133, 136.Steinmetz, H., 287.Stensson, N., 282.Stepp, 182.StiSrba-Bohrn, J., 288.Stern, H. J., 222.Stern, P. L., 37.Stevens, R. G., 40.Stevenson, A., 103.Stewart, A. W., 9.Stewart, C. P., 143, 190.Stiebeler, I’., 43.Stirnson, F. J., 158.Stiven, 182.Stock, &4., 29, 39, 41, 43304 INDEX OF AUTHORS’ NAMES.Stockdale, D., 39.Stohmann, 196.Stoklasa, J., 225.Stoklossa, G., 271.Stoll, M., 100, 101.Stone, H.W., 157.Stone, J. F. S., 86, 222.Strassner, 192.Straus, 156.Strecker, W., 62.Such, J. E., 18.Sugden, S., 29.Sundius, N., 274.Sylvester, N. D., 51.Tacke, B., 203.Takahashi, K., 67, 188.Tamhane, V. A., 224.Tammann, G., 34, 262.Tanenbaum, A. K., 75.Taylor, C. S., 47.Taylor, G. I., 242.Taylor, G. S., 225.Tempus, F., 227.Terasaka, M., 93.Terry, H., 55.Thallinner, W., 184.Thannhauser, 137.Thielmann, F., 91.Thomas, A. W., 165.Thomas, E. E., 206.Thomas, E. M., 82.Thomas, J. S., 35, 36.Thomas, M. D., 207.Thomassen, L., 46, 249, 252.Thompson, J. G., 43.Thompson, P. F., 170.Thomson, E., 288.Thomson, (Sir) J. J., 27, 28.Thorne, P. C. L., 25.Thorpe, J. F., 70, 71, 72, 103, 106,107, 112, 113.Thunberg, T., 221.Tiddy, K., 160.Tietze, E., 59.Tiffeneau, M., 115, 133.Tilitschhev, M., 139.Timms, G.M., 142, 143.Toeldte, W., 120.Touplain, F., 176.Townend, D. T. A., 20.Townsend, J. S., 3.Tramm, H., 33.Traube, W., 58, 145.Treadwell, W. D., 174.Trenel, M., 58.Tressler, K. M., 44.Trevan, 183.Troger, J., 149.Trothandl, O., 155.Tropsch, H., 67, 159.Truffaut, G., 211.Truog, E., 223.Tschermak, G., 270.Tschitschibabin, A. E., 146.Tschugaev, L. A., 55, 56.Tsuboi, S., 291.Tulaikov, N. M., 209, 216.Tunnicliffe, 190, 192.Turner, E. E., 144.Tutin, F., 190, 227.Tutton, A. E. H., 258.Uhl, A., 173.Underwood, H. W., 86.Urasov, G., 39.Urbain, G., 45, 46.ValdiguiQ, A., 163.Vanschiedt, A. A., 49.Varenkamp, O., 148.Vavon, G., 57.VBgard, L., 246, 248.Venlsataramaiah, V., 34, 53.Verhoeff, J.A., 168.Verhulst, J. H., 227.Vernadsky, V. I., 273.Vernon, C. G., 168.Verzyl, E. J. A. H., 175.Veself, V., 97.Vicente, E., 219.Voicu, J., 210.Voigt, J., 164.Vorliinder, D., 53.Vortmann, G., 95.Wachi, H., 89.Wada, I., 172.WBschor, I<., 93.Wahl, A., 139.Wakefield, H. F., 170.Waksman, S. A., 212, 215.Walker, 192.Walker, T. L., 271, 283, 287.Walls, N. S., 21.Wallstein, R., 43.Walton, G. P., 227.Walton, J. H., 50.Wandenbulcke, F., 176.Wann, F. B., 211.Warburg, O., 193, 221.Ward, C. F., 68.Wardlaw, W., 51.Warington, (Miss) K., 219.Washington, H. S., 236, 261.Watt, 188.Wattenberg, H., 174.Way, J. T., 204.Weatherill, P.F., 30.Weber, 193.Webster, T. A., 188, 220.Weidel, H., 147INDEX OF AUTHORS’ NAMES. 305Weidenhagen, R., 78.Weigel, O., 271.Weigert, F., 221.Weile, M., 48.Weiler, G., 89.Weinberg, A. A., 157.Weiser, H. B., 36.Weiss, B., 136.Weissenberg, K., 248, 252.Wells, L. S., 13.Wells, R. C., 285, 288.Werner, E. A., 223.Werner, S., 46.Wertheimer, 192, 193.Wester, D. H., 216.Wevm, F., 250.Wheeler, R. V., 20.Wherry, E. T., 234, 236.Whitaker, J. W., 159.Whitby, S., 162.White, G. F., 75.Whitehorn, J. C., 164.Whitford, E. J., 50.Whitman, J. L., 166.Whitney, M., 200.Whittier, E. O., 16G.Wibaut, J. P., 146.Widmark, 179.Wiedrnaim, H., 138.Wigglesworth, 184.Wild, E., 130.Wildmar, F. M. P., 174.Wiley, B. C., 203.Wilkendorf, R., 88.Wilkes, S. H., 170.Wilkie, 95.Will, H., 138.Willard, H. H., 53, 173, 175.Williamson, E. D., 277, 278.Willis, L. G., 208, 218.Willstatter, R., 88, 124, 153, 166,TVilsdon, 201, 202.Wilsey, R. B., 249, 250.Wilson, B. D., 214.Wilson, H. A., 6.Wilson, W. C., 119.Windaus, A., 91, 143.Windisch, H., 170.Winegarden, 182.Wingler, A., 169.Winogradoff , L. , 1 7 1169.Winogradsky, S., 213.Winter, 178, 180, 181, 182,Winterstein, E., 99.Wintgen, R., 25.Wise, C. R., 52.Witzemann, 179.Wlodek, J., 227.Wohlisch, E., 15.Wolffenstein, R., 170.Wood, A. S., 71.Wood, C. E., 18.Wood, J. K., 49.Wood, R. W., 4.Woodrow, 184.Woodward, I., 256.Woollett, 95.Wormall, A., 228.Worsley, R. R. le G., 52.Wright, F. E., 285.Wulff, G., 248.Wyckoff, R. W. G., 232,Wylam, B., 80, 83.236, 246, 250, 254, 260.Yamada, M., 35, 241.Yamamoto, R., 98.Yant, W. P., 159.Yntema, T. O., 47.Young, J. F. T., 241.Yu, C. L., 165.h%Eek. A.. 46.Zadek, F.; 69.Zalkind, J., 63.Zambonini, F., 40, 45, 236.Zdobnickf, V., 225.Zechmeister, L., 62.Zeeman, P., 8.Zeglin, H., 166.Zeidler. F., 42.Zeiss, R., 30.Zelinski, N. D., 88, 116.Zemplhn, G., 76.Zerweck, W., 136, 137.Zetsche, F., 89.Ziecler, K., 91.ZilVa, i87.Zinsser, 198.Zintl, E., 174.Zobel, F., 134.Zocher, H., 26.184.234, 235

ISSN:0365-6217    

DOI:10.1039/AR9232000293

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

INDEX OF SUBJECTSAbietic acids, estimation of, 165.Acetaldehyde, preparation of, 65.Acetals, synthesis of, 65.Acetamide, preparation of, 86.Acetic acid, glucinum salt, crystalstructure of, 253.lead tetra-salt, as an oxidisingagent, 90.cellulose ester, organosols of, 24.Acetic acids, bromo- and chloro-,preparation of, 68.Acetylene, polar character of, 60.Acids, 67.aliphatic, bromination of, 67.djcarboxylic, rotation of menthyland octyl esters of, 17.fatty, and their derivatives, struc-formation of films by, on liquids,Acid chlorides, hydrogenation of,Acraldehyde, detection of, 162.Adrenaline, estimation of, 164.L4gricultural analysis, 160.Akrochordite, 283.Alcohols, 61.Aldehydes, 64.ture of, 243.22.89.catalytic dehydration of, 58.aliphatic, purity criteria for, 63.preparation of, S9.condensation of sodium cyano-acetate with, 73.detection of, 162.Aldehydopyrroles, 137.Alkali halides, crystal structure of,249.metals, action of, on ethers andhydrocarbons, 9 1.salts, conductivity of, in flames, 6.urates, jellies of, 26.Alkaline earth sulphides, crystalstructure of, 249.Alkaloids, 152.morphine, 154.in plants, 227.detection of, 161.estimation of, 166, 174.Alkyl hypochlorites, decompositionsulphides, action of cyanogenof, 66.bromide on, 87.Alkylamino-others, preparation of,Alkyl glycerols, 64.Alkylvinylcarbinols, preparation of,Allantoin, estimation of, 166.Alloxantin, structure of, 145.Alloys, crystal structure of, 237.Ally1 cyanide, use of potassiumAllylveronal, bromination of, 129.Aluminium alloys, 39.silicates, 39, 272.Alums, crystal structure of, 246.Amalgams, use of, in analysis, 170.Ambatoarinite, 283.Amines, photosynthesis of, 86.aromatic, oxidation of, 90.Amino-acids, ionisation of solutionshinohydroxy-acids, synthesis of, 88.Ammonia, properties of, 47.additive compounds of metallicAmmonium chloride, equilibrium offerric chloride, water, and, 54.double salts of mercuric chlorideand, 38.Triammonium hydrogen sulphate,hydrosulphide, 35.87.63.cyanide in preparation of, 87.of, 11.halides with, 48.35.Ammonium sulphides, 36.Amygdalin, biose of, 80.Amyloses, 84.Analysis, agricultural, 160.combustion, 163.electrochemical, 173.gas, 159.inorganic, 167.organic, 161.physical, 157.polarimetric, 158.spectroscopic, 157.water, 175.Anhalonidine, synthesis of, 154.Anthracene, crystal structure of, 251.action of, on alcosols, 25.Anthracene group, 121.Anthraquinone, 2-nitro-, 90.Anthraquinone-2-sulphonic acid,sodium salt, dry distillation of, 122.Anthrone, reduction of, 12 1.3 0INDEX OF SCBJECTS. 307Antigens, residual, 198.Antimony, atomic weight of, 31.electrolytic deposition of, 174.perchlorate, 50.hydroxides, 49.oxide, crystal structure of, 247.sulphide, compound of cuproussulphide and, 36.Arachidic acid, estimation of, 165.Argentojarosite, 284.Armangite, 284.Aroma& -compounds, type theoryArsenic allovs with tin, 45.of, 112.trihalides," preparation of, 49.trioxide, crystal structure of, 247.detection of, 168.estimation of, 174.1 -Aryloxanthronyls, 123.Atomic weights, 29.Atoms, dimensions of, 257.Azelaic acids, bromo-, oxidation of,70.Azotobacter, fixation of nitrogen by;210.Azulene, 98.Bacteria, specificity of, 198.Baicalein, 145.Baicalin, 145.Beckmann tramformation, 115.Benzaldehyde, nitration of, 04.Benzene, fluorescent spectra of, andformula, Ladenburg's, 102.crystal structure of, 255.Benzene, nitro-, compound of sul-phuric acid and, 04.2 : 3-dinitrochloro-, nitration of, 95.isoBenzfuroin, 93.Benzidines, oo-dinitro-, 119.Benzil, conversion of, into benzilicacid, 117.action of 4-nitro -2-aminodiphenyl-amine with, 129.Benzoic acid, p-fluoro-, nitration of,94.Benzoin condensation, 92.Benzoins, substituted, 93.Benzophenones, reduction of, 89.Beneoquinonebromomethide, 3:5-di-Bilirubin, structure of, 137.Biphenylene sulphide, synthesis of,Bis-2-methylbenzothiazoline-1 : 1-Bismuth crystals, thermal conductiv-its derivatives, 9.bromo-, 124.136.spiran, 140.ity of, 258.perchlorates, 50.estimation of, 171.light by, 257.Blende, refraction and absorption ofBlood, lactic acid in, 197.sugar in, in diabetes, 181.Boron, atomic weight of, 29.valency of, 28.trichloride, 39.hydrides, 38.Brass, crystal structure of, 240.Brassidic acid, structure of, 69.Bromine, combination of ethyleneBromates, estimation of, 170.Butadiene, structure of, 61.Butane, a8-dibromo-, preparation of,Ay-Butenyldiethylamine, 87.and, 59.75.Cadalene, 100.Cadmium, detection of, 168.salts, reduction of, 38.Caz4um iodides, molecular structureCalabar bean, alkaloids of, 155.Calcite, crystal structure of, 219.Calcium carbonates, synthesis ofvarious forms of, 276.salts, deposition of, in cartilage, 189.sulphate dihydrate, 37.thiosulphate hexahydrate, crystalstructure of, 234.estimation of, 169.of, 29.Camsellite, 284.Caoutchouc, constitution of, 61.Capsaicin, constitution of, 98.Carbocyanines, preparation of, 151.Carbohydrates, 76.Carbon, vitreous, 40, 250.effect of helium on specltra of, 7.mowoxide, explosive combustion ofmixtures containing, 20.estimation of, 159.Carbonates, dissociation of, 277.estimation of, in water, 176.Cartilage, calcification of, 188.Catalytic hydrogenation, 57, 88.Celloisobiose, nature of, 84.Callulose, methylation of, 85.Celtium, 45.Cerium oxide, crystal structure of,249.Chlorine, active, 53.tetroxide, 53.Hydrochloric acid, compound ofPerchlorates, 53.Chlorites, 63, 271.Chloroselenic acid, 52.Chlorosulphonic acid, absorption ofChloroxiphite, 284.Cholesterol, detection of, 162.Chondrin, distinction between gliitinand, 163.2 : 4-a-Chromenes, 144.nitric oxide and, 47.ethylene by, 58308 INDEX OF SUBJECTS.Chromium trioxide, solubility of, inCh.~yt?anthmum cinerarimf olium, pyre-Cinnabar, crystal structure of, 247.Citral, p-cymene from, 101.Clam, hormone from tissues of, 180.Cobalt iodides, 55.Co baltinitrit es , 5 5.Codeine, structure of, 127.Codeinone, hydroxy-, reduction of,133.Cod-liver oil, vitamins in, 67, 187, 188.Cohesion, 254.Colloids, 22.Colour of brown solutions, 158.Co-ordination, 26, 29.Copellidine, separation of pyrrolidineCopper salts with thallium, 36.Cupric oxide, hydrates of, 36.Cuprous phenyl, 125.sulphide and, 36.Cuprates, 36.aqueous nitric acid, 53.thron from, 98.estimation of, 172.and, 138.sulphide, compound of antimonyCoralyne, 128.Cornetite, 284.Corydaline, degradation of, 154.Corydalis caaa, alkaloids from, 155.Corypalmine, 155.o-Coumaraldehyde, preparation of,Creedite, 285.m-Cresol, sulphonated, nitration of,95.Crotonaldehyde, preparation of, 64.Crotonic acid, yyy-trichloro-, synthesisCrotonic acids, isomeric, 69.Cryptocyanine, formula for, 151.Crystals, structure of, 230.rotatory polarisation in, 258.atomic radii of, 236.cleavage of, 256.isomorphism of, 236.symmetry of the molecules in,inorganic, structure of, 246.organic, structure of, 251.93.of, 69.233.Curite, 285.Cyanamide, polymerisation of, 85.isocyanines, preparation of, 151.isoCyanine colouring matters, 141.Cyanogen bromide, action of alkylHydrocyanic acid, preparation of,sulphides with, 87.85.m-Cymene, 93.p-Cymene from citral, 101.Cysteine, reduction by, 192.Diabetes, sugar in blood in, 181.Diaboleite, 285.7 : 9-Dialkyl-4 : 5-dihydrouric acids,BP’-Dialkylglutaric acids, aa’-di-bromo-, esters, action of alkalison, LOG.Diazotisation, 94,aa’-Di-n-butoxytrimethylamine, 87.Dimethindiazidines, 128.4 : 4’-DiethoxyphenylcycZohexyl-amines, isomeric, 89.Diethyloctaphenylsilicotetrane, 125.Diketones, compounds of selenium andtellurium tetrachlorides of, 66.4 : 5-Dimethoxyphthalonic acid, 105.Dimethylacrylic acids, esters, con-densation of ethyl oxalate with,73.2 : 6-Dimethylbenzbisthiazole, 141.Dimethylhexenediols, isomeric, 63.1 : 1 -Dimethylcyclopropane, ww-di-bromo-, reduction of, 116.Diphenyl derivatives, stereochemistryof, 118.Diphenylamine, 4-nitro- 2-amino-,action of benzil with, 129.Diphenylenequinone, tetraiodo-, 95.2 : 3-DiphenylindoneY 93.Diphosphatoferric acid, 49.4 : 4’-Dipyridyl, action of cyanogenbromide with, 148.Diquinon ylme thanes, c oloured salts,150.Disaccharides, 59.Disiloxan, 41.Dispersion, refractive and rotatory,Dixenite, 285.Drying, effect of, on various sub-Earth, distribution of elements in theEchinopsine, constitution of, 153.Electrical conductivity, 13.Electrochemical analysis, 173.Electrodes, antimony, 173.Electrode potentials, 13.Electrolytes, conductivity of, 13.Electrolytic reduction a t the cathode,Elements, thermal ionisation of, 5.Enzymes in plants, 228.Erucio acid, structure of, 69.Eserine, and its derivatives, 155.Ethane, tetranitro-, 8-dipotassiumEthers, preparation of, 62.4-hydroxy-, 129, 132.14.rotatory, 257.stances, 32.crust of, 261.quinhydrone, 173.ionisation of, 10.amphoteric, 11.34.derivative, 74.action of alkali metals on, 91INDEX OF SUBJECTS.309Ethyl alcohol, preparation of, 62.dehydration of, with phosphorusB-nitro-, synthesis of, 88.ether, mechanism of formation of,62.Ethylene, absorption of, by chloro-sulphonic acid, 58.combination of bromine and, 59.separation of propylene and, 169.d-Ethylm-hexylcarbinol nitrite,optical properties of, 16.Ethylidenemalonic acid, reductionof, 73.Ethylphenylacetylene, B-chloro-, 93.Eudalene, 100.Explosions, gaseous, 20.Explosion pipette, Hempel, 160.pentoxide, 63.Ferric salts. See under Iron.Fertilisers, replacement of potassiumestimation of phosphoric acid in,thin, structure of, 257.by sodium in, 217.161.Films, surface formation of, 21.Finnemani te, 2 8 5.Flagstaffi te, 2 8 8.Flames containing salt vapours, con-ductance of, 6.Formaldehyde, sources of, 64.formation of, in plants, 220.properties of, 65.Formic acid, estimation of, 165.Gallotannin, estimation of, 165.Gallium, atomic weight of, 30.Gas analysis, 159.Gases, explosions in, 20.Geneserine, and its derivatives, 156.Gentianose, structure of, 81.Gentiobiose, structure of, 80.Germanite, 285.Germanium, extraction and proper-hydride, 43.estimation of, 172.inert, 34.ties of, 43.Glass, replacement of sodium-iod in,13.Glucinum oxide (glucim), extractionof, 37.Glucokinin, 181.Z-Glucosan, constitution of, 78.y-Glucose, 182.Glucosides, 76.Glutaconic acids, substituted, iso-merism of, 71.Glutaric acids, dibromo-, esters, effectof substitution on isomerismin, 72,Glutathione, 190.Glutin, distinction between chondrinGlycerol, detection of, 162.Glycine, preparation of, 86.Glycogen in muscle, 196.relation of, to insulin, 183.Glycols, dehydration of, 133.Glycollic acid, thio-, reduction by,Glyoxalines, bromo-derivativcs, 142.4-Glyoxalylaminoacetic acid, 143./I- Glyoxalylisopiperidine, 144.Gold, coagulation of, in borax beads,Graphite, pure, 41.€In?matic acid, synthesis of, 137.Hafnium, 45.detection and estimation of, 282.Halides, structure of, from com-pressibility, 256.Halogens, estimation of, 103.Halogenation, 74, 90.Helium, band spectrum of, 8.critical potentials of, 3.trans - c ycZoHeptanespirocyclopropane -2 : 3-dicarboxylic acid, 103.Heusler alloys, 241.Hewettite, 285.afi-Hexa-amylose, structure of, 83.Hexahydropht halide, 9 1.Hexamethylenetetramine, constitu-crystal structure of, 251.as a microchemical reagent, 167.n-Hexanes, substituted, synthesis of,cycZoECexenylacetone, 110.Hexose, monophosphoric ester, 188.Hibernium, 263.Hoelite, 289.Homocoralyne, instability of, 129.Homoisoquinoline, 134.Humic acids, 209.Hydrazine, preparation of, 47.of, 246.and, 163.192, 193.25.electrometric oxidation of, 175.tion of, 86.78.dihydrochloride, crystal structureHydrifia verticilhta, photosynthesiaby, 221.Hydrocarbons, 5 7.and their derivatives, intramole-cular rearrangement of, 75.action of alkali metals on, 91.Hydrogen, secondary spectrum of, 6.critical potentials of, 1.diffusion of, through metals, 34.adsorption of, by palladium, 35.as a valency standard, 27.active, 34.atom, life period of, 4.ions, concentration of, 169, 173.sulphides, 50310 INDEX 03’ SUBJECTS.Hydroxylamine, detection of, 168.Hyposulphites.See under Sulphur.Indene compounds, tautomerism of,Indigotin, condensations of, 135.Indium, estimation of, 172.Indoisooxazole-y-carbosylic acid, 1 44.Indophenine, structure of, 136.Inorganic analysis, 167.Insulin, 177.Interferometer, universal, 258.Inyoite, 286.Iodine, reaction of phosphorous acidwith, 49.Ions, dimensions of, 257.Ionisation of electrolytes, 10.Ionisation potentials, 1.Iron, atomic weight of, 30.corrosion of, 54, 173.carbide, crystal structure of, 250.Ferric chloride, equilibrium of am-monium chloride, water, and,54.111.phosphates, 54.sulphates, 275.Iron, estimation of, 170.separation of manganese and, 172.Isatin series, isomerism in, 139.Isomorphism, 23 6.Isoprene, action of hydrogen halideswith, 59.Kasolite, 286.Katoptrite, 286.Ketens, preparation of, 6G.Ketones, 64.aliphatic, purity criteria for, 63.cyclic, synthesis of, 92.4-Ketotetrahydro-1 : 5-heptabenz-thiazine, 134.Lactic acid in blood, 197.Lactones, formation of, 91.Lanthanum, preparation and proper-Lead, atomic weight of, 32.ethyl, 58.Leifite, 286.Lignin, structure, of, 210.Lignoceric acid, estimation of, 165.Liquids, effect of drying on the proper-ties of, 33.organic, spreading of, on water ormercury, 22.analysis of, 157.Lithium and its hydride, crystalstructure of, 250.halides, crystal structure of, 260,hydrosulphide, 35.platinocyanide, 55.formation of, in muscle, 106.ties of, 40.d-Longif-1 : 2-dione, 99.d-Longifolene, 99.isoLongifolic acid, 99.Magnesium sulphide, crystal struc-ture of, 249.estimation of, 169.Magnesylamine, 75.Malic acid, estimation of, polari-metrically, 158.Maltose, structure of, 80.isoMaltose, structure of, 82.Manganese, preparation and reactionsMannitan, structure of, 59.Margarosanite, 286.Mendipite, transformations of, 279.Mercury, atomic weight of, 31.of, 64.separation of iron and, 173.purification of, 37.salts, reduction of, 37.Mercuric halides, double salts of,2 : 2’-Mercurydithienyls, 135.Rlesitylenebisdiazonium chloroauratc,amino-, 94.Metahewettite, 285.Metals, crystal structure of, 241.distortion and slip-planes in, 243.Rlctallic chlorides, reduction of, withMethane, production of, from watcr-chlorination of, 74.estimation of, in mine gases, 159.Methyl alcohol, purification of, 61.ether, compound of hydrogenF-Methyl-n-amyldiethylamine, 87.3 - Methylcamphor, 103.As-Methyldihydroarsindole, 144.Methyl ethyl ketone cyanohydrin,73.1 -Methylglyoxnline alkyliodides,action of heat on, 134.Methylglyoximes, isoi-neric, $G,r-Methylmorphimethine, 127.~-Methylcyclopropeiie- 1 : 2-dicarb-Ileyerhofferite, 2 8 6.dilfoil oil, szuleno froAm, 98.Minasragrite, 2 86.\linerals, geographical distribution3 8.sodium, 35.gas, 41.chloride with, 63.oxylic acid, 107.of, 264.synthesis of, 254.optical constants of, 290.pseudomorphs of, 278.weathering of, 200.new, 283.radioactive, haloes surrounding,263.Rontgen ray examination of, 281.spectral analysis of, 157INDEX OFMolecular rearrangement, 11 6.Molecules, dimensions of, 257.Molybdenite, crystal structure of,247.Molybdenum, estimation of, intungsten, 1 7 1.Monosaccharides, 7 6.Morphine alkaloids, 164.derivatives, decomposition of, 127.Mucic acid, estimation of, 166.Muconic acid, structure of, 61.Muconic acid, ad-dibromoethyl ester,isomerides of, 70.Muscle, contraction of, 194.stability, 126.structure, 20.Naphthalene, hydrogenation of, 88.Nnphthalene-2-sulphonic acid, di-azonium compound of, 97.pemxaphthindigotin, preparation of,139.Naphthoic acids, sulphonation of, 97.a- and &Naphthols, distinctionNeon, purification of, 34.Nephelometer, Kleinmann, 16;.Neutralisation, chemical, 130.Nickel, atomic weight of, 30.sols, preparation of, 25.arsenide, crystal structure of, 251.detection of, 168.Nicotine, estimation of, 166.Nicotinonitrile, 6-chloro-2 : 4-dihydr-Nitric oxide.See Nitrogen dioxide.Nitrogen, fixation of, 210.sulphonation of, 97.between, 163.OXY-, 146.compounds in plants, 222.oxides, absorption of, 160.dioxide, compound of hydrochloricper- or tetr-oxide, dissociation of,Nitric acid, estimation of, 172.Nitrates, detection of, 168.Nitrites, triple, 40.detection of, in water, 176.N~~~OSOCOCCUB, fixation of nitrogen by,212.Nitrosylsdphuric acid, absorptiondicycZoNonane, 104.aliphatic, 85.acid and, 47.19.spectra of, 47.d-sec-Octyl alcohol, dispersion of, 16.Organic analysis, 1 6 1.compounds, long-chain, structureOrgano-metallic compounds, iso-of, 242.morphism of, 256.3UB JECTS.,31 IOrganosols, preparation of, 24.Osmosis in plants, 225.Oxalic acid, ethyl ester, condensationof, with dimethylacrylic esters,73.ethylene ester, decomposition of,139.detection of, 163.Oxidation, 90.biological, 190.Oxygen, detection of, 167.Oxygenases, 194.Oxyhaemoglobin, rate of reductionof, 19.Palladium, adsorption of hydrogenby, 35, 241.Pancreatic secretion, 177.Paramagnetism a t low temperatures,258.Paravauxite, 288.Pascoite, 287.Pellotine, synthesis of, 154.Pentaerythritol, crystal structure of,252.Pentamethyl arbutin, synthesis of,79.Pentathionic acid.See under Sul-Permeability, 226.Persulphuric acid. See under Sul-phur.Petroleum, genesis of, 57.Phenanthraquinone, 2 : 4 : 6 : 7-tetra-nitro-, 119.Phenetidine, hydrogenation of, 80.Phenol iodide, diiodo-, 95.Phenylanthrone, 12 1.2-Phenylbenzoselenazole, 142.Phenylapocamphor, 103.N-Phenylcarbazole, p-nitro-, 131.Phenylhydrazine, preparation of, 89.B-Phenylhydroxylamine, 2 : 4-di-nitro-, 96.B -Phenylpropddehyde, p -ni tro -, pre-paration of, 11 1.Phosphides, 48.Phosphophyllite, 287.Phosphorus, black, 48.phur.trichloride, preparation and oxide-organic, estimation of, 164.Phosphorous acid, reaction ofestimation of, in presenoe oftion of, 48.iodine with, 49.phosphoric acid, 169.Tetraphosphoric acid, 49.Phosphotungstates, 53.Photosynthesis, 220.Physical analysis, 157.m-Pilocarpine, 152.n- and i~o-Pilocarpines, 152312 INDEX OF S-OBJECTS.Pinacol-pinacolin transformation,Pinacyanol, 141.Pinanes, stereoisomeric, 103.Pinocamphane, 103.Pituitary extracts, therapeutic actionof, 184, 185.Plants, alkaloids in, 227.assimilation of, 220.value of boron to, 219.carbohydrates in, 226.chlorophyll in, 227.constituents of, 226.enzymes in, 228.extracts, therapeutic value of, 181.value of manganese to, 219.synthesis of nitrogen compoundsosmosis in, 225.pigments in, 227.respiration of, 224.influence of soil on growth of, 216.urease in, 223.vitamins in, 229.Platinum bases, 56.Pneumococci, specific substance from,Polarimetric analysis, 158.Polarity, induced alternate, 131.c-Polyoxymethylene, 65.Polysaccharides, 81.Potash-felspar, melting point of, 270.Potassium, spark spectrum of, 8.chloride, conductivity of mixturesof sodium chloride and, 13.chloroiridiate, action of hydrazinehydrochloride with, 55.hydrogen fluoride, crystal structureof, 248.hydroxylamineisodisulphonate, 47.detection of, 55.estimation of, 172.115.in, 222.198.Praseodymium, estimation of, 172.Procellose, 84.Proline, synthesis of, 138.cycZoPropene, 110.Propionic acid, glucinum salt, crystalstructure of, 253.Propylsne, bromination of, 74.separation of ethylene and, 159.p-isoPropylphenylacetaldehyde, 124.cycloPropylcycZopropane derivatives,Protopectin, 227.Purine derivatives, synthesis of,Purpurogallin, formation of, 124.“ Pyrethron,” 98.Pyrethronic acid, 98.Pyridine group, 146.methides, 146.Pyridinecarboxylic acids, elimination102.145.of ammonia from, 147.Pyridinium bromides, quaternary, 90.Pyrimidines, 145.Pyrobelonite, 2 87.Pyrocatechol, bromo-, 91.Pyrogallol, bromo-derivatives, 91,Pyrone group, 144.Pyrrole reaction, 163.Pyrroles, substituted, preparation of,Pyrrolidine, preparation of, 138.Pyruvic acid, bromination of, 68.136.cyano-, 136.Quartz, crystal structure of, 247.Quinoline group, 149.Racemic acid, crystal structure of,Radiation potentials, 1.Raffinose, structure of, 81.Rays, Rontgen, abnormal reflectionRespirometer, new, 161.Rhodium, estimation of, 171.Ricinine, constitution of, 152.Rickets, 186.Ring formation, 134.252.of, 254.3afroIe dibromide, 90.santene, 11 6.%opine, 153.Scutellaria baicalensis, 145.searlesite, 287.seeds, germination of, 224.Selenium, atomic weight of, 31.tetruchloride, compounds of dike-nitride, 52.oxychloride, solubility of metallictrioxide, 52.Selenic acid, estimation of, 157.Selenious acid, estimation of, 157.electrometric estimation of, 175.tones with, 66.chlorides in, 52.3elenophens, 136.z-Selinene, 101.lhellolic acid, dimethyl ester, 101.Silicohydrocarbons, 12 5.Silicon, atomic weight of, 30.crystal structure of, 249.hydrides, 4 1.dioxide (silica), structure of, 42.Silicates, constitution of, 265.Silver iodide, crystal structure of,nitrate, double salts of mercuricdry fusion of, 275.249.iodide and, 38.;imonellite, 289.3oap solutions, constitution of, 25INDEX OFSodium, action of, on organic com-pounds in liquid ammonia, 75.alloys with mercury, spectra of, 8.borates, 39.bromate and chlorate, opticalchlorate, crystal structure of, 248.chloride, conductivity of mixturesof potassium chloride and, 13.thiosulphates, compounds of cop-per salts and, 37.Disodium tricuprous thiosulphate,61.Soils, absorption of electrolytes by,202.activity of, 257.acidity of, 207.colloids in, 200.effect of drying on, 201.flocculation of, 202.humus in, 209.nitrogen compounds in, 210.phosphates in, 215.influence of, on plant growth, 216.action of sodium salts on, 205.solution, 208.partial sterilisation of, 215.sulphur compounds in, 214.analysis of, 161.estimation of carbon in, 160.estimation of humus in, 160.Solutions, brown, measurement ofcolour of, 158.Sound, velocity of, 19.Spectra, discharge, 6.Rontgen ray, 9.Tesla-luminescence, 9.Spectroscopic analysis, 157.Spencerite, 287.Spinels, electronic structure of, 256.Starch, constitution of, 81, 287.crystal structure of, 253.Sterols, detection of, 162.Substitution, 94.Sucrose, constitution of, 79.Sugars, structure of, 76.acetone derivatives of, 76.reducing, estimation of, 166.y-Sugars, 77.Sulphomonas thXo-oxidam, oxidationSulphur, combination of hydrogendioxide, structure of, and itstm’oxide, physical properties of, 51.Hyposulphites, estimation of, 170.Persulphuric acid, estimation of,Pentathionic acid, production of,of sulphur by, 215.and, 50.oxidising action, 50.170.52.Tantduxn double fluorides, 49.SUBJECTS .31 3Tartaric acid, ethyl ester, rotatoryestimation of, polarimetrically, 158.&Tartaric acid, estimation of, 165.Tautomerism, 70.ring-chain, 106.three-carbon, 107.dispersion of, 17.Tasine, constitution of, 99.Tellurium tetrachloride, compoundsof diketones with, 66.estimation of, 170.halides of, 87.148.145.131.152.fuchsone, 122.of, 77.Tetra-alkylammonium halides, per-Tetrabenzyldilutidylviolet iodide,Tetrabenzyldipyridylviolet iodide,Tetrahydrocarbazole, nitration of,Tetrahydroisoquinoline, synthesis of,4‘ : 4”-Tetramethyldiaminoanthra-&Tetramethyl y-fructose, structureTetramethyl galactose, structure of,8-Tetraphenylethane, reduction of,Thallium salts with copper, 36.Thallous nitrate, double salts ofThebaine, constitution of, 154.Thermal ionisation, 5.Thiophens, 135.Thorium chromates, 43.Thymol, preparation of, 93.Thyroid, hormone from, 186.Thyroxin, 186.Tin, white, slip-planes in, 242.alloys with arsenic, 45.tetraiodide, crystal structure of,estimation of, 1i1.trichloride, 43.rr I I .by potassium, 92.mercury halides and, 38.oxide, crystal structure of, 249.bromination of, 96.248.Titanium, atomic weight of, 30.Torsometer, wave-length, 258.Trevorite, 287.Trigonite, 287.Triphenylmethane derivatives, 120.Triquinonylmethanes, coloured salts,150.Trisaccharides, 79.Tungsten carbides, 53.Tungstenite, 288.Turpentine, Indian, terpene from,Tyrosine, bromo-, 91.9 9.Ultrabasite, 288314 INDEX OF SUBJEUTS.Uranium oxide, crystal structure of,Urea, crystal structure of, 252.Ureese in fungi, 225.249.Valency, 28.Vauxite, 285.Velocity of reaction, 18.Villamaninite, 288.Viscosimeter, falling-sphere, 24.Vitamin-A from cod-liver oil, 6 i .in plants, 229.Vitamin-D, 187.Vitamins, fat-soluble, 186.electron theories of, 26.Water analysis, 175.Weinschenkite, 288.Welsium, 40.Wood spirit, separation of consti.Wurtz-Fittig synthesis, 58, 75.tuents of, 67.Xylenol-blue, bromo-, 160.Xylose, structure of, 77.Yeast, active substance from, 180.Zinc, allotropy of, 37.salts, reduction of, 35.nitride, 37.sulphide, phosphorescent, 37.crystal structure of, 251.detection of, 16s.estimation of, 172.electrometric estimation of, 176.Zirconium trichlorido, 43

ISSN:0365-6217    

DOI:10.1039/AR9232000306

出版商:RSC    

年代:1923

数据来源: RSC