摘要:

ANNUAL REPORTSON THEPROGRESS OF CHEMISTRYANNUAL REPORTSON THEPROGRESS OF CHEMISTRYF O R 1909.ISSUED BY THE CHEMICAL SOCIETY.aornrniftrc o f Bzrblicatioir :HORACE T. BROWN, LL. D., F.R. S.A. W. CHOSSLEY, D.Sc., Ph.D., F.R.S.H. R. DIXON, M.A., F.R.S.WYNDHAM R. DUNWAN, M.A., F.R.S.M. 0. FORSI'ER, D.Sc., Ph.D., F.R.S.C. E. GROVES, F.R.S.J. T. HEW IT.^, M.A., D.Sc., Ph.D.A. MCKENZIE, M.A., D.Sc., P1l.D.G. T. MORGAN, D.Sc.A. Scom, M.A., D.Sc., F.R.S.Sir EDWAKD THORPE, C.B., LL.D.,K. bfELDOLA, F. H..S.P. R. S.d.? btl ur :J. C. CAIN, D.Sc., Ph.D.S u b - 6bifox :A. J. GREENAWAY.H. R. BAKER, M.A., D.Sc., F.R.S.C. H. DESCH, D.Sc., Ph.D.A. D. HALL, M.A., F.R.S.W. D. HALLIBURTON, M.D., F. R.S.A. HUTCHINSON, M.A., Ph. D.H. 0.JONES, AI. A., D.Sc.A. LAPWORTH, D.Sc.A. 11. LING, F.I.C.F. SODDY, M.A.'r. M. LOWKY, D.s~.VOl. VI.LONDON:#URNEY & JACKSON, 10, PATERNOSTER ROW, E.C.1910RICHARD CLAY AND SONS, LIMITED,BREAD STREET HILL, E.C., ANDBUNG AY, SU FFOLKCONTENTS.PAGEGENERAL AND PHYSICAL CHEMISTRY. By T. M. I~O\V1LY, D.Sc. 1INORGANIC CHEMISTRY. By 11. B. BAKEK, M.A., D.Sc., F.R.S. . 33ORGANIC CHEMISTRY.LAPWORTH, D.Sc. . . . . . . . . . . 56STEREOCHEMISTRY. By H. 0. JONES, K A . , D.Sc. . . . . 110ANALYTICAL CHEMISTRY. By ARTHUR ROBERT LING, F.I.C. . . 136PHYSIOLOGJCAL CHEMISTRY. By W. D. HALLIBL'RTON, M.D., F.R.S. 165AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY.By A. D. HALL, M.A. . . . . . . . . . 185MINERALOGJCAL CHEMISTRY. By ARTHU~ HUTCHINSON, M.A., Ph.D.201RADIOACTIVITY. By FEEDERICK SODDY, M.A. . . . . . 233By CECIL H. DEscIr, D.Sc., Ph.D., and AwrHuTABLE OF ABBREVIATIONS EMPLOYED I N THEABBREVIATED TITLE.A . . . . .Ainer. Chern. J. . .Amcr. J. Pharm. .Anzer. J. Physiol. .Amer. J. Sci. . .Anal. Fis. Quim. .Analyst . . .Annalcn . . .Ann. Chirn. anal. .Ann. Chim. Phys. .Ann. Inst. Pmteur .Ann. of Botany. .Ann. Physik . .Ann. Report . .Anit. sci. Univ. Jassy.Arb. Kais. Gewnd. Amt.Arch. cx-pt. Path. Pharna.Arch. Pharm. . .Atti R. Accad. Sci. Torino.Atti II. Accad. Liiacei .Ber. . . . . .Ber. Dezst. bot. Gcs. . .Ber. Deut. physikal. Gcs. .Bio-Chem. J. . * .Biochem. Zeitsch. . .Boll. chirn. farm. . .Brit. Med. J. . . .Bull. Aead.roy. Belg. .Bull. Acad. Sci. Cracow .BdZ. Acnd. Sci., St. Pe’ters-bourg . . . .Bull. Assoc. Chip.. Siscr.Dist. . . . .Bull. Imp. Inst. . .Bull. SOC. chiw,. . .Bull. SOC. chirn. Belg. .Bull. Soc. franc. Min. .Centr. Bakt. Par. . .Centr. Min. . . .Chem. Zentr. . . .Chem. Ncws . . .Ch.em. Weekblad . .Chem. Zeit. . . .Cam;7t. rend. , . .REFERENCES.JOURNAL.Abstracts in Journal of the Chemical Society. *American Chemical Journal.American Journal of Pharmacy.American Journal of Physiology.American Journal of Science.Anales de la Sociedad Espaiiola Fisica y Qnimica.The Analyst.Justus Liebig’s Annalen der Chemie.Anndes de Chimie analytique appliqude h l’Iudnstrie,Annales de Chimie e t de Physique.Annales de l’lnstitut Pasteur.Annals of Botany.Aniialen der Physik.Annual Reports of the Chemical Society.Annales scientiifiqucs de l’Universit8 de Jassy.Arbeiten der Kaiserlichc Gesundheitsamt.Archiv. fur experimentelle Pathologie und Pharmako-Archiv der Pharmazic.Atti della Reale Accademia delle Scienze di Torino.Atti della Reale Accademia dei Lincei.Berichte der Deutschen chemischen Gcsellschaft.Berich te der Deutschan bo tanischen Gesellschaf t .Berichte dcr Deutschen physikalischen Gesellschaft.The Bio-Chern‘cal Journal.Biochemische Zeitschrift.Bollettino chimicq farmnceutico.British Medical Journal.Academie royale de Relgique-Bulletin de la ClasseBulletin international de l’Acad6mie des Sciences deBulletin de 1‘Academie Impdriale des Sciences deBulletin de l’hsociation des cliimistcs d3 Sncreric e tBulletin of the Imperial Institute.Bulletin de la Soci6tB chimique de France.Bulletin de la SociBtk chimique de BeIgique.Bulletin de la SocidtB franpaise de Mindralogie.Centralblatt fur Bakteriologie, Parasitenkunde undCentralblatt fur Minerdogie, Geologie und Palaeonto-Chemisches Zentralblatt.Chemical News.Chemische Weekblad.Chemiker Zeitung.Corn tes rendus hebdomadaires des Sdances doh l’dgriculture, b la Pharmacie e t A la Biologie.logie.des Scicnces.Cracovie.St.P6tersbourg.de Distillerie.Infektionskrankheiten.logie.f’ AcadBrnic des Sciences.The year i s not inperted in refereucee to 190viii TABLE OF ABBREVlATIONS EMPLOYED IN THE REFERENCES,ABBREVIATED TITLE.Deut.landto. Presse . .Gazzetta . . . .Gummi-Zcit. . . .J. Agric. Sci. . . .Jahrb. Min. . . .Jahrb. Min. Beil-Bd. .hhrb. Badionktia. Elektro-n i k . . . . .J. Amer. Chern. Xoc. . .J. Hid. Chem. . . .J. Chim.phys. . . .J. Gasbeleucht. . . .J. Inst. Brewing. . .J. Iron and Steel Inst. .J. Pharm. Chine. . .J. Physical Chem. , .J. Physiol. . , .J.pr. Chem. . , .J. Buss. Phys. Chem. SOC. .J. SOC. Chem. Ind. . .J. Soc. Dyers . . .Landw. Jahrb. . . .Landw. Versuchs-Stat. .Mem. Cdl. Sci. Eng. Ky6tciMem. Manchester Phil. SOC.Metnllurgie . . .Min. Mag. . . .Monatsh. . . . .Mon. Sci. . . . .Oesterr. Zeitsch. Bcrg. Hut-tenwesen . . .P$iiger's Archiv. . .Phawic. J, . . , .Pharm. Zeit. . . .Pharm.Zentr-h.. . .Philippine J. Sci. . .Phil. Mag. . . .Phil. Trans. . . .Physical Rev. . . .Physikal. Zeitsch. . .Proc. . . . . .Proc. Amer. Acad. . .Proc. Amer. Physiol. Xoc. .Proc. Camb. Phil. SOC. .Proc. K. Akad. Wetensch.Proc. Physiol. SOC. . ,Proc. Roy. Soe. . . .Proc. Roy. SOC. Edin. .Quart. J. exp. PhysioE. .Qilart. J. Geol. SOC. . .Amsterdam.JOURNAL.Deutsche laudwirthschaftliche Presse.Gazzetta chimica italiana.Gummi-Zeitung.Journal of Agricultural Science.Neues Jahrbuch fur Mincralogie, Geologie undNeues Jahrbuch fiir Minerdogie, Geologie undJahrbuch der Radioaktivitat und Elektronilr.Journal of the American Chemical Society.Journal of Biological Chemistry, New York.Journal de Chimie physique.Journal fur Gasbeleuchtung.Journal of the Institute of Brewing.Journal of the Iron and Steel Iastitute.Journal de Pharmacio et de Chimie.Journal of Physical Chemistry.Journal of Physiology.Journal fur praktischo Chemie.Journal of the Physical; and Chemical Society ofJournal of the Society of Chemical Industry.Journal of the Society of Dyers aiid Colourists.Landwirtschaftliche Jahrbiicher.Die landwirtschaftlichen Vorsuchs-Stationen.Memoirs of the College of Science and Erigineering,Memoirs and Proceedings of the Manchester LiteraryPalaeon t ologie.Palaeontologie.Boilage-Band.Bussia.Ky6t6 Imperial University.and Philoeonhioal Society.Metallmgie.Mineralogical Magazine and Journal of the JNiiieral-ogGaI Sociei'y.Wissenschaften.Monatshefte fiir Chemie und verwandte Theile andererMoniteur scientifique.Oesterreichische Zeitschrift fur Berg- unclHuttenwesen.Archiv fiir die gesammte Physiologie des MenschenPharmaceutical Journal.Pharmazeutische Zeitung.Pharmazeu t ische Zen tral halle.Philippine Journal of Science.Philosophical Magazine (The London, Edinburgh andDublin).Philosophical Transactions of the Royal Soclety ofPhysical Review.Physikalische Zeitschrift.Proceedings of the Chemical Society.Proceedings of the American Academy.Proceedings of t h e American Physiological Society.Proceedings of the Cambridge Philosophical Society.Koninklijke Akademie van Wetenschappen te Amster-dam.Proceedings (English version).Proceedings of the Physiological Society.Yroceedings of the Royal Society.Proceedings of the Royal Society of Edinburgh.Quarterly Journal of experimental Physiology.Quarterly Journal of the Geological Society.iind der Thiere.LondonTABLE OF ABBREVIATIONS EMPLOYED IN THE REFEREXCES.ixABBREVIATED TITLE.Rec. trav. chim. . . .Bend. Accad. Sci. Fis. Mat.Napoli . . . .Aev, gdn. Chim. pure et appl.Xci. Proc. Roy. Dubl. J’oc. .Sitzwngsber. K. Akad. Wiss.Tech. Quart. . . .Trans. . . . .Trans. Faraday SOC. . .Tsch. -twin.. Mitt. . .Verb. Ges. deut. Natur-forsch. Aerxte . . .Zeitsch. awl. Chem. . .Zeitsch. angew. Chm. .Zeitsch. amrg. Chenh. . .Zeikch. Chent. Id. Kolloide.Zeitsclh. Elektrochem. . .Zeitsch. Kryst. Min. . .Zeitsch. Nahr. Genussm. .Berlin.Zeitsch. ofentl.Chem. .ZeLtsch. physikal. Chem. .Zeitsch. physwl. Chern. .Zeitsch. prakt. Geol. . .Zeitsch. Schiess. Speng-Zeitsch. Ver. deut. Zuckerind.stoflw. . . . .Zentr. Phusiol. . . .JOURNAL.Receuil des travaux chirniques des Pays-Bas et de laRendiconto dell’ Accademia delle Sienze Fisiche eRevue g6ndrale de Chimie pure et appIiquee.Scientific Proceedings of the Royal Dublin Society.Sitmngsberichte der Koniglich Preussischen AkademieTechnology Quarterly.Transactions of the Chemical Society.Transactions of the Faraday gociety.Tschermak’s Mineralogische Mitteilungen.Verhandlung der Gesellschaft deatschen NaturforschetZeitschrift fur analytische Chemie.Zeitschrift fur angewandte Chemie.Zeitschrift fur snorganische Chemie,Zeitschrift fur Chemie und Industrie der Kolloide.Zeitschrift fur Elektrochemie.Zeitschrift fiir Krystallographie und Mineralogie.Zeitschrift fur Untersuchung der Nahrungs- undZei tschrift fur offentliche Chemie.Zeitschrift fiir physikalische Chemie StochiometrieHoppe-Seyler’s Zeitschrift fur physiologische Chemie.Zeitschrift fiir praktische Geologie.Zeitschrift fur das Schiess- und Sprengstoffwesen.Zeitschrift des Vereins der deutschen Zucker-Zentralblatt fur Phvsiolotzie.Belgique.Matematiche-Napoli.der Wissenschaften zu Berlin,und Aerzte.Genussmittel.und Verwandtschaftslehre.Indnstrie

ISSN:0365-6217    

DOI:10.1039/AR90906FP001

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

INORGANIC CHEMISTRY.IN 8 part 6f the subject, which has practically onIy one fargegeneralisation t o depend upon, it is found difficult to give a generalidea of the progress of a year’s work. A large number of newfacts, of greater or less value, have been accumulated, but how farthey will tend to the advance of the general theory it is impossibleto say. (( Science moves but slowly, slowly, Creeping with invisiblesteps.” Owing to the cust.om which has grown up of publishingresults as soon as any have been obtained, the year’s progress seemsto consist of small bits of research work, often, it is true, of greatimportance in themselves, but the significance of which cannot beappreciated without a careful study of what has gone before. Inan ideal chemical world, nothing would be published until a com-plete account of the subject of research could be presented.But,apart from the general question of publishing carefully worked outinstalments of a large research, the scramble for priority, happilynot common in this country, is often responsible for the appearanceof immature work. I f papers of this kind were withdrawn bytheir authors as soon as they found that they could not confirmtheir results, no great harm would be done, Very frequently,however, the papers are left uncontradicted, to produce great con-fusion in the mind of the chemical student.Some attempt has been made in this report to show, underdifferent headings, some general results of the increase of know-ledge of particular parts of the subject, but naturally they mustbe incomplete.More or less isolated facts are given, as in previousyearg, under the groups in which the principal elements areclassified.I n his Presidential Address, Sir William Ramsay1 gave furtherresults of his experiments on the possible transformation of elements.It wits thought that solutions of thorium shouId, after longstanding, give rise to small quantities of helium. Accordingly, 270grams of thorium nitrate were purified and dissolved in water.The solution was introduced into a flask provided with a, well-greased stopcock, and the flask was exhausted repeatedly. It wasTrans., 1909, 95, 632.REP,-VOL, VI. 34 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.kept for three years. After freeing the gas collected from carbondioxide, nitrogen, hydrogen and oxygen, the residue was testedspectroscopically, but the presence of helium was doubtful.Sub-sequent experiments led to the same result. It was found, however,t h a t carbon dioxide was present in considerable quantity. Afurther experiment wits made in which the grease of the stopcockwas protected from the action of the solution, and still carbondioxide was found in the solution. Further experiments weremade on thorium nitrate, to see if radium emanation would breakdown thorium into carbon. The gas collected showed the presenceof carbon dioxide. Similar experiments with solutions containingother elements of the same family as carbon, namely, silicon andzirconium, also yielded carbon dioxide.A further account ofsimilar experiments by Sir William Ramsay and F. L. Usher 2 givesa comparison of the amounts of carbon obtained when onecubic millimeter of radium emanation wits allowed to act on thevarious solutions :Solution of.. ................ H2SiF6. Ti(BO,),. Zr(NO,),. Th( NO,),. Pb(ClO,)?.Carbon ....................... 0.518 0.982 1.071 0.8i3 2.93 0.968 0.102 itig,I I1 I I1The emanation was collected from a radium bromide solutioncontaining 0.21 gram of metallic radium, and the amount ofemanation used varied from 0.0649 to 0.1120 cubic millimetre. Theexperimental skill required in working with such exceedingly smallquantities is prodigious. It is to be hoped, with the advent of theRadium Institute, that larger quantities of the material may shortlybecome available, arid everyone will look forward with great interestto the repetition of the experiments on a larger scale.A possiblesource of error in the experiments with thorium nitrate has beenpointed out by 0. Angelucci.3 I t was found that a concentratedsolution of thorium nitrate, placed in a dilatometer, showed aconsiderable increase in volume. After some months, thesolution deposited acicular crystals having the composition of6Th(NO3),,Th(C,O,),,48H,O. It is suggested that the carbon di-oxide evolved from the solutions of thorium nitrate is reallyproduced by the decomposition of the very soluble double oxalateand nitrate of the metal.I n connexion with the production of helium by the breakingdown of radium, Sir William Tilden has made a suggestion thatthe other inert gases, neon, argon, krypton, and xenon, may them-selves have been the result of the breaking down of elements of2 Ber., 1909, 42, 2930 ; A ., ii, 850.3 Atli R. Accnrl. Lincci, 1909, [v], 18, i, 526 ; A . , ii, 742ISORGANIC CHEMISTRY. 35higher atomic weight than radium. Such elements may conceivablybe still present in the earth's crust.Of the eighty-one elements, no less than twenty-seven have atomicweights which are multiples of unity to the first decimal place, andit is perhaps natural that many chemists believe, although perhapswith reservations, in the truth of Prout's hypothesis. Manyattempts have been made of late years to reconcile the hypothesiswith facts, of which perhaps the least artificial is the one ofA.C. and A. E. Jessup.4 Another of these attempts which was,on its publication, received with perhaps a little too much enthu-siasm, is that of A. C. G. Egerton.5 This author supposes that thedivergence of the atomic weights from whole numbers is causedby the excess or defect; of electrons. If N is the number of theelement in the order of the atomic weights, the accurate atomicweight is given by the formulae:For " even " elements, ill = A & 0*0978A, where ,4 = 2N.For odd elements, M =d +_0*0078(A - l), where A =3iV+ 1.The weight of an electron is taken as one-thousandth that ofan atom of hydrogen, and 0.0078 would represent a group of eightelectrons.For the first twelve elements, the agreement of the calculatednumbers with the most recent atomic weight determinations isgood.Aluminium and silicon, about the atomic weights of whichthere may perhaps be some doubt, show a difference of 0.1. Forthe elements between sulpb.ur and nickel, the above formuh donot hold, but, by introducing arbitrary factors, agreement betweenthe calculated and observed numbers is obtained.points out that most of the agreement indicated byEgerton is due to mathematical necessity, and he shows that proofof the hypothesis could only be established if the atomic weightswere known to the third place of decimals. Moir himself tentativelyadvances another hypothesis. H e assumes that the fundamentalcause of valency in an element of valency n. is caused by thepresence in it of m atoms of a sub-element of atomic weight 0.0089.Thus the primordial stuff in an atom of hydrogen weighs 0-9989.Sixteen times this weight plus twice the atomic weight of the sub-element gives 16.000 for the atomic weight of oxygen.For thirty-five elements, the difference between the calculated and the usuallyaccepted atomic weights amounts in most cases to less than 0.04.For the remaining atomic weights, an arbitrary number of atomsof a second sub-element of atomic weight 0.1 is assumed. Thisbeing done, an agreement of the same order as the first is obtained.J. Moir4 P11,il. Mag., 1908, [vi], 15, 21 ; A., 1908, ii, 96.1'mns. 1909, 95, 238, &id., 1752.D ( i 36 ANNUAL REPORTS ON TEE PROCXREBlg OF CHEMISTRY.One of the difficulties which will strike the readers of the paperwill be the different valencies ascribed to similar elements, sulphur,for instance, is diad, and chromium, hexad, but the modesty withwhich the whole speculation is put forward tends to disarmcriticism.Atomic Weights,There has been very considerable activity during the year in thisbranch of chemical work, It is unfortunate that there still remainssome doubt as to the exact ratio of the atomic weight of silver tothat of oxygen.Nearly three-quarters of the atomic weights dependon this relation, and until it is established there must always besome uncertainty. Many attempts have been made to determinethis ratio directly by the analysis of silver oxide, but this substanceis difficult t o obtain in a pure state.When dried a t the highesttemperature compatible with safety, it still retains 2.13 per cent.of water. The oxide contains, moreover, less than 8 per cent. ofoxvgen, and on this account presents extraordinary difficulties asregards its accurate analysis. The chief atomic weight deter-minationq are the following.Chlorine.-A complete analysis of nitrosyl chloride, NOCI, hasbeen effected by P. A. Guye and G. FIuss.7 The weighed substancewas distilled over hot silver, which combined with the chlorine; theresidua1 gas was then decomposed by hot copper, which took upthe oxygen, and, finally, the nitrogen was absorbed by metalliccalcium. The direct ratio of oxygen to chlorine, thus found, was16 : 35.468. The value for nitrogen found was 14.006.An interest-ing and valuable paper by R. W. Gray and F. P. Burt gives theresults of the study of hydrogen chloride. The density of this gaswas determined and it was also analysed volumetrically. The hydro-gen chloride was prepared by three methods: (1) from sulphuricacid and sodium chloride, (2) from sulphuric acid and ammoniumchloride, (3) from silicon tetrachloride and water. The gas wassolidified and fractionally distilled. I n the density determinations,two bulbs were used for measuring the gas, one of soda-glass andone of silica. Both were of comparatively small volume, less than500 C.C. The gas, having been measured in one of the bulbs, wasdrawn into an exhausted bulb containing cocoa-nut charcoal cooledbp liquid air.The increase in weight of this gave the weight of themeasured volume of hydrogen chloride. Special experiments wereundertaken to find the volume of gas adsorbed by the surface of*he glass bulb. In spite of the great difficulties attending workon a gas so soluble and hygroscopic, very fair concordance wasobtained in successive experiments.7 J. Chuim. Phys., 1908, 6, 782 ; A,, ii, 135. Trans,, 1909, 95,1633INORGANIC CHEMISTRY. 3’7The second part of the research consisted in the determination ofthe volumetric composition of hydrogen chloride. This was effectedby the use of heated aluminium. Elaborate precautions were takento ensure the purity of the gas and the absence of volatile impuritiesin the metal. The agreement of the ,different experiments was verygood, The final result for the atomic weight of chlorine was 35.460,comparing with the value of 35.463 obtained by Dixon and Edgar 9in their admirable research on the combustion of hydrogen inchlorine, and with 35.461 obtained later by Edgar.10 Anotherpaper by 0.Scheuer11 deals also with the density of hydrogenchloride. Calculating from his numbers, we obtain the atomicweight of 35.464 for chlorine.Carbon.-An important paper by A. Scott 12 on the atomic weightof carbon gives an unexpected value for this constant. Carbonhas hitherto been regarded as one of the elements which mostnearly conform to Prout’s hypothesis, having the atomic weight12.00. Scott, however, finds that this value is a t least one-thou-sandth part too low.The determination was made by the methodwhich is regarded as the most trustworthy of all atomic weightmethods, namely, the estimation of bromine by silver. The saltsused were tetraethylammonium bromide and tetramethylammoniumbromide, and were prepared with the utmost care. They are onlyvery slightly hygroscopic, and, since they are stable up t o 150°,there is no difficulty in drying them. The silver used was the sameas that used in the estimation of bromine in ammonium bromide.Hence, by subtracting the molecular weight of ammonium bromidefrom the molecular weights of the tetra-alkyl bromides, values forthe molecular weights of two hydrocarbons, C8H,, and C,H,, areobtained. Taking hydrogen as 1.007 and silver 107.88, the valuesfor carbon of 12.019 and 12.017 are found.The individual deter-minations agree extremely well, and the author seems to haveexcluded every possible source of error. I n order to explain thiscomparatively large difference between Scott’s value and those ofDumas and Stas, Roscoe, Erdmann and Marchand, and others,Sir Edward Thorpe l3 has drawn attention to a recent paper ofP. A. Guye and N. Zachariades.l* These chemists state that whena very fine powder is weighed, so much air is condensed on it, oroccluded by it, that the weight is seriously affected. I n the caseof finely-powdered potassium chloride, a difference of 32 mg. onPhil. Trans., 1905, A, 205, 169 ; A . , 1905, ii, 696.lo Ibid., 1908, A, 209, 1 ; compare A . , 1908, ii, 577.l1 Compt.rend., 1909, 149, 599; A , , ii, 991.l2 Trans., 1909, 95, 1200.l3 PTOC., 1909, 25, 284.l4 Compt. rend., 1909, 149, 593; A., ii, 98938 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.100 grams was observed. Scott?l5 in reply, has published a seriesof experiments on the point. He finds that, with potassiumchloride, the difference amounts to only 0.3 mg. on 100 grams, andthis error he very reasonably attributes to a hastily constructedcounterpoise. The writer made some experiments of the same kindthree years ago in connexion with another atomic weight deter-mination. I n moist air, all the fine powders tried increased con-siderably in weight, although the substances were not deliquescent;precipitated silica is a familiar example, whilst in dried air no suchincrease can be noticed.Hence the increases in weight observedby Guye and Zachariades were probably due to water and not tocondensed air.A new determination of a different. kind does not confirm Scott’svalue. G. Baume and F. L. Perrot 16 have determined the densityof highly purified methane. They obtain the number 12.004 forthe atomic weight of carbon.lodine.-Many chemists have attributed the anomalous positionof tellurium and iodine in the periodic classification to an error inthe determination of the atomic weight of iodine, since there hasalways been a possibility that some chlorine was present in theiodine used. Stas, for instance, dried iodine over calcium chloride,and it has been recently shown that some chlorine is set free inthese circumstances. I n order t o exclude the possibility of anyelement of lower atomic weight being present in the material used,G.P. Baxter and G. S. Tilley17 have carefully crystallised iodicacid. This was converted by judicious heating into iodine pent-oxide, and this reduced by hydrazine. The hydriodic acid wasprecipitated by silver, and by combining the ratio Ag: I with theratio Ag: Ii05, the atomic weight of 126.891 is obtained for iodine,and the low value of 107.85 for silver.Tellurium-The atomic weight of tellurium has been the subjectof two researches. V. Lenher18 has employed &he double bromideof potassium and tellurium, K,TeBrG. The salt is beautifullycrystalline, but it suffers from the disadvantage that it very readilyundergoes hydrolysis with water, so much so that Wills, in usingthe salt for the same purpose in 1879, wits compelled to pick outthe perfect crystals with forceps.Lenher overcame this difficultyby crystallising from dilute hydrobromic acid, and he found thathe could dry the substance satisfactorily without decomposing it.A weighed quantity of the salt wits heated in a current of chlorine.l6 Proc., 1909, 25, 286.16 Compt. rend., 1909, 148, 39; A . , ii, 77.17 J. Amer. Chm. SOC., 1909, 31, 201 ; A., ii, 225,18 Bid., 20 ; A,, ii, 230INORGAXIC CHEMISTRY. 39Bromine and tellurium chloride were expelled, so that the ratioKzTeBr,: 2KC1 was obtained. The atomic weight of tellurium,deduced from sixteen very concordant determinations, was 127.55,being still 0.6 above the atomic weight of iodine.P. E. Browningand W. R. Flint 19 have stated that they have separated two distinctsubstances from tellurium which have the atomic weights 126.49 and128.85. Their method, the fractional precipitation of telluriumtetrachloride by water, had been previously tried. Baker andBennett 20 found identical atomic weights for the element obtainedfrom the first and the last fractions of the precipitation. I n thenew work of the two American chemists, two fractions wereobtained, one of 50 grams, and the other of 13 grams. The atomicweights were obtained by three methods: (1) Conversion of thebasic nitrate into the dioxide, (2) a modification of Brauner’spermanganate method, (3) precipitation of the dioxide from thebasic nitrate by ammonia and acetic acid.The mean results are,as stated above, 126.49 for the least soluble and 128.85 for themost soluble fraction. Their result, if confirmed, would be of greatinterest. It may be pointed out, however, that if the mean atomicweight of both fractions is calculated, which would represent theatomic weight of the tellurium before fractionation, it is found to be126.89, instead of 127.55, as found by other workers. This wouldseem to indicate that the tellurium originally used had beeninsufficiently purified, or that the methods used in the atomic weightdeterminations were not trustworthy. One of the authors is con-tinuing the investigation.Molecular Weights.A very considerable amount of work has been done during theyear on the determination of molecular weights by cryoscopic andebullioscopic methods.Since Beckmann 21 showed that, in allsolvents, iodine has the molecular weight corresponding with I,,it has been assumed that when the solutions are brown, combinationhas taken place between the iodine and the solvent. To test thieview, experiments have been undertaken 2, to determine the freezing-point depression produced by iodine and certain liquids, firstseparately and then together, in the solvents bromoform andethylene dibromide. It was found that it was only with liquidswhich formed brown solutions that the total depression was lessl9 Amer. J. Sei., 1909, [iv], 28, 347 ; d., ii, 996.21 Zeikch. physikal. Chem., 1907, 58, 543 ; A., 1907, ii, 340.!a J.H. Hildcbrand and B. L. Glascock, J. Amer. Chem. Soc., 1909, 31, 36 ;Trans., 1907,91, 1849.d., ii, 22540 ANNUSL REPORTS ON THE PROGRESS OF CHEMISTRY.than the separate depressions, thus indicating that chemical com-bination had taken place. The possibility of chemical actionbetween the solvent and the solute compels one to accept with somereserve some recent determinations of the molecular weight ofselenium in melted iodine 23 and the similar determinations for thesame element dissolved in fused mercuric chloride.24 In the lattersolvent, dilute solutions give depressions of the freezing point whichindicate variations of the selenium molecule from Se8 to Se,. Similarexperiments, with fused mercuric chloride as solvent, gave forsulphur a molecular weight, a t all dilutions used, corresponding with8,.Tellurium, it is pointed out, does react chemically with themercuric chloride, reducing it to calomel.Silent Discharge.The study of the effect of electric discharge on gases is one ofgreat difficulty, because there is little doubt that the action iscomplex. The results may be caused by a t least three differentfactors: (1) heat, (2) light, and (3) a specific influence of the electriccurrent, akin to electrolysis in solution. Until comparativelyrecently the effect was supposed to be due to heat alone, and theincreased yield of ozone obtained when the silent discharge wassubstituted for the spark discharge was ascribed by Brodie to thelower temperature attained.Some experiments by A. Holt, jun.,25give some help towards the elucidation of the problem its to which ofthese factors has the most influence. It has already been shown byDixon26 and by Colliez7 that carbon dioxide is decomposed byelectric sparks whether it is moist or dry, and that the shorter(and hotter) the sparks, and the lower the pressure of the gas, thegreater is the decomposition. It has also been proved 28 that ultra-violet light had no effect on moist carbon dioxide, but that tl;edried gas was decomposed to an extent which varied inversely asthe pressure. Holt’s experiments show that with the silent dis-charge there is decomposition in the dried gas to a very con-siderable extent, 48 per cent. at 30 mm.pressure, and that theextent of the decomposition varies inversely as the pressure. Theresult in this case thus corresponds with the results of the actionof ultraviolet light. I n the case, however, of the moist gas, a verystriking difference is observed. Instead of there being no action,Qs G. Pellini and S. Pedrina, Atti R. Accad. Ldncei, 1908, [v], 17, ii, 78 ;a4 F. Olivari, ibid., 1909, [v], 18, ii, 94 ; A . , ii, 805.95 Trans., 1909, 95, 30.Ibid., 1901, 79, 1063.28 Chapman, Chadwick, and Ramsbottom, Trans., 1907, 91, 942.A,, 1908, ii, 833.26 Ibid., 1885, 47, 571INORGAKIC CHEMISTRY. 41considerable decomposition is observed, and this decomposition ISgreater when the pressure is increased. Unfortunately, no memure-ments were made of the amount of ozone formed from the liberate-3oxygen, and until the further experiments are published it wouldbe useless to speculate as to the origin of this very remarkabledifference.It was shown by Brodie29 that in the decomposition of carbondioxide, dried only by sulphuric acid, as much as 85 per cent.ofthe oxygen produced was converted into ozone, so that the change3CO+ 0, = 3c0, can scarcely proceed from left to right, a con-clusion which was confirmed by the work of Remsen andSouthworth.30 Oxygen therefore has little or no oxidising powerwith regard to carbon monoxide. If, however, other oxidisablegases are passed with oxygen through a silent discharge tube, ithas been recently shown that o'xidation does take place.31 Whena mixture of hydrogen and oxygen in the proportion of 2 : 1 byvolume, or with more hydrogen than this, is so treated, water isproduced in considerable quantities, but if the oxygen is in excess,no hydrogen peroxide is formed, but only ozone.Chlorine withoxygen gives chlorine monoxide, and hydrogen chloride gives hypo-chlorous acid. Carbon disulphide is notr oxidised by this method,whilst ammonia gives small quantities of hydroxylamine, but nonitrous acid. It is rather remarkable that carbon monoxide andchlorine appear not to react when passed together through anozoniser.Co mtb us t io n.Notable advances towards the understanding of the theory ofcombustion have been made by H. B. Dixon and his pupils inrecent years. One of the most disputed points in connexion withthis work has been the determination of the temperature a t whichgaseous mixtures undergo inflammation.Experiments by Askenasyand V. Meyer 32 gave for electrolytic gas results varying from 5 1 8 Oto 606O, whilst Relier,= working with the gaseous mixturepassing through a, heated tube, obtained 845O as the ignition-pointof the same mixture. The variation of the temperatures found isundoubtedly due to the influence of the surface of the vesseI used,Most substances act as either positive or negative catalysts, anduntil this influence could be eliminated or allowed for, no trust-worthy results could be expected. By a most ingenious arrange-29 Phil. Trans., 1874, 164, 83.g1 E. Comanducci, R e d . dccad. Sci. Pis. Mat.Nap&, 1908, [iii], 15, 15 ;32 Annalen, 1892, 269, 49 ; A, 1892, 938.33 Ann. Chim. Phys., 1897, [vii], 10, 521 ; A , , 1899, ii, 85.3o Ber., 1875, 8, 1414.A., ii, 47742 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.ment, H. B. Dixon and H. F. Coward% have succeeded in ignitingthe gases out of contact with any solid material. One gas waspassed through a wide porcelain tube, which was heated electrically,while the other passed up a narrow tube fixed along the axis of thowide tube. The temperature was measured by a thermo-junctionplaced either in the narrow tube or just above its orifice. Thstemperature was gradually raised until ignition occurred, and thisignition took place a t a point above the orifice. That the ignition-temperature was not altered by varying the material of the jet wasshown by a series of experiments in which fused quartz, Jena-glass, and soda-glass were employed.I f the rate of passage ofhydrogen through the inner tube, and oxygen through the outerone, was maintained above a certain limiting value, and if thediameter of the outer tube was beyond 40 mm., nearly constantvalues approximating to 600° were obtained. When air was sub-stituted for oxygen, the very interesting result was obtained thatthe ignition-temperature was unaltered. For carbon monoxideburning in oxygen, also, the ignition-temperature of 650° wasobserved, whilst the same gas ignited in air at 6 5 1 O . Theignition-temperatures of methane, ethane, propane, ethylene,acetylene, cyanogen, hydrogen sulphide, and ammonia were alsodeterEined.A valuable summary of t.he work done a t the ManchesterUniversity on the mechanism of the combustion of hydrocarbonswas given as a Friday evening discourse a t the Royal Institutionby W.A. B0ne.35 It was shown that the suggestion of H. E.Armstrong, made many years ago, that the combustion of a hydro-carbon takes place through the formation and subsequent decom-position of hydroxylated molecules, has received very considerableexperimental support. The preferential combustion either of carbonor hydrogen is an idea which must now be abandoned. By theisolation of large quantities of aldehydic products as the result ofthe combustion of hydrocarbons a t low temperatures, it has beenproved that, in these circumstances, Armstrong’s hypothesis is wellgrounded. When the researches were carried on at higher tem-peratures and under conditions approximating to those in ordinaryhydrocarbon flames, it became evident that although the phenomenaobserved were different, the mechanism of the reaction was essen-tially the same at high as at low temperatures.The influence of mere traces of water on the combustion ofsubstances in oxygen and other chemical actions has not yetreceived an adequate explanation.In 1893 Sir J. J. Thornson3634 Trans., 1909, 95, 514.36 Phil. Nag., 1893, [v], 86, 913.as iVature, 80, 82INORGAXIC CHEMISTRY. 43showed that if the force holding atoms together in a molecule wereelectrical in its nature, the presence of liquid drops of high specificinductive capacity would tend to loosen the bonds between theatoms, and so increase the tendency for chemical action to takeplace.The difficulty of accepting this explanation was that itseemed impossible that drops of liquid water could exist in a gas con-taining a very small quantity of water vapour. J. s. TownsendF7however, has shown that in a gas ionised by Rontgen rays thereis a great decrease in the mobility of the ions when a small quantityof water (represented by 0.1 mm. pressure) is present. When morewater is added, visible liquid drops are produced. Hence it isprobable that with still smaller amounts of water than were presentin Townsend's experiments, aggregations of water molecules wouldbe produced if ions existed in the gas, and Sir J.J. Thomson'sexplanation may hold good. H. B. Baker38 has found that anincrease in the ionisation of a mixture of hydrogen and nitrousoxide, a t 530°, produces a corresponding increase in the rate ofaction between the gases. Lime, which has been shown to ionise agas to a considerable extent, increased the normal rate of unionby five times; thoria, which is a, much more powerful ionising agent,increased the rate of action by twenty times; whilst with radiumbromide the gases exploded directly the temperature of combinationwas reached. Similar experiments with the carefully dried gasesshowed &hat the ionising agents had no effect on the combinationof the gases. The hypothesis that, unless water and gaseous ionsare both present, chemical union cannot take place, is tentativelyadvanced.The Combination of Salts with Water.The use of salts containing water of crystallisation for atomicweight determinations has been of late years regarded as impossible.Mallet 39 pointed out, in regard to the alums, that the water wasalways in excess of the calculated quantity, and Richards40 made amost careful investigation of the water in crystallised bariumchloride.I n the same circumstances, the excess of water retainedwas remarkably constant, but by varying the state of division ofthe salt, large differences were observed. I n no circumstances couldthe theoretical amount of water be obtained. Richards drew theconclusion that no atomic weights with any pretensions to accuracycould be found by using salts which contained water ofcrystallisation.'' PTOC.Roy. ~ O C . , 1908, 81, 464.Wilde TJecture, 1909 ; Mem. JIamhcstcr Phil. sbc., 1909, [iii], 53, 16.38 Stas Memorial Lecture, Trans., 1902, 81, 204.lo Zeitsch, physikal. Chem., 1903, 46, 189 ; A , , 1904, ii, 24244 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.P. A. Guye and D. E. Tsakalotos41 assert that it is possible, byworking under proper conditions, to obtain the theoretical loss ofwater from crystallised barium chloride, For this statement theyrely on the constancy of the loss experienced on heating the salt.Since, however, they state that the salt was not sufficiently purefor the atomic weight of barium to be deduced, their results mustbe accepted wit>h some reserve.It may be possible, and it is evenlikely, that salts with water of crystallisation may be eventuallybrought into use in accurate work, but until such accurate workis done with highly purified materials, so that atomic weightsobtained by their use can be compared with those obtained byunexceptionable methods, the results obtained by the employmentof salts with water of crystallisation must be looked upon withsuspicion.The opacity which sometimes makes its appearance in hithertoclear crystals has been investigated in the case of sodium sulphateby D. Gernez.42 A 66 per cent. solution of this salt, cooled below8O in absence of dust, deposits crystals of the heptahydrate,Na2S04,7H20, and the mother liquor remains supersaturated withrespect to the decahydrate, Na2S04,10H20.On adding a crystal ofthe decahydrate, crystallisation occurs through the liquid until itreaches the solid hep tahydrate. This then loses its transparency,and becomes opaque. The opacity is ascribed to the formation ofdecahydrate in the mother liquor occluded in the crystals of hepta-hydrate. This explanation is supported by the fact that when afragment of the porcelain-like mass is added to a supersaturatedsolution of the decahydrate, crystallisation is induced. The factscan be demonstrated in a lecture experiment in the following way.The heptahydrate solution is allowed to crystallise in a U-tube,which has a constriction near the bottom, and the crystals arepressed into a solid cake in the constricted part.On adding acrystal of the decahydrate in one arm of the tube, crystallisation ofthis hydrate takes place down this arm. When the solid plug isreached, opacity is produced in it, and the formation of the decachydrate proceeds without interruption up the other arm of thetube. The following salts behave in the same way: Na&k04,4H20and Na&rO4,10H20, Ca(N0,),,3H20 and Ca(N0,),,4H20,N+S,O,, 2H20 and Na2S20,,5 H20.Since in many cases ammonia seems to be capable of replacingwater of crystallisation, molecule for molecule, as in the well-knowninstances of CuS04,5NH, and CuS04,4NH,,H,0, special interestattaches to the compounds which have been prepared of salts41 J. Chim. Phys., 1909, 7 , 214 ; A., ii, 475.42 Compt.rend., 1909, 149, 77 ; A,, ii, 729INORGANIC CHEMISTRY'" 45with hydrazine. Some of these compounds were prepared in1894,43 such as NiS04,3N2H4, ZnS04,2N&,, ZnC12,2N2H4, andCdC12,2N2H4,H20. A compound with copper nitrate, Cu(N 03)2,N2H4,has also been obtained. I n some new experimentsp4 a large numberof salts have been examined in respect of their combination withhydrazine. The substances formed are in general crystallinepowders insoluble in water, but soluble in acids and in ammonia.The authors have arrived a t the interesting conclusion that onemolecule of hydrazine replaces two molecules of ammonia. Thehydrazine cannot, as a rule, be driven off from the compoundswithout decomposing the salts, which may indicate a more definitecombination than is supposed t o exist between salts and the waterwith which they crystallise.Comparing the compounds formedwith hydrazine with the hydrated salts, the following seem toexhibit a relation : NiS0,,3N2H4 and NiSO,,GH,O, NiC12,3N2H4and NiC1,,6H20, Ni(N0,),,3N2H, and Ni(NO,),,GH,O, CdS0,,2N2H4and CdS0,,4H20, FeC1,,2N,H4 and PeCl2,4H,O, hInC12,2N2H4 andMnC12,4H;0, and others. On the other hand, there are manyinstances in which this relation does not hold: BaC12,2N2H4 andBaC1,,2H2O, SrC1,,2N2H, and SrC1,,6H20. It is probable that afurther study of the three types of association which is foundbetween salts and (1) water, (2) ammonia, (3) hydrazine will bringto light facts which will elucidate the very difficult question of theway in which water of crystallisation is connected with the con-stitution of the salt.Metals and Alloys.The very interesting experiments carried on in the Universityo i Utrecht on the breaking up of metallic tin have shown that thismetal is not alone in being metastable. Most of the metals inordinary use are liable to change, although fortunately this changedoes not commonly take place at the ordinary temperature.E.Cohen and K. Inouye4j have shown that if a pattern is etchedby nitric acid on a sheet of lead and the sheet kept in contact withanother strip at 180° for some hours, the pattern appears on thesecond strip. Contact under pressure, a t the ordinary temperature,does not induce the changc. SimiIar effects have been produced bythe contact, at elevated temperatures, between zinc and zinc, brassand copper, copper and copper, and bismuth and bismuth.Themetals used had all been rolled out into strips, and therefore hadbeen subjected t o severe mechanical strain.43 Curtius and Schrader, J. pr. Chem., 1894, [ii], 50, 311 ; A., 1895, ii, 10.44 H. Franzcn and 0. von &layer, Zeitsch. anorg. Chm., 1908, 60, 247;45 Chem. WeekbZad, 1909, 6, 881 ; A,, ii, 1008.A., ii, 4046 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTXY.A large amount of work has been done on alloys, and in manycases distinct compounds have been isolated, whilst in other casestheir existence has been indicated by the form of the freezing-pointcurves and other methods. A new method has been described forthe production of liquid alloys of sodium and potassium.46 Ifpotassium is melted in a vacuous Jena-glass flask with sodiumhydroxide, and the temperature raised to 250°, a layer of the liquidalloy NaK, is formed, even in presence of excess of sodiumhydroxide.On similarly treating potassium hydroxide withsodium, the liquid alloy NaK is formed, but on largely increasingthe proportion of the hydroxide and raising the temperature to350°, the alloy NaK, is the chief product. G. Masing,47 workingwith metals under pressures of 5000 atmospheres, has come to theconclusion that, contrary to t.he results of the well-known researchesof Spring, pressure has no influence in bringing about the diffusionor combination of metals, but its effect is confined solely to thebringing of the metals into close contact.G. Tammann and Masing48find that after compression the particles of metals can be dis-tinguished by the microscope lying side by side, and combinationgoes on slowly a t the ordinary pressure. For instance, the electricalconductivity of a block of lead and thallium immediately aftercompression was that of a mechanical mixture of the metals. Thisincreased by 60 to 75 per cent. in the course of a month, showingthat combination had taken place.Group I .The existence of a true sodium alum, which has been oftenasserted and denied, has been the subject of an investigation byW. R. Smith.49 This author confirms the work of Aug650 andWadmore,51 and shows that sodium alum forms mixed and layercrystals with other alums.Sodium alum has also been prepared byN. I. Surgunoff,52 who shows that the crystals are cubic if theyseparate from a solution which is supersaturated a t ZOO or below.Above this temperature the crystals formed are monoclinic.It is not generally realised how oxidisable solutions of sodiumsulphite are in the air. The likelihood of impure material havingbeen used has led to the study of this salt by H. Hartley and4G G. F. Jaubert, BUZZ. SOC. chirn., 1908, [iv], 3, 1126; A., ii, 41.47 Zeitsch. anorg. Chem., 1909, 62, 265 ; A., ii, 669.48 Zeitsch. Elektrochern., 1909, 15, 447 ; A., ii, 669.49 J. Amer. Chem. SOC., 1909, 31, 245 ; A., ii, 239.5o Compt. rend., 1830, 110, 1139 ; A., 1890, 1059.b1 Proc., 1905, 21, 150.w Bull.Acnd. Sci. St, P&ersbowg, 1909, 1057 ; A., ii, 1001i NORU A N I C CH E M ISTRY, 47W. H. Barrett.53 Three forms of the salt have been previouslydescribed : N+SO,, Na2S0,,7H,0, and Na,SO3,10H2O. The authors,working with extreme care, have been unable to confirm theexistence of the decahydrate. The crystalline form (hexagonalprisms) of the anhydrous salt has been determined, and thesolubility and transition temperature from the heptahydrate toanhydrous salt have been measured.The long-discussed question of the possibility of the existence ofcuprous sulphate has a t last been settled by the preparation of thepure salt.54 The preparation is carried out by the action of methylsulphate on cuprous oxide in absence of water :Cu,O + Me2S0, = Cu,SO, + Me,O.Ethyl sulphate behaves in a similar way.The action is carried ona t a temperature of 160O. The cuprous sulphate is washed withether, moisture being rigidly excluded, and dried in a vacuum.When dry, the new salt is stable in air, but is decomposed rapidlyby water with evolution of heat:Cu2S04 (solid) + Aq = CuSO, (dissolved) + Cu solid + 21 cals.The development of heat in this roaction shows a difference fromthe behaviour of other cuprous salts, and it explains why theprevious attempts to prepare the sulphate in aqueous solution haveresulted in failure.The curiously coloured salt obtained by the action of sulphuricacid on a mixed solution of ferrous and cupric sulphates 55 has beenexamined by A. J. Allmand.56 The red colour of the salt changesto chocolate-brown on heating, and finally to mauve.Only a verysmall quant.ity of ferric salt is present. The author’s experimentslead t o the conclusion that the salt is a solid solution of the generalcomposition (CuFe) SO,,H,O, but, since the colour of CuSO,,H,Ois pale blue and FeS0,,H20 is white, the red colour of the com-bination is still a mystery.The formula ascribed to the black powder which separates onthe anode when silver nitrate solution is electrolysed has beenstated to be Ag7N0,,.57 It has been considered 58 that its formationis preceded by that of a crystalline pernitrate of silver, AgNO,. Theblack powder has been reexamined, and it has been proved that53 Trans., 1909, 95, 1184.64 A. Recoura, Conzpt.rend., 1909, 148, 1105 ; A., ii, 579.65 A. Scott, Trans., 1897, 71, 564.56 Zeitsch. nnorg. Chem., 1909, 61, 202 ; A., ii, 238.57 0. s d c , ibid., 1900, %, 305 ; A . , 1900, ii, 595.58 G. Baborovskjr and B. Kuzma, Zeitsch. Elektrochem., 1908, 14, 196 ; A,, 1908,ii, 378 ; G. Cxborovskq’ and G. Kunna, Zeitsch. physikal. Chenz., 1909, 67, 48 ;A,, ii, 66648 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY,it consists of a true peroxide of silver, Ag8Q4, containing occludedsilver nitrate.One, whichhas the formula 2KBO,,HiO, is obtained by adding cold 3 per cent.hydrogen peroxide solut.ion to a saturated solution of potassiummetaborate, KBO,. The perborate is precipitated by the addition ofmethyl alcohol. After standing, the salt is filtered and washed withice-cold water.It is crystalline and soluble to the extent of 2.5parts in 100 parts of water at Iso. The dry salt is stable in air,but in water it slowly loses oxygen. The second salt, 2KB0,,H,02,is obtained in a similar way, except that the hydrogen peroxide isof 30 per cent. strength. It is stable in air, but deflagrates whenheated to 1 5 0 O . It is less %oluble in water than the former salt.Both the new substances have strong antiseptic properties.Two perborates of potassium have been prepared.59Group I V .The mixture of gases evolved on treatment of magnesium silicidewith hydrochloric acid has been investigated by P. Lebeau. Twohydrides, SiH4 and Si,H,, were isolated in a state of purity, andtt more easily condensable substance, probably Si,H4, was shownto be the source of the spontaneously inflammability of the othertwo hydrides.The case for the analogy between silicon and carbon, as regardsthe formation of chain derivatives, has been summarised byJ.Emerson Reynolds.60 He makes the interesting suggestion thatthe function of silicon compounds, which have long been known asconstituents of living tissue, is not merely to act as strengtheningmaterial, but that they are essential to cell-formation, just ascarbon compounds are. The analogy between these two elementshas been strengthened by the isolation of what are probably five-and six-silicon-atom chains. A. Besson and L. Fournier61 havesubmitted chlorosilicomethane to the action of the silent discharge,and fractionally distilled the resulting l i p i d in a vacuum.Themain products are: (1) Si4Cllo, a colourless, oily liquid, which, whendecomposed by water, gives a white substance resembling silica inappearance, but emits sparks and ignites when gently rubbed;(2) Si,c"ll4, a white solid, which melts a t 170°, and also gives acombustible substance with water; (3) a solid, yellow mass, solublein light petroleum, which apparently consists of a mixture of higherchlorides.59 C. von Girsewald and A. Wolokitin, Ber., 1909, 42, 865 ; A , , ii, 312.6O Roy. Inst. hkprbs, 1909.81 Comp?. rend., 1909, 148, 839 ; 149, 34 ; A,, ii, 399, 663INORGANIC CHEMISTRY. 49Group V.Very different compositions have been assigned to the chlorideof nitrogen obtained by the action of chlorine on ammoniumchloride, many chemists having asserted that it contained hydrogen.The substance, after solution in carbon tetrachloride, has beenproved62 to be NCI,, direct estimation of hydrogen showing thatthere is less than one atom of hydrogen to each hundred atoms ofnitrogen.Another chloro-derivative of ammonia has been prepared in apure state by F.Raschig.63 Equimolecular quantities of ammoniaand sodium hypochlorite react according to the equation :NaOCl+ NH, = NH,C1+ NaOH.By distilling in a vacuum, a faintly yellow, unstable oil is obtained.This substance, to which the author gives the name of chloroamine,reacts vigorously with alkalis, giving ammonia and nitrogen : blacknitrogen iodide is precipita,ted from a solution of potassium iodide,whilst with ammonia a small quantity of hydrazine is produced.Nitrosyl perchlorate, NO-ClO,,H,O, has been prepared by K.A.Nofmann and A. Zedtwitz 64 by passing oxides of nitrogen, preparedby the action of nitric acid on sodium nitrite, into perchloric acid.The salt is obtained in colourless, doubly refracting leaflets, whichare slightly hygroscopic. Water produces decomposition, resultingin a green solution. Alcohol, ether, acetone, and primary aromaticamines ignite when mixed with the new perchlorate, producingviolent explosions.Although ammonium hydroxide exists in small quantity in asolution of ammonia, the compound has not hitherto been isolated.3’. F. Rupert65 has obtained a solid having the compositioncorresponding with NH,OH, which is probably a definite compound.The freezing points of solutions of ammonia of concentrations from4.1 to 100 per cent.have been determined, and the results plottedas a curve, which shows maxima a t 49 per cent. and a t 65 percent. The monohydrate should contain 48.6 per cent. of ammonia,and the hydrate, 2NH,,H,O, 65.4 per cent. The behaviour ofhydrazine under the influence of different oxidising agents has beenstudied by A. W. Browne and F. F. Shetterly.66 It is shown thatthe oxidation can proceed in three ways: (I) with formation offairly large quantities of azoimide and ammonia, when hydrogen6‘2 D. L. Chapman and L. Vodden, Trans., 1909, 95, 188.G;5 Yerh. Ges. deqst. Naturforseh. Aerlze, 1907, 11. i, 120 ; A , , ii, 232.G5 J.Amer. Chenz. h’oe., 1909, 31, 866 ; A . , ii, 726Bli ]bid., 221, 7S3 j A , , ii, 233, 658,Ber., 1909, 42, 2031 ; A . , ii, 668.REP.-VOL. VI. 50 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.peroxide, potassium chlorate, or potassium persulphate are used inacid solution; (2) with formation of little or no azoimide but largequantities of ammonia, when the oxidation is effected by potassiumpermanganate, manganese dioxide, or ferric oxide in presence ofsulphuric acid; (3) with formation of little azoimide or ammonia,as is the result of the use of potassium iodate, mercuric oxide, ormercuric chloride. Persulphuric acid gives about 40 per cent. ofthe possible yield of azoimide, but Thiele's method,"7 which employsa mixture of hydrazine and ethyl nitrite, is still the most effective.Continuing his patient study of the nitrites, P.C. RSy68 hasshown that if a. solution of ammonium nitrite is heated in avacuum very little gas is evolved below 40°; on cooling, most ofthe salt crystallises. If the temperature is raised to 70°, slowdecomposition takes place, but a considerable quantity of the saltappears as a sublimate. There is as yet insufficient evidence toshow whether the salt has sublimed unchanged, or whether dis-sociation and recombination have taken place.Two new solid hydrides of phosphorus have been prepared.69Calcium phosphide, on treatment with water, gives a mixture which,on passing over granular calcium chloride, gives a yellow deposit.On treatment with cold dilute hydrochloric acid, the calciumchloride is dissolved, and the solid left is washed with water andthen with alcohol and ether.The hydride is a canary-yellowpowder, which, when first prepared, has no odour. On standing inthe air, it rapidly changes, especially in sunlight, giving off aspontaneously inflammable phosphine. It is remarkably insolublein reagents, and on analysis it is stated to have the compositionP,,H6. On heating in a vacuum, it turns red and evolves purephosphine, the residue being the second new hydride,5P,,H6 = 6P9H2 + GPH,.The second hydride is stable in dry air, but in presence of moistureit is converted into phosphine and phosphoric acid.Group VI.The ordinary ozone tube used in the laboratory rarely gives anylarge percentage of ozone, 3 to 8 per cent.being the usual yield.Chemists will be glpd to know of the simple and convenient processdescribed by F. Fischer and K. Bendixsohn.70 The ozone is preparedby the electrolysis of dilute sulphuric acid, the anode exposing very67 Bw., 1908, 41, 2681 ; A . , 1908, ii, 940.6y A. Stock, W. Bottcher, and W. Lenger, Ber., 1909, 42, 2839, 2847;70 Zeitseh. nnorg. Chem., 1909, 61, 13 ; A , , ii, 136.68 T,rans., 1909, 95, 384.A . , ii, 7 2 i INORGAXIC CHEMISTRP. 51little surface to the liquid. The most effective anode is made byimbedding platinum foil in glass and grinding away the edge so thatonly a line of 0.1 inm. breadth is exposed. The proportion ofozone in the oxygen evolved amounts to as much as 23 per cent.The methods adopted have been hitherto insufficient to decidebet.ween the two formulze assigned to Caro's acid, H,SO,71 andH,S,O,.72 The analysis of salts is inconclusive, since a salt, MHSO,,is indistinguishable from M,S,O,,H,O, as in the historic instanceof sodium hyposulphite.Two new researches, however, support theformer formula, showing that the acid is monobasic. H. Ahrle73has prepared a nearly pure (92.3 per cent.) acid by the interactionof 100 per cent. hydrogen peroxide and sulphur trioxide. Thisprocess was preferred to that of the action of hydrogen peroxideon sulphuric acid, since the equationwas found to be reversible. The experiments show that the acidis monobasic, confirming those of T. S. P r i ~ e .7 ~ The strong acid isstable below Oo, but decomposes slowly at the ordinary temperature.Catalytie agents, such as finely-divided platinum, produce explosivedecomposition. R. Willstatter and E. Hauenstein75 have prepared thetwo acyl derivatives, C6H,*CO*O*O*S03K and C,H,*S02*O*O*S03K.These acyl derivatives are not per-acids, but behave as mixedperoxides of persulphuric acid and acyl. The benzoyl derivative,for example, is deconiposed by alkalis into Caro's salt and abenzoate, thus :C,H5*CO*'O*O*S03H + H20 = H*O*O*S03 + C6H,*C0,H,and by acids into sulphuric acid and benzoyl hydrogen peroxide:C,H,*CO*'O*O*SO3H + H20 = H*O*O*CO*C,H, + H,SO,.The acyl derivatives are monobasic acids, and thus the formulaH2S05 for Caro's acid is confirmed.Many chemists have doubted the existence of sulphur dichloride,but the question may be considered as settled by the work ofE.Beckmann.76 The liquid, produced by the action of chlorine onsulphur monochloride, S,Cl,, can be distilled a t low pressures withpractically no decomposition. It solidifies at -8OO. I n solution inliquid chlorine, it has a molecular weight corresponding with theformula SCl,, and the same formula is arrived at from cryoscopicH,O, + H,SO, H,SO, + H,OBaeyer and Villiger, Ber., 1901, 34, 853 ; A , , 1901, ii, 380.Armstrong and Lowry, Proc. Roy. SOL, 1902, 70, 94 ; A., 1902, ii, 558.73 J.pr. Chem., 1909, [ii], 79, 129; A,, ii, 395 ; Zeitsch. angew. Chem., 1909,74 Trans., 1906, 89, 53.76 Ber., 1909, 42, 1839 ; A , , ii, 566.7ti Zeilsch.physikal. Chern., 1909, 65, 289 ; A., ii, 137.22, 1713 ; A , , ii, 804.E 52 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.measurements in xylene, ethylene dibromide, acetic acid, andbromine.Many formulze have been ascribed t o perchromic acid. Accordingto E. H. Riesenfeld,77 there are two such acids: HCrO,, whichis blue, and H,C'rO,, which is red. These two acids give rise tosimilarly coloured salts. The molecular weight of the blue pyridinesalt has been determined by the cryoscopic method, the solution inwater having been used. Since, however, considerable dissociationtakes place in this solution, the amount of dissociation had to beseparately measured. The molecular weight corresponds with theformula C5H5N,HCr05.The decomposition of the free acid takesplace too rapidly for its molecular weight to be determined. Thered potassium perchromate is obtained by the action of chromicacid on a cooled mixture of potassium cyanide and hydrogendioxide.On the other hand, W. Oechsner de Coninck78 maintainsMoissan's formula H,CrO, for perchromic acid, and compares theperchromates with the peruranates which he has obtained by theaction of alkalis on uranyl chloride in presence of air, for example :2U02C1, + 4K20 + 0, = 4KC1+ 2K,U05.Group VII.Nothing can be of more value to the science than the exhaustivestudy of one particular action. Such a study, if complete, couldnot fail to throw light on the most difficult of problems, the natureof chemical attraction. The period of induction in the union ofhydrogen and chlorine has been investigated by D.L. Chapmanand his co-workers for some years past, and it is now certain thatthe speculation that this period was occupied by the moleculesgetting up a certain type of vibration must finally be abandoned.It was shown79 that a trace of ammonia is responsible for a longinduction period. The ammonia would produce nitrogen chloride,which itself strongly inhibits the action. It has also been proved 6othat, contrary t o the statement of Bunsen and Roscoe,*1 excess ofeither of the.reacting gases, hydrogen and chlorine, to the extent of6 per cent. has no influence on the rate of union. The influence ofoxygen as inhibiting the action was first pointed out by Bunsenand Roscoe (Zoc.cit.). Their observation has been confirmed, andfrom quantitative measurements Chapman and NacMahon 82 have77 Ber., 1908, 41, 3941 ; A . , ii, 51.78 Bull. Acud. roy. Belg.. 1909, 175 ; A., ii, 318.79 Burgess and Chapman, Trans., 1906, 89, 1433.*O D. L. Chapniaa and P. S. MacMahon, ibid., 1909, 95 135.Phil. Trans., 1857, 147, 390. 82 Tmt.-s., 1909, 95, 959INORGANIC CHEMISTRY, 53drawn the conclusion that if the relation of oxygen present to thesensitiveness of the mixture, which they have established for smallquantities of oxygen, holds with infinitely small quantities ofoxygen, then the sensitiveness of pure hydrogen and chlorine wouldbe infinite, in other words, these gases would combine in the dazk.Nitrogen, carbon dioxide, and nitrous oxide only act? as diluents,whilst nitric oxide acts as an inhibitor. It is pointed out that theinhibiting gases are all capable of reaction with the constituents ofthe explosive mixture.Iodine dioxide, obtained first by Millon in 1844, has been pre-pared in a pure condition by M.M. Pattison Muir.83 By actingwith concentrated sulphuric acid on iodic acid until iodinebegins to be evolved, and allowing the mixture to cool, a yellow,crystalline crust is obtained. This, after washing with water, andthen with ether, gives the pure dioxide of iodine. Owing to itsinsolubility and its decomposition on heating, its molecular weightcould not be found. By the direct action of sulphur trioxide oniodine dioxide, a solid compound, I;O4,3S0,, was obtained.A substance which is possibly another oxide of iodine has beenobtained by F.Fichter and F. Rohner 84 by the action of ozonisedoxygen on iodine dissolved in chloroform. A yellowish-white pre-cipitate is produced, which is very sensitive to moisture and readilydeliquesces to a black syrup. This ready absorption of water seemsto distinguish it from the dioxide described above. The per-centages of iodine and oxygen determined by the analysis of thisproduct add up to only 97, but on the results of these analyses theauthors ascribe the formula I,O, to the substance. There mustremain some doubt as to its real constitution until a purer producthas been obtained. Chloroform very strongly retained seems t obe the impurity.Group VIII.The mechanism of the process of the cementation of iron has beenlong doubtful.Contributions towards the solution of this problemare made in two recent papers. G. CharpyB5 has shown that irontakes up carbon from carbm monoxide, but whether iron carbonylwas first formed was not investigated. It has been believed thatcarbon can be taken up directly when heated with iron, but theexperiments on which the belief was based have not been unexcep-hionable. A new series of experiments has been published, in whichgreat care has been taken to exclude the possibility of gaseouss3 Trans., 1909, 95, 656.84 Ber., 1909, 42, 4093 ; A., ii, 991.Compt. rend., 1909, 148, 560; A., ii, 40554 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.compounds either being present or being formed.Strgar-charcoal,purified by heating in chlorine, was heated with iron t o 1000° ina vacuous glazed porcelain tube, the iron being freed from occludedgases by a preliminary heating in a vacuum. I n these circum-stances, no cementation took place. Since, however, it was possiblethat the contact of the two elements was insufficient, they werepacked into a steel cylinder provided with a finely perforated screwstopper. I f the scopper was loose and the cylinder and its contentswere heated in the vacuous tube, it was again impossible to findany evidence of union. When, finally, t.he cylinder was treatedin the same way, with the screw stopper exerting great pressure onthe mixture, as much as 0.3 per cent. of carbon was taken up bythe iron.The conclusion, therefore, must be drawn that undermanufacturing conditions, the cementation of iron takes placeentirely through the agency of gaseous compounds. The passimstate of iron is a phenomenon which, like the rusting of the samemetal, seems to be of perennial interest. The existence of a thinfilm of oxide on iron, which has been rendered passive by any of thewell-known methods, has been denied on optical grounds.86 It isshown,87 however, that by making bright iron the anode in theelectrolysis of strong sodium hydroxide, the passive state is inducedby the formation of a layer of oxide so thin as not sensibly tointerfere with the reflecting power of the surface.I f the force which binds water of crystallisation to salts is distinctfrom ordinary chemical attraction, the same thing probably appliesto the union of substances with hydrogen peroxide. Many com-pounds have been obtained by means of hydrogen peroxide, in whichit is hard to say whether a real peroxidised compound has beenprepared, or if the hydrogen peroxide is in a state of associationsimilar to that of water of crystallisation. A peroxide of nickel88has been prepared by the addition of a cooled alcoholic solution ofpotassium hydroxide to a mixture of nickel chloride and hydrogenperoxide at -5OO. It is a greyish-green powder, having the com-position NiO,,sH,O, which gives all the reactions of hydrogenperoxide, easily liberating this substance when treated with diluteacids. For this reason, the authors believe that it has a different;constitution from that of the black nickel dioxide, which is obtainedby the action of sodium hypobromite on nickel hydroxide,S. Tanatar,8g however, finds that the dioxide prepared by the latter86 W. J. Miiller and J. Konigsberger, Zeitsch. Elektrochem., 1907, 13, 659 ;A., 1907,ii, 924.87 P. Krassa, ibid., 1909, 15, 490 ; A . , ii, 738.88 G. Pellini and D. Meneghini, Zeilsch. anorg. Chem., 1908, 60, 178 ;88 Ber., '1909, 412, 1516; A., ii, 484.A., ii, 50INORGASIC CHEMISTRY. 55process will reduce potassium permanganate, and will also givehydrogen dioxide when treated with hydrogen cyanide. There are,however, other differences between the substances, and Tanatarregards the greyish-green dioxide as a molecular compound,NiO,H,O,. At present there is no evidence to show which of theformulze is the true one.A new oxide of platinum has been discovered by L. Wohler andF. Martin.90 By the electrolysis of a solution of platinic hydroxidein 2N-potassium hydroxide, a golden-yellow crust forms on theanode. This was found to have the composition K20,3Pt0,. Bythe action of cooled acetic acid, the trioxide of platinum wasobtained as a brown powder. The trioxide readily loses oxygen,and it slowly liberates chlorine from dilute hydrochloric acid. Itis without action on dilute sulphuric, nitric, and acetic acids, whilstconcentrated sulphuric and nitric acids convert it into the dioxide.It does not decompose hydrogen dioxide.H. B. BAKER.Ber., 1909, 42, 3326 ; A., ii, 898

ISSN:0365-6217    

DOI:10.1039/AR9090600033

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

ORGANIC CHEMISTRY.THE publication of the Index to the Society’s Jorxrnal a t the sametime as the Annual Reports makes it superfluous to attempt anaccount of all the numerous Iines of investigation in organicchemistry which have been pursued during the year, even were sucha task possible to accomplish within the limits of a Report. Theworker interested in any particular line of inquiry will naturallyturn t o the index for information as to the work which has beendone in connexion with that branch, whilst the Ronours student,desirous of following the course of research, is not absolved bythe reading of a Report from the duty of consulting the originalmemoirs. The task of an Annual Reporter is rather that ofindicating the main channels into which research is being directed,and the most important theoretical and practical advances madewithin the period covered, keeping more particularly in view therequirements of those workers in other departments who maydesire to know the progress of studies related to, but not directlyconnected with, their own.Considering, however, the great numberand diversity of investigations in organic chemistry, it is inevitablethat the full bearing of many should not be discernible untilsufficient time has elapsed for them to fall into proper perspective,whilst the incomplete condition and indecisive results of othersrenders it impossible to summarise them in an adequate manneruntil further material has been accumulated.The recent development of research in organic chemistry exhibitsevidence of the great influence of the study of physics on the onehand, and of biology on the other.The application of physico-chemical methods to the study of organic compounds is largelyresponsible for the increasing interest shown in the relation ofphysical properties to chemical constitution, and in the mechanismof reactions. Whilst the older structural organic chemistry, aimingprincipally at the synthetical formation of compounds and thedetermination of constitution, was mainly concerned with the finalproducts of a given reaction, more and more attention isnow being devoted ta the dynamical aspects of reactionsORGANIC CHEMISTRY, 57embracing the quantitative study of velocity, etc., as well as themolecular lnechanism by which the interchange is effected.Intimately connected with such inquiries is the study of theinfluence of catalytic agents, such as “contact substances” inprocesses of oxidation and reduction, acids in esterification orsubstitution by halogens, metallic salts in condensation, and minutequantities of diverse substances in the acceleration of isomericchange.The chemical importance of certain physical properties, notablycolour and fluorescence, in their relation to structure, has beendealt with in several previous Annual Reports. The volume ofmaterial is this year even greater, and we are still far from possess-ing a complete theory of the phenomena.The tendency to employdynamical hypotheses, rather than to assign to purely staticalconfigurations the power of producing absorption or raonance underthe influence of light-waves, continues to be conspicuous in memoirsdealing with this question, but a comprehensive physical explanationis as yet lacking.The formulation of ideas of structure in terms ofthe electron theory has so far made little progress in organicchemistry, the conception being still too indefinite for immediateapplication to so complex a problem. A few such attempts havebeen made during the past year,l but it has not been found possibleto represent the linkings of atoms by means of electrons in such away as to secure general acceptance.Reference was made in last year’s Report (p. 74) to theimportance of the subject of unsaturation. It is hardly anexaggeration to say that the distribution of residual affinity in themolecule, with all that it implies, is the central problem of organicchemistry at the present time.The influence of unsaturated ordouble linkings on the properties of a compound, the changes invalency and linking involved in the formation of additive com-pounds, which so often precedes substitution or exchange of radicles,and the nature of the so-called “ partial valencies,” are questionswhich recur in one form or another in investigations dealing withthe greatest possible variety of compounds and of reactions. Inthis direction, also, conspicuous advances have to be recorded.On the other hand, the influence of bioIogy is seen in severalbranches of work. Steady progress is being made in the study ofsubstances of bio-chemical importance, the attack being directedfrom two quarters, namely, the investigation of productsobtained by the degradation of complex compounds, and thesynthesis of progressively larger and larger molecules with theJ. 31.h’elson and K. G . Falk, School of Nines Qtuz~terly, 1909, 30, 179 ;A,, i, 349 ; B. Fldrscheim, Proc., 1909, 25, 26158 ANNUAL REYOKTS ON THE PROGRESS OF CHEMISTRY.object of reaching the structure of the naturally occurring com-pound in an upward direction.The problems concerning the relationship between the chemicalproperties and the physiological functions of the proteins,polypeptides, cholesterol, lecithin, and other constant constituentsof living organisms, are now beginning to assume definite shape,and their solution may soon make rapid progress.The great interest attaching to the chemistry of the alkaloids,and of such substances as adrenaline, is closely connected withtheir physiological activity.When a number of derivatives, relatedto a compound of one of these classes, are studied chemically andphysiologically, it is often possible to obtain a relation between itcertain type of structure and the exhibition of activity. Valuableas such rules are within the limits of a particular group, thereare few broad generalisations applicable to widely different sub-stances. Here, as elsewhere, the mode of distribution of residualaffinity in the molecule is evidently of primary importance.Several researches, of great intrinsic interest, are omitted fromthis Report on account of the publication, too late to be incor-porated fully, of important contributions which can be betterdiscussed, in the light of further research, in the Report for nextyear.The nature of carbor,ium and oxonium compounds and thestructure of the complex cyanides are among the subjects thediscussion of which is thus postponed. Our knowledge of the twocolouring matters which infinitely surpass all others in theirimportance for life, namely, hzemoglobin and chlorophyll, has madegreat strides during the past year, but the researches so farpublished are incomplete, and there is some reason to expect thatthe Reporters for 1910 will be able, in dealing with the wholesubject, to record the discovery of the key to the problem.Some of the more important theoretical advances are consideredfirst, followed by an account of new practical methods and generalreactions, and the, report closes with a description of recent workin several groups of compounds which have engaged attentionduring the past year.Unsaturation.For a long time it has been recognised that the polar character ofa substitutive group influences the whole chemical behaviour of asubstance in which it is found.negative ” groups,or those which as “ions” move towards the positive pole duringelectrolysis, usually raise the dissociation constant of an acid inwhich they are present as substituents, whereas “ positive ” radicleshave the opposite effect. Nevertheless, this is not consistently theI n particularOKGANIC CHEMISTBY. 59case, and frequently the reverse is noticed.Vorlander2 calledattention to the fact that the general influence of a group is notmerely dependent on its polar character, but also on its state ast o saturation. Werner, Nichael, Flurscheim, and others haveendeavoured to develop views of tho affinity values of atoniiclinkings which combine both these factors, and Werner, from suchviews, has deduced thatl elements of decidedly electropositive ornegative character will be most defir,itely affected in their com-bination by this polarity, whilst those of intermediate character,such as carbon and hydrogen, will act almost independently of suchpolar character.Thiele was the first to enunciate in one form the principle thatthe effect of unsaturation is not merely exhibited in an apparentattraction for external agents, but is also partly exerted on therest of the molecule.The mutual interaction of such residualaffinities in different. parts of the molecule tends to alter in amarked degree its external relations, so that, when two points ofresidual affinity are found in one molecule, the total residualaffinity outwardly displayed is not the sum of those which wouldbe exhibited by each in absence of the other. This may be repre-sented in accordance with Werner’s suggestion, by imagining thatthe attractive force of free affinity of any atom is always disposedin part externally, but also in part internally, thus absorbing aportion of the affinity of the atom in its neighbourhood.For example, i f a multivalent atom X is attached to a secondmultivalent atom Y, and the strength of the bond uniting themis normally represented by I, then, if X becomes possessed of freeaffinity either by a change of valency or by becoming one of apair of doubly linked atoms, part of the resulting free affinityis exerted externally and part internally, so that’ the bond whichattaches it to Y now has a tenacity somewhat greater than 1.Thus, if the compound :>X-Y<i becomes a-X=Y-c, theresult will be that X, in virtue of its unsaturation, exercises someexternal attractive power, but also binds a more firmly than before,the same applying to Y and c in their mutual relations.Thiele’s case of the conjugation of double linkings is evidentlyonly a special case of this.x=Y-Z=Wno internal mutual engagement of the residual affinities, theexternal effect of the system might be represented asThus, if there were in; :but the subsidiary affinities of Y and Z become partly (or sometimes_.... x=+. i=w __.. ~,Annalen, 1902, 320, 110; A., 1902, ii, 25060 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.wholly, when the molecule is symmetrical) mutually engaged, andthe system behaves as.__. -.-... ._.. . ... . ..... - X=Y-CX ._.. or -...xJY-z=w-. --Syrnmctrical. Unsymmetrical.Werner explains tfie replaceability of the a-hydrogen atom ina carboxylic acid3 by assuming that the residual a5nity of thecarboxyl oxygen absorbs much of the affinity of the carbon atomof the group, which thus but weakly binds the a-carbon atom, theexcess affinity of which thus released then becomes disposedexternally, and thus attracts substituting agents :This particular explanation is certainly not satisfactory, and isprobably incorrect, as the evidence is all against the assumptionthat bromine acts directly on the acids, but in favour of the viewthat the enolic forms of these intervene.Flurscheim 4 applies the foregoing principle to the affinities ofacids and bases, commencing with the proposition that an un-saturated atom X, replacing a hydrogen atom in the a-position,leads to the following distribution of affinity, in which abnormalityin the strength of the linking is indicated by the thickness of theline representing it::X-k--CO--O-H, .the effect on the ionisable H-atom being to render it less firmlyattached to the oxygen, so that this atom is more easily displaced,and the dissociation constant or the affinity of the acid is increasedby the presence of X in the a-position.With X in the &position,the reverse would hold true:..: X-&-d-CO-O-H.This holds good with the anilino-fatty acids, in which (althoughaniline is basic in character) the a-anilino-derivatives (I) arestronger than the unsubstituted acids, whilst the 6-anilino-derivatives (11) are weaker :. .Ph* NII *6* 6’ CO,H . . Ph*NH*& C0,H(1.1 (11.1Similarly, among unsaturated isomeric acids, the aP-derivativeis the strongest.Viertzljahrschr.Ziiriche. Naturf. Ges., 189 1.Trans., 1909, 95, 715ORGANIC CHEMISTRY, 61I n this sense to halogen atoms and oxygen as well as to tervalentnitrogen is ascribed an unsaturated function capable of manifest-ing itself in this manner, and generally the magnitude of the effectthus exerted is termed the “ quantitative factor.”The replacement of hydrogen by another atom or group will, itis suggested, produce an effect dependent on the “quantitativefactor,” and also on the polar character of the atom or group, andthese may mutually assist or oppose one another according tocircumstances, and in particular to their relative positions. Thus,m-hydroxybenzoic acid is stronger than benzoic acid, butp-hydroxybenzoic acid is weaker.The order of the groups as to their ‘‘ quantitative factors ” isarrived a t by considering their orientating influence on substitutionwhen they are directly attached to a benzene nucleus.Such apreliminary classification of groups is given.To estimate relative polarity, consideration is taken as to theeffect of groups on the affinity of substituted benzoic acids. I n themeta- and para-isomerides, steric influence is of little effect, andin these two positions the quantitative influence has oppositeeffects; the polar effect, on the other hand, is not inverted in thismanner, so that when the influence of a group in the meta-positionis p + p, in the para-position it is approximately p - p ; one-half thesum p f p + p - q = p is therefore a fairly good measure of the2polarity of the group.The results thus obtained render it feasible to estimate, by aconsideration of the rates of esterification of acids, the relativcsequence of groups on their steric effects, and a preliminary tablefor these is given.Finally, the author applies his numerical data to foretell quali-tatively the effect of the replacement of hydrogen by numerousatoms and groups on the affinities of acids and bases, and withmore than ordinary success; in one of the few cases where hisconjectures were not in harmony with previous measurements aredetermination of the affinity constant confirmed his prediction.Whilst many of the author’s data are arrived at.by theoreticalassumptions which may finally prove to be invalid, it must beadmitted that in their application, at least to the cases dealt with,they lead to conclusions which are wonderfully near the truth,and the paper should stimulate a very general interest in some ofthe purely theoretical aspects of organic chemistry.Only a few of the many other contributions to the study ofcompounds containing unsaturated linkings can be mentioned.The formation and decomposition of ozonides has been utilised b62 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.a number of investigators as a means of determining the natureand position of double linkings in the molecule.The simplestrepresentative of the class, ethylene ozonide, has been prepared bythe action of ozonised air on dry ethylene at -70°, and proves tohave the simple formula : yH2*Q>o, It undergoes decompositionCH9*0with water in two different ways, yielding, on the one hand,formaldehyde and hydrogen peroxide, and, on the other,formaldehyde aad formic acid.5 It is probable that ordinaryoxygen sometimes attaches itself to double linkings in the sameway as ozone.Thus the atmospheric oxidation of &methyl-hydrindone to phthalic and benzylmethylketone-o-carboxylic acidsis best explained 6 by assuming that the enolic form of the ketonetakes up oxygen, and that the 0.8 linking is ruptured by water :-CH2->C Me] - -+C 6 H , < g p c M e -+ [ C,H&(OH) 0--0 IC,H4<(& H *COMeThe ketonic acid then undergoes in part a similar rearrangementand oxidation, the products being phthalic and acetic acids.An important test of the validity of Thiele’s law of additionto conjugated double linkings is afforded by the study of thedibromide of s-diphenylbutadiene : C6H5*CH:CH*CH:CH*CGH5.Thiele’s theory led him to regard the dibromide as symmetrical, butsome of the reactions of the compound having led to doubt on thispoint, the oxidation by means of ozone was undertaken.7The products proved to be dibromocinnamaldehyde and benz-aldehyde, proving the bromine atoms t o be in the a& and notin the as-position. It will appear that whilst the addition ofhydrogen always follows Thiele’s rule, that of bromine is equallylikely to occur at a double linking without shifting of bonds.Itis therefore necessary to determine the constitution of the dibromidein each individual case.Nitrogen peroxide follows Thiele’s rule,8that is, it is added in the as-position. It is suggested that theaddition of H and NO, takes place in single radicles, whilst thatof bromine takes place primarily in the form of molecules, Br,.The addition of hydrazine and hydroxylamine to unsaturatedacids has also been studied,g and whilst it was found impossibleC. D. Harries and R. Koetschau, Ber., 1909, 42, 3305 : A . , i, 755.A. H. Salway and F. S. Kipping, Trans., 1909, 95, 166.7 F. Straw, Bcr., 1909, 42, 2866 ; A., i, 638.* H. Wieland, Annulen, 1908, 360, 299 ; A , , 1908, i, 517.A. Riedel and E. Schulz, Annalen, 1909, 367, 14 ; T. Posner and K. Rohde,Bw., 1909, 42, 2785 ; A . , i, 581, 649ORGANIC CHEMISTRY. 63to obtain an additive compound from hydrazine and cinnamenyl-acrylic acid or ester, hydroxylamine was readily added in thea/3-position :C,E; CH: CH* C H: CH* CO,E t.* *If we consider the carbon atoms cinly, addition according toThiele’s rule would occur in the By-position. The observedreaction is, however, in accordance with the rule if we take intoaccount the carbonyl group, addition taking place a t the middlelinking, not of the group *C:C*C:C*, but of the equally conjugatedsystem *C:C=C:O. This type of reaction is now under systematicinvestigation.Diethoxythioxan behaves as a conjugated compound, closelyS resembling thiophen.10 I t s low additivepower distinguishes it from the open-chain/ ;; \ sulphides, and even suggests steric hin-QHz $ YH2 drance, which is, however, excluded.TheOEt*CH $ CHaOEt known mutual influence of atoms in the\ ;; / 1: 4-position suggests that the residualvalencies of the oxygen and sulphuratoms saturate one another across thering, thus accounting for the low reactivity.The stability of the linking between carbon and amidic nitrogenis greatly affected by the neighbourhood of an ethylenic linking.When this is immediately adjacent-, C:C*N, the CON union is moreeasily ruptured on reduction, unless the C:C group forms part of abenzene or similar ring. When the double linking is one stepremoved, C:C*C*N, either an open-chain or a benzenoid linkingsuffices to facilitate the rupture, but in the former case only if theunsaturated group is a large one, such as cinnamyl, a small group,such as allyl, being without inAuence.11 Thus, aniline is unaffectedby reducing agents, cinnamyltrimethylammonium chloride andsodium amalgam yield phenylpropylene and trimethylamine, whilsttrimethylallylammonium chloride is unchanged./ii\\;;/0Colour and Constitution.The problem of the colour of organic compounds is so intimatelyconnected with that of the distribution of unsaturated linkings inthe molecule that its consideration may follow a t this point.Amarked feature of the year’s work on the constitution of colouredsubstances has been the attention devoted to additive compounds,l o H. T Clarke and S. Smiles, Trans., 1909, 95, 992.H. Emde, Arch. Phnrz., 1909, 247, 314, 833, 351, 369 ; A, i, 708, 70964 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.particularly to those of the quinhydrone type.As regards thequinhydrones, the hypothesis proposed by Willstiitter,l2 whichassumes an oscillatory interchange of quinonoid linkings betweenthe two components of the molecular compound, must now beregarded as untenable, coloured compounds having been obtainedin cases where such oscillations are completely excluded. Thus,tetrachloro-p-benzoquinone forms strongly coloured qui'nhydrones~ A ~ with quinol dimethyl ether and with tetra-0 NMe, methyl-p-phenylenediamine.13 There is herecI/\cl /\ no possibility of interchange.Clll 1Jc1 () p-Benzoquinone and p-benzoquinonedi-imineform many coloured compounds of similar typeNMe2 with benzidine and other diamines. Fluorenoneresembles the quinones in yielding a coloured additive productwith p-phenylenediamine.The additive compounds of quinoneswith a single equivalent of monohydric phenols are also coloured.l4Werner 15 regards the picrates of hydrocarbons as compounds ofthe quinhydrone type, in which the residual affinity of the nitro-group plays the same part as that of the quinone oxygen atoms,and there is no rearrangement of the nitro- to an isonitro-group. Trinitromesitylene yields coloured compounds with anilineand alkylanilines, and even such simple nitro-compounds as chloro-picrin, CCI,*NO,, and tetranitromethane are capable of formingsimilar molecular combinations. Labile hydrogen is, of course,absent in these cases. The depth of the colour increases in thehydracarbon series from benzene to anthracene, thus following thesame order as the picrates.Tetranitromethane may even beemployed as a reagent for the detection of double carbon linkings,as it gives distinct yellow colorations with unsaturated aliphatichydrocarbons. The &unsaturated acids respond to the test, butnot their a-isomerides.Addition to nitrogen takes place in certain cases, trimethylamine,for instance, giving a brown coloration with tetranitromethaue.Hydrazones are also capable of forming coloured additive productswith polynitro-compounds, provided that the residual affinity of thenitrogen is not too much reduced by the presence of negativegroups. Thus, the phenylhydrazone and phenylmethylhydrazoneof piperonaldehyde yield stable, coloured compounds with picramideor picryl chloride.16An oscillation of linkings between the acid or basic groups wasv 0l3 Ann.Report, 1908, 124.l3 W. Schlenk, AnnaZeE, 1909, 368, 271, 277, 295 ; A . , i, 807, 808.l4 K. H. Meyer, Ber., 1909, 42, 1149; A., i, 395.l5 Ber., 1909, 42, 4324; A., 1910, i, 20.R. Ciusa, Atti R. Accad. Lineei, 1909, [v], 18, ii, 100 j A., i, 787ORGANIC CHEMISTRY, 65proposed by Baeyer17 to account for the colour of the triphenyl-methane dyes. Schlenk has put this suggestion to the test bypreparing p-tetr amethyldiaminofuc hsone,0I .which proves to be a true dye, and not merely a quinhydrone,although oscillation of the kind proposed by Baeyer is impossible.A further argument against Baeyer’s oscillation hypothesis isafforded by the fact that the trimethyl ether of tetrachlorogallein,although precluded by its formula from exhibiting such oscillatoryinterchange, nevertheless forms coloured salts and esters.l*The influence of conjugated double linkings on colour has beenstudied in an extensive series of unsaturated ketones and theirsalts.19 The parent substances chosen for comparison are di-styryl ketone and dibenzylidenecy clopentanone :QHz-p%C,H,* CH :CH*C* CH: CH* C,H, and C,H,*CH: C* C C: CM*C,H,.I...0 0The introduction of the ring lias the expected effect of deepeningthe colour (shifting the absorption band towards the red) to anextent which is practically equal in all the derivatives examined.The replacement of hydrogen atoms in the phenyl residues byalkyl or alkyloxy-groups causes a change in the same direction,whilst an increase in the length of the chain of conjugated linkings,by the replacement of benzylidene by cinnamylidene, greatly deepensthe colour.Compounds closely resembling the triphenylmethane derivativesare obtained when one or more of the phenyl groups in the latterare replaced by diphenyl residues.20 The methane linking is in allcases in the para-position, and the colour is progressively deepenedby the substitution of diphenyl for phenyl, triphenylcarbinol saltsbeing yellow, and tridiphenylcarbinol bluish-red, the intermediatemembers being yellowish-red and red.This fact is used by Schlenkas an argument against the representation of the dyes as quinonoid,Ann. Report, 1907, 117.W.R. Orndorff and T. G. Delbridge, Amer. Chcnt; J., 1909, 42, 183;Fury1 has a greater effect than phenyl.A., i, 733.l9 H. Stobbe, Annalen, 1909, 370, 9 3 ; A., 1910, i, 43.2o Schlenk, Zoc. cit.REP.-VOL. VL. 66 ANNUAL KEPORTS ON THE PKOGRESS O F CHEMISTKY.as an abrupt change of colour, such as might be expected to occuron passing from. c= /=\P to :c= /=L/=\/H,\=/\x \=/-\=/\xis not observed.Further evidence has been brought forward for the view thatthe yellow solutions of triphenylmethyl contain a quinonoid modifi-cation. Gomberg and Cone’s important paper 21 appeared too lateto be discussed here, and will be mentioned later in connexion withthe general nature of carbonium and oxonium salts.A solution of tri-p-bromotriphenylmethyl chloride in liquidsulphur dioxide yields, after some time, a colourless solid solution ofthe original substance and 4-chloro-4’ : 4//-dibromotriphenylmethylbromide.22 The occurrence of this change indicates an intermediateformation of a quinonoid compound :C( C,H4Br),Cl -+ f- -+ t-The existence of two isomeric triphenylmethyl magnesiumchlorides, however, seems to be definitely disproved.23 All thereactions of the magnesium compound, with the exception of thatwith aldehydes, lead to a homogeneous product, and this reactionis valueless for such purposes, as even the reaction betweenmagnesium benzyl chloride and formaldehyde is found to take placein two ways, yielding both benzylcarbinol and o-tolylcarbinol.Triphenylmethyl chloride forms coloured additive compoundswith phenols, a study of which has led to the suggestion 24 that intriphenylmethyl the free valency of the carbon atom unites withthe centric valencies of the benzene rings, destroying theirsymmetry and producing colour.The variety of formula proposed for the phthaleins and theirsalts is very great, and the insufficiency of any statical formula torepresent all the colour-relations of the substance is well seen inthis class.S. F. Acree and E. A. Slagle,25 after reviewing thequinonoid and other formulE, and the hypotheses of oscillatinglinkings and of coloured free ions, consider them all to be unsatis-factory, and prefer t o regard the coloured salts as analogues ofthe quinhydrones.Instead, however, of leaving the exact natureof the reciprocal influence of the quinone and phenol groups an21 Annulcn, 1909, 370, 142 ; A., 1910, i, 55.22 M. Gomberg, Ber., 1909, 42, 406 ; A., i, 144.23 A. E. Tschitschibabin, ibid., 3469 ; A., i, 778.34 A. von Baeyer, ibid., 2624 ; A., i, 641.25 Amer. Chenh. J., 1909, 42, 115; A., i, 650ORGANIC CHEMISTKY. 67open question, as has been done by several recent workers on thequinhydrones, these authors propose the following formula for thecoloured salts of phenolphthalein :C,H;CO,NaReference has been made in the last two Annual Reports to thenumerous instances of compounds yielding two or even moredifferently coloured series of metallic salts.I n many of these casesthere is some uncertainty as to whether the difference is due totrue chemical isomerism, or to the more subtle polymorphism, suchas is met with in the red and yellow modifications of mercuriciodide. Although a complete molecular explanation of colour mustundoubtedly account for even such cases, they are incapable ofexpression by the ordinary structural formulze. The numerousstructural differences assumed to exist between two series ofdifferently coloured alkali salts of the same compound are, as arule, unsupported by chemical evidence, and rest only on theobserved fact of a physical difference.Some further interesting observations have been made in thisclass.The o-nitrophenols are known to give both red and yellow saltswith alkalis.The salts with organic bases are, however, all yellow,and have nearly the same shade of colour, whilst the red alkalisalts vary greatly. The yellow alkali salts are labile, and yieldorange equilibrium mixtures in solution.26Colourless compounds, such as ethyl 2 : 4 : 6-trinitrophenyl-malonate, yield coloured compounds with sodium ethoxide, whichexist in a labile and a stable f o r d 7 As the additive compoundfrom nitroanthracene is colourless, it appears that, as in previousinstances, two nitro-groups must be in some way involved.The cyclic oximinoketones, of which violuric acid is a type,present an exh'aordinary complexity in the colour of their metallicderivatives. The colourless esters must be derivatives of +-violuricacid, but two series of coloured salts may be obtained.The changesof colour due to changes of temperature, solvent, etc., have beeninvestigated in a great number of cases.2826 A. Korczydslri, Ber., 1909, 42, 167 ; A . , i, 148.27 A. Haritzsch and N. Picton, ibid., 2119 ; A!., i, 467.2s A. Hantzsch, ibid., 966 ; A. Hantzsch and P. C. C. Isherwood, ihid., 986 ;A. Hantzsch and B. Issaias, ibid., 1000 ; A. Hantzsch and W. Kernmerich, ibid.,1007 ; A,, i, 331, 333, 338, 336.F 68 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The salts of violuric acid with organic amines are either blueor red, mixed salts often being obtained.29 One modification isfrequently labile, but there is no rule governing the direction ofthe spontaneous change, sometimes the blue and sometimes thered salt being the stable form.Violuric acid is coloured in solution,and not colourless, as described by Hartley. The colourless $-acidis present in increasing quantity as the temperature of the solutionis lowered.30The methiodides of many cyclic bases are coloured, althoughthe bases themselves are colourless. Hantzsch, from observationsof the colour of substituted acridonium and pyridinium compounds,concludes 31 that the colour is due to the formation of complexmolecules, probably united by means of the iodine atoms. Thus,5-phenyl-1 O-methylacridonium chloride is only slightly yellow, andproves to be unimolecular in chloroform solution, whilst theblackish-brown iodide is termolecular. The differences of colourpersist in the solid state, and occasionally modifications having adifferent colour niay be isolated in a labile form.Similarobservations have been made with pyridine methiodide, which isstrongly coloured and termolecular in chloroform solution,32 andwith the methiodide of ethyl cinchonate, which is red, becomingyellow on taking up water of crystallisation.33 The reduction of apyridine ring to piperidine causes the disappearance of the colour.Mechanism of Chemical Change.Succeeding a period of many years when the systematic study ofthis aspect of organic chemistry was confined to a few schools, agreat change is noticeable, and organic chemists can no longerbe reproached with neglect of this side of their subject. Many ofthe theories recently advanced are doubtless open to the criticismthat they are highly speculative, but this is inevitable in a newsubject so shrouded in obscurity, and the amount of harm that.may sometimes be done by an erroneous theory is usually out-weighed by the stimulus to research which is given by a happy hit.A problem is frequently unsolvable by direct attack, but satis-factory guiding principles may often be arrived a t by indirectmeans, or by a process of trial and error.The question of the mechanism of homogeneous catalysis by acidsis perhaps an example of such a problem, and this appears to beT.Zerewitinoff, Ber., 1909, 42, 4802.F. G. Donnaii and W. Schneider, Trans., 1909, 95, 956.&era, 1909, 42, 68 ; A., ii, 198.H. Decker and P.Remfrey, J. pr. Chenz., 1909, [ii], 79, 339 ; A., i, 408.32 C. I<. Tinkler, Trans., 1909, 95, 921ORGANIC CHEMISTRY. 69yielding, although very gradually, to combined attack from allpoints. I n connexion with that section of it which deals with themechanism of esterification in alcohol, the largest proportion ofcredit for recent advances must be assigned to H. Goldschmidt,whose work shows that this phenomenon is the exact counterpartof ester hydrolysis in water, and, so far as the catalyst only isconcerned, is mainly or wholly dependent on the ionised partof it. I n view of this result, it is impossible to follow Michael’s 34contention, that the non-ionised molecules of the catalyst form theintermediate complexes. All workers a t this subject are probablyagreed that a t an intermediate stage the catalyst, or part of it,forms a reactive complex, but it is not yet agreed whether it iswith the alcohol or the carboxylic acid in the first instance. It iseasy to show that kinetic experiments cannot distinguish betweenthese two possibilities, and the problem will no doubt be solvedby less direct evidence, such as the following.Acids act as catalysts at the ordinary temperature in innumerablereactions in which carbonyl compounds take part, and accelerate,or even bring about, a variety of changes in which aldehydes andketones as well as carboxylic acids and esters take part.Acetylationby acetic anhydride is greatly aided by traces of mineral acids.and this applies to the acetylation of amines 35 as well as alcohols,and the function of the catalyst is doubtless similar in all thesecases, but the significant feature here is the observation made byMiss Smith and ‘Orton that it is only with the weak bases that theaccelerating effect of the catalyst is marked; broadly, in other wordsit appears that the greater the opportunity for ammonium saltformation, the less is the influence of the catalyst.It is hardlyreasonable, therefore, to suppose that a salt of the amine is anecessary stage, and the only adternative is the initial formation ofa compound of catalyst and carboxylic acid. The analogy betweenammonium and oxonium salts (salts of amine and alcohol) suggeststhat the same conclusion holds true in the case of esterification.I n this connexion it is noteworthy that Michael considers that inesterification brought about by acid catalysts, the velocity ofreaction is conditioned by the affinity between these and thecarboxylic acid.36 I n view of this opinion and Goldschmidt’sexperiments, there is some hope that a general agreement is near athand.Direct proof is still wanting, however, that carboxylic acidsform ionisable complexes with mineral acids, and the aid of physical34 Ber., 1909, 42, 310 ; A . , ii, 219.95 Miss A. E. Smith and I(. J. P. Orton, Trans., 1909, 95, 1060 ; J . J. Blanksma,36 A. Michael, Bey., 1909, 42, 310 ; A., ii, 219.Chm. Weekblncl, 1909, 6, i 1 7 ; A . , i, 77970 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.chemists must be invoked t o suggest methods for deciding thisquestion.Attention has repeatedly been drawn to the fact that the processof direct esterification differs in many respects from the samephenomenon when effected by the agency of a catalyst, and isdoubtless regulated by a different mechanism.37The velocity of formation of carbamide from ammonium cyanatein aqueous solution was shown by Walker and Hambly to beproportional to the product of the concentrations of the ammoniumions and of the cyanate ions: NH,=+CNO=CO(NH,),.Thespecific inductive capacity of the medium in which the trans-formation occurs, however, is found to have no obvious effect onthe velocity, and it is suggested that the reaction occurs betweenfree ammonia and free cyanic acid.38 This view certainly leadsto the same expression for the reaction velocity:EC,[[N%l,][CNO’] = [NH4CNO] =K,[NH3][HCNO],and brings the reaction into line with the cases where an amine actson alkyl- and aryl-carbimides, as ionisation of the latter is excluded.a-Halogen substituted fatty acids are converted into thecorresponding hydroxy-compounds by water, and the evidence indi-cates that it is mainly the undissociated part of the acid whichis attacked by the water molecules.On the other hand, when thesodium salts are altered by water or alkali, it appears to be theanion which is mainly concerned, and here alkalis appear to belittle more efficient than water itself. This is attributed to thecircumstance that similar electrical charges on the anion and thehydroxyl ion result in a mutually repulsive effect.Silver salts inaqueous solution also attack the members of this group of acids,and, as in other cases, their behaviour is abnormal. Results suchas these promise to throw light on the mechanism of halogendisplacement, and in particular on the Walden inversion.39Alkyl iodides act on the anion of sodium thiosulphate, and theorder in reactivity of the halogen compounds corresponds withthat observed when they act on ethyl sodioacetoacetate, trimethyl-amine, and sodium ethoxide; in other words, the reaction belongsto the first type of Donnan and Miss Burke’s classification. It isconsidered possible that the iodides may exist in two molecularstates, but no definite suggestions as to the nature of these aremade.4037 A.Michael, Ber., 1909, 42, 310 ; A., ii, 219 ; A. Michael and K. J. Oechslin,Bey., 1909, 42, 317; A . , ii, 220 ; H. Goldschmidt, M. Asriel, V. K. Lund, and0. Udby, Zeitsch. Elelctrochem., 1909, 15, 4 ; A., ii, 129.33 A. Michael and H. Hibbert, Annalcn, 1909, 364, 129 ; A., i, 214.3R G. Sentcr, T~ans., 1909, 95, 1827.iD A. Slator and D. F. Tmiss, ibid., 93ORQANTC CHEMISTRY. 71The suhstances which undergo the phenomenon known as isomericchange may be divided into two classes, the first comprising thosein which the migrating atom or group cannot be shown to bereadily separable from the remainder of the molecule undergoingthe change, and the second those in which there is evidence of apossible divorce of the mutually labile portions of the moleculeduring the transformation.I n the first category may be placedthe Hofmann reaction and allied changes, the Beckmana change,the migration of alkyl groups in the pinacolin and similar trans-formations; and in these cases the failure of all efforts to discoverany separate existence of the migratory groups leads naturally tothe supposition that here true intramolecular changes of structuretake place; a t least the burden of proof must rest with those whowould deny the justness of this conclusion.The azoimides of acids yield carbimides and nitrogen when heated,the first published instance 41 of this transformation being that ofcinnamoylazoimide into cinnamenylcarbimide :CHPh:CH*CO*N, -+ CHPh:CH.NCO + N,,and other cases42 have since been described.To convert an acid into the carbimide, it is oiten only necessaryto heat the acid chloride in an indifferent solvent with commercialsodium azoimide until nitrogen ceases to be evolved.43The formation of alkylcarbamides from bromoamides and acidazoimides suggests the possibility that nitrile oxides are intermediateproducts, but in the opinion of those who have investigated thisquestion such a view is not tenable.44The wandering of a group from one atom to the adjacent onesuggests a change of two units in the valency of one of the lattera t the stage where migration occurs:X*A.B< -+ A:B*X or X*A:B -+ )A*B*X,and this hypothesis, although in no case an indispensable one, isnow frequently invoked in explanation of such changes.ThusStieglitz's plan for the Hofmann reaction is :R*CO*NBrNa -+ R*CO*N< -+ C0:N.R.I n excellent accord with such a proposition is the transformationof azibenzil (I) and of the sodium derivative of desyl chloride (11) 45into diphenylketen :M. 0. Forster, Trans., 1909, 95, 433.G. Schroeter, Ber., 1909, 42, 2336; A., i, 617 ; R. Stoermer, ibid., 3133; A.,i, 785.43 G. Schroeter, ibid., 3356 ; A., i, 773.44 G . Schroeter, ibid., 2336 ; A., j, 617 ; H. Wielnnd, ibid., 4207 ; A , , i, 923.4.5 G. Schroeter and C. Caspar, ibid., 2336 ; A . , i, 61772 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.NPh*CO*CPh<g -+ N, -I- Ph*CO*CPh< -+ CO:CPh,.(1.1(11.1Ph*CO*CPh<E: -+ NaCl+ Ph*CO*CPh< -+ COZCPb,.Numerous instances of the conversion of azimido-compounds intotetrazole or triazole, or of tetrazole into triazole, derivatives havebeen recorded.*e As in these and similar cases the migratorygroup is held by the remainder of the molecule a t two differentpoints, it is impossible t o decide the category to which they belong.The instance where phenyl appears to migrate in a triazole ring isadmittedly analogous to the reversible decomposition and reproduc-tion of diazoamino-compounds,*7 and may possibly be representedby a scheme such as:N- NPh\ m7TTin which case the migration of the phenyl group would be moreapparent than real.The second class of isomeric changes, namely, those in which themigratory atom or group may easily be removed in some formfrom the remainder of the molecule under conditions similar tothose obtaining during the transformation, includes the cases ofdesmotropic change, as in keto-enolic conversion, isomeric changein sulphonic acids, and numerous instances of migration of anatom or group from a position outside a benzene nucleus to a pointin the nucleus itself.I n such cases the labile isomeride has oftenbeen regarded as an intermediate product in the sense that thenuclesr-substituted form arises by an intramolecular or quasi-intramolecular transformation of the first, although the possibilityremained that the stable substance was produced by a separatesubstitution process, in which the agents were continuouslysupplied by the decomposition of the labile isomeride.A recentpaper marks an epoch in the development of these extremelydifficult inquiries. As the result of a long series of experiments,a conclusive decision has been given against intramolecular theoriesof the migration of halogen in substituted acylanilides :--f c~/\NHA~. /--\\-/ \-/ \NCIAc45 M. 0. Forster, Trans., 1909, 95, 184 ; R. StoIIB, J. pr. Chenz., 1908, [ii], 78,544 ; Ber., 1909, 42, 1047 ; A., i, 123, 337 ; H. von Pechmann and W. Bauer,Ber., 1909, 42, 659 ; A., i, 270.47 0. Dimroth, AnnaZen, 1909, 364, 183 ; A., i, 267ORGANIC CHEMISTRY. 73Armstrong’s view that hydrogen chloride is the active catalystis confirmed, but this substance acts in virtue of the fact that inits presence an equilibrium is set up, in which free chlorine isproduced :R*NClAc + HC1 t+ R-NHAc + Ch.The free chlorine ahtacks the anilide reversibly at the *NH*group, and irreversibly in the nucleus, so that finally the nuclear-substitution product alone remains. The quantitative evidence,although decisive, is too complicated to give in detaiL4*It is desirable to avoid the temptation to generalise from thisone case, and such attempts must now be worse than useless.Itdoes not follow, for example, that the change of hydrazobenzeneinto benzidine or of methylaniline into toluidine, etc., are not dueto true intramolecular migrations, so that each case must be decidedby sound experimental treatment, and a model is not far to seek.Amongst other isomeric rearrangements, the remarkable migra-tion of acyl groups in derivatives of phenols containing amino- orimino-groups is of great intrinsic importance, and derives additionalinterest from the part it has played in the controversy respectingthe constitution of hydroxyazo-compounds and quinonehydrazones.The conditions under which the migration takes place have beenstudied by A~wers,~g whose conclusions are based on a- large massof experimental material.The spontaneous migration of acyl fromoxygen to nitrogen always occurs when the nitrogen is in thea-, P-, or y-position in an ortho-side-chain, provided that thenitrogen atom is sufficiently basic. A reduction in the negativecharacter of the acyl group hinders the migration, but does notcompletely inhibit it. Benzoyl wanders less readily than acetyl,the difference being particularly marked in hydrazines when thea-position is blocked, so that migration, if occurring at all, mustbe to the P-nitrogen atom.When the a-position is already occupiedby an acyl group, the migrating group, if the heavier of the two,may displace the other. Thus acetyl is not only displaced fromCH2*NAc*NHph when X is benznyl, but also ox its position in R<in the presence of an alkali when X is propionyl.I n the simplest case,N H,*C,H,*OAc + NH A c*C,H,*OH,the reaction is not quite instantaneous, and it is occasionallypossible to isolate the intermediate O-ester. I f o-nitro-p-tolyl48 K. J. P. Orton and W. J. Jones, Trans., 1909, 95, 1456 ; Proc., 1909, 25, 233.49 K. Aumters, Ber., 1909, 42, 267 ; Annulen, 1909, 364, 147 ; 365, 278, 291,314, 343 : K.iluwers and F. Eisenlohr, ibid., 369, 209 ; A., i, 187, 222, 436, 437,439, 441, 91574 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.benzoate is reduced by zinc in acetic acid solution in presence ofacetic anhydride, the amino-group is acetylated as fast as it isformed, and the product is the O-ester, o-acetylamino-ptolylbenzoate, When this is treated with dilute alcoholic soda, theheavier benzoyl group displaces the acetyl, forming o-benzoylamino-p-cresol. A mere trace of alkali is often sufficient to initiate theisomeric change.Auwers interprets his results as indicating that the acyl migratesin a free state, a supposition which presents certain difficulties.The fact that the change is confined to ortho-compounds suggeststhe intermediate formation of a ring, and such an explanation wasput forward by McConnan and Titherley in 1906.A further studyof reactions of this class confirms this view.50 The change of 0-into N-benzoylsalicylamide is reversible, and is readily representableas occurring through the intermediate formation of a, hydroxy-metoxazone :the fact that phenyldihydro-1 : 3-benzoxazone is converted into'N-benzoylsalicylamide on oxidation proving the relationship of thisring to the acylated amide. Similar rings may be assumed in all theobserved cases. If the rearrangement were due to simple wander-ing of the free acyl groups, it is difficult to see why it should notoccur in many para-compounds.Isomeric change is often brought about by the influence of light.The change from yellow to red when many phenylhydrazones areexposed to light was attributed by Chattaway51 to the trans-formation of the hydrazone into its azo-isomeride, and thisconclusion was confirmed and extended by the spectroscopicobservations of Baly and Tuck.52 The occurrence of such photo-tropic changes in the hydrazone series is found to be very irregular,the only regularity found among a number examined being thatall the P-naphthylhydrazones are phototropic, but none of thea-series.53 The rapidity of change is greatly increased by thepresence of a small quantity of a non-phototropic substance, iso-morphous with that undergoing the change.54 For instance,anisaldehydephenylhydrazone, containing 1 per cent. of anisylidene-benzylamine, is more rapidly and more intensely coloured by lightthan the pure substance.The decolorisstion taking place in theA. W. Titherley and W. L. Hicks, Trans., 1909, 95, 908.51 Trans., 1906, 89, 462.53 M. Padoa and 3'. Grazinni, Atti h!. Accad. Lincei, 1909, [v], 18, ii, 269 ;A . , i, 964.74 M. Padoa, ibid., i, 694 ; A., i, 676.5z Ibid., 982ORGANIC CHEMISTRY. 75dark is usually accelerated by the presencc of an isomorphousadmixture.Salicylidene-m-toluidine, OH*C6H,*CH:N*C,H,Me, and four othercompounds of the same group, are found to change from yellow toorange on exposure to light, the violet rays being the active agency,but no regularity in the exhibition of phototropy in the group hasbeen disc~vered.~s The replacement of the hydroxylic hydrogen bymethyl, however, destroys the phototropic properties.The changein darkness is the reverse of that in the light.The diphenyloctatetrenes 56 and the stereoisomeric as-diphenyl-ethylene, CPh,:CH,,57 are other new examples of phototropic sub-stances, the transformation in the latter case being the reverse ofthat brought about by heating.Determination of the Constitution of Tautomeric Compounds.The use of tertiary amines 58 for distinguishing between acids andpseudo-acids has been applied in two interesting investigations.One of these deals with the structure of hydrogen cyanide, whichis found not to yield salts with tertiary amines a t Oo, but merelyto polymerise, although trialkylammonium cyanides are known tobe capable of existence.Primary and secondary amines, however,do yield unstable salts; and it is argued that these bring abouta structural change in the hydrogen cyanide, the salts beingderived from the tautomeric form. The imidic structureC:NH or CiNH is deduced from general consideration to be thatof the true acid, so that hydrogen cyanide itself is H-CIN, orformonitrile.59 The communication is a useful contribution to thealready somewhat voluminous literature on this subject, and it issatisfactory to note that the results help to strengthen the viewwhich has been adopted by most recent workers on the subject.A similar investigation on cyanic acid was more difficult, owingdoubtless to the greater " affinity" of the acidic form.Mosttertiary amines give cyanates with this compound, together withsome cyamelide, but triisoamylamine does not give any salt onmixing with the acid at -loo. The triisoamylamine salt, preparedin another way, is found to be quite stable under the conditionsemployed, and it is therefore concluded that free " cyanic " acidhas the pseudo-acid or imido-configuration, CO:NH, the salts beingderived from CN*OH.55 A. Senier and F. G. Shepheard, Trans., 1909, 95, 441, 1943.w R. Stoermer, ibid., 4865.n8 Aim. Report, 1908, 90.59 A. Mich:Lel and H. Hibbert, Annnleit, 1909, 364, 64 ; A., i, 91.H. Stobbe, Ber., 1909, 42, 565 ; A., i, 21976 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Catalytic Actions of Metals and Inorganic Substances.The methods introduced by Sabatier and Senderens have beenextended within the last two years, and catalytic action at hightemperatures can now be utilised for prgparations which involveprocesses of reduction, hydration, dehydration, oxidation, andelimination of halogen hydride.There is no reason to doubt thatthe method is capable of still wider application.It has been recorded in a previous report60 that a t 300° alcoholis decomposed by the catalytic action of alumina, yielding ethylene ;it has since been observed61 that a t somewhat lower temperatures,namely, between 240° and 260°, and employing an alumina obtainedby adding acid to a solution of sodium aluminate, the dehydrationprocess results in the quantitative production of nearly pure ether.A good yield of methyl ether is obtained by the same process a t250-370°, whilst propyl alcohol behaves in a different manner,being mainly converted into an ethylenic hydrocarbon, only 30 percent.being transformed into dipropyl ether ; isobutyl alcohol yieldsisobutylene exclusively.Heated alumina converts acetic anhydride a t 300-380° intoacetone and carbon dioxide, and if anhydrous thorium dioxide issubstituted for alumina, the preparation of ketones from the higheracid anhydrides is readily accomplished. Even with the free acidsa t 400° it has been found possible to prepare diethyl ketone,dipropyl ketone, and diisopropyl ketone. Formaldehyde and carbondioxide are the products when formic acid is passed over thoriumdioxide a t 200-250°.62Senderens has studied the mechanism of the process,63 and con-cludes that a salt is formed from the acid and the metallic oxide,which is then decomposed.Although thorium oxide is the most suitable contact material,the oxides of uranium give very good results.It seems essentialthat the speed of salt-formation and decomposition should not differvery greatly, consequently, very feebly basic oxides, such as thoseof iron, aluminium, and chromium, or too strongly basic ones, suchas those of calcium or zinc, do not give satisfactory results.Primary aliphatic alcohols may be converted into amines whenin contact with ammonia and oxides, such as thorium dioxide ortungsten trioxide, a t high temperatures.64do Ann. .&port, 1908, 77.61 J.B. Senderens, Compt. remi., 1909, 148, 927 ; A , , i, 286.62 J. B. Senderens, Zoc. cit.63 Cosnpt. rend., 1909, 149, 233 ; A . , i, 627.P. Sabatier and A. Mailhe, ibid., 148, 898 ; A . , i, 292ORGANIC CHEMISTRY. 7 7Another novel use of contact reaction, a t high temperatures, isin the preparation of aromatic nitro-compounds.65 It is found thatzinc and copper oxides readily absorb nitrous fumes, and if amixture of air and the vapour of an aromatic hydrocarbon ispassed over the product a t 300-350°, nitration takes place. Nitro-benzene, for example, is obtained in quantitative yield by usingnitrous fumes produced by electrical methods from the atmosphere,and by combining the process with the reduction method of Sabatier,a method is devised for the direct and continuous production ofaniline from benzene.The employment of nickel oxide with hydrogen under highpressures has been found to be the most efficient means of fullyreducing polynuclear hydrocarbons. Fluorene is reduced a t 285Oand 120 atmospheres to decahydrofluorene, and finally to perhydro-fluorene, and acenaphthene yields successively tetra- and deca-hydro-acenaphthene.Retene furnishes first the dodecahydro-derivative,and finally perhydroretene.66An interesting synthesis of ethylene from carbon monoxide andhydrogen has been accomplished a t comparatively low temperatures,use being made of reduced nickel distributed on coke a t 95-looo;6 to 8 per cent. of ethylene is obtained, without any trace offormaldehyde. Contrasted with the usual results obtained by thecatalytic reduction process, this result is decidedly abnormal, asthe formation of methane would be expected.Formaldehyde wasalso absent when carbon dioxide was reduced, and in this case bothethylene and methane were formed.67Mention was made in last year’s report 68 of the discovery of thepowerful reducing effect at the ordinary temperature of hydrogen inpresence of E,alladium hydrosol, and the work has been considerablyextended.69 I n one particular the method has advantages over allother reduction processes, namely, in the preparation of saturatedketones from their ap-unsaturated derivatives,70 for the latter, whensubjected to the action of other reducing agents, usually yieldalcohols or pinacones.Allied to the foregoing method is that recently used for reducingphenanthrene; here hydrogen was led into a boiling etherealsolution of the hydrocarbon in presence of platinum-black, whenti5 Cheniische Fabrik Grunan Lsndshoff & Meyer Akt.-Ges., D.R.-P.207170 ;A., i, 295.W. N. Ipatieff, Ber., 1909, 42, 2092 and 2097 ; A., i, 466 and 472.67 E. I. Orloff, J. Iztiss. Phys. Cfzern. SOL, 1908, 40, 1588 ; A., i, 77.6J Arm. Report, 1908, 76.69 C. Paal and li. Roth, Ber., 1909, 42, 1541 ; C. Paal and J. Geium, ibid.70 A. Skita, ibid., 1627 ; A., i, 479.1553; C. Paal and W. Hartniann, ibid., 545; A., i: 358, 381, 54578 ANNUAL REPOKTS ON THE PROGRESS OF CHEMISTRY.in six to eight hours nearly pure 9 : 10-dihydrophenanthreae wasobtained. The reaction also took place at the ordinary temperature,but required some two days to reach c0mpletion.7~Practical Methods and General Reactions.When carbon dioxide is passed into aqueous solutions of alcohols,simple or polyhydric sugars, or other hydroxy-compounds inpresence of lime, soluble calcium double salts of the type(R*O*CO,),Ca are formed.These are unstable, however, anddecompose when heated ; in solution they are only capable of existingin equilibrium with their generators or dissociation pr0ducts.7~A useful method of obtaining an aldehyde from the correspond-ing acid chloride consists in first converting the latter into theacid cyanide by Claisen's method, and then, from the a-carboxylicacid which this furnishes on hydrolysis, the phenylimideof the aldehyde is prepared by boiling with aniline in accordancewith Bouveault's directions, and is decomposed by dilnte sulphuricacid into aldehyde and aniline73:R*C'O*C1-+ R*CO*CN --3 R*CO*CO,H -+ R*C:NPh -+ R*CHO.The preparation of acraldehyde,, hitherto a tedious and disagree-able operation, is much simplified if orthophosphoric acid, withsodium chloride, is used as dehydrating agent.The materials usedneed not be very dry, large quantities may be employed, and theoperation may be conducted on a water-bath.74 The use of ortho-phosphoric acid as a dehydrating catalyst in preparative work ismost advantageous, owing to the absence of carbonising effects, butit does not yet seem to have been sufficiently fully investigated, inspite of the striking demonstration of its utility given by Newthsome years ago.When aldehydes are made from most primary alcohols by meansof a solution of chromio anhydride on acetic acid, poor yields areobtained, owing t.0 the formation of acetates derived from theenolic forms of the aldehydes : >C:CH=OAc. These enolic aldehydeacetates may also be prepared by boiling the aldehydes with aceticanhydride ; in this manner, for example, phenylacetaldehyde givesrise to phenylvinyl acetate :C,H,*CH,*CHO -+ C,H,GH:CH*OA~.7l J.Schmidt and E. Fraser, Ber.; 1908, 41, 4225 ; A . , i, 19.'i2 M. Siegfried and S. Howwjanz, Zeitsch. physiol. Chem., 1909, 59, 376 ;73 F. Mauthner, Ber., 1909, 42, 188 ; A., i, 160 ; compare L.Bouvenult, Conapt.74 G . F. Bergh, J. pr. Chem., 1909, [ii], 79, 351 ; A , , i, 363.A., i, 352.wrzd., 1896, 122, 1543; A., 1896, i, 649ORGANIC CHEMISTRY. 79The acetates are easily oxidised by ozone, so that the discoveryprovides a novel method for the degradation of aldehyde^,'^ andone instance where important results have been obtained in apply-ing it is dealt with in the section on the terpenes.Aldehydes form hydroxamic acids with benzenesulphohydroxamicacid and sodium hydroxide, and this forms a good distinctionbetween aldehydes and other compounds :R*CH:O + HO*NH*SO, h --+ R=C(OH):NOH + SO,H*Ph.It is interesting that y-hydroxyaldehydes, such as erythrose orarabinose, do not respond, owing to the engagement of the carbonylgroup in ring formation, and as y- and 6-hydroxy-, -keto-, and-amino-aldehydes give negative results too,- a similar ring structuremay be present in these ; hydroxymethylene compounds, also, givenegative results.76Sulphur monochloride, S,Cl,, acts on the sodium salts of carboxylicacids suspended in petroleum, and appears to yield compounds inwhich S, replaces the hydrogen of two molecules of the acid; forexample, sodium benzoate yields a compound which is probably(C,H,-C02*S)z.These compounds decompose readily, and sometimesspontaneously, the products being sulphur, sulphur dioxide, andthe acid anh~dride.~7Oxalyl chloride proves to be an interesting synthetic reagent,resembling carbonyl chloride in many of its reactions. Thus, itcondenses with dimethylaniline to form p-tetramethyldiaminobenzil,NMe,-C,H4*CO*CO*C,H4*NMe,.78 In other cases it behaves as achlorinating agent, resembling phosphorus pentachloride :R1R2C0 + COCl-COCl= R1R2CC12 + CO + C02.70Alkyl chlorocarbonates are found to be convenient alkylatingagents in a number of cases.The mixed carbonic esters of phenolslose carbon dioxide on heating, and pass into alkyl ethers ofphenols : Ar*O*CO-OR = CO, + Ar0O.R. This is a general reaction,although not always taking place with equal readiness.80 The samereagents may be employed to esterify carboxylic acids, the mixedanhydrides, R.CO*O-CO*Rl, formed a t first decomposing spon-taneously. 81The use of derivatives for the protection of hydroxyl groupsi6 A. Angeli and G. Marchetti, Atti R.Accad. Lincei, 1908, [v], 17, ii, 360 :n W. S. Denham, Trans., 1909, 95, 1235.78 H. Staudinger and H. Stockinann, Ber., 1909, 42, 3485 ; A , , i, 796.H. Staudinger, ibid., 3966 ; A , i, 905.8o A. Einhorn, ibid., 2237, 2772 ; A., i, 568, 645.81 J. Herzog, ibid., 2557 ; A., i, 568.F. W. Semmler, Ber., 1909, 42, 584, 1161 ; A., i, 239, 364.A., i, 1280 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.during the condensation of acids to form poIypeptides was intro-duced by Fischer, and has found numerous applications. The con-densation of methyl chlorocarbonate with salicylic acid does nottake place under the usual conditions, but is readily accomplishedin presence of dimethylaniline.82A new series of oxidising agents, which may prove valuable onaccount of the smoothness with which they react, consists of thenitrates of aldehydes and ketones.83 Anthracene, for example, maybe dissolved in benzaldehyde nitrate by gently warming, and pureanthraquinone crystallises on cooling.Borneo1 is oxidised tocamphor.True nitroso-compounds, containing the group :CH*NO, areusually difficult to obtain, owing to the ease with which thisstructure undergoes change into the isomeric oxime group,:C:N-OH. A simple and general method for the preparation ofa-nitroso-esters consists in passing nitrous fumes from nitric acidand arsenious anhydride into P-ketonic esters at O o :CH,*CO*CHR*CO,Et -+ NO*CHR*CO,Et.The esters are blue liquids, often unstable to light, and are rapidlychanged by water or alkalis, the colour disappearing owing toconversion into oximino-compounds, or, in part, to polymerisation.With Caro's reagent or hydrogen peroxide, they are converted intothe corresponding nitro-e~ters.8~Carbolqdrates and their Allies.The aldepentoses and aldehexoses may be divided into fourgroups, according to the configuration of the three carbon atomswhich are adjacent to the terminal *CHO group, and it is possibleto ascertain in a simple manner the class to which any particularsugar must be referred.The sugar is condensed with chloral, andthe product, its " chloralose," is examined; if this is found identicalwith one of those already known, the class to which the aldosebelongs is decided. If not, the chloralose is oxidised; chloralicacids (I) are obtained-substances which contain only five of theoriginal carbon atoms of the sugar, the terminal carbon atoms ofthe hexose molecule remote from the *CHO group having dis-appeared :QH * CH( OH).O*~H*CCl,O<CH--- C(0H) C0,H'(J.)m E. Fischer, Ber., 1909, 42, 215 ; A., i, 161.83 A. A. Shukoff, D.R.-P. 206695; A., i, 238.84 J. Schmidt and K. T. Widmann, Ber., 1909, 42, 497, 1886 ; A , , i, 134, 453ORGANIC CHEMlSTRY. 81Four isomerides are theoretically capable of existence, correspond-ing with the four above groups of aldoses, and the identity of theproducts from any sugar determines the series to which it belongs.All the isomerides have been described except that correspondingwith talose and ribose. As an instance of the manner in whichthe method may be applied, it may be stated that arabinose yieldstwo such chloralic acids, and one of these is identical with one ofthe pair which is furnished by galactose; a similar partial identityis observed in the acids obtained respectively from xylose anddextrose.85A suggestive method, probably capable of wide application, forattacking the certain questions arising in the study of sugarderivatives depends on the principle that methylation of the freehydroxyl groups protects these from attack during subsequentoperations. Thus the constitution of the condensation product oflaevulose with acetone has been shown, with some degree of certainty,to be represented by (I):7 0 - 1~H,*~H,*~H*~H*CH*CH,.OH0 0 0 0\/ \/CMe, CMe,and (11)obtainedis the most probable structure for the monomethyllzevulosefrom it by hydrolysis, the evidence being that the lattersubstance yields, on d l d oxidation, an acid which has the com-position of dihydroxydirnethoxybutyric acid, but is incapable offorming a lactone.86It is interesting that a-monomethyllmulose gives a positive resultwith tthe Tollens test, which was supposed to be applicable onlyto pentoses.Biologically the synthesis of sugars from formaldehyde is areversible process, but hitherto the question of the artificial pro-duction of formaldehydes from a sugar by a simple chemical processa t the ordinary temperature has not been closely investigated. Theelectrolysis of dextrose solutions in dilute sulphuric acid leads to achange, which is the inverse of the type of the usual syntheticprocess : =CHCOH)*CH:O = -CH:O + CH,:Q, and formaldehyde,d-arabinose, and oxidation products are found in the resultingSFi M.Hanriot, Cow@. rend., 1909, 148, 487, 640 ; A., i, 206, 287.86 J. C. Irvine and A. Hynd, Trans., 1909, 95, 1220.REP. -VOL. VI. 82 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.solutions. I n association with the fact that pure glycerose has beenobserved to yield a pentose when condensed, pointing to de-polymerisation of the glycerose in the above sense, the observationis a very significant one, and suggests new lines of attack on theproblems relating to the manner in which the organism attacks itsf aods in building new molecular complexes.87Definite light has been thrown on the configuration of fucose byoxidising it with dilute nitric acid, when a trihydroxyglutaric acidis obtained, which is the optical antipode of that which rhamnosewith known constitution yields in similar circumstances. The con-figuration of fucose 88 is therefore (I) :H H OHi)H bH H(1.1A novel synthetic method for the preparation of disaccharides hasproved successful in a t least one instance, and promises to be ofgreat importance. A substance of the type of trehalose is the firstto be prepared by this process, which consists in shaking P-aceto-dextrose in moist ether with silver carbonate, or by agitating asolution of the tetracetylaldose with phosphoric oxide.The result-ing octa-acetyldisaccharide is easily hydrolysed by baryta water,yielding the new sugar, in this case isotrehalose, C12H2201,, whichdoes not reduce Fehling’s solution, and yields dextrose on hydrolysiswith a~ids.8~Investigations on the physical properties of the carbohydrates ofhigh molecular weight have led to numerous striking observations,and among the most interesting of these is the discovery that themolecular volume of soluble starch is only about nine-tenths ofthat calculated on Traube’s data for the formula C6H1005, althoughthe observed value for solid anhydrous starch, on the other hand,is nearly the normal one.The suggestion is advanced by Cross andBevaqg0 and supported by M. Traube, that the anomalous valuefor soluble starch is to be accounted for by the occurrence of ringformation.Recent investigations on the composition of the products termed‘( cellulose hydrates,” including mercerised cellulose, indicate thatwhen freed from all traces of hygroscopic moisture, these substanceshave the same composition as ordinary cellulose, namely, (C6H1005)2L ;87 Ti-.Liib, Biochem. Zeitsch., 1909, 17, 132, 343, 516 ; A . , i, 352, 456, 767 ;compare also Ann. Report, 1908, 88.88 R. TolIens and F. Rorive, Ber., 1909, 42, 2009 ; A., i, 555.89 E. Fischer and I<. Delbruck, ibid., 3776 ; A., i, 533.C. F. Cross and E. J. Bevan, ibid., 2198, 2204 ; A,, i, 555.CH,~CH(OH)~~---&--~CHOORGANIC CHEMISTRY. 83those termed ‘‘ hydrocelluloses,” on the other hand, appear. tocontain chemically combined water, and in this sense are truecellulose hydrates, analogous in composition to the more complexproducts of starch hydrolysis.91Before concluding this chapter, attention may be drawn toexperiments showing that (‘ 8-hydroxy-methylf furfuraldehyde ” isformed by the dry distillation of hexoses or on heating thesecompounds with dilute acids,g2 ketoses yielding a larger proportionthan aldoses.The substance has often been mistaken for furfur-aldehyde, and it plays an important part in certain well-knowntests. The observations recall Fenton’s work on bromomethyl-furfuraldehyde, to which the hydroxyaldehyde is closely related,and the most recent evidence tends to show that the hydroxyl groupin the latter replaces a hydrogen atom in the methyl group, andnot one in the ring?3 as is usually assumed.Ketens.Researches in the keten series have not been very numerous.The conditions of formation of keten from a-halogenated acetylhalides have been investigated,94 and a comparison of the productsof polymerisation of ketens has led t o the conclusion 95 that thebimolecular compound described 96 as acetylketen, CH,*CO:CH:CO,is really a cyclic compound, O:C<-cd>C*OH, its chemicalinertness being opposed to the open-chain formula.CHEthyl ethylketencarboxylate, co2~~>C:C0, differs greatly fromthe other disubstituted ketens, being colourless and incapable offorming additive compounds.97 It readily polymerises to form acyclobutane derivative, and in its properties resembles rather thealdo-ketens, with only one substituting group, t,han the keto-ketens.I n the action of fatty triamines on isobutyryl chloride, dimethyl-keten is first formed, polymerising immediately to 1 : S-diketotetra-methylcyclobutane, CMe,<EE>CMe,, and an additive com-pound, Cn/Ie,:CO,NEt,, is formed at the same time.g5 SeveralDl H.Ost arid I?. Wcsthoff, Clmn. Zeit., 1909, 33, 197 ; A . , j, 210.w W. Albc-rda van Ekenstciii anti J. J. Blnnksma, C‘he%z. 7FeekbZad, 1909, 6,217 ; d., i, 288.H. J. 13. Feuto11 and V. BoLinson, T?raizs., 1909, 95, 1334.H. Stautlinger and J. Kubinsky, Ber., 1909, 42, 4213 ; A., i, 880.m H. Staudinger and S. Bereza, Ber., 1909, 42, 4908.yti Ann. Report, 1908, 84.y7 Staudinger and Bereza, Zoc. cit.9s E. ‘Wedekind and 31.Miller, L’er., 1909, 42, 1269 ; if., i, -150.G 84 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.compounds of similar composition have been obtained, and havebeen found to have very great stability, entirely unlike the pre-viously known keten bases, which have all the characters of mereadditive products. The reactions of the new “ ketenium” com-pounds point rather to a cyclic structure, it being impossible todecide at present between the alternatives :R,C--C:O R,C. C-0.\/NEt,\/ andNEtFuroxam, b’itrile Oxides, and FuZrninic Acid.Among the heterocyclic rings which contain nitrogen directlyattached t.0 oxygen, and are thus derived from hydroxylamine ordihydroxylamine, the so-called “ glyoxime peroxides ” are a t presentevoking much interest.According to Wieland and his co-workers,Dgthese are in reality derivatives of furoxan (11), which is an oxideof furazan (111), the structure previously attributed to “ glyoximeperoxide ” being represented by (I) :$H--EHN*O*O*N SH-EH N*O*N(1.1 (11. ) (111.)Furoxans may be formed by polymerisation of nitrile oxides, towhich Wieland attributes the general formula /’\ The firstrepresentative of this series, benzonitrile oxide, was originallyobtained by Werner on removing the elements of hydrogen chloridefrom benzhydroximic chloride :0R*C=NPh*CCl:NOH -+ Ph*CNO + HCI.A more general reaction for preparing these substances in atermolecular form is offered by the mode of spontaneous decom-position in solution of the alkali salts of the nitrolic acids:NO,*CR:NOH = HNO, + R-CNO.In this manner, termolecular oxides of formonitrile, acetonitrile,and benzonitrile are formed readily enough.Their reactions closelyresemble those of benzonitrile oxide itself, and they are prone toundergo transformations which recall the well-known Hofmannchange which bromoamides undergo in presence of alkali; thus thephenyl derivative in hot xylene is quantitatively converted intophenylcarbimide : (PhOCNO), = SPh*N:C:O.H. Wieland and L. Seniper, Annalen, 1907, 358, 36 ; H. Wieland andA. Gmelin, Ber., 1908, 41, 3512 ; ibid., 1909, 367, 52 and 80 ; A., 1908, i, 108,1013 ; 1909, i, 609 and 610 ; Ann. Reprt, 1907, 161.Compare Ann. Eeport, 1907, 138ORGANIC CHEMISTRY’. 85Analogies are drawn between cyanuric acid (I) and the ter-molecular nitrile oxides, for which the formula (11) is suggested :co CR-0HN/\N€I N-/\N/oc()co O<RG(JC\nN H N-0(1.) (11.)There is a close relationship between the nitrile oxides andfulminic acid, on the one hand, and furoxans (or glyoximeperoxides ”) on the other.Benzonitrile oxide, whea forrned by thespontaneous decomposition of benzylnitrolic acid, polymerises todiphenylfuroxan :--3 2CPh:N0\/$Ph*CPhN-O-N- ’ >o,but methylnitrolic acid, in similar circumstances, gives rise tofulminic acid :CH:N\/ --f C:N*OH.0A further connexion between fulminic acid and the furcxanshas been elicited by a recent investigation of the substance whichKekul6 obtained from bromine and mercury fulminate. This sub-stance, long known as (‘ dibromonitroacetonitrile,” appears in realityto be dibromofuroxan :which is attested by the ease with which it yields oximino-derivatives of oxamide with ammonia and organic bases.2Fulminic acid is found to be soluble in ether, and also to bevolatile in the vapour of that liquid a t low temperatures.Metafulminuric (isocyanuric) acid is the sole product of its spontaneouspolymerisation, and for this polymeride the formulaCH*$XN*OH*%---C:N*oHis adopted as the most satisfactory one in view of the most recent?evidence.3H. Wieland, Ber., 1909, 42, 803, 816, 820, 4199 ; H. Wieland and H. Hew,H. Wielnad and H. Hess, ibid., 43, 1346; A . , ii, 369.ibid., 4175, 4199 ; A . , i, 215, 216, 217, 882, 8S486 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Proteins, Polypeptides, and Amino-acids.I n this section of organic chemistry the progress is very steady,and there are signs that before long the intricacy of this subjectmay challenge comparison with that of colouring matters.Therecognition of the component groups and their mode of attachmentin natural materials probably occupies first place in the estimationof chemists, and whether the methods are analytic or synthetic isof small consequence provided that they are trustworthy.Abderhalden’s work on the proteins has already attracted muchattention, and among his interesting communications during theyear, one on the products of partial hydrolysis of certain proteins isunusually suggestive, although not altogether novel in principle.*He proposes t o undertake systematic researches on the products ofthe partial hydrolysis of complicated proteins, and to separate andexamine the intermediate products, with a view to ascertainingwhat is the structure of each.I n other words, he intends toexamine the structure of each by finding the way in which theultimate residues are linked in pairs or trios.He has already made preliminary examinations of several com-plicated proteins in this manner, including edestin. This furnishesthree polypeptides, of wliich one contained the residues of glutamicacid and trytophan, another those of glutamic acid, tryptophan,and leucine, and the last those of tyrosine, glycine, and leucine.I n this connexion Mathieu suggests measuring the speed of hydro-lysis of proteins by acids.With gelatin, “breaks” are found inthe curve obtained, which are considered to indicate successivestages in the hydrolysis. Numerous communications on the com-position and cleavage products of natural proteins by acids haveappeared, and the use of hydrofluoric acid in this connexion is beingcarefully examined.5 The dilute acid yields, according to the con-ditions imposed, varying proportions of diamines and amorphouspolypeptides ; the latter in certain instances give crystalline picrates.The method has been applied to pepsin extract and gelatin withdefinite results, and as the acid does not give rise to condensationof the simpler molecules, it is concluded that the products of partialhydrolysis represent pre-existing natural complexes.Importantdevelopment along these lines may be expected in the near future.The action of cold alkalis on the prot“eins has also given someinteresting results. It is found that certain protamines undergo aE. Abderhalden, Zeitsch. p h y s d Chem., 1909, 58, 373, and 62, 315 ; A . , i, 273,L. Hugounenq and A. Morel, Cmnpt. rend., 1909, 148, 236, and 149, 41 ;859.A . , i, 195, 685ORGANIC CHEMISTRY. 87diminution in rotatory powers, probably in the main a result ofracemisation, although hydrolysis can be detected< when the actionof the alkali is prolonged a t higher temperatures.6A novel method for isolating the monoamino-acids obtained inthe hydrolysis of the proteins has been suggested, depending on thefact that their betaines, unlike those of the diamines or polypeptides,are easily prepared by methylation and form characteristic auri-chlorides which are very easily isolated.7The synthetic production of polypeptides is being pushed on withundiminished vigour, but only a short reference to some of theresults can be given here.Starting with the products obtained by the action of phosphoruspentachloride on benzoylpiperidine, Braun has succeeded in effectinga new synthesis of inactive lysine.8 By similar methods, E.Fischerand G. Zempl6n have synthesised ornithuric acid (dibenzoyl-a8-diaminovaleric acid) and proline 9 from piperidine, and theseauthors have also resolved proline into its optically active isomerides.A variety of synthetic polypeptides with Z-leucine, a-alanine,glycine, Z-cystine, glutamic acid, and other residues have beendescribed.1°An interesting group of natural vegetable acids, for which thename “etholides” is proposed, is found in certain Conifem.Themembers resemble the polypeptides in their structure, but theunits are linked by oxygen instead of nitrogen. They are, in otherwords, systems of condensed hydroxy-acids, and their general struc-ture may be represented as:R~CH(OH)*[CH2],~CO*O~CHR’~[CH2]~*CO~0*CHR’’~[CH,I. . . .CO,H,when R, R’, R”, etc., and n, m, p , etc., may or may not beidentical.11 ’Put ref act ion of A mho-acids.It will be remembered that amino-acids are converted by yeastsinto the next lower alcohols with loss of ammonia and carbondioxide.During the putrefaction of such compounds, on the otherhand, the amino-group may be replaced by hydrogen instead of byhydroxyl, with or without loss of the carboxyl group. Asparticacid first loses its amino-group and gives succinic acid, whichA. Kossel and F. Weiss, Zeitscfi. physiol. Chem., 1909, 59, 492; 60, 311 ;A., i, 542.7 R. Engeland, Ber., 1909, 42,,2962 ; A., i, 856.8 J. von Braun, ibid., 839 ; A., i, 229.10 E. Fischer and J. Steingroever, AnnaZen, 1909, 365, 167 ; E. Fischer and0. Gerngroas, Ber., 1909, 42, 1485 ; A., i, 366 and 367, etc.11 J. Bougault and L. Bourdier, Compt. rend., 1908, 147, 1311 ; A,, i, 82.Ber., 1909, 42, 1022; A., i, 30388 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY,afterwards furnishes carbon dioxide and propionic acid ; glutamicacid is converted into butyric acid.12Similarly, tyrosine gives rise to p-hydroxyphenylethylamine.13a-Amino-acids, containing primary or secondary amino-groups,yield chloroamino-derivatives with solutions of hypochlorites, whichat 40-50° are converted into the aliphatic aldehydes, or aldehydeswith one carbon atom less than the original amin0-a~id.l~The other products are ammonia or a primary amine and carbondioxide :NHR*CR’R”*CO,H -+ NRC1.C R‘R”*CO,Na --+NHR + R’*CO*R” + 00, + NaC1.This discovery promises not only to furnish a novel method forobtaining ketones and aldehydes from natural amino-acids, butmay also prove to be of considerable value in determining the con-stitution of new amino-acids and in discriminating between theseand various polypeptides.aydroaromatic Compounds.Recent controversies on the terpinenes and on substituted di-hydrobenzenes illustrate the very considerable difficulties whichbeset the path of the experimenter in this field, and it is evidentthat hydroaromatic compounds are exceptionally labile, so thatevidence as to constitution must be based on methods which admitof no possibility of structural change ; moreover, genera1isat;ions areequally dangerous. A compound to which the constitution 1: l-di-methyl-A2:5-~ycZohexadiene was ascribed by Harries and Antoni 15on apparently quite reasonable grounds, has recently been shown tobe a mixture of 1 : 2- and 1 : 3-dimethylcycZohexadienes.1~Previous results had suggested that when either of the methylgroups of the complex :CMe, migrate, they are afterwards foundattached to adjacent carbon atoms, but the appearance of the1: 3-dimethyl derivative in the above mixture shows that the ruleis not an infallible one.The behaviour of benzene derivatives when subject to the actionof reducing agents is capricious. Thus, m-hydroxybenzoic acidsyield the hexahydro-derivatives quite readily with sodium and amylalcohol, but those acids which contain the hydroxyl and carbonylgroups in the pa,ra-position are not appreciably changed under thesel2 L.Borchardt, Zeilsch. physiol. Chem., 1909, 59, 96 ; A . , i, 210.l 3 G. Barger, ibzd., 1908, 61, 188 ; A., i, 701.l4 K. Langheld, Ber., 1909, 42, 392, 2360; A., i, 138, 557.l5 A?tna,len, 1903, 328, 88 ; A ., 1903, i, 613.l6 A. W. Crossley and Miss N. Renouf, Y’rans., 1909, 95, 930ORGANIC CHEMISTRY. 89conditions,l7 and the explanation of this is not yet forthcoming.The o-hydroxybenzoic acids, as is well known, are converted by ringfission into derivatives of adipic acid.The odour of violets, which is associated with certain aldehydescontaining the group :C:~*CHO, has been the subject of a lengthyseries of investigations. Various aldehydes were prepared, includingthe following :CMe, CMe, C Me,H,C/\CH, /\CH, CHO*C/\CH,HCII bHMeCHO.C(,,!CHM~ ".'."b)CHM* \/CH c-CHO CH2(1.) (11.) (111.)From the results it is concluded that for an aldehyde to possessthe perfume of violets (a) it must contain the cyclogeraniolene ring,( b ) the aldehyde group must be in the ortho-posit"lon with referenceto it methyl group or a dimethyl group, and if it lies betweenthem, and therefore is ortho to both, the odour is intense.18The relative stabilities of saturated carbon rings are in fairaccordance with the requirements of Baeyer's strain theory, althoughit does not supply a full explanation of all the facts.Recentobservations tend, on the whole, to strengthen the view that thesaturated pentamethylane ring is the most stable one. The caseof unsaturated rings is not so simple, and a t present no generalrule can be drawn.When ethyl pentane-a@k-tetracarboxylate,CO,Et* CHz*C( COZE t)z*CH2.CHz*CH2*CO2Et,reacts with sodium, it furnishes a cyclohexane derivative (I),although it might equally well have yielded a cyclopentanederivative (II).19CO,Et.c<cq.CJ3, C(oNa)->C(C0,Et)*CH2*C0,EtAgain, in the cyclic condensation of diketones, it appears that theunsaturated five-carbon ring is most easily produced, the six-carbon(11.1l7 0.Baudisch, G . S. Hibbert, and W. H. Perkin, jun., Trans., 1909, 95, 1870 ;0. Baudisch and W. H. Perkin, jun., ibid., 1883; A. N. Meldrum and W. H.Perkin, jun., ibid., 1889.l* G. Merling, R. Welde, H. Eichwede, and A. Skita, Aitnalelt, 1909, 366, 119 ;A . , i, 479.l9 Miss M. E. Dobson, J. Ferns, and W. H, Perkin, jun., Trans,, 1909, 95, 201090 ANKUAL REPORTS ON THE PROGRESS OF CHEMISTRY.ring with difficulty, whilst the formation of a seven-carbon ring hasnot yet been observed.2OSeven-membered rings, containing an atom of nitrogen, appeart o be formed with some ease.For example, methyl eaminoamylketone picrate, when merely heated a t looo, is converted into thepicrate of cyclo-2-methyldehydrohexamethyleneimine 21 :CH* CH,*$JH2NH*CH,*CH,CMe<Cyclic compounds show striking . irregularities. cy cZoButanedicarboxylic acid (I) is attacked by fuming hydrobromic acid atlooo, giving the open-chain compound (11). Further, if (I) isbrominated, it yields the bromo-derivative (111), and this is quan-titatively converted by zinc and acetic acid into the original cyclo-butanedicarboxylic acid (I). On the other hand, the gemdimethylderivative of (I), namely, norpinic acid (IV), is quite stable 22 underconditions which lead to ring scission with (I) :C0,H CO,H C0,Hd0,H(1.160,H(IV. 1A similar change in stability, but in the opposite sense, is noticedin nopinol, the six-carbon ring in which is rendered more stable bythe replacement of hydrogen by methy1.23Two interesting cases of the elimination of an alkyl group from adialkylated aniline owing to ring formation were described almostsimuItaneously.24 Thus, when ethylaniline and ethylene dibromidewact in the proportions 4: 1, the products are diphenyldimethyl-ethylenediamine (I) and ethylaniline hydrobromide ; when the pro-portions are 2 : 1, diphenylpiperazine (11) and diethylamine hydro-bromide are formed:NMePh* CH,* CH,*NMePh NPh<g2::2>NPh(1.) (11.120 E.E. Blaise and A. Koehler, Compt. rend., 1909, 148, 852 ; A., i, 287.21 S. Gabriel, Ber., 1909, 42, 1249; A., i, 492.z2 W. H. Perkin, jun., and J. L. Simonsen, Trans., 1909, 95, 1166.23 Wallach, AnnaZm, 1907, 356, 211 ; A., 1907, i, 936.2J H. R. LeSueur, Trans., 1SO9, 95, 273; J. C. M. Dunlop and H. 0. Jones,ibid., 416ORUANIC CHEMISTRY. 91The interaction of ethylaniline and ad-dibromoadipic acid alsoleads to the formation of a ring compound and diethylanilinehydrochloride.Terpenes and Allied Compounds.The output of papers on thik section of organic chemistry hasnot been appreciably less than usual, and much of it has containedmatter of fundamental importance. It will not be possible to dealwith more than a small proportion of these, and recent work onthe constitution of camphor derivatives, terpinenes, etc., mustinevitably be left for inclusion in subsequent reports.Generalinterest this year has been arrested mainly by the progress in thechemistry of fenchone, pinene, and camphene.Fenchone.-A definite step towards agreement ,on the subject ofthe constitution of this ketone has been taken, Wallach’s formulabeing abandoned by its proposer as incompatible with the resultsof his most recent re~earches.~~ Two others have been proposed,namely, (I) by Semmler, and (11) by Glover:CH,*CH-CMe, CH,*CH,*CMeCH,*bMe-CO I I 6~~ i I $Iq CH,* CH--CO(1. ) (11.1The former is, for various reasons, the one which finds mostgeneral favour, and readily accounts for the formation of dehydro-fencholenic acid, but Wallach is not yet prepared t o acceptit without reserve.Last year .Bouveault and Levallois were able26 definitely toestablish the formula for dihydrofencholenamide (fencholamide)(11), the substance into which fenchone is converted by sodamide:CHThe complete synthesis of this compound, for which Wallachproposes the term fencholamide, as it is the analogue of camphol-amide in the fenchone series, has now been accomplished, dihydro-campholenic acid (compare section on camphene) being an25 0.Wallach, AnnaZe?h, 1909, 369, 63 ; A., i, 811.26 Conapt. rcnd., 1908, 146, 180; A , , i, 1908, 19392 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.intermediate step. This acid was converted into its chloride, andthe product, by the Friedel-Crafts reaction, into its phenylketone (I), from which a sodium derivative is obtained by theaction of sodamide. The sodium atom is readily exchanged formethyl, and the resulting ketone (11) undergoes the normal decom-position with sodamide which leads to the production of benzene anddihydrofencholenamide (fencholamide) 27 (111) :CH CH CH //I\\\I//7H2 I CHMe, /’I\\ /’I\\ YH, 1, CHMe, YH, I CHMe,CH, y H 2 COPh CH, y H 2 COPh CR2 y H 2 CO*NH,\ \i/ \\I// CMe CMe CH\(1.) (11.) (111.)Camp1tene.-Consideration of Semmler’s recent researches on thisinteresting hydrocarbon or mixture of hydrocarbons, combined withthe synthetic work of Bouveault and his collaborators, make itappear probable that the stage preceding a general agreement onthe question of its exact nature has been reached.CH CH0 L.Bouveault and G. Blanc, Compt. rend., 1909, 148, 1524 ; compare alsoL. Bouveault and Lovallois, ibid., 1399 ; A., i, 497, 595OHGANIC CHEMISTRY. 93Etard’s camphenilanaldehyde (11) yields an enol-acetate, and thircan be reduced to camphenelyl alcohol, from the chloride of which,on treatment with sodium and alcohol, camphene (I), mixed with alittle isocamphene, is regenerated. Thus, the central nuclei andthe mode of attachment of the side groups are proved to be identicalin camphene and camphenilanaldehyde.Wagner’s camphenilone (V) is produced by the action of moistozone on either camphene or enolcamphenilanaldehyde acetate (111),and there is no reason to suppose that this most trustworthyoxidation method can lead to those bewildering structure changes sofrequent in the terpene series 28; the weak link in the chain ofevidence is probably the next one (where the degradation processis more violent and probably less trustworthy from this point ofview than those used elsewhere, and, furthermore, the step has notyet been retraced). On heating camphenilone with sodamide, it isconverted into the amide of dihydrocampholenic acid (VI), thetotal synthesis of which has been accomplished in the followingmanner.Starting from P-isopropyladipic anhydride, this was converted byheating into 3isopropylcycZopentanone (VII), which was identifiedwith a ketone obtained from camphenilone.By reduction, thecorresponding alcohol was obtained.The corresponding bromo-derivative in ether reacted with magnesium and carbon dioxide,yielding finally a carboxylic acid (VIII), the amide of whichproved to be identical with that obtained directly fromcamphenilone 29 :CH CH(VII. ) (VIII.)P&ene.-The syntheses from nopinone of P-pinene and fenchenethrough nopinolacetic acid were recorded in the previous report.0. Wallach has now succeeded 3O in isolating synthetic lzvorotatorya-pinene from the products of the destructive distillation of thisacid in a current of hydrogen, proving its identity by showing thatit furnishes Z-pinonic acid on oxidation.In connexion with synthetic terpenes, an important paper has28 F. W. SemmIer, Ber., 1909, 42, 246, 962; A., i, 170, 3122g L.Bouveault and G. Blanc, Compt. rend., 1908, 147, 1314 ; A . , i, 108.30 Aannlcn, 1909, 368, 1 ; A., i, 72694 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.appeared, giving generalisations of the results obtained with cyclichydroxy-acids during the past few years.31 It is found that thehydroxy-acids of the typeobtained by the action of zinc and ethyl bromoacetate on cyclicketones, are dehydrated in either or both of two ways, yielding theproduct (I) or (11), the course of the reaction depending on thestructure of the acid as well as on the nature of the dehydratingagent :H2 H H2 __ H,\--/=2 H2 H2 H2(1.) (11.1H/” \:CH-CO,H H /--~H,~co,H2\--/Usually potassium hydrogen sulphate or phosphoric oxide f avoursthe formation of (I), and acetic anhydride, of the semi-cyclic type(11).The acids of type (I), when heated alone, tend to give hydro-carbons of the semi-cyclic type, migration of the double linkingtaking place when the carbon dioxide is eliminated.I n some cases the hydroxy-acids themselves cannot always beobtained by the saponification of their esters without undergoingpartial hydrolysis t o the cyclic ketone and fatty acid:-CO,Hand in these instances the acids themselves undergo the same changewhen heated alone, so that the above unsaturated acids cannot beprepared from them by the ordinary methods.Diazo- and Azo-Compozmds.The controversy, referred to in the last two Annual Reports,32 asto the constitution of diazonium salts, has been continued in theform of a series of polemical papers by Hantzsch 33 and Cak3* Insupport of the quinonoid formula proposed by the latter, an analogyis drawn between benzenediazonium chloride (I) and p-benzo-31 0.Wallacli, Annalen, 1909, 365, 255 ; A., i, 383.‘J‘3 1907, 120 ; 1908, 136.33 Ber., 1909, 42, 394, 2137 ; d., i, 193, 5%.s4 Ibid., 1205 ; if., i, 445ORGANIC CHEMISTRY. 95quinonechloroimide (11), both of which are decomposed byboiling with water, the rupture taking place at the junction of theHO:/=\:N-Cl \-/(1.1 (11.1nitrogen with the ring. Both compounds are explosive, and reactsimilarly with conceEtrated hydrochloric acid, yielding chloro-benzene and chlorophenol respectively. The parallel must not bepressed too closely, as it is impossible to regard the formula (I) asthat of a typical quinone, but it is suggestive.One objectionbrought against the new formula, that whilst originally introducedto account for the non-existence of aliphatic diazonium salts itfailed to explain the non-existence of simple aliphatic azo-compounds, has since ceased t o be valid, owing to the isolation ofazomethane, the simplest representative of its class. Hydrazo-methane, CH,*NH*NH*CH3, prepared by the hydrolysis of itsdif ormyl derivative, is readily oxidised, and azomethane is obtainedas a colourless gas, condensing to a liquid which is pale yellow a tOo, but becomes colourless before solidification, near - 78O.S Thecompound has considerable stability, which is actually reduced bythe introduction of aryl groups, for azotriphenylmethane,CPh,*N:N*CPh,, is found to be incapable of more than momentaryexistence, decomposing spontaneously into nitrogen and triphenyl-methyl.36 Unlike the corresponding derivatives of benzene, the azo-compounds are less stable than the hydrazo-derivatives.Takinginto account the character of the known azo-derivatives of sub-stituted fatty acids, it is evident that the presence of aromaticnuclei is unnecessary for the formation of azo-compounds, and thefact that all attempts to prepare diazonium salts in the fatty serieshave failed, gains considerably in importance.The great increase in stability conferred on diazonium salts bythe introduction of heavy substituting groups 37 has been furtherstudied, and it is found that,the compounds obtained by diazotisingas-benzoylmethyl-p-phenylenediamine, NBzMe*C6H,*NH,, are ex-ceedingly stable, even the perchlorate being non-explosive.38 Thesesalts are colourless, but they do not differ in any other respect fromthe stable coloured salts previously prepared, so that there is noreason to assume any difference of constitution.35 J.Thiele, Ber., 1909, 42, 2575 ; A . , i, 560.37 A m . Rcport, 1907, 121.38 G. T. Morgan and Miss M. Alcock, Trans., 1909, 95, 1319.H. Wieland, ibid., 3020; A., i, 83696 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The diazotisation of amines containing strongly acid groups,such as dinitroanilines, is difficult or impossible under ordinaryconditions, and a remarkable method of overcoming the difficultyhas been discovered, consisting in the use of concentrated nitricacid as the solvent.Nitrous acid being introduced by the additionof a nitrite or of the required quantity of a sulphite, diazotisationproceeds quietly and without secondary reactions, even a t so higha temperature as 70O.39 This fact depends on the great stability ofthe diazonium nitrates towards nitric acid, a property also observedin the diazotisation of polyhalogen derivatives of p-aminodiphenyl-amine in sulphuric acid, diazonium nitrates being obtained in placeof the expected sulphates.40 It is possible to recrystallise thesenitrates from hot concentrated nitric acid without decomposition,whilst alcohol immediately eliminates the diazonium group.It has long been known that amino-derivatives of certain non-benzenoid cyclic systems, namely, antipyrine, triazole, and tetronicacid, are capable of forming diazonium salts.In each of thesecases the carbon atom to which the amino-group is attached isdoubly linked to a neighbouring atom in the ring (nitrogen intriazole, carbon in antipyrine and tetronic acid). The formulationof the diazonium salt in accorda’nce with Morgan’s modification ofthe quinonoid formula is possible in each instance, the chloridesbeing :resp ectively.41It will be noticed that in all these cases, as in the derivatives ofbmzene, the carbon atom to which the amino-group is attached isdoubly linked to another atom of carbon or of nitrogen. Thenecessity of such it distribution of residual affinity in the diazotisablemolecule may be held t o afford it sufficient explanation of theexistence of diazonium compounds in certain cases, and their non-existence in others.No further progress has been made in elucidating the structureof the diazotates, but, on the other hand, the mechanism of couplingin the formation of azo-dyes has been the object of further experi-ment, with the result of confirming the ,view42 that the reactiontakes place through the intermediate formation of an O-azo-derivative.Thus, diazotised p-nitroaniline reacts with 2-naphthol-l-sulphonic acid in sodium carbonate solution to form a soluble39 0. N. Witt, Ber., 1909, 42, 2953 ; A . , i, 855.40 P. Jacobson, Annabn, 1909, 367, 332 ; A,, i, 683..il M.0. Forster and R. Muller, Trans., 1909, 95, 2072.42 Ann. Repoyt, 1908, 142OKGXNIC CHEMISTRY. 97compound, S0,h’a*C,,~16*O*~’:N*C6H4=No~7 having the same COlouras the stable, insoluble azo-compound into which it readily passesby rearrangement.43 A more complex compound, Thich may alsobe regarded as an O-azo-derivative, is suggested as the cause of theorange colour observed in the formation of “ para-nitraniline red ”from P-naphthcl under certain conditions of alkalinity.44 I n thecoupling of diazotised p-phenylenediamine with the amine to formBismarck brown, C6~~,[N,*C6H3(~I3[,),],,~HC1, the factor deter-mining the velocity is found by a colorimetric method to be thehydrolysis of the hydrochloride, indicating that the coupling of thediazonium salt takes place with the free amine liberated by hydro-lysis. Both amino-groups are diazotised simuMane~usly.~~ Re-actions of this type evideiitly lend themselves well to quantitativestudy.Further evidence has been obtained in favour of the view,originally suggested and rejected by KekulB, that the “ diazoniumperbromides ” are really halogen-substituted arylhydrazines.Theprincipal facts in favour of this constitution are (1) the facilitywith which the perbromides react with ammonia t o form diazoimides,(2) their formation from bromine and aromatic hydrazines inacetic acid solution, (3) the formation of unstable additive corn-pounds on the further addition of bromine. The principal evidencefor the more generally accepted perbromide formula is the readydecomposition of these compounds into diazonium salts and bromine.I n the action of alcohol on these eompounds, decomposition takesplace in two ways, as indicated by the scheme:C,H,Br + N, + Br,C6H,*rJ*Br Hausing Blomstrand’s formula for the diazonium bromide, the lattercompound then decomposing, with the formation of benzene,phenol, and brominated derivati~es.4~The complete replacement of the hydrazine hydrogen by bromineonly takep place in acid solution.I n presence of alkalis, a numberof different products may be obtained by varying the conditions,but all depend on the progressive substitution of bromine forhydrogen in the hydrazine group, followed by a secondary reaction4:; H.T. Bucherer, Ber., 1909, 42, 47 : A., i, 193.44 M. Prud‘homme and A. Colin, BdZ. SOC. chim., 1909, [iv], 5, 779 ; A., i, 684.45 V. H. Veley, Trans., 1909, 95, 1186.4ti F. D. Chattaway, ibid., 862.REP. -VOL. VT. 98 ANNUAL EEPORTS ON THE PROGRESS OF CHEMISTRY.of the N-substituted hydrazine. Thus, the dibromo-derivativeundergoes the typical diazo-decomposition, forming bromobenzene :C,H,- -7- -BrBr- -N-,-HHydrazobenzene is also formed by the union of two mono-substituted molecules :C,H, N H* N HC1 C,H,*NH- -N- -el HC,H,-NH*NHCl --+ C,H,*NH- -N--H i- 61being subsequently converted into azobenzene and diphenyl by theaction of the halogen.I n the presence of a large excess of a strong acid, the basic *NH,group is saturated, and so protected against substitution, and the:NH group is then the first to be attacked.The N-halogen com-pound thus produced is of the same type as the acyl halogen amino-compounds, and undergoes rearrangement, under the influence ofthe acid, to an ortho- or para-halogen derivative, the substituententering the nucleus in one or other of these positions.47When an alkaline solution of a normal diazohydroxide isoxidised with hydrogen peroxide, the product is a mixture of thesalts of a benzenediazoic acid and of it nitrosophenylhydroxyl-amine :Ar*N: N-ONa/ \ xAr *N : N* ONa .. Ar ON: N* ONa .. 0 0presenting an analogy to the oxidation of an oximc:CH,: N*OHJ 11 \OH*CH:N*OH CH,:N*OH -+ (CH,*NO,)Benzenediazoic acid is to be regarded as phenylnitroarnine,C,H,*NH*NO,, capable also of reacting in the tautomeric form.Nitrosophenylhydroxylamine is also tautomeric, reacting asb'The nitrobenzene obtained by the oxidation of a diazotate isentirely a secondary product, formed by the decomposition ofnitro~ohydroxylamine.~847 F.I). Chattaway, Trans., 1909, 95, 1065.' 8 E. Bamberger and 0. Baudisch, Ber., 1909, 42, 3568 ; A., i, 977ORGANIC CHEMISTRY. 59,4 niline-b lack.The oxidation of aniline to p-benzoquinone by the action ofchromic acid, simple as it appears, is a reaction of which themechanism has been little understood. The explanation usuallygiven, that 8-phenylhydroxylamine is first formed, isomeric changeto p-aminophenol then taking place, followed by oxidation toquinone, is certainly untenable, as phenylhydroxylarnine does notpass into aminophenol under the conditions of the experiment.Neither is it possible t o consider that the intermediate product isp-aminodiphenylamine, as has been suggested by Nover, as thelatter compound is not completely convertible into quinone in thecold.The fact, long ago observed, that aniline-black is first formed,has now been utilised as the basis of a complete explanation of thereaction.49 Pure aniline-black, prepared by oxidising aniline withonly one-quarter of the theoretical quantity of chromic acid, andsubmitting the product to careful purification, is proved to havethe composition C48H36N8. It is quantitatively convertible intop-benzoquinone by oxidation with lead peroxide, a reaction indi-cating that all the aniline residues are united in the para-position.The estimation of the oxygen consumed in its formation shows thatthe molecule, of eight aniline residues, is three times quinonoid, thatis, its formula is:NPh: C6H,: N C,H,*NH* C,H,*NH*C,H,*N: C,H,: N* C,H,*N: C6H4: NH,the position of the two inner quinonoid residues being arbitrarilyassumed.The constitution is confirmed by oxidation with hydrogenperoxide, whereby two atoms of hydrogen are removed, and afourth nucleus becomes quinonoid.The resulting compound isdarker in colour than the less fully oxidised aniline-black, butresembles it in its general properties, and is quantitatively con-vertible into p-benzoquinone. It may be obtained directly fromaniline by the use of an excess of a slowly acting oxidising agent.Hydrolysis of either compound removes one-eighth of the nitrogenas ammonia, thus fixing the number of nuclei united in a chain aseight, and compounds containing :O in place of the terminal :NHare obtained, the remainder of the molecule being unchanged.Theoxygen derivative of the compound containing four quinonoidgroups is the most complete representative of the aniline-blackseries, as both the base and its salts are dead black, and the changeto green on treatment with sulphur dioxide, observed in the lowermembers of the series, is entirely absent.d9 R. Willstdtter and 8. Dorogi, Ber., 1909, 42, 2147, 4118 ; A.: i, 535, 975.H 100 ANNUAL REPORTS ON THE PROGRESS O F CHEMISTRY.The fact that the yield of p-benzoquinone obtained when aniline-black is oxidised with chromic acid does not exceed 85 per cent.is explained by the above formula, the terminal, unsubstitutedbenzene nucleus being destroyed. The same behaviour is observedin the oxidation of simpler partial quinonoids. Thus, only one-halfof the molecule of quinoneanil :is oxidised by this process, whilst lead peroxide and sulphuric acidconvert both rings into p-benzoquinone.This difference in theaction of the two oxidising agents has proved of value in fixing theconstitution of emeraldine and the termolecular imines formed bythe polymerisation of' quinonedi-imines.50 Emeraldine contains nonebut para-junctions, whilst the termolecular imines contain a singleortho-junction.H. T.Bucherer51 has argued that the ready decomposition ofindamines by acids, taken together with the stability of aniline-blackand emeraldine, excludes the possibility of the formula: proposedby Willstatter, and an azine formula is preferred. There is, how-ever, no direct evidence for the azine constitution, which is notreadily reconcilable with the ultimate complete conversion intop-benzoquinone by oxidation. The same objection applies to theclosed ring formula proposed by A. G. Green,s2 which contains bothortho- and para-linkings :/Nil=\.\-/\/\ / \\/ \ /\NH-/-\/I 11 C,H,*NeC1 N.\=/Compounds Exhibiting Ketinaino-enanie Isornei-ism 07' Tautornerism.A very large class of nitrogenous compounds of both open-chainand cyclic structure owe many of their peculiarities to the circum-stance that they contain nitrogen either doubly bound to anotheratom or attached to one of a doubly bound pair, thus:*N:X*Y or >N*X:Y.This class includes amides, imino-derivatives of ketones andacids, and the more complex series of ureides, cyanic and cyanuricacid, and allied substances, and these show so many characters50 R.Willstatter a i d H. Iinbli, Ber., 1909, 42, 4135 ; A., i, 976.51 Ber., 1909, 42, 2931 ; A . , i, 820.52 J. SOC. D y c ~ s , 1909, 25, 188 ; A . , i, 612ORGANIC: CHEMISTRY. I 0 2in common that much is to be gained by adopting asuggestion from J. F. Thorpe53 to treat them as closely allied sub-stances. They become ‘‘ tautomeric ” in certain circumstances, if,for example, a hydrogen atom is affixed to the outer doubly boundatom, or this may even occasionally result in a definite dynamicisomerism :--3 -N*X:Y *N:X*YH t- HRetimine form.Eiiarne form.The case where both X and Y are carbon atoms may be discussedfirst. Thorpe and Best have made a systematic study of these cases,and during the past few years have studied very thoroughly theway in which such substances may be formed and their generalproperties. They generalise as follows, referring to those whichcan exist in the two forms:4-C-6H *c-c=c* I ’ 1 ; andi4 NH(;I. ).Eiiame or aniino-forin.(1:)Ketimine or imiiio-form.and to the number of “negative” groups (that is, unsaturatedgroups of the type *CN, *CO,Et, etc.) attached to the carbon atomsto which dots are affixed.( a ) With three or more such groups, the amino-configuration(11) is adopted, and the hydrochlorides at once dissociate withwater, regenerating the free amino-compound.( b ) With one suchgroup, the compounds assume the striicture (I), being true imino-compounds, and the hydrochlorides with water yield ammonium - -*C*C*CH, . .. .0chloride and the corresponding keto-compound proper,(c) With two negative groups, tautomeric or merotropic phenomenaoccur, and the hydrochlorides are mixed salts of the amino- andimino-types. The conclusions are supported by a mass of con-vincing experiment a1 evidence .54Compounds closely related to carbanlide are receiving much atten-tion, especially as the commercial article, “ calcium cyanamide,” is aconvenient source of some which have hitherto been difficult toprepare in quantity.Dicyanodiamide and guanidine,55 for example,are now easily prepared in large quantities. Recent investigationsseem to prove that the former is not acidic, and does not formsalts, as has been supposed, those previously described being derived53 Proc., 1909, 25, 309.54 S. R. Best and J. F. Thorpe, Trms., 1909, 95, 1506;.55 C. Ulpiani, D.R.-P. 209431 ; A., i, 701102 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.from dicyanodiamidine.56 The 0-methyl ethers of dialkyliso-carbamides, NR,*C(OMe):NH, which can be prepared by the actionof sodium alkyloxides on dialkylcyanamides, have very strikingproperties. They are strongly basic oils, uniting with one equivalentof mineral acids to form neutral salts, and they attack the skinmuch as potassium hydroxide does.Their hydrochlorides decom-pose quantitatively when heated, yielding methyl chloride and thecarbamide :NR,*C(OMe):NH*HCI = NR,*CO*NH, + CH,CI.Heated alone, they give the cyanamide and the alcohol fromwhich they were made, but in aqueous solution they furnish thecarbamide and methyl alcoho1.57I n extension of work on aliphatic chloroamines, it is found thatchlorine may replace any or all of the hydrogen atoms directlyattached to the nitrogen in carbamide or its alkyl derivatives. Thedichloro-derivative, CO(NHCl),, when treated with ammonia, yieldsy-urazine :which is very stable, but is decomposed by strong sulphuric acidat 1 20-130°, furnishing carbon dioxide and hydrazine sulphate.As the process is easily exhibited in a test-tube, it may be recom-mended as a lecture experiment t o demonstrate the synthesis ofhydra~ine.~*A Ikdoids.Considerable advances have been made in the knowledge of thealkaloids which accompany coniiiie in hemlock.8-Coniceine (I) hasbeen synthesised by reducing the lactime of piperidylopropionicacid (11):2>CH,yH2*CH,* 7 H*CHCH,*CH,*N- CO 2>CH,7H2* CH,. H *CHCH,*CH,*N---CH,(1- 1 (11.)and P-coniceine (2-a-allylpiperidine) was found in its racemic form,and afterwards resolved into its active components, among theproducts obtained by heating 2-P-hydroxypropylpiperidine withphosphoric oxide.59It was an inference from earlier work that conhydrine must beeither a- or P-hydroxypropylpiperidine ; the most recent evidence56 N.Caro and H. Grossmsnn, Chcm. Zcit., 1909, 33, 734 ; A., i, 558.67 R. H. McKee, Amer. C~LCYIZ. J., 1909, 42, 1 ; A . , i, 635.58 F. D. Chattaway and D. F. 8. Wiinsch, Trans., 1909, 95, 129 ; F. D.5y I<. Liiffler and H. Kaim, Ber., 1909, 42, 94, 107 ; A., i, 179, 180.Chattaway, ibid., 235ORGANIC CHEMJSTRY. 103points definitely to the former as the correct constitution. Con-hydrine and $-conhydrine appear to be structurally different, andnot mere stereoisomerides, for they do not furnish the same productswhen dehydrated. P-$-Conhydrine is a mere hydrate of conhydrine,and the 4-conhydrine described by Ladenburg and Adam is reallya mixture of two bases separable by crystallisation of their hydro-chlorides.Lellmann’s €-coniceine is a mixture of two isomeric baseshaving the structure 60 :YH,*CH,*F)H*F)H,CH2*CH20N--CHMe’There have been numerous researches dealing with the constitu-tion and synthesis of the more complex alkaloids. In the tropinegroup, several of the tropeines have been examined physiologically,and t*he rule, often repeated in text-books, that the presence ofboth a benzene residue and an aliphatic hydroxyl in the side-chaincontaining the carboxyl group is necessary for the exhibition ofactivity, has been shown to be invalid.61 The view that tropineand $-tropine are internally compensated compounds with cis-truns-isomerism has been confirmed,62 and the affinity constants of thevarious tropine bases have been compared by a colorimetricmethocl.63Both cinchonine and cinchonidine yield the same ketone,cinchoninone, on oxidation, and are therefore stereoisomericsecondary alcohols.Quinine and quinidine similarly yield the samequininone. Both cinchoninone and quininone are tautomeric, andexhibit mutarotation,G* the two stereoisomeric modifications beingconvertible into one another through the enolic form. Bothcinchonine and cinchonidine yield the same methyl derivative. Oneof the most characteristic reactions of the alkaloids of this group istheir conversion into an imino-ketone, in this case cinchotoxine,when their hydrogen sulphates are heated.65I n order to test the stability of the grouping :N*C*CH*OH,another 1 : 2-hydramine, P-piperidyl-a-phenylethyl alcohol, wasexamined, but was not found to undergo this decomposition, itsstability being much greater than that of the alkaloids.666o K.Loffler and G. Friedrich, Ber., 1909, 42, 107 ; I(. Liiffler, ibid., 116, 948,960 ; C. Engler, ibid., 559 ; K. Loffler and R. Tschunke, ibid., 929 ; A . , i, 180,181, 324, 326, 327... .61 H. A. D. Jowett and F. L. Pyman, Tmns., 1909, 95, 1020.62 M. Barrowcliff and F. Tutin, ibid., 1966.63 V. H. Veley, ibid., 1.‘-l P. Rabe, Annalen, 1909, 364, 330 ; A . , i, 252. ‘,’ Tbtcl., 365, 353, 366; A , , i, 407, 408.P. Rabe and W. Schneider, ibid., 377 ; A , , i, 413104 ANNUAL REPORTS ON THE PROGRESS OF CTIEMISTRY.The complete synthesis of papaverine and laudanosine (N-methyl-tetrahydropapaverine) has been effected, the former compoundbeing prepared from aminoacetoveratrone and liomoveratroylchloride, followed by reduction and elimination of water.67Papaverine yields tetrahydropapaverine on reduction, and methyl-ation of this converts it into laudanosine.68 The latter alkaloid hasbeen directly synthesised by combining hoi-noveratroyl chloride withhomoveratrylamine, converting into dihydropapaverine by elimina-tion of water, reducing the rnethochloride of the latter, andresolving the racemic alkaloid obtained. This is the first completesynthesis of an opium alkaloid.69Narcotine and hydrastine are known to yield cotarnine andhydrastinine respectively when oxidised with manganese dioxide,together with opianic acid.As laudanosine behaves in a similarmanner, yielding veratraldehyde and a basic degradation product,TOother related compounds have been examined, and the reaction isfound to be perfectly general for substituted l-benzyltetrahydro-i~oquinolines,~~ the aldehyde obtained being that corresponding withthe substituted benzyl group. Compounds containing alkyl insteadof benzyl do not undergo the change. The reaction is likely t.oprove valuable in the study of the rarer alkaloids, especially thoseof the opium group, in which such a structure is probably offrequent occurrence.The formula for narceine, proposed by Freund and Frankforter,contains the group -CH,*CO*, uniting two benzenoid rings.Thepresence of this group has been confirmed by a comparison ofnarcindonine with diketo-a-phenylhydrindene.72 Narceine, accordingto the annexed formula, is a derivative of deoxybenzoincarboxylicacid :OM' CH2*CO( )OMe/-Me ,C0,HCH,*CH,*NMe,(/\/CH,<OI I\/\and it yields narcindonine by a similar reaction to that by whichthe parent substance is converted into .diketo-a-phenylhydrindene.Narcindonine forms red enolic salts with alkalis, and colourless67 A. Pictet and A. Gams, Compt. rend., 1909, 149, 210 ; A . , i, 671.68 F. T,. Pyman, Trans., 1909, 95, 1610.69 A. Pictet and Mlle. M. Finkelstein, Compt. rend., 1909, 148, 925 ; A . , i, 323.70 F. L. Pyman, Trans., 1909, 95, 1266.7l F. L. Pyman, ibid., 1738.72 M. Freund and P.Oppenlieim, Ber., 1909, 42, 1084 ; A . , i, 410ORGANIC CHEMISTRY. 105ketonic salts with acids. When its niethiodide is heated withsodium liydroxicle, narcindone,is formed.Constitzc tion of Nut urally 0 cczwriny Sub stances.An inquiry into the nature of the dye employed by the Romans,and generally known as ‘‘ antique purple,” has led to very interest-ing results. The adrectal glands of species of Murex and Purpuracontain a colourless fluid, which becomes purple or violet onexposure to light. Archzeological evidence indicates Mzcrexbmndaris as the principal source of the dye, and 12,000 individualsof this species were used in the in~estigation,7~ this large quantityyielding 1.4 grams of the crystalline dye. The colouring matterwas readily found to be a member of the indigo group, and analysisshowed the molecule to contain, mast unexpectedly, two atoms ofbromine.The properties of the colourless parent. substance sug-gesting that the molecule was doubled in the development of thecolour, a symmetrical dibromoindigotin was suspected, and a com-parison with the four possible isornerides, prepared synthetically,proved the dye to be identical in spectroscopic behaviour, solubilityrelations, etc., with 6 : 6/-dibromoindigotin. It dyes wool a reddishshade of violet, which accords with the frequent comparison ofthe antique purple by classical writers with amethyst, violets, andeven with indigo vapour (Pliny). The nature of the colourlessparent substance remains undetermined.Having regard to the occurrence of derivatives of indole in animalexcretory products, the presence of an indigo compound, althoughnobel, is comprehensible, but the occurrence of a brominatedderivative under such conditions is probably unprecedented.Substitution of indigotin in the 6 : 6/-position favours a red shade,thc 6 : 6/-dichloro-derivative being also reddish-violet, whilst 6 : 6/-di-methoxythioindigotin is even orange-red, the 5 : 5’-derivative beingviolet.An important investigation of the process of fermentation ofindican by its specific ferment, indimulsin,74 has thrown much lighton the reactions involved, and has accounted for the principal lossesin the technical process of extraction, but does not lend itself t osummarisation.The ‘‘ decay ” of indoxyl is considerably checked73 P.Friedlander, Ber., 1909, 42, 765 ; A., i, 262,74 A. G. Perkin and F. Thomas, Trans., 1909, 95, 7 9 3 ; F. Tholnas, W. P.Hloxam, and A. G . Perkin, ibid., 824106 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.by the presence of sulphuric acid during the fermentation. “ Indigo-brown” is shown75 to be formed by the oxidation of indoxylicacid, which is very likely to be formed during the fermentationby the action of carbon dioxide on indoxyl.Important results have been obtained in the group of compoundscharacterised by their effect in increasing the blood-pressure, thebestrknown member of the group being adrenaline. This substanceis a derivative of catechol, and has the constitution :OH/-\OH/ \CH(OH)*CH,*NHMe.\-/The corresponding ketone is also active, and the presence of themethyl group is unessential. It has now been found that thecorresponding compounds containing only a single hydroxyl in thepara-position are also active. The ketone closely resembles thatderived from adrenaline, but the increase in physiological activitybrought about by the reductiog of :CO to -CH*OH is much lessmarked when only one hydroxyl is present.76 The activity isinhibited by the introduction of methyl into the a- or P-position.77There is a close resemblance between adrenaline and ergot, andan active principle has been isolated from aqueous extracts of thelatter substance which exhibits a close chemical, as well asphysiological, relationship, namely, p-hydroxyp henylethylamine :OH/-\CH,* CB,*NH,.The synthetic product, obtained by the reduction of p-hydroxy-phenylacetonitrile, is proved to be identical with ihnt present inergot.78 The same compound is obtained, in better Xield, by actingon anisaldehyde with nitromethane :\--/OMe*C,H,*CHO + Ne*NO, = OMe-C,H,*CH:CH*NO2 + H,O,reducing the product, and removing the methyl group by means ofhydrogen iodide.79 The properties of ergot are now fully accountedfor by the presence of this base and of ergotoxin.The &position of the hydroxyphenyl group in the chain is notessential to the activity of the molecule, for a-p-hydroxyphenylethyl-amine, sOH*C,H,*CHMe*N€I,, is found 80 to resemble the fi-isomeridein this respect.75 A.G. Perkin, Trans., 1909, 95, 847.713 F.Totin, F. W. Caton, and A. C. 0. Ham, ibid., 2113.77 K. Biittcher, Ber., 1909, 42, 853 ; A., i, 152.78 G. Barger, Trans., 1909, 95, 1123 : G. Rarger and G. S. JValpole, ihid., 1720.79 I(. W. Rosenmnnd, Ber., 1909, 42, 4778.Ro Tutin, Caton, and Hami, Zoc. citORGANIC CHEMISTRY. 107The alkaloid hordenine, obtained from barley, has the con-OH/-\CH2*CH2*NMe,,and is therefore the dimethyl derivative of the ergot base.Methylation of the latter compound leads under all conditions to theformation of hordenine methiodide, and it is not possible to stopthe reaction at an intermedfate point. The synthesis of hordeninehas, however, been effected from phenylethyl alcohol, the chloridefrom which, treated with dimethylaniline, yields the base,C,H,*CH;CH,*NMe,, from which the para-hydroxy-derivativerequired is readily obtained by nitrating, reducing, and boiling thediazo-compound with acid.81 The physiological action of hordeninewas studied by Camus in 1906, and was found to consist in anincrease of the blood-pressure, as in the other instances taken fromthis group.The fact that phenylethylamine and its substituted derivativeshave been recognised amongst the products of digestion, and alsoamongst the substances formed by the putrefaction of proteins,taken in conjunction with the observations mentioned above, pointsto the high physiological importance of the group.The composition of naturally occurring tannin approaches thatof a digallic acid, and that constitution is most generally assignedto it, in spite of its optical activity. The natural product isconsidered by M.Nierenstein82 to be a mixture of digallic acidwith leucotannin, in which the two rings are united by the group*CH(OH)*O*. The penta-acetyl derivative of tannin yields penta-acetyl-leucotannin on reduction, and an additional acetyl group maythen be introduced, in accordance with the formula:AcO AcO OAcstitution :\-/The behaviour of the original compound on oxidation is inaccordance with the formula proposed. The separation of theconstituents of the natural mixture is difficult.83 Methyltannincontains five methoxyl groups, and appears to be a mixture of thepentamethoxy-derivatives of digallic acid and of leucotannin.8481 G. Rarger, Trans., 1909, 95, 2193.Ber., 1909, 42, 1122, 3552 ; d., i, 402, 948.L. I!. Iljin, ibid., 1731; A., i, 503.*4 J. Herzig and V. Renner, Monntsh., 1909, 30, 543 ; A., i, 71.7108 ANNTJAT, REPORTS ON THE PROGRESS OF CTIEICITSTRY.Organic Comp,ozc?zcl.s of Sulphur and Selenium.A very large amount of important work has been done in thisGeld during the period covered by this report, but for the mostpart it is of the specialised character, which cannot be dealt withusefully in such a summary, therefore only those points whichappear t o have a somewhat general interest or applicability havebeen included.Hydrogen sulphide acts on dry imino-esters, R*CGNH, OEt in muchthe same manner as water does on their hydrochlorides; inethereal solution the dry gas converts them into ammonia andOEG" P-thion-esters," R*CGS , which are compounds with ratherremarkable properties. They do not yield the thio-acids onhydrolysis, but usually react with ammonia, yielding the correspond-ing amides, R*C<tH2, which may therefore occur as secondaryproducts in the preparation of the P-thion-ester.85Thioformamide, HS*CH:NH S:CH.NH,, may be prepareddirectly from formamide by the action of phosphorus pentasulphide,and appears to be tautomeric in the sense here indicated, and itsaqueous solutions are sufficiently acidic to redden litmus. Whenheated, it yields iminoformyl cyanide, NH:C€I*CN, and may beconverted into thiazole with chloroacetaldehyde, and into a newring compound, thiazoline (I), with bromoethylamine salts 86 :The investigation of thio-oxalic acid and its esters has furnishedresults of very general interest. The esters are obtained by theaction of oxalyl chloride on mercaptans, and are usually yellow,crystalline compounds, which react with alcoholic solutions of alkalihydrosulphide, yielding t.He mercaptan and a salt of thio-oxalicacid, (COSH),, which, when liberated from its salts, a t oncedecomposes. The salts give characteristic precipitates or colorationswith solutions of the salts of heavy metals, particularly of nickeland cobalt.A remarkable reaction is described by Heiduschka, who has foundthat ammonia attacks p-toluenesulphinic acid in benzene solutionin such a manner as to form tolyl disulphoxide and toluene-sulphonic acid :3R*S02H = R*S02*S*R + R*SO,H + H20.g5 M. Matqui, Mein. G'oll. ,%i. Ens. KyGtd, 1908, 1, 385 ; A., i, 469.fi6 R. Willstiitter and T. Wirth, Ber., 1909, 42, 1908 ; A., i, 45ORGANIC CHEMJS’l’KY. 109The acid decomposes in the same manner when melted or boiledwith water .87Toluenesulphinic acid is formed when the corresponding sulphonylchloride is acted on by a solution of sodium arsenite or sulphite,arsenate or sulphate being produced; in order t o account for this,the formula R*SO*OCl is proposed for sulphonyl chlorides, and itis surmised that sodium hydroperoxide is formed at an intermediatestage, but as the results seem capable of other and more simpleexplanations, this suggestion seems unlikely to command confidenceunless supported by more direct experimental evidence.88Aromatic sulphinic acids yield ferric salts, which are precipitatedeven in strongly acid solutions, and are easily filtered and washed,being, moreover, stable in dry air. As they yield ferric hydroxideand sodium sulphinate with sodium hydroxide, the isolation of thesulphinic acids when prepared f rorn the amines by Gat.termann’smethod is most conveniently affected by taking advantage of thisproperty.89The relative instability of the oxidised selenium compounds, ascompared with the corresponding sulphur derivatives, is wellillustrated in the properties of the analogue of benzenesulphonicacid, namely, benzeneselenonic acid, C,H,= SeO,H, which is easilyobtained by heating benzene with selenic acid at l l O o . It is soreadily reduced that aqueous sulphurous acid converts it intophenyl selenomercaptan if a silver salt is present to fix the latteras it is formed. Even hydrochloric acid is oxidised by it, theproduct in this instance being benzeneseleninic acid, C6H5*SeO2H.9OCECIL H. DESCH.ARTHUR LAPWORTH.A. lieiduschka, Ycrh. Gcs. dcut. Nattwforsch. Acrzte., 1907, ii, 170 ; A., i,144.88 A. Gutmann, Ber., 1909, 42, 480 ; A., i, 144.J. Thonias, Trans., 1909, 95, 342.H. MT. Donghty, Amw. Chenz. J., 1909, 41, 326 ; A., i, 296

ISSN:0365-6217    

DOI:10.1039/AR9090600056

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

STEREOCHEMISTRY.THE present report deals with the progress of stereochemistry duringthe two years which have elapsed since the last report on thisbranch of chemistry appeared. Some of the more striking develop-ments which have taken place during this period have beenmentioned in the report on Organic Chemistry for 1908, but, inorder t o secure continuity, it will in some cases be necessary torefer to these again.The past two years have been marked by great activity on thepart of the numerous workers in this most interesting and pro-ductive field, and the output of important work has been so greatthat it is difficult, within the narrow limits of this report, to dojustice even to all the work which has an obvious bearing on generalprogress; consequently a number of researches which have addedto the sum of our knowledge must of necessity be left unmentioned.A good deal of attention has been paid to the problem ofeffecting a complete asymmetric synthesis, and a number of papershave been published in which an account is given of attempts madeto bring this about by the use of circularly polarised light, or of acombination of magnetic and electric fields ; hitherto all theseattempts have led to negative results, but the use of emulsin foreffecting asymmetric synthesis has been made successfully in anumber of cases,The allied problem of separating the synthetic mixture of enantio-morphous isomerides has also attracted attention, and the work ofOstromisslensky has shown it in it new aspect, since it is clear thata separation can be effected without the actual use of one of theenantiomorphs, or even of an optically active substance, but merelyby using a substance isomorphous with the active substance.The attempts to verify experimentally van’t Hoff’s prediction,that optical activity could be due to enantiomorphism of themolecule without being assignable to a single asymmetric atom,have now been brought to a successful issue.The resolutionof two substances of this class has been announced: first, 1-methyl-cyclohexylidene-4-acetic acid, by Perkin, Pope, and Wallach,and, secondly, 4-oximi~iocycZohexanecarboxylic acid, by Mills andMiss Bain. In both cases the molecule is devoid of a plane ofsymmetry, but contains no atom which is asymmetric accordinSTEREOCHEMISTRY.111to any of the accepted definitions of an asymmetric atom. Thecase of 4-oximinocycZohexanecarboxylic acid acquires additionalinterest on account of its important bearing on the Hantzsch-Wernerhypothesis concerning the isomerism of oximes.The study of the quantitative relations of optical activity hasbeen the subject of a very large number of communications, thegeneral trend of which has been to demonstrate, first, the importanceof the chemical character of the groups in the molecule as distinctfrom their mass, and, secondly, that the value of the rotatorypower is more dependent on the solvent, on temperature, and onthe wave-length of the light used than had hitherto been suspected.The Walden inversion and the closely allied subject ofracemisation have received a great deal of attention, and, in regardto the former, the results obtained have complicated mattersvery considerably by showing that some of the conclusionsdeduced from Walden's original observations and from Fischer'swork in 1907 are not applica'ble in other cases, but, a tthe same time, new facts lend support to other conclusions,and these will probably be found universally applicable.Thus itappears that the Walden inversion is dependent on the presenceof a carboxyl group attached to the asymmetric carbon atom, andthat it is never caused by the action of phosphorus pentachloride.A very large number of new optically active substances have beenprepared, and among them a, second compound owing its activityto silicon.The investigations which have added a new type of molecularstructure causing optical activity to those already known may beconsidered first.The acid resolved by Marckwald and Meth,l melting at 40-41°,and stated by them to be 1-methylcycZohexylidene-4-acetic acid,has eventually been proved 2 to be the isomeric 1-methyl-93-cycZo-bexene-4-acetic acid, whilst the acid prepared by Perkin and Popeand by Wallach, melting st 66O, possesses the structure representedby the above formula.This acid has been resolved 3 by the fractional crystallisationof its brucine salt from dilute alcohol. The complete separation ofthe two salts was found to be extremely difficult, owing to theformation of mixed crystals of the salts dAZB and ZAZB, but boththe active acids have been obtained pure, melting at 52*5--53O,and having [aJD+-8lo in 0.7 per cent.solution in absolute alcohol.Ber., 1906, 39, 1171 ; A., 1906, i, 360.See Tram., 1909, 95, 1791, for references.a Perkin, Pope, and Wallach, ibid., 1789112 ANNUAL REPORTS ON THE PROGRESS OF CHEMIS'l'lLI'.The racemic acid melts at 66O, and a mixture of this with one ofthe active acids can be found melting a t as low a temperature as43--44*5O; hence the melting-point curve for mixtures of the d- andI-acids must be of the same type as that of the dimethyl tartrates.Another exceedingly interesting example of a substance owingits activity to enantiomorphism of the molecule has been found in4-oximinocyclohexanecarboxylic acid,y Hco2~>"<cld CH ;.&C:N *CHA preliminary account 4 only has appeared, in which the resolutionof the acid by fractional crystallisation of its quinine salt from ethylacetate is described.The sodium salt, after removal of the quinine,was found t o show a rotation of -4.4O in aqueous solution in a2-dcm. tube, and this activity was a t once destroyed by the additionof acid, Further details of this work will be awaited with interest,since the behaviour of this substance has an important bearing, notonly on the demonstration of a new type of molecular structurecapable of causing optical activity, but- also on the Hantzsch-Werner hypothesis of the stereoisomerism of oximes, which wouldreceive the very strongest confirmation if this acid can be provedto have the structure assigned to it above, and, a t the same time,to exhibit optical activity. I n this case the molecule can onlybe devoid of a plane of symmetry if the hydroxyl group attachedto the nitrogen atom is deflected to the right or left in the planeof the ring.An alternative formula containing an asymmetriccarbon atom seems possible, namely :but if this were the constitution, it is not easy to understand whyacidification should cause the disappearance of activity, whereasthis can be explained with the aid of the oximino-formula.It has long been recognised that molecular asyminetry or enantio-iiiorphism of the molecule is the essential cause of activity, althoughthe asymmetry could usually be referred to a single atom, fourvalencies of which were occupied in linking four different groups;in the cases mentioned above a somewhat modified definition of anasymmetric atom would include the case of the atom "yf>C<in the first case,44 and "2Z>C<in the second.The problem of effecting a complete asymmetric synthesis, that is,producing an optically active substance without the aid of anotherW.H. Mills and Miss A. M. Kain, Proc., 1909, 25, 177."See A. E. Everest, Chem Nczus, 1909, 100, 295 ; A., 1910, ii, 6STEREOCHEMISTRY. 113optically active substance, has been attacked vigorouslyz but hithertowithout success.Several reactions which are influenced by light have been carriedout in circularly polarised light ; thus, the acids CN-CMeEt*CO,Hand CO2H*CC1Me-CC1Me*COzH lose carbon dioxide under theinfluence of light in presence of uranium salts, yet when the incidentlight had been passed through a, magnetic field the product wasinactive.5 Similarly, the change of r-o-nitrobenzaldehydediamyl-acetal in solution in r-amyl alcohol into amyl o-nitrosobenzoateunder the influence of circularly polarised light gave rise to aninactive compound,6 and the exposure of copper racemate tocircularly polarised light also gave no r e ~ u l t .~The experiments first mentioned have been criticised by A. Byk,Swho points out, quite correctly, that the combination of ordinarylight and a magnetic field would not be expected to give any result,since the light is not circularly polarised.The union of bromine with methyl fumarate and with methylcinnamate has also been carried out under the influence of super-posed magnetic and electrostatic fields? but the products wereinactive.A large number of syntheses, which, t o distinguish them fromthe above, may be described as partial asymmetric syntheses, andin which an optically active substance is used, have been carriedout.When the union of benzaldehyde and hydrocyanic acid isbrought about under the catalytic action of emulsin, d-benzaldehyde-cyanohydrin is produced, and from this pure Z-mandelic acid canbe obtained.1° A number of other aldehydes also give opticallyactive cyanohydrins under the influence of emulsin.11Ernulsin is also found to destroy d-benzaldehydecyanohydrin morerapidly than its antimeride, so that the latter is in excess whenemulsin acts on the synthetic dl-mixture.12Syntheses of active substituted glycollic acids have been effectedby the action of Grignard's reagent on d-amyl pyruvate and ond-amyl phenylglyoxylate.13 A comparison of the results nowobtained with those previously obtained leads to the conclusionthat the greater the optical activity of the active group presentF.Heiile and H. Haakh, Ann. Report, 1908, 107.P. Freundlor, Ber., 1303, 42, 233 ; A., i, 164.A. Cotton, J. Chim. Phys., 1909, 7, 81 ; A., ii, 278.Be?.., 1909, 42, 141 ; A., i, 130.Y. A. Guye and G . Dronginine, J. Chim Phys., 1909, 7, 97 ; A . , ii, 278.lo L. Rosemthaler, Biochc7n. ZeitscJL., 1909, 14, 238 ; d., i, 74 ; S. J.M. Auld,l1 L. Roscnthaler, Biochem. Zeitsch., 1909, 17, 257 ; A., i, 622.19 K. Feist, Arch. Pharm., 1909, 247, 226 ; A., i, 589.l3 A. McKenzie and H. A. Miiller, Trans., 1909, 95, 544.Trans., 1909, 95, 927.KEP.-VOL. VI. 114 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.in a molecule during the asymmetric synthesis the greater is itsdirective influence on that synthesis. Mandelic acid having[aID - 15'6O has been obtained by the reduction of Z-menthyl phenyl-glyoxylate and subsequent hydrolysis, racemisation during the actionof potassium hydroxide having been prevented by acetylation of thehydroxyl group.Some very interesting observations have been recorded on theseparation of d + Z-mixtures of enantiomorphous compounds. Thus, acrystal of Z-asparagine added to a supersaturated solution of sodiumammonium &tartrate causes the separation of a quantity of thed-tartrate, with which it is isomorphous, and so does a crystal ofany alkali salt of dtartaric acid.14 A crystal of the Z-tartrate causesthe deposit of a crop of leevorotatory crystals. Further, it wasfound that it is not necessary that the nucleating material shoulditself be active if it be isomorphous with the tartrate, and thereforepresumably tetart~ohedral ; thus, a crystal of glycine added to thesupersaturated solution of dZ-asparagine causes a deposit of eitherthe d- or Z-compound, the same crystal always producing a crop ofcrystals having 8 rotatory power of the same sign.These observations afford another method of distinguishing aracemic compound from a &-mixture ; from a supersaturatedsolution of the former the crystals deposited when the solution isnucleated with a suitable material would be inactive, whereas thelatter would yield an active deposit under the same conditions.A large number of experiments on the slow, spontaneouscrystallisation of solutions of sodium ammonium dl-tartrate weredescribed in 1898, and now further interesting observations on thissubject are recorded.15 When the solutions were allowed toevaporate in the laboratory, the first deposits obtained were usuallydextrorotatory ; thus, for example, in one series of experimentsdealing with nineteen solutions, sixteen gave dextrorotatorydeposits ; when the solutions were allowed to evaporate in desiccatorsso as to exclude dust, the proportion of dextrorotatory depositswere smaller, thus in two series of experiments it was 5 to 4 and11 to 8. It seems therefore probable that the preferentialdeposition of dextrorotatory material is caused by inoculation bythe dust of the laboratory, or by the presence of an extremelyminute excess of a-tartrate, which is very difficult to removecompletely from the racemate.The deposit would naturally beexpecte t o have the same sign of rotation as that of the first crystalactually formed from the solution.A new aspect of the difficulties attending the resolution of acidsand bases by the crystallisation of a salt with an active base orl4 I. Oatramisdensky, Ber., 1908, 44, 3035 ; A., 1908, ii, 913.8'.8. Kipping and W. J. Pope, Trans., 1909, 95, 103S'I'EREOCHEMISTKY. 115acid has been revealed by experiments that have shown that whena base can be resolved by means of an active acid this active base isnot necessarily capable of resolving the dl-acid.16 Thus, d-methyl-hydrindamine. was used to resolve dl-sulphobenzylethylpropylsilicyloxide, but the active acid does not resolve dl-methylhydrindamine,and the latter is not resolved by d-mandelic acid, whereas eitherthe d- or Z-base is capable of resolving dl-mandelic acid.It is therefore clear that the mixture dAdB+dAEB does notalways behave in the same way as dAdB + lAdB ; one of these pairsmay form a partly racemic salt, and therefore the constituentscannot be separated by crystallisation, while the other pair doesnot, and is therefore separable.A new method for determining whether a primary or secondaryamine is or is not externally compensated has been based on theuse of oxymethylenecamphor.17The method is identical in principle with that involving the useof an active acid chPoride,ls but is more convenient, since oxy-methylenecamphor is readily obtainable.This substance condensesreadily with amines to form crystalline compounds of the type (I) :&CH*NH*Rl4 co(1.1 (11.)which can be separated into two components if the amine used isex tern a1 1 y com p ens a te d .The compounds derived from primary amines usually exhibitmarked mutarotation, which, it is suggested, is due to the existenceof the dynamic isomerides (I) and (11).This view is supported by the following facts: first, equilibriumis reached in a few minutes in the presence of a smallquantity of sodium ethoxide, and, secondly, the derivative ofmethylaniline shows no mutarotation.The compounds derived from o- and p-nitroanilines do not exhibitmutarotation, whereas that of m-nitroaniline does ; t.his, it issuggested, is due to the suppression of one dynamic isorneride bythe strongly acidic nitro-group, which is more closely associatedwith the imino-group in the ortho- and para- than in the met%derivative.The case of ac-tetrahydronaphthylamine is interesting; the com-pound from this substance and oxymethylenecamphor appears tobe homogeneous, but exhibits mutarotation.These observationscan readily be explained on the same assumption as that which wasadoptedI9 to account, for the fact that this substance undergoesl6 Kipping, Trmzs., 1909, 95, 408.l8 F. S. Kipping and A. H. Salway, ibid., 1904, 85, 438.W. J. Pope and A. W. Harvey, I'Tu~Ls., 1901, 79, 74.l7 ITT. J. Pope and J. Read, ibid., 171.1 116 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.almost complete racemisation when liberated from its salts.this case the following scheme would represent the changes :I nC* CH:N-CH*CH,*CH, C: CH*NH*CH CH,*CH,C H / I I 1 ZCSHl*’Il I I\C*OH OH,-C,H, 14\co CH,- --C6H4(1.) (11.1 . , , .C*CH,*N: C CH,*CH,and C H ’11 I I1 4 \ ~ . ~ ~ CH,-C,H,(111.)Thus, owing to a tendency for the nitrogen to become doublylinked to the (asymmetric) carbon atom in the ring, the compound(I) is converted into two forms (I1 and 111), of which the latter isno longer asymmetric as regards the tetrahydronaphthylamine partof the molecule, and consequently in solution the d-form would bereadily converted into the I-form and vice versa, and no separationwould be effected.Several amino-acids have been resolved by the action of yeastin the presence of sugarFo and the optical antimerides of the naturalsubstances have been thus obtained.Thus, d-phenylalanine,d-serine, I-phenylaminoacetic acid (impure), and a-amino-a-methyl-butyric acid have been prepared.Methylisoserine was readily resolved in the form of its benzoplderivative by means of quinine or brucine,21 and the formylderivative of a-amino-n-hexoic acid similarly by the use of brucine.22Synthetic a- and 8-cincholeuponic acids have been resolved bymeans of brucine, and d-8-cincholeuponic acid, to obtain which thebrucine salt of the acetyl derivative was used, is found to beidentical with the acid obtained from quinine and cinchonine.23I n spite of the fact that difficulties have been encountered sofrequently in the resolution of sulphonic acids, dl-camphorsulphonicacid from synthetic camphor can be resolved readily by means ofb r u ~ i n e .~ ~Our knowledge of racemic, pseudo-racemic, and partly racemiccompounds has been extended, for, in addition to the interestingwork of Kipping already mentioned, the following observationsare recorded.Tetrahydroquinaldine hydrogen tartrate forms a partly racemicsalt above 59O, but below this temperature the two salts areseparable by cry stallis at ion .25The melting-point curve of the I-menthyl d- and I-mandelatesF. Ehrlicli and A.Weadel, Zeitscl~. Vcr. deut. Zuckeyind, 1908, 198 ; A., 1908,i, 268. 21 P. W. Kay, Annalew, 1908, 362, 325; A . , 1908, i, 772.21 z). NarIio, zbid., 333 ; A., 1908, i, 772.23 A . Wohl and R. Maag, Ber., 1909, 42, 627 ; A . , i, 254.24 13. Itcmald, ibid., 3136 ; A., i, 811.25 A. Ladeliburg ancl W. liwmiaiiii, L’cr., 1908, 41, 966 j d., 1908, i, 364STEREOCHEMISTRY. 117examined in 190726 showed that a definite partly racemic com-pound was formed. The solubility in alcohol of I-menthyl dl-man-delate in presence of each of the d- and I-mandelates separately hasnow been examingd a t different temperatures.* The curve is of theordinary double salt type, and there is no evidence of the existenceof a transition point between 35O and -15°.27Further information concerning the melting-point curves ofpseudo-racemic mixtures has been acquired by the study of certaind- and r-amyl derivatives.28 The melting-point curve of a pseudo-racemic mixture is usually a horizontal straight line, and this istrue in the following cases: d- and r-1-amyl 3-nitrophthalates, thecompounds themselves and mixtures of them melting a t 116O, d-and r-2-amyl 3-nitrophthalates melting a t 155O, CC and r-amylphenylcarbamates melting a t 31°, and d- and r-P-methylvaleramidesmelting at 126O. The melting-point curve of a pseudo-racemicmixture had been found to show a maximum in the case of thecarvoximes, and the first instance of a minimum has now beenobserved in the case of d- and r-amyl carbamates.The problem of racemisation, especially when it occurs duringchemical transformations, and the allied problem of the Waldeninversion continue to attract attention, and many valuable con-tributions to our knowledge of the mechanism of these processeshave to be noted.It is found z9 that if d-amyl alcohol is converted into d-amylbromide by means of phosphorus tribromide, the bromide obtainedhas [aID 4*25O, but when hydrobromic acid is used the value of[aID is only 3*68O.Therefore partial racemisation occurs duringthe action of hydrobromic acid.I f now d-amyl bromide is con-verted into d-amyl acetate by the action of silver acetate a t 150°,and the latter hydrolysed by means of 22 per cent. sodiumhydroxide solution, the amyl alcohol obtained shows a rotation ofonly - 1 * 0 8 O in a 5 cm. tube instead of - 2'29O. The racemisationhas not taken place during the hydrolysis of the d-amyl acetate,since if this is prepared directly from the alcohol and acid andhydrolysed, the alcohol is recovered with unchanged rotation.Further, if the d-amyl bromide is converted into the iodide,and the latter into the acetate by the action of potassiumacetate, the amyl alcohol obtained on hydrolysis has a rotatorypower of -2.13O, whereas if silver acetate is used instead ofpotassium acetate, the alcohol obtained finally has a rotatory powerof -1'53O.The racemisation therefore takes place during theaction of silver acetate on the bromide, and, to a less extent, on26 Ann. Report, 1907, 185.27 A. Fincllay and Miss E. M. Hickmans, Trans., 1909, 95, 1386.23 W. Marckwald and E. Nolda, Ber., 1909, 42, 1583 ; A., i, 350.29 TIT. Marckwald and E. Nolda, loc. cit118 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.the iodide. This case t.herefore closely resembles the Waldedinversion.Another case which resembles the Walden inversion was foundin the action of nitrous acid or of nitrosyl bromide on active phenyl-aminoacetic acid, when inactive mandelic or phenylbromoacetic acidwas produced. It is noteworthy that in this case racemisation wasalmost complete when the ethyl ester of the active amino-acid wasused.30The study of Z-benzoin and its derivatives has revealed a numberof cases in which racemisation takes place very readily.31 &Benzoinitself is stable in the cold, but is rapidly racemised in presence ofan alkaline catalyst; its methyl and ethyl ethers show the samebehaviour, the former being completely racemised in the cold bya O*l13N-solution of alcoholic potash in five minutes. The ethersare also racemised by heat.The racemisation in these cases is readily explained by keto-enolic change taking place, thus :Ph*QH*OHPh*CO+ Ph*g*OHPh*C*OH' cThis view is supported by independent evidence32 that benzoincan react as the enolic form.The change of Z-pinene into dipentene under the influence ofaqueous-alcoholic sulphuric acid has been examined, and it hasbeen shown that active terpineol and an ether are first formed;these are then converted into Z-limonene and then finally intodipentene.33A similar case of almost complete racemisation was observedwhen synthetic active terpineols were dehydrated by the action ofmagnesium methyl iodide in the cold, or of anhydrous oxalic acida t looo; the dipentene produced showed a, specific rotatory powerof only 5O.34The change of Z-amygdalin into a mixture of unequal quantitiesof d- and Z-amygdalin (the prefixes d- and Z- here indicate thecharacter of the mandelic acid obtainable from the amygdalin) hasbeen shown to be brought about by the catalytic action of alkalis,but the change 35 is complicated.A brief summary of our knowledge of the Walden inversion wasgiven in 1907,36 including the work done during that year by30 E.Fischer and 0. Weichhold, Ber., 1908, 41, 12.86 ; A., 1908, i, 419.31 H. Wren, Trans., 1909, 95, 1594,33 W. N. Haworth, ibid., 486.M I<. Fisher and W. H. Perkin, jun., Trans., 1908, 93, 1871.D(i J. W. Walker and V. K. Krieble, Trans., 1909, 95, 1435.36 A m . .Report, 1907, 190.W. A. Smirnoff, J. Buss. Phys. Chem. SOC., 1909, 41, 996; A., i, 942.A more detailed historical acconnt was given byk McKenzie and G. W. Clough, Trans., 1908, 93, 811STEREOCHEMISTRY. 119Glycine on \ 1\NH3chlorided-Valine t- d-Valylglyciiie NH3 d-a-BromoisovalerylglycineHydrolysis t-IICOH orAg20I A ~ .~ o and 1J. hydrolysis$I - VaIin e HNOZ d-Hydroxyisovaleric acid. -+A consideration of the above series of changes shows conclusivelythat, in this case, ammonia, and nitrosyl bromide act in the sameway, and so also do potassium hydroxide and silver oxide, whereasin all cases previously examined these reagents acted differently,and, apparently, potassium hydroxide and ammonia were normalin their action while nitrosyl bromide and silver oxide wereabnormal.It seems probable that, in this case, ammonia behaves abnormally,and silver oxide normally, since the behaviour of ammonia isdifferent while that of silver oxide is the same when the carboxylgroup is protected by being converted into a *CO*NHR group.Nitrous acid aIso appears to depart from its usual habit, andto behave abnormally.It is suggested that the differences are dueto the isopropyl group.37 F;. Fischer and H. Scheibler, Ber,, 1908, 41, 889, 2891 ; A,, 1908, i, 324, 857120 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.A study of the transformations of active mandelic acid and alliedsubstances 38 has shown t,hat the phenyl group also exerts a distinctinfluence on the course of the Walden inversion, and it certainlyfavours the occurrence of extensive racemisation during thechanges. The following scheme summarises the first series of trans-formations which were studied :d-Mandelic acidI p a 5 I 9 E-Phen ylchloroacetic,acid1 mao@r + Z-Mandelic acid NaOMe I I I IAgzO f 4 1 Me12-Phenylmethoxyacetic acid f-The action of phosphorus pentachloride on the esters ofd-mandelic acid yields the esters of Z-phenylchloroacetic acid, andtherefore it is highly probable that this action is optically normal.Consequently the action of silver oxide is also normal, while thatof sodium hydroxide is abnormal; thus, the rule which applies inthe case of derivatives of malic and propionic acids is reversedhere.It is also concluded that, of the two methylating agents used,sodium methoxide is the one which causes a Walden inversion.Transformations effected by means of ammonia and of nitrousacid have also been studied by the same workers, and these maybe summarised as follows:d-C,H,*CH(OH)*CO,H $?%.Z-C,H,*CH(NH,)*CO,H+K-H~OHp 5 II(E-C,H,*CH(NH,).CO,H HNO~ j Z-C6H5*CH( OH) C02HAs pointed out already, almost complete racemisation takesplace during the action of nitrous acid on phenylaminoaceticacid, and this is also true for the action of phosphorus penta-chloride and of ammonia, so that the products examined in thesecases have only a very feeble rotatory power.The action of nitrosyl bromide on 2-phenylaminoacetic acid wasalso examined, and produced T + d-phenylbromoacetic acid.A consideration of the above transformation of d- into Z-mandelicacid shows that a Walden inversion takes place either at one of thethree stages or at all three, and that nitrosyl bromide and ammoniabehave in the same way.The simplest assumption to make is that3* A. McKenzie and G . W, Clough, Trans., 1908, 93, 811 ; 1909, 95, 777STEREOCHEMISTRP.121the action of ammonia is abnormal here as it is in the case ofa-bromoisovaleric acid.No Walden inversion takes place when the asymmetric carbonatom is in the &position with respect to the carboxyl group, sincethe following transformations have been effected 39 :PCljAgzOand the same result is obtained if the methyl ester is used.The Walden inversion is therefore a complicated process, thecourse of which is not determined entirely by the mode of action ofthe reagent used, but is largely influenced by the group attachedto the asymmetric carbon atom, since, for instance, the action ofammonia on a halogen acid produces inversion when a phenyl orisopropyl group is attached to the asymmetric carbon atom, anddoes not when a methyl group or a -CH,*CO,H group is presentinstead,The following conclusions, however, have been firmly establishedby the recent work.(1) The Walden inversion is dependent on the presence of acarboxyl group attached to the asymmetric carbon atom, and doesnot take place when the carboxyl group has been converted into*CO,R or *CO*NH*R.(2) The action of phosphorus pentachloride is normal, whilethat of nikrosyl bromide is abnormal.A large number of new substances exhibiting optical activityhave been prepared in addition to those already mentioned,but many of these must be left unmentioned.Reference hasbeen made to the preparation of optically active terpineols 40and of Z-benzoin 41 in the Annual Report for 1908.A number ofderivatives of Z-benzoin have now been prepared, including itsmethyl and ethyl ethers, carbanilido-Z-benzoin, and the a-oxime ;d-benzoin has also been prepared.42 The a-oxime of Z-benzoinexhibits marked mutarotation when dissolved in acetone, aceto-phenone, or benzaldehyde, but the rotatory power does not changein solution in chloroform, alcohol, or ethyl benzoate. It is sug-gested that the great increase of rotatory power observed is dueto the partial conversion of the a-oxime into the 0-oxime, but thiscould not be isolated.Two inactive forms of ad-dihydroxyadipic acid are known ; underthe action of heat one of these, melting a t 1 4 6 O , gives a dilactone;the other, melting a t 1 7 4 O , gives a lactone-lactide.A study of theconfigurations of these acids shows that the internally compensatedZ-CH,*CH(OH)'CH,*CO,H r+ d-CH,*CHCl*CH2*C02H,39 E. Pischer and H. Scheibler, Ber., 1909, 42, 1219 ; A , , i, 359.40 Ann. Report, 1908, 98.4l Ibid., 109. 42 H. Wren, Tram., 1909, 95, 158122 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.(meso) form should give a lactone-lactide, and the externallycompensated form should give the dilactone, and this predictionhas been verified by the resolution of the isomeride, melting a t146O, into its optically active components by means of ~inchonine.~~The isomeride melting at 174O could not be resolved by the samemethod.The two optically active forms of thiolactic acid have beenisolated by reduction of the corresponding dithiodilactic acids,which were separated by means of d- and Z-a-phenylethylamine.4*The thiolactic acids exhibit a very much greater rotatory power,[a], & 45-5O, than the lactic acids.The active prolines have been separated by the crystallisation ofthe strychnine salts of their m-nitrobenzoyl derivatives.45Natural I-serine has been converted into the correspondingchloro-acid, and this, when treated with barium hydrosulphide atlooo, and the product oxidised by atmospheric oxygen in presenceof ammonia, yields cystine, having [a], - 210°, while naturalcystine has [a], - 224O, and the two are therefore the same, allowingfor small quantities of impurity in the synthetic product.46It is interesting to note that the two optically active methylhydrogen mesotartrates have been separated by the crystallisationof their strychnine salts.47The study of optically active reduced naphthoic acids has nowbeen completed by the resolution of A3-dihydro-2-naphthoic acid bymeans of menthylamine.45 The value of [MI, for the acid insolution in chloroform is less than that of A2-dihydro-1-naphthoicacid, but it shows a greater rotatory power than this in solutionin benzene.For the purposes of comparison, phenylallylacetic acid,a-phenylvaleric acid, and P-phenyl-a-ethylpropionic acid have alsobeen resolved by means of menthylamine.Some interesting contributions have been made to our knowledgeof the sugar group, including a new method for determining theconfiguration of three out of the four asymmetric carbon atoms in+H(OH)~HO + CHO.CC1, = CH(OH)*CH(OH)*CH(OH)*CH2*OH 7 84 5 6$He;! H (OH)*O-+ H* 6C13CH--- C( OH) CH( OH) *CH,*OH' o<2 4 1 (i43 H.R,. Le Sueur, Trms., 1908, 93, 716.44 J. M. LovQn, J. pr. Chem., 1908, [ii], 78, 63 ; A., 1908, i, 714.45 E. Fischer and G. ZemplBn, Ber., 1909, 42, 2989 ; A., i, 793.46 E. Fischer and I<. Itaske, Ber., 1908, 41, 893 ; A., 1908, i, 325.47 W. Marckwalci and L. ICarczag, Ber., 1909, 42, 1518 ; A . , i, 361.*R R. H. Pickard and J . Yates, T'rrms., 1909, 95, 1011STEREOCHEMISTRY. 123aldohexoses.4D Sugars combine with chloral to produce compoundscalled chloraloses (see equation on p. 122), which on oxidation givechloralic acids of the formula :The isomerism of the latter depends on the configuration of thethree asymmetric atoms numbered 2, 3, and 4 in the originalsugar.If, therefore, two sugars give the same chloralic acid, theconfiguration of these three carbon atoms must be the same.It is probable, however, that difficulties would arise in theapplication of this method, owing to the production of two newasymmetric carbon atoms, 1 and 7, during the formation of thechloralose, and it is probable therefore that this would be a,mixture in all cases, and, even if one constituent predominated toa large extent, this would not necessarily be the same from twosugars, such as dextrose and d-mannose.An interesting addition has been made to our knowledge of theaction of alkalis on sugars. Since dextrose and d-mannose areconverted by the action of alkalis into lfevulose, and a similarchange takes place in the case of d-galactose, it was to be expectedthat I-gulose and I-idose would yield I-sorbose under the sametreatment, and it has been shown that this change is effected byb a r ~ t a .5 ~ The change is precisely analogous to the well-knownchanges mentioned above, and may be represented thus :CHO CH,*OH CHOH ~ O H 6:0 HO&HH ~ ~ O H -+ HAOH -+ H-h-OHHO*&H t- HO-&H +- H O ~ HHAOH H&OH HAOHI I ~H;OH CII,*OH CH,*OHI-Gulose. I-Sorbose. I-Idose.The four sugars, I-gulose, I-idose, d-talose, and I-ribose, have beenpurified by conversion into various substituted phenylhydrazonesand recovering the sugars by treatment with formaldehyde orbenzaldehyde.The last was obtained in a crystalline state whenrecovered from its p-bromophenylhydrazone 51; it has [a], 18.8O,and shows no mutarotation.The polyhydric alcohols, d-talitol 52 and /3-glucoheptitol,53 have49 M. Hanriot, Compt. rend., 1909, 148, 487 and 640 ; A., i, 206, 287.5O W. Alberda van Ekenstein and J. J. Blanksma, Bee. Irav. chim., 1908, 27, 1 ;51 Idem. ; Chent. Weekblntl, 1908,5,577; A . , 1908, i, 951; ibicl., 1909,6,37:I;A., i, 456.ti2 G. Bertrand and P. Bruneau, Compt. rend., 1908, 146, 482 ; A . , 1903, i, 249.53 L. H. Philippe, ibid., 1908, 147, 1481 ; A , , i, 136.A., 1908, i, 1361% ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.been prepared in a pure crystalline state by the reduction ofd-talonic acid and P-glucoheptose respectively.An interesting relation f;as been worked out between the rotatorypowers of the two dynamic isomerides of aldoses and those of thea- and P-glucosides of the same sugar.54It is assumed that the two forms of a sugar are stereoisomerideson the Tollens’ formula, just as the glucosides are:OH~H*CH(OH).CH(OH).CEC.CH(OH)-CH,.OR.I 0 -- I -Then it is found (1) that the difference between the values of[MI, of the a- and P-forms of all the aldehydic sugars, and of alltheir derivatives in which the terminal asymmetric carbon atom(marked *) is not affected, is a nearly constant quantity, and (2)that the sum of the values of [MI, for derivatives of the a- and&forms, in which only the terminal carbon atom is affected, is equalto the sum of the values of [MI, for the two forms of the sugar.I f the contribution of the terminal carbon atom to the value of[MI, be represented by A, and that of the other asymmetric carbonatoms by B, then the [MI, for the a- and P-forms will be repre-sented by (A+B) and (-A+B), and the difference will be 2A,which is approximately the same for all sugars, since the otherasymmetric atoms seem to have little influence on the rotatorypower of the terminal carbon atom.For the corresponding glucosides the values of [MI, would be+ A/+ B and - A/ + B, since the terminal carbon atom is the onlyone affected, and the sun1 (2B) should be the same as that forthe a- and P-forms of the sugar.The following numerical data selected from those given will showthe degree of agreement obtained, which is only approximate.The differences between the values of [MI, for a- and /3-forms areas follows: Glucose, 160; galactose, 157; arabinose, 162.The sum of the values of [MI, for a- and P-glucoses is 232.7, J J 7, ,, a- ,, P-methylglucosides is 243.9 9 I , 97 ,, a- ,, P-ethylglucosides is 252.A very large number of papers dealing with the quantitativestudy of optical rotatory power have appeared, and the result hasbeen to establish still more clearly the complicated nature of theproblem.Many factors must be taken into account besides themasses of the group attached to the asymmetric carbon atom,and in some cases the chemical character of a group entirely out-weighs the influence of its mass.This was quite clearly shownby Betti’s work in 1907,56 and several investigations now supplyfurther instances of a similar kind.54 C. S. Hudson, J. Amer. Chena. SOC., 1909, 31, 6 6 ; A., i, 135.55 Awn. Report, 1907, 179STEREOCHEMISTRY. 125D. A. Chardin and S. Sikorsky66 give the details of theexamination of derivatives of active amyl and hexyl alcohols under-taken with the view of determining the value of the "atomic productof asymmetry." Fairly consistent values for the atomic product foroxygen can be obtained in this way; thus, the value 129 is obtainedfrom hexyl alcohol, and 132 from amyl alcohol, while theoryrequires 139. No explanation can be offered of the fact that thesign of the quantity deduced from the two alcohols is different.The values obtained for bromine are, however, much more divergent,and tend to show the limited applicability of the method.A claim has been made57 that the simplified expression( a - b ) ( a - c ) ( a - d ) ( b - c ) ( b - d ) ( c - d ) gives values for the asym-metry product in better agreement with the actual values of [MI,found for forty-two derivatives which were examined; but this iscontroverted very successfully in a later paper,5* in which it isshown also that no " rotation equivalents '' can be assigned to eachgroup.Assuming the above expression to apply, it is shownmathematically that in a case like that of mandelic and phenyl-chloropropionic acids the ratio of the values of for the methyland ethyl esters of these two acids should be the same, whilethe actual ratios found are 0.535 and 1.060 respectively.Two cases are recorded in which considerable rotatory poweris exhibited by compounds in which two of the groups attached tothe asymmetric atom have the same weight and differ only in con-stitution.Thus, cyanopropylisopropylacetic acid was resolved bymeans of its brucine salt, and found to have [MID 1 8 2 O in toluenesolution.59 p-Tolylbenzylmethylallylammonium hydrogen d-tar-trate was resolved, and the basic ion was found t o exhibit amolecular rotatory power of 246O, which is considerably greaterthan that of the compounds containing the phenyl and p-bromo-phenyl group in place of the p-tolyl group.60A number of papers deal with the influence of unsaturation onrotatory power, but, although it is found that the introduction ofan ethylene linking usually increases the value of the rotatorypower, this is by no means always the case.The results obtained with bornyl, menthyl, and amyl esters ofphenylpropionic, cinnamic, and phenylpropiolic acids are discussed,61but no general conclusion can be deduced from them, and it isclear that the influence of unsaturation is in many cases small.lii J.12uss. Phys. Ct~em. Soc., 1908, 40, 502 ; A . , 1908, ii, 548 ; J. Chim. Ph,ys.,1908, 6, 179 and 584 ; A., 1908, ii, 470 and 912.57 E. Rose and F. A. Willers, Zcitsc7~. physiknl. Chenz., 1909, 65, 702 ; A . , ii, 361li8 J. W. Walker, J. Physical Che~n., 1909, 13, 574 ; A., ii, 846.59 E. Fischer and E. Flatau, Sitzungsbcr.K. Aknd. Wiss. Berlin, 1909, 876 ;B" R. W. Everatt and H. 0. Jones, Y'ram., 1908, 93, 1789.61 T. 1'. Hilclitcli, Il'rans., 1908, 93, i.A . , i, 628126 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTHY.The menthyl esters and brucine salts of a series of nine saturateddibasic acids have also been examined, and here also the influenceof constitution is not very marked. In the case of the esters, therotation of the oxalate is the greatest ( - 378O), and that of theadipate is next in order of magnitude (-352O), while that of thesebacate is least, 319'. The results with the salts are almostparallel, with the exception of the oxalate, which has the smallestrotatory power.62The iiifluence of contiguous, unsaturated groups on opticalactivity is discussed63 and examined in the case of some aromaticesters and salts of camphoric and P-camphorsulphonic acids, andthe conclusion is drawn that contiguity of unsaturated groupsproduces abnormal effects on the optical rotatory power.I n boththe lastrmentioned cases, the original papers should be consulted,since an adequate account of this work cannot be given here.An account has appeared of an extensive investigation64 of theeffect of replacing a methyl group or hydrogen atpm in an acid bya phenyl group on the rotatory power of the menthyl esters, andthe following conclusions are drawn from the results.(1) The replacement of a methyl group by a phenyl group isusually accompanied by a decrease of rotatory power, as, forexample, menthyl crotonate has [u]: - 9 lo, while menthyl cin-namate has [a]: 77"This conclusion does not appear to be justified from the datagiven, since the values of molecular rotatory power should be com-pared ; these are 204O and 220° respectively.Further, this conclusionis not in agreement with the results obtained with many other com-pounds, or with those on substituted bornylamines mentioned later,and it is not borne out by the results quoted below.(2) The assemblage of electronegative (phenyl) groups near theasymmetric system decreases the rotatory power ; thus, menthylP-phenylcinnamate has [MI, - 137O, and menthyl a-phenylcinnamate[MID - 1 9 3 O , compared with 220° for menthyl cinnamate.(3) The influence of the phenyl group increases it5 it becomesmore distant from the asymmetric system.A comparison of thefollowing three pairs of substances does not, however, appear tobear out this conclusion : [MI?. Difference................... + 31"+ 9- 58Menthyl propionate - 160", , phenylacetate ............... 191,, i3-pheuylpropionate ......... 169..................... ,, butyrate 160,, hexoate 165,, 8-phenylvalerate 107....................................A number of acyl-bornylamines have been prepared and their62 T. P. Hilditch, Trans., 1909, 95, 1578.6* H. Eupe, Annalen, 1909, 369, 311 ; A., i, 927.63 T. P. Hilditch, Ibid., 331STEREOCHEM18TKY. 127rotatory powers examined 65 in solution in methyl and ethyl alcohols,in glacial acetic acid, and in pyridine. The compounds nowexamined, taken in conjunction with the alkylbornylaminesexamined by Forster,66 enable an interesting comparison to be made.The introduction of an alkyl group into bornylamine increasesthe dextrorotatory power very considerably, but the differencebetween the rotatory powers of the various alkyl compoundsis not very striking.All the acyl compounds, on the otherhand, are hvorotatory. The aliphatic acyl derivatives have verydifferent rotatory powers in the different solvents, the order ofmagnitude being ethyl alcohol, methyl alcohol, acetic acid, pyridine,but the influence of pyridine on the rotatory power of formobornyl-arriide is apparently abnormal. I n the aliphatic acyl series, amaximum is found either at the acetyl or the propionyl member inthe different solvents.The members of the aromatic acyl series of compounds are alsolzevorotatory, except in certain cases in pyridine solution, when thecompounds become dextrorotatory.The nitrobenzobornylamidesare more strongly hvorotatory than the toluobornylamides, andthe relation between the rotatory powers of the ortho-, meta- andpara-compounds is, in some cases, in agreement with theoreticalpredictions. The original paper should be consulted for thedetailed discussion of the results.The study of certain derivatives of camphorquinone 67 has ledto the production of substances of enormous rotatory power, andto interesting resu1t”s showing the great influence of unsaturationand of chemical character of the groups present on rotatory power.Camphorquinone condenses readily with aromatic amines to giveC:N*Rcompounds of the type C8H14<l , and with diamines to give cocompounds containing two camphorquinone residues.The results obtained by a study of the rotatory powers of thecompounds in pyridine or chloroform solutions bring out thefollowing principles illustrated by the compounds the formulz andmolecular rotatory powers of which are given below.A conjugated double bond ( a ) acting alone produces a smallincrease in rotatory power; ( b ) while in co-operation with a benzenering its influence is greatly increased.(a) is illustrated by a comparison of the rotatory powers of1 and 2, and of 5 and 6, while ( b ) is illustrated in the same wayby comparing the difference between 1 and 2 with that between3 and 4, and the difference between 5 and 6 with that between7 and 8.65 P.P. Flmklarid and P. Barrow, Z’rans., 1909, 95, 2017 and 2026,66 Y’rans., 1899, 75, 934.67 If. 0. Forster and T. Thornley, ibid., 1909, 95, 942128 ANNUAL REPORTSYH*NH,( l ) C8H14<~:0 735".(4)ON THE PROGRESS OF CHEMISTRY.151". 1750".CH*NHPh.'SHl4< c: ' 0 J309".5XCH,also ( 5 ) C,HI,<(?H*CH3 c:o ' (6) C8Hl*<C:0 '50". 209".1020". 348"The introduction of a hydroxyl group into the phenyl group inthe para-position in (3) raises the rotatory power to 4240O.The phenyl group here exerts a greater influence when close tothe asymmetric system than when more remote from it, which isshown by comparing the rotatory powers of 3 and 7 above withthose of:832".789".Pope and Read.The introduction of a second phenyl group has a depressingeffect in some cases, as may be seen by comparing the rotatorypowers of (7) and (9) with those o f :907". 420".respectively.The compound C,H14< C:N*C6H4'S:?>CsH,4 I has a molecular c:o 0: crotatory power of 6173O in pyridine solution, which is the highestyet observed.Attention has been called to the desirability of studying therotatory powers of substances for light of different wave-lengths,and a method of obtaining monochromatic light of the requisiteintensity has been described.68Certain observations made recently have also shown thedesirability of this very forcibly. Thus, ethyl tartrate, a substancethe rotatory power of which, under different conditions, has receivedmore attention than that of any other substance, has been shown 69to exhibit anomalous rotatory dispersion either when pure or whenmixed with chlorobenzene or tetrachloroethylene. In the first two6s T.M. Lowry, Proc. lhy. Soc., 1908, A, 81, 472 ; A., ii, 200.6B H. Grossmaiin, SCT., 1909, 42, 2646 ; A . , ii, 713STEHEOCHEMTSTRP. 129cases there is a maximum of rotatory power in the green, whilethere is a minimum in the last case.The coloured xanthates and xanthogenides of menthol andborneol have also been shown to exhibit anomalous rotatorydispersion in the neighbourhood of their absorption bands.70The investigation of the rotatory power of ethyl tartrate indifferent solvents has been considerably extended by Patterson andhis colleagues.The rotation in fatty halogen derivatives71 and in aromatichalogen derivatives 72 has been examined without any very strikingresults, but the study of aromatic nitro-derivatives 73 has yielded themost remarkable results yet obtained.The specific rotatory powerof ethyl tartrate in a-nitronaphthalene a t infinite dilution is + 6 5 O ,while in s-trinitrobenzene under the same conditions it is -30°,thus surpassing both the upper and the lower limits previouslyobserved, in formamide + 30*4O, and in ethylene dibromide - 1 9 O .The dependence of rotatory power on temperature was also investi-gated, and it has been found that in one solvent the temperaturea t which a maximum rotatory power occurs is apparently inde-pendent of the concentration.A relationship has been establishedbetween the maximum rotatory power and the temperature atwhich it occurs, which relationship appears to be independent ofthe nature of the solvent and of the concentration. The laevo-rotatory power of ethyl tartrate in acetylene tetrabromide decreasesvery rapidly with increasing temperature, until above SOo thesolution becomes dextrorotatory.Quinoline and benzaldehyde have also been added to the listof solvents e~arnined.7~ Solutions of ethyl tartrate in the formershow a very marked maximum of specific rotatory power of 29O,when the concentration is represented by 44 per cent. of ethyltartrate, which roughly corresponds with two molecular proportionsof quinoline to one of ethyl tartrate.It mL&, however, be notedthat the concentration a t which the rotatory power is a maximumis not the same at different temperatures.The influence of mixed solvents on the rotatory power of ethyltartrate has also been examined,75 the solvents chosen, ethylenedibromide and nitrobenzene, having widely different effects on therotatory power of the solute, ethyl tartrate, and also very differentdensities. The influence of each solvent on the rotatory power wasL. Tschugaeff, Be?., 1909, 42, 2244 ; A . , ii, 631.71 T. S. Patterson and D. Thomsou, Trans., 1908, 93, 355.72 T. S. Patterson and D. P. McDonald, ibid., 936.73 T. S. Patterson, ibid., 1836.74 T. S . Patterson arid D. P.McDonald, Trans., 1909, 95, 321.75 T. S . Patterson and H. H. Montgomerie, ibid., 1128.REP.-VOL. VI. 130 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.found to be proportional to its volume, and it was possible tocalculate the rotatory power of the solutions from their compositionsand the known influence of each solvent separately on the rotatorypower of the solute.The method of applying the change in the rotatory power whichethyl tartrate undergoes in different solvents to the investigationof intramolecular change in inactive substances mentioned in 1907 76has now been further extended.77 The change of piperonalsyn-oxime, anissynaldoxime, and w-isonitrotoluene into their dynamicisomerides has been studied, and it has been found that the rateat which these changes proceed is an exceedingly sensitive test forthe purity of the ethyl tartrate.The change of ammonium thio-cyanate and ammonium cyanate did not seem to proceed so regularlyas the others. It is possible that this may be due to interactionof the ethyl tartrate with these substances.Whether we shall ever be able to unravel the compEcatedproblems of the relation between rotatory power and chemicalconstitution and of the influence of solvents on rotatory power isdoubtful at present; but it is clear from what has been said abovethat much more experimental work will be required before we caneven fix upon the data which are to serve as a basis for theoreticaldiscussion, since, if phenomena like those already mentioned areexhibit'ed, it is useless to attempt to discover general laws or tofound a theory on the results obtained with light of one wave-length until it has been proved that anomalous rotatory dispersionis not exhibited by the substances or solutions under examination.The most important contributions to our knowledge of opticalactivity of silicon and nitrogen compounds have already beenmentioned in 1908,7* so that a brief reference must suffice here.A second asymmetric silicon compound, of the same type as thefirst resolved in 1907, has now been resolved.79 This compound,dl-sulphobenzylethylisobutylsilicyl oxide, was again resolved by theuse of methylhydrindamine, and the two d- and Z-sodium salts werefound to have specific rotatory powers of f10.5°, which is nearlytwice as great as that shown by the corresponding compound con-taining the propyl instead of the isobutyl group.The differencesbetween salts of Z-menthylamine, of bornylamine, or of cinchoninewith the two acids are again very slight.No compound containing a single asymmetric silicon atom has yetbeen resolved, although in the case of dFbenzylethylpropylisobuty1-silicanesulphonic acid indications were observed that resolution was76 Ann. &port, 1907, 154.77 T. X. Patterson and A. McMillan, Trans., 1908, 93, 1041.78 Ann. lieport, 1908, 108, 109, 175.TY F. 8. Kipping and B. D, W. Luff, Truns., 1908, 98, 2090STEREUCHEMISTRY. 131being effected by crystallisation of the cinchonine hydrogen salt,which gave two fractions of specific rotatory power, +57.l0 and+ 73*8O, and this observation is being pursued.*OA new type of nitrogen compound exhibiting optical activityhas been found in methylethylaniline oxide.81 The d-bromo-camphorsulphonate of this base was resolved, and from thesolution of the less soluble, dAZB, salt the picrate was pre-cipitated and converted into the chloride by treatment withhydrochloric acid.The chloride, NMeEtPhCl*OH, has [MI, - 41°,and on treatment of the solution of this chloride with baryta therotatory power falls to - 2 5 O (but no racemisation has occurredsince the rotatory power rises again to - 4 1 O on the addition ofhydrochloric acid). This solution, it is assumed, contains the freebase, probably NMeEtPh(OH),, which contains a nitrogen atomwith only four of the five groups actually different.There is, however, a difference in character between the twohydroxyl groups, since only one of them behaves as a basic hydroxylgroup and is replaceable by an acid radicle.It is easy t o account for the occurrence of optical activity in thiscompound with the aid of the pyramidal configuration for thenitrogen atom, since if one of the hydroxyl groups is situated a tShe base of the pyramid and the other at the apex, the arrangementOHshown in the figure is obtained, is devoid of a plane of symmetryand therefore capable of giving rise to optical activity.An optically active compound containing two nitrogen atoms,one of which is asymmetric, C7H7*NMePhBr*CH,*CH,*NMePh,has been resolved 82 by crystallisation of the d-camphorsulphonateand of the d-bromocamphorsulphonate, the salt of the Z-base is muchless soluble than that of the d-base in the first case, while thereverse is true for the bromocamphorsulphonate.The iodide of the I-base has [M],-411’5°, and that of the d-basehas + 403’2O in alcohol.Autoracemisation t.akes place in solutionin chloroform and in alcohol, but takes place much more rapidlyin the former case than in the latter.8o F. S. Kipping and H. Davies, Trans., 1909, 95, 69.5. Meisenheimer, Ber., 1908, 41, 3966 ; A., i, 20.E. Wedekind and W. Ideyer, ibid., 1909, 42, 303 ; A,, I, 186.K 132 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Further instances are recorded of the formation of two com-pounds, when an asymmetric nitrogen atom is produced in acompound already containing an asymmetric carbon atom.Thus &men thy1 iodoaceta t a combines with N-ethyltetrahydroiso-quinoline to give two salts, having [a], - 44'9O and - 17.54O respec-tively. These give betaines, which become inactive very qui~kly.~3Similar results have also been obtained with N-n-propyltetrahydro-i~oquinoline.8~.It has also been shown that the addition of an alkyl haloid toan active N-alkylated coniine or conhydrine and to 2-phenyl-6-methylpiperidine results in the formation of two stereoisomericquaternary ammonium salts, but that active alkaloids, coniineexcepted, yield only one.Such stereoisomerides were obtained onlyfrom piperidine derivatives having a heavy substituent in position 2,and it is concluded that this is necessary in order to give therequisite stability to the group attached to the nitrogen atom.This view is confirmed by obtaining the active N-ethyl-a- andP-pipecolines and forming their additive compounds with benzylbromide or iodide; from these no isomerides could be separated.Similarly, the additive compound of active amyl iodide and l-methyl-2-pipecoline seemed to be homogeneous.Therefore a methyl orethyl group attached to the nitrogen atom and a methyl group inposition 2 does not seem to confer the requisite stability on thecompound .s5This conclusion, however, is not necessary, since it is quitepossible, as in the case of the cyanohydrin of mannose, that one ofthe two possible compounds is formed in very small quantities, andso might be entirely overlooked even after very careful examinationhad been made.Further,'a methyl group was found adequate inthe first case of this kind examined, namely, the addition of alkyliodides to methyl-d-amylaniline, in which case two well-charncterisedisomerides are produced.86In the study of phenyl p-tolyl hydrogen phosphate,PO(OPh)( O*C,H,)*OH,*7some indication has been found that asymmetric derivatives ofphosphorus can be resolved into their optically active constituents.The salts of this acid, with eight optically active bases, wereexamined without any indication being obtained that these saltswere mixtures; the melting points and specific rotatory powers ofthe most and least soluble fractions were in each case found to be83 E.Wedekind and 0. Wedelcind, Ber., 1908, 41, 456 ; A., 1908, i, 258.84 E. Wedekind and F. Ney, ibid., 1909, 42, 2138 : A., i, 514.s5 M. Schnltz, ibid., 1908, 41, 2005 ; A., 1908, i, 678.88 H. 0. Jones, Trans., 1905, 87, 135.B7 F. S. Kipping and €3. D. W. Luff, ibid., 1909, 95, 1993STEREOCHEMISTRY. 133identical. Slight indications that the acid was a mixture wereobtained from an examination of the salt with dZ-hydrindamine,but more definite evidence was obtained when the d-hydrindamidewas examined. This was separated by fractional crystallisationinto two fractions, the less soluble melting at 1 2 7 O and having[ ~ ] , - 1 7 * 4 ~ , while the more soluble melts a t 82-88O and has[a], - 21-2O.Similar results were obtained with the Z-menthyl-amide. This investigation is being continued, and it seems probablethat phosphorus will soon be added to the list of elements whichare capable of giving rise to optical activity.The problem of the isomerism of the cinnamic acids still continuesto attract considerable attention, and although several interestingcontributions to this subject have appeared, the problem is stillfar from a satisfactory solution.It is suggested 88 that allocinnamic acid and the two isocinnamicacids are polymorphs. A t 1 0 5 O all three acids are converted intothe acid, melting at 4 2 O , and this, when inoculated with the iso-cinnamic acid, melting at 5 8 O , or with aZlocinnamk acid, imme-diately crystallises as a mass of the inoculating acid.This view is, however, not accepted by E.Erlenmeyer, jun.,gg andit has also been shown that a specimen of the iso-acid, melting a t5B0, was unchanged after keeping for ten or fifteen years in thedark.g0A further complication has now been introduced into the problemby the discovery that synthetic cinna.mic acid is not a homogeneouss u b ~ t a ~ n c e . ~ ~ By means of fractional crystallisation of the acid,or better by fractional distillation of the ethyl ester, a new acidhas been isolated which melts at 1 2 8 O , has the same molecularformula as cinnamic acid, and therefore is stated to be a newisomeride and is called a-heterocinnamic acid. An amorphous formof this acid is obtained by saponification of the ethyl ester withcold alcoholic potash; this also melts a t 12B0, but differs from thea-acid in solubility; it is called hetero-j3-cinnamic acid, and canbe converted into hetero-a-cinnamic acid by repeatedly dissolvingit in light petroleum.It is clear that before the problem of the isomerism of thecinnamic acids can be solved, a careful investigation of theproperties of mixtures of the ordinary and allocinnamic acids, suchas melting point,, solubility, and crystalline form, must be carriedout.There is a t present little or no information on any of thesepoints, and n o evidence that the supposed isomerides are not mixed88 E. Biilmann, Ber., 1909, 42, 182 ; A., i, 155.89 Ber., 1909, 42, 521 ; A . , i, 155.90 C. Liebermann, ibid., 1027 ; A., i, 303.E.Erlenmeyer, ibid., 502 and 513 ; A., i, 156134 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.crystals or even definite molecular compounds, similar to the com-pound of triphenylmethane and benzene or even to quinhydrone,which may yet give normal values for molecular weight owing todecomposition in solution.A very large number of isomeric oximes are known, and forthe existence of isomeric ketoximes no explanation has been offeredexcept that of stereoisomerism suggested by Hantzsch and Werner.The existence of isomeric aldoximes can be explained on struc-tural grounds, but the existence of isomeric oxygen ethers, suchas C6H5*CH:N*O*C7H7, is definite evidence in favour of thehypothesis of stereoisomerism, although the N-substituted aldoximes,C,H,*CH--N*CH,, are very probably derived from the structural\/0isomeride. Now, although about dne hundred and forty ofthese N-substituted aldoximes are known, there is no indicationof the existence of isomerides in any but two cases, the methylderivatives of benzaldoxime and anisaldoxime. These cases havenow been re-examined,92 and it has been shown in both cases that thesupposed isomerides are monohydrated forms of the ordinaryAT-methyl compounds. Consequently, in the case of benzaldoxime,for exampIe, there exist the two oximes, two oxygen ethers (forexample, benzyl), and one nitrogen ether.An examination of the behaviour of the isomeric forms of theoximes of benzaldehyde, of the three nitrobenzaldehydes, and ofp-triazobenzaldehyde towards diazomethane has shown that theanti-aldoximes yield varying amounts, from 6 to 50 per cent., ofO-methyl ethers, whereas the syn-compounds, with one exception,are unchanged.93The authors are led, therefore, to accept the stereochemicalexplanation of the isomerisin of oximes, although it does not offera ready explanation of the difference in the behaviour of the syn-and anti-f orms, and suggest a modification of the Hant.zsch-Wernerhypothesis to account for the stability of the two isomerides.The view proposed assumes that the carbon atom, doubly linkedt o the nitrogen atom, exerts some attxactive force on the oxygenatom of the hydroxyl group, thus using to some extent the residualvalency of the latter. This is represented diagrammatically eitheras :The first method of representation makes the carbon atomg2 J. Scheiber, Annalen, 1909, 365, 215 ; A., i, 391.93 11. 0. Forster and F. P. Dunn, Trans., 1909, 95, 425S'I'E El E OCH E bI I 6TR Y, 135asymmetric, and is therefore improbable. The second may beregarded favourably on further investigation, since it does in somemeasure remove the difficulty of accounting for the comparativestability of the two forms.This view receives support from the fact that among the six typesof doubly linked nitrogen compounds :a*CH:N*QH, i>C:N-bH, ;>C:NvNH*(T, :>C:N*NHyCO*NH,,a*CH:N-b, and a*NIN*b,isomerism has been definitely established in the case of t.he first fouronly, and in these the atom, marked with a dot, attached to thenitrogen on the side remote from the double linking is possessedof residual or supplemental valency. It is clear that, in the nearfuture, interesting developments are to be expected in connexionwith the Hantzsch-Werner hypothesis of the stereoisomerism cfoximes.H, 0. JONES

ISSN:0365-6217    

DOI:10.1039/AR9090600110

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY.THE writer of this report has endeavoured to collate the voluminousliterature of this subject so as to form an epitome of the year’swork which shall be something more than a mere list or subject-matter index, t o show, in fact., the general trend of the investigationsin analytical chemistry. He is sensible that many omissions musthave been made, but in view of the comprehensive character ofthe subject, covering as it does the whole range of chemistry, thelimit of knowledge of any single reviewer is sufficient excuse forfaults of this kind. I n the selection of matter the writer has notbeen guided only by the novelty of the observations, but has takenaccount of those papers dealing with the revision of existingmethods. The somewhat large number of references to the work ofpast years has been given with the object of completing as far aspossible the historical portion of the subjecbmatter for the guidanceof those engaged in research work.The research schemeinaugurated by the Society of Public Analysts and other AnalyticalChemists has during the year thoroughly justified its existence, andis responsible for several interesting investigations.General.J. Wetzel 1 describes an apparatus for the distillation of mercury.For the purification of mercury, by passing it through a liquidsuch as dilute nitric acid, an apparatus has been devised byL. J. Desha.2 J. H. Hildebrand 3 recommends for the same purposea modification of L. Meyer’s method.4A new form of the von Babo-Krafft continuous mercury pumphas been devised by C.Hansen.5 A safety valve for water pumps,consisting of an automatic cut-off valve to prevent any variationin the water pressure, is described by C. Gerhardt.6Chem. Zeit., 1908, 32, 1228; A., ii, 145.Anzer. Chem. J., 1909, 41, 152 ; A., ii, 315.J. Amer. Chem. Soc., 1909, 31, 933 ; A., ii, 734.Zeitsch. anal. Chem., 1863, 2, 241.Zeitsch. angew. Chem., 1909, 22, 337.Zeifsch. unccl. Chem., 1909, 48, 460 ; A . , ii, 724ANALYTICAL CHEMIS’I‘RY. 137An ingenious apparatus for the preparation of gases is thatdevised by M. Gasnier.7 It has the advantage over Kipp’sapparatus that the pressure remains constant whatever the amountof gas withdrawn. E. E. Reid 8 describes a gas regulator which iscontrolled electrically.R. 0.E. Davis9 describes a modification of P. A. Kober’sapparatus,l* mhireby ammonia may be expelled quantitatively froma liquid by a current of air without distillation. This may proveuseful in dealing with liquids having a tendency to froth. Thesuggestion can be applied to the Kjeldahl method (see alsoJ. Sebelien, A. Brynildsen, and 0. Haavardsholmll). A usefulbulb-trap for ammonia distillations has been devised by F. Dudy.l2H. G. Parker13 proposes to perform precipitations in a platinumcrucible to the mouth of which is attached a glass tubular portionso that the whole, when fitted together, forms a flask. Subsidenceof the precipitate is brought about by centrifuging, and it is washedby syphoning.W. 0. Snelling14 describes the preparation of pIatinum felt foruse in the Munroe crucible.15 A list of the precipitates that maybe collected in the crucible, and of solvents for the removal of themfrom the felt, is given by 0.D. Swett.16 A filtering crucible, inwhich use is made of spongy platinum instead of asbestos, isdescribed by 0. Brunck.17 H. J. F. de Vries 18 puts forward a claimof priority for this crucible, which he has employed in the estimationof potassium.19 He describes the method of preparing the plat~inurnlayer.L. W. Bosart, jun.,20 recommends a mixture of cotton seed oil (10parts) and beeswax (1 part) for an oil-bath; the flash point of themixture is about 300O.An absorption apparatus, which is a combination of a Volhard’sflask with a Winkler’s absorption spiral, is described byH.Wolbling.21No estimations are recorded.Bull. Soc. chim., 1909, [iv], 5 , 56 ; A., ii, 223.Amer. Chem. J., 1909, 41, 148 ; A., ii, 296.J. Amer. CJwm. SOC., 1909, 31, 556 ; A., ii, 615.lo Ibid., 1908, 30, 1131 ; A , , 1908, ii, 626.l1 Chcm. Zeit., 1909, 33, 785; A . , ii, 757; F. W. Gill and H. S. Grindley,l2 Ibid., 1158 ; A . , ii, 1050.l3 J. Anaer. Chem. Soe., 1909, 31, 549 ; A . , ii, 610. l4 Zbid., 456 ; A., ii, 431.l6 J. Amer. Chem. Soc., 1609, 31, 928 ; A., ii, 755.l7 Chem. Zeit., 1909, 33, 649 ; A . , ii, 826.l9 Compare ibid., 1907, 4, 231, 455 ; 1908, 5, 176, 261 ; A , , 1907, ii, 504, 719 ;‘O J. Amer. Chem. SOC., 1909, 31, 724 ; A,, ii 563.21 Chem. Zeit., 1909, 33, 449.ibid., 1249 ; A., ii, 1051.l5 Chem.News, 1888, 58, 101 ; A., 1888, 1333.Chem. Weekblad, 1909 6, 816; A., ii, 1060.1908, ii, 430, 534138 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.C. L. Jackson and L. Clarke22 have devised a modification ofBcheibler’s extraction apparatus.23 It is suitable for u8e with largeguantities of material.K. von der Heide24 gives a description of several new forms ofpercolating and extraction apparatus. An apparatus for extractingplant products with a solvent a t its boiling point has been devisedby 8. J. M. Auld and S. S. Pickles.25 F. Record26 has improvedthe apparatus previously described 27 for extracting a solid andsimultaneously filtering the solution obtained, A. H. Fiske 28describes an apparatus for the extraction of liquids with ether.An ingenious condenser for an extraction apparatus is that of@.Fraschina.29 R. Fritsch30 has devised an apparatus which issuitable for extracting liquids with ether or for purifying etherfrom alcohol.J. Schroeder 31 describes an apparatus for determining the solu-bility of substances a t the boiling point of a solvent.D. D. Gadaskin 32 finds that it is advantageous to employ beads ofaluminium instead of glass in a dephlegrnator column; and severalnew forms of deplegmators adapted for liquids of high boiling pointare described by M. M. Tichwinsky.33 P. Malvezina4 has re-modelled the Lebel-Henniger column so that it resembles inprinciple the Coffey still. G. S. Walpole 35 has devised a gas-dryingapparatus for use with a, mechanical pump when conductingdistillations under diminished pressure.J.Lewkowitsch 36 gives a description of a new refractometerdevised by Harland on the Kohlrausch-Abbe principle, and showsits advantages over other refractometers.An important paper dealing with the correction of the specificgravity of liquids for the buoyancy of air is that of J. Wade andR. W. Merriman.37Airier. Chem. J., 1909, 42, 287 ; A., ii, 826.z3 Ber., 1880, 13, 338,24 Zeilsch. Nuhr. Genussm., 1909, 17, 315 ; A , , ii, 431,25 Chcm. News, 1909, 99, 242; A,, ii, 563.26 Ibid., 53 ; A,, ii, 223.27 Ibid., 1908, 97, 280 ; A., ii, 223.Amer. Chem. J., 1909, 41, 510 ; A., ii, 656.29 Giorn. Rarm. Chim., 1909, 58, 111 ; A., ii, 564.Chem. Zeit., 1909, 33, 759 ; A., i, 517.31 Zeitsch.anal. Chem., 1909, 48, 349 ; A., ii, 646.32 J. Rztss. Phys. Chem. SOC., 1909, 41, 66 ; A,, ii, 378.3y Ibid., 81 ; A., ii, 378.31 Bul2. SOC. chim., 1909, [iv], 5, 835; A. ii, 826.1 3 ~ Proc., 1909, 25, 97.s6 J. SOC. Chem. Ind., 1909, 28, 7737 Tram., 1909, 95, 2174ANALYTICAL CHEMISTRY. 139Gas Analpsis.J. F. Spencer 38 describes a, modification of Hempel’s gas burette,which obviates the inconvenience of the air space between theburette and the absorbing liquid. A useful volumeter with baro-metric correction has been devised by Herrna11.3~G. de Voldere and G. de Smet40 describe a t length their methodof calculating the composition of gas mixtures from data, such asthe quantity of oxygen required for complete combustion and thecontraction which occurs.41 For the estimation of carbon monoxidein admixture with methane and hydrogen, V.Nesmjeloff shows42that an accurate method is to pass the gases over copper oxide a t250°.J. Mai 43 proposed the application of Victor Meyer’s principle ofmeasuring vapour density to technical gas analysis. In a morerecent paper 44 he has simplified and improved the suggested method.G. von Knorre45 proposes a modification of Jager’s method46for the estimation of nitrogen in coal gas. After absorbing thecarbon dioxide, carbon monoxide, hydrocarbons, and oxygen, thegas is passed to and fro over copper oxide at 250° until no furtherreduction in volume occurs.S. H. Davies and B. G. McLellan47 describe a modification ofLunge and Zeckendorf’s method of estimating carbon dioxide inair, which appears both rapid and accurate.A most importantand exhaustive paper is that of W. J. A. Butterfield on theestimation of carbon dioxide and other impurities in air.48The proposal of A. Koepse149 to obtain il continuous register offhe composition of a gas mixture by comparing the resistance of awire suspended in the gas mixture with that of a second wiresuspended in air or a gas mixture of constant composition, mightprobably find practical application.P. Lemoult50 describes the calculation of the calorific power38 Ber., 1903, 42, 1786 ; A., ii, 609.39 Bull. Xoc. chint. Belg., 1908, 22, 440 ; A., ii, 181.4O Bull. Acnd. TOY. Belg., 1909, 622; A., ii, 755.41 See also Rev. gbn.Chim. pure et appl,, 1907, 9, 395 ; 10, 233.42 Zeitsch. anal. Chem., 1909, 48, 232 ; A, ii, 519.43 Ber., 1902, 35, 4229 ; A., 1903, ii, 98.44 Ibid., 1908, 41, 3987 ; A., ii, 89.45 Chem. Zeit., 1909, 33, 717 ; A., ii, 698.46 J. Gasbekucht., 1898, 764.47 J. SOC. Chem. Ind., 1909, 28, 232 ; A., ii, 438.48 Analyst, 1909, 34, 257.49 Ber. Dcutsch. physikal. Ges., 1908, 814 ; 1909, 237 ; d., ii, 89, 610.so $&veJh J&r. Cong, Appl. Chenb,, 4naZyst, 1909, 34, 375140 ANNUAL REPORTS ON THE PROGRESS O F CHEMISTRY.of combustible gases.calorimetry obtained with the calorimeters of Junker and Boys.J. H. Coste51 gives some useful data in gasInorganic Ch enaist ry .Qualitative.-In continuation of his work with A. A. Noyes andE. B. Spear,52 W. C.Bray53 deals with the separation of the alkaliearths and alkalis. E. Ebler 54 precipitates barium in mixtureswith strontium and calcium by addition of concentrated hydro-chloric acid. W. A. R. Wilks 55 makes the interesting observationthat one part of sodium can be detected in 50,000 parts of waterby the formation of insoluble aluminofluoride on addition of areagent prepared by dissolving moist alumina and copper acetate inhydrofluoric acid (compare W. C. Ball, p. 146). The reagent doesnot precipitate potassium or ammonium. According to A. Richaudand Bidot,56 the formation of a blue coloration on addition ofphosphotungstic acid and alkali to a ferrous salt is a more delicatetest than the ferricyanide reaction. A. del Camp057 states that0.005 mg.of zinc in 1 C.C. may be detected by the blue colorationproduced on addition of ammonia and resorcinol. P. Lernaire68observes that cadmium and uranium salts give a yellow precipitateon addition of a solution of thiosinamine containing sodiumhydroxide. Cadmium only is precipitated by hydrogen sulphide inacid solution, and uranium only by ammonium sulphide. J. H.Pollok 59 shows by spectrographic analysis that the impurities incommercial thallium are lead, copper, and aluminium. E. Ccvelli 60states that arsenites (but not arsenates) may be reduced t o arsineelectrolytic all^ in alkaline solution. P. B. Dallimore 61 has devisedit new apparatus for carrying out the Gutzeit test for arsenic.According to Dauvt5,62 when aluminium foil is immersed in a solutionof auric chloride, colloidal gold is produced.63N.Schoorl has continued his studies on the detection of metallic51 J. Soc. Chem. lid, 1909, 28, 1231.52 Ann. IZcporf, 1908, 181.53 Tech. Quart., 1908, 21, 450 ; d., ii, 431.54 Zeitsch. anal. Chem., 1909, 48, 175 ; A., ii, 347.55 Proc. Camb. Phil. Soc., 1909, 15, 7 6 ; A . , ii, 618.56 J. Pharm. Chim., 1909, Evil, 29, 230 ; A., ii, 550.57 A n d . Fi.7. Quim., 1909, 7, 63 ; A., ii, 439.68 Ann. Chim. anal., 1909, 14, 6 ; A., ii, 187.59 Sci. Proc. Roy. Dzs6Z. Soc., 1909, 11, 338 ; A., ii, 620.Chem. Zeit., 1909, 33, 1209 ; A., ii, 1052.61 Pharm. J., 1909, [iv], 28, 324 ; A., ii, 344.6a J. P h m . Chim., 1909. [vi], 29, 241 ; A., ii, 352.63 Compare Carnot, Compt. rend., 1883, 97, 105 ; A., 1884, 115AN ALPTICAL CHEMISTRY.141salts microscopicdly.64 M. E. Pozzi-Escot suggests detectingnickel and cobalt microscopically as dimethylaminobenzene-sulphonates. The same author 66 describes the reactions of a largenumber of metals with psulphobenzeneazodimethylaniline (heli-anthin), and the appearance of the derivatives under the microscope.E. Covelli 67 states that “ abrastol ” (calcium B-naphthol-a-sul-phonate) and concentrated sulphuric acid (formation of red ring)is a delicate test for nitrous acid, and conversely. J. Peset 68 givesdirections for carrying out Mitscherlich’s test for phosphorus, andhe shows that by its means 0.0085 mg. of phosphorus can bedetected with certainty. A method has been devised for thedetection of white phosphorus in matches by Sir T.E. T h ~ r p e . ~ ~It consists in heating the match or match-composition in a closedbulb containing carbon dioxide a t 40-60°. The crystals of whitephosphorus which sublime may be distinguished microscopically.Quantitative.Indicators.-W. Neriist 70 has devised a lecture experiment todemonstrate that different indicators exhibit their colour change a tdifferent concentrations of hydrogen arid hydroxyl ions. Whenmethyl formate is added to a N/lOOO-solution of barium hydroxideat 18O, phenolphthalein is decolorised instantaneously, whilst litmus,cyanine, p-nitrophenol, and methyl-orange change respectively afterone, fifteen, thirty, and one hundred and twenty minutes.M.. Handa71 points out that the nearer the concentration ofhydrogen ions required to produce the colour change in a givenindicator is to 10-7N,72 the more delicate is the indicator.He showsthat when measured by Nernst’s method, above described, methyl-red is slightly less delicate than litmus, and cyanine less delicatethan methyl-red. S. P. L. Sorensen 73 describes an absolute electro-metric method of estimating the concentration of hydrogen ions,and another method based on the titration of known mixtures ofprimary and secondary phosphates. The concentration of hydrogenions in a liquid at the sensitive point of twenty different indicators64 Ann. Beport, 1908, 183 ; Zeitsch. anal. Chcm., 1909, 48, 209, 401, 593, 762,831 ; A., ii, 521, 762, 831, 938.65 Ann.Chim. unal., 1909, 14, 207 ; A., ii, 705.67 Boll. ehim. farm., 1909, 48, 63 ; A., ii, 452.68 Zeitsch. unnl. Chew., 1909, 48, 35 ; A., ii, 265.69 Trans., 1909, 95, 440. 70 Ber., 1909, 42, 3178 ; A., ii, 878.71 Ibid., 3179 ; A., ii, 931.72 Compare Fels, Zeitsch. EZeLtrochem., 1904, 10, 208 ; Ann. Report, 1904, 22.73 Biochem. Zeitsch., 1909, 21, 131 ; Compt. rend., Carlsberg, 1909, 8, 1 ;Ball. Xoc. chirn. Belg., 1909, 23, 299 ; A . , ii, 760.A., i, 861142 ANNUAL REPORTS ON THE PROGRESS OF @HEXISTRY.is given. W. H. Emerson and H. N. DumasT4 confirmW. R. Orndorff and J. A. Black’s statement75 that tetrachloro-phenolphthalein is superior to phenolphthalein as an indicator fortitrating alcoholic solutions of organic acids. They point out thatsolutions of stearic and palmitic acids are partly esterified whenevaporated with alcohol.Metah-F.A. Gooch and R. S. Bosworth76 show that silvermay be precipitated quantitatively in neutral solution as chromateThe silver chromate filters better if it be dissolved in ammonia andthe latter boiled off. Volumetrically the excess of chromate or thesilver chromate itself (solution in potassium iodide) may beestimated iodometrically.77 Another volumetric method of esti-mating silver is described by R. S. Bosworth76; it consists intitrating with iodine the excess of arsenite required for the reductionof a silver salt. E. Pannain79 has devised a new apparatus fordetermining the end-point when titrating a silver salt by GayLussac’s method. According to J.M. Wilkie,sO lead in presenceof a sufficiency of ferric (but not ferrous) iron is completely pre-cipitated by ammonia. For the separation of lead and bismuth,J. C. Galletly and G. G. Henderson 81 recommend Clark’s method 82with certain modifications for the separation of lead and bismuth.J. J. Fox83 has investigated the solubility of lead sulphate inconcentrated solutions of sodium and potassium acetate. I n theformer case it is found that the solid phase consists of PbSO,,whilst in the latter the solubility of the lead sulphate is found tobe due to the formation of lead acetate and potassium sulphate, thesolid phase consisting of PbK,(SO,),, which also results by mixingpotassium sulphate with an excess of lead acetate. The same authorhas showns4 that with solutions of ammonium acetate up to aconcentration of 3N, the solid phase consists of lead sulphate, butwith more concentrated solution, crystals of the compositionPb(NH,),(SO& were obtained. B.Odd0 and A. Beretta85 statethat lead may be titrated with potassium chromate, using s-di-phenylcarbazide as indicator. I n another paper 86 they employ this74 J. Amer. Chem. Xoc., 1909, 31, 949 ; A . , ii, 770.75 Amer. Chem. J., 1909, 41, 349 ; A., i, 389.7o Amer. J. Sci., 1909, [iv], 27, 241 ; A., ii, 346.77 Ibid., 302 ; A., ii, 438.79 Gaxzctta, 1909, 39, ii, 240 ; A., ii, 937.a1 Analyst, 1909, 34, 389 ; k., ii, 833.82 J. SOC. Chem. Ind., 1900, 19, 26 ; A., 1900, ii, 371.83 Trans., 1909, 95, 878.Proc., 1907, 23, 200.sa Qaszetta, 1909, 39, i, 671 ; A., ji, 764.s6 Ibid,, 666 ; A., ii, 766.78 Ibid., 257 ; A., ii, 928.J.SOC. Chem. Ind., 1909, 28, 636 ; A., ii, 703ANALYTICAL CHEMISTRY. 143indicator in the titxation of mercurous salts with sodium chloride.J. Enox87 confirms the accuracy of the method of titratingmercuric salts with thiocyanate devised by Rupp and Erauss,88 buthe shows that silver cannot be estimated in presence of mercuryby the Gay Lussac method as they suggest, because some of thec1’ ions unite with the Hg” ions to form undissociated mercuricchloride. Conditions are described, however, whereby the pre-cipitation of silver chloride is complete in presence of mercuricnitrate. H. Wegelius and S. Kilpi89 show that prior to pre-cipitation of mercury as sulphide from solutions containing iodides,the latter must be removed by warming with moist silverchloride.In the estimation of copper by liberation of iodine,F, M. Litterscheid90 titrates the iodine with arsenious acid.F. A. Gooch and H. L. Ward91 estimate copper by precipitationas oxalate, and titration of the latter with permanganate.G. Coffetti 92 describes a method of estimating cuprous oxide inmetallic copper by extracting it with ammonia in an atmosphereoE hydrogen. A special apparatus is used, which has since beenmodified by R. H. Greaves,93 who points out that the presence ofarsenic, antimony, or iron vitiates the results; antimony and ironare seldom present. H e suggests a means of overcoming the errordue to arsenic. W.Vaubel94 states the conditions of alkalinityunder which zinc, copper, and cobalt may be precipitated quanti-tatively. After investigating several methods for the estimationof antimony and tin, E. Cahen and G. T. Morgan95 show thatVortmann and Metzl’s methodg6 effects the separation of the twometals, but is only trustworthy for estimating antimony. Czerwek’smethod, on the other hand,97 gives accurate results for theestimation of tin, but not of antimony. With certain modifications,Henz’s method g8-antimony as trisulphide and tin electrolytically-gives accurate results. I n separating antimony and tin,L. W. McCay 99 makes use of the fact that antimony only is pre-cipitated when hydrogen sulphide is passed through a solution to87 Tram., 1909, 95, 1768.** Bar., 1902, 35, 2015 ; A . , 1902, ii, 475.89 Zcitsch. anorg. Chcm., 1909, 61, 413 ; A . , ii, 350.Chem. Zcit., 1909, 33, 263 ; A , , ii, 348.g1 Amer. J. Sci., 1909, [iv], 27, 448 ; A!., ii, 703.92 Gnxxetta, 1909, 39, i, 137 ; A., ii, 349.93 Cham. News, 1909, 100, 233 ; A., ii, 1054.9.1 Zcitsch. angew. Chem., 1909, 22, 1716 ; A., ii, 532.95 Analyst, 1909, 34, 3 ; A., ii, 187.98 Zeitsch. anal. Chm., 1905, 44, 525 ; A., 1905, ii, 655.97 Ibid., 1906, 45, 505; A., 1906, ii, 708.9t) Zeitsch. anorg. Chem., 1903, 37, 1 ; A., 1904, ii, 150,99 J, Amer. Chem. SOC., 1909, 31, 373 ; A., ii, 351144 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.which hydrofluoric acid and sodium acetate have been added.W. Schultel shows that metallic antimony is precipitated fromsolutions of thioantimoniates by aluminium or tin.The latter maybe made quantitative. G. Panajotow 2 shows that antimonysulphide is insoluble in 15 per cent. hydrogen chloride, whilsttin sulphide is soluble. Making use of these facts the two metalsmay be estimated accurately. K. Meyer 3 dissolves the tin in“ t i n plate” by boiling the latter with sodium peroxide, andweighs the residual iron. When lead and zinc are present theyalso dissolve, and it is then necessary to estimate the tin by adirect method.G. Edgar4 makes use of the f a c t that in mixtures with arsenicor antimonic acid, vanadic acid alone is reduced by oxalic ortartaric acid, whereas the three are reduced by sulphurousanhydride, to estimate these acids.J. Knox5 points out that thesolubility of bismuth trisulphide in alkali sulphides must depend onthe formation of a complex anion with the sulphur cation.In view of the accuracy of the dichromate method, which ispractically independent of conditions, it is surprising that so manychemists turn their attention year by year to the titration of ferrousiron by permanganate in the presence of hydrochloric acid. Thismethod can at best be described as empirical, requiring as it doesstandard conditions for accuracy. But if this be true in thetitration of pure ferrous salts, it applies a fortiori in the analysisof ores where constituents of unknown influence are present. Theestimation of iron by titration with permanganate in presence ofhydrochloric acid has been studied by W.C. Birch,6 who finds thatFresenius’s method, namely, addition to the solution, after thetitration, of a volume of ferrous solution equal to that originallypresent, retitration, and repetition of this three or four times untila constant reading is obtained, is inaccurate on the evidence whichFresenius himself adduces as well as by his (Birch’s) experiments.I n a subsequent paper7 he recommends metallic copper as a reducingagent for ferric iron. J. A. N. Friend8 shows that to ensureaccuracy in the hydrochloric acid-permanganate method, thetitration must be performed slowly, that a sufficiency of manganoussulphate must be present, and that the dilution of the ferrous* I?le?allurgie, 1909, 6, 214 ; A., ii, 522.Ber., 1909, 42, 1296; A,, ii, 523.Zeitsch.angow. Chein., 1909, 22, 68 ; A., ii, 187.Zeitsch. anorg. Chew&., 1909, 62, 77 ; A., ii, 441.Trans., 1909, 95, 1760.Chem. News, 1909, 99, 61, 73 ; A., ii, 268.Ibid., 273 ; A., ii, 621.Trans., 1909, 95, 1228ANALYTICAL CHEMISTRY. 145solution should be such as to ensure a good end-point withoutreducing the accuracy of the titration. The concentration of thehydrogen chloride must not exceed m/4. Later he showsg thatpractically the same precaution must be applied in the estimationof small quantities of ferrous iron by titration with N / 2 5 per-manganate. G. C. Jones and J. H. JefferylO have determined theconditions in the hydrochloric acid-permanganate method, underwhich the error in the Reinhardt modification of this method l1 ispractically negligible, constant, and independent of the amount ofiron present.R.B. Gage12 points out that the iron in magnetite may beestimated by decomposing the mineral with hydrofluoric acid, and,after adding sufficient calcium fluoride to precipitate the phosphate,titrating with permanganate. J. S. MacLaurin and W. Donovan l3show that when iron ores are roasted successively in a current ofair and of hydrogen, and dissolved in sulphuric acid, titration withpermanganate gives accurate results. Miss E. Hibbert 14 makes useof the reduction of methylene-blue by titanous salts and its non-reduction by ferrous salts as the basis of a method of estimating ironand titanium in mixtures. M. E.Pozzi-Escot 15 describes a methodof separating quantitatively iron, aluminium, zinc, and chromium.H. GrossmannI6 has investigated J. A. Sanchez's method of esti-mating nickel in the presence of cobalt, and condemns it. L. L. deKoninck 17 deals with the precipitation of cobalt as potassiumcobaltinitrite. I n the separation of nickel and cobalt by theRosenheim-Huldschinsky method, M. Pritze l* prefers treatmentwith dimethylglyoxime to a second shaking with amyl alcohol-ethermixture.For the gravimetric estimation of magnesium as pyrophosphate,E. Raffa 19 recommends as precipitant. an N / 2-solution of ammoniumdisodium phosphate; 0.3 to 0.5 per cent. of magnesium should bepresent in the liquid, and the precipitate should be washed with2.5 per cent.ammonia solution. Another series of experiments hasbeen carried out by the same author20 on the precipitation of9 Proc., 1909, 25, 224.10 Analyst, 1909, 34, 306 ; A., ii, 704.l2 J. Amer. Chem. Soc., 1909, 31, 38'1 ; A., ii, 350.13 J. Soc. Chem. Ind., 1909, 28, 827 ; A., ii, 833.l4 Ibid., 189 ; A., ii, 351.15 Bull. Scc. chim., 1909, [iv], 5, 558 ; A., ii, 621.16 Zeitsch. angew. Chem., 1909, 22, 2005 ; A., ii, 941.17 Bull. SOC. chim. Belg., 1909, 23, 11 ; A., ij, 269.1s Chem Zeit., 1909, 33, 694 ; A., ii, 705.l9 Gazretla, 1908, 38, ii, 556; A., ii, 183.Chem. Zeit., 1889, 13, 323.Ibid., 1909, 39, i, 154 ; A., ii, 347.REP.-VOL. VI. 146 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.magnesium as ammonium magnesium arsenate, but under no con-ditions are the results as good as those obtained by the phosphatetuethod.F. Hundeshagen 21 separates calcium from large quantitiesof magnesium by precipitation as sulphate in presence of alcohol.Accarding to R. Brandenburg,22 the ammonia evolved on boilingcement with a solution of ammonium bromide in absolute alcohol isa measure of the free calcium oxide in cement. W. C. Ball 23 showsthat the formation of a yellow precipitate,5Bi(N10~)~9CsN0~,6NaNO,,when potassium bismuth nitrite containing 1 per cent. of czesiumnitrate is added to a sodium salt, is a convenient means of detectingand estimating sodium. A solution of sodium bismuth nitrite maybe used for the detection of cesium and rubidium,W. J. Miiller 24 estimates thallium by titrating a thallous solutionwith permanganate or iodine.0. Hauser and F. Wirth 25 describea modification of V. Borelli's method of estimating thorium inmonazite sand. V. Borelli has subsequently published anotherpaper on the subject.26 E. Wedekind and S. J. Lewis2' point outthat zirconium has not yet been obtained in the pure state, andhave devised methods for the estimation of the most commonlyoccurring impurities. P. E. Browning and H. E. Palmer 28 showedthat cerium might be estimated in presence of other rare earths byprecipitation with an excess of potassium ferricyanide in alkalinesolution, the resulting ferrocyanide being titrated with per-manganate in the acidified filtrate. In a subsequent paper 29 theyshow that the same principle may be applied for the estimation ofthallium.I n this case the precipitated thallic hydroxide may alsobe weighed as Th20,. F. J. Metzger,30 to estimate cerium inpresence of other rare earths, makes use of the fact that ceroussulphate is oxidised to ceric sulphate by bismuthic acid, the excessof the latter being titrated with permanganate. To prevent theprecipitation of basic bismuth salts, the presence of ammoniumsulphate is necessary.31 0. Hauser and F. Wirth 32 separate ceriumfrom cerite earths by treating with ammonia and hydrogen peroxide21 Zeitsch. ofentl. Chem., 1909, 15, 85 ; A., ii, 438.22 CTzem. Zeit., 1909, 33, 880 ; A., ii, 832.24 Chem, Zeit., 1909, 33, 297 ; A,, ii, 348.25 Zeitsch. nngew. Chem., 1909, 22, 484; A., ii, 352.26 Gaxxetta, 1909, 39, ii, 425 ; A., ii, 522.27 Traizs., 1909, 95, 456.28 Zeitsch. nnorg.Chenz., 1908, 59, 7 1 ; A., ii, 736.29 16id., 1909, 62, 218 ; A., ii, 620.30 J. Amer. Chem. Soc., 1909, 31, 523 ; A , , ii, 620.23 Tram., 1909, 95, 2126,Compare also W. Gibbs, Amer. Chent. J., 1893, 15, 546 ; A , , 1894, ii, 47 ;A. Waegner and A. Miiller, Bcr., 1903, 36, 282 ; A , , 1903, ii, 242, '' Zeitsch. anal. Chem,, 1909, 48, 679 ; A , , ii, 940ANALYTICAL CHEMISTRY. 147and passing a current of chlorine through the liquid in a specialform of apparatus. G. Edgar 33describes the iodometric estimation of vanadic, chromic, and ferricoxides in mixtures containing the three. A. W. Gregory 34 proposesto estimate vanadium by a tintometric method depending on thechange in colour (violet to orange) which takes place on additionof strychnine. Iron interferes, and must be removed previously.P.Jannasch and W. Jilke35 show that phosphoric oxide may bevolatilised from the phosphates of iron, chromium, uranium, zinc,nickel, cobalt, and manganese when these are heated in a currentof carbon tetrachloride. P. Jannasch and H. F. Harwood36 showthat vanadic oxide may also be volatilised similarly. 3’. J. Metzgerand C. E. Taylor 37 have devised a method of estimating columbiumin presence of tantalum. It consists in adding succinic acid to asolution of the two in concentrated sulphuric acid, when thecolumbium may be reduced with amalgamated zinc and titratedwith permanganate. For the estimation of tantalum, columbium,and titanium, papers by W.B. Giles3* and L. Weiss and&I. Landecker 39 may be consulted. The paper by the authors lastnamed is a most valuable contribution to the subject. W. E. vonJohn 40 deals with the estimation of tantalum and columbium.J . 1’. Lehalleur41 gives some details for the estimation ofmolybdenum, vanadium, tungsten, nickel, and chromium. E. Collettand M. Eckardt42 review the subject of the estimation ofmolybdenum in molybdenite, and recommend a method. W. Traubmann 43 fuses molybdenite with sodium peroxide under standardconditions, and claims in this way to avoid the solution of certainextraneous metals, besides rendering the estimation more rapid.M. Tschilikin 44 shows that tungsten may be precipitated quanti-tatively in acid solution in the cold by means of a-naphthylaminehydrochloride.The tungsten is weighed as WO,.E. Knecht and Miss E.Nibberth5 propose to titrate tungsten dioxide wilh a ferric salt.The cerium is weighed as dioxide.The composition of the precipitate is(C,,H,N),(~V03),,3H~O.s3 Amer. J. Sea’., 1909, [iv], 27, 174 ; A., ii, 269.35 J. pr. Chew,., 1909, [ii], 80, 113; A . , ii, 769.36 Jbbid., 127 ; A., ii, 767.37 Zeitsch. anorg. Chem., 1909, 62, 382 ; A., ii, 702.38 Chem. Netus, 1909, 99, 1 ; A., ii, 352.39 Zeitsch. anorg. Chein., 1909, 64, 65 ; A., ii, 942.40 Chem News, 1909, 100, 154.41 Mon. ,S’ci., 1909, 23, i, 263 ; A., ii, 704 ; compare Jaboulay, Eev. ye‘n. Chim42 Seventh Inter. Cong. AppZ. Chein. ; Chem. Zeit, 1909, 33, 1968 ; A., ii, 94143 Chem. Zeit., 1909, 33, 1106 ; A ., ii, 942.44 Ber., 1909, 42, 1302 ; A,, ii, 522. 45 Proc., 1909, 25, 227.34 PYOC., 1909, 25, 232.pure. AppZ., 1909, 12, 142; A., ii, 705.L 148 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY,The disappearance of the blue colour due to tungsten pentachloridemarks the end of the reaction, or thiocyanate may be used ilsindicator. According to A. Gutbier and M. Riess,46 rhodium maybe estimated by precipitating it as metal by hydrazine sulphate.Non-metals.-The observation of H. Endemann 47 that the directtitration of hydrogen peroxide with alkali and phenolphthaleinindicates only half the acid present has been refuted by 0. L i i ~ ~ i n g . ~ ~A. Stahler 49 proposes to estimate hydroxylamine by reduction toammonia with an acid solution of a titanous salt.E. Goutdmpoints out that when steel is dissolved in potassium cupric chloride,occluded gases are given off, and these must be allowed for in theestimation of carbon, A. A. Blair 51 states that under these con-ditions no hydrocarbons are formed. E. R. Marle 52 observes thatcarbonates may be estimated in presence of nitrites by liberatingthe carbon dioxide by means of potassium dichromate; in presenceof sulphides or of sulphites the reaction must be completed by theaddition of sulphuric acid owing t o the formation of a basiccarbonate of chromium. B. Lowinger 53 describes a volumetricmethod of estimating bicarbonates .in admixture with normalcarbonates.54 A. Sanin 55 proposes to estimate nitrites in presenceof nitrates by boiling with a dilute solution of hydroxylamine hydro-chloride of known titre towards N / 20-sodium hydroxide andphenolphthalein, and titrating. A.Hes 56 deals with the estimationof nitrates by Busch’s “ nitron ” method, especially with theinfluence of various substances on the results. B. F. Howard and0. Chick 67 show that nitrates may be estimated gravimetricallyas cinchonamine nitrate. According to A. Kleiber,5* the whole ofthe nitrogen in alkali nitrate is obtained as ammonia when asolution is heated with hydrochloric acid, stannous chIoride, andiron filings.In the gravimetric estimation of halogens, E. Alefeld 59 proposes46 Ber., 1909, 42, 1427 ; *4., ii, 523.47 Zeitsch.ungew. Chem., 1909, 22, 673 ; A., ii, 432.48 Ibid., 1549 ; A , , ii, 826.49 Ber., 1909, 42, 2695 ; A . , ii, 758.50 h’evcnth Int. Cong. Appl. Chem.; Compt. rend., 1909, 148, 988 ; A., ii, 519.51 J. Iroa and Steel Inst., 1909 ; A., ii, 519.52 Trans,, 1909, 95, 1491.53 Chenz. Zeit., 1909, 33, 1174 ; A., ii, 1053.54 Compare E. C. Sutherland, ibid., 1240.55 J. Russ. Phys. Chem. SOC., 1909, 41, 791 ; A., ii, 935.56 Zeitsch. a w l . Chetn., 1909, 48, 81 ; A., ii, 265 ; compare M. Busch, ibid.,368 ; A., ii, 615 ; C. Paal and A. Ganghofer, ibid,, 545 ; A., ii, 759 ; P. Pooth,ibid., 375 ; A . , ii,*615.57 J. Soc. Chem. Ind., 1909, 28, 53 ; A., i, 176.58 Chem. Zeit., 1909, 33, 479 ; A . , ii, 517.6y Zeitsch. anal. Chem., 1909, 48, 73 ; A., ii, 262ANALYTICAL CHEMISTRY.149to add a small quantity of ether before the addition of silvernitrate. This coagulates the silver halide without heating.V. Rothmund and A. Burgstaller 60 recommend shaking with etherto coagulate silver Fialide, and thus prevent it from reacting withsilver thiocyanate in Volhard’s method.have modified Frenkel’s method62 of estimating chlorine in presenceof palladium. V. Rothmund63 shows that boiling with titaniumsesquisulphate (twice the theoretical quantity) is a convenientmeans of reducing perchlorates; the excess may then be titratedwith a ferric salt. According to A. Stiihler,6* it is best to estimatethe chloride formed. E. Knecht 65 states, however, that titrationwith a ferric salt, using thiocyanate as indicator, is quite accurate.To estimate the alkalinity of bleaching powder, K.J. P. Ortonand W. J. Jones 66 add a known excess of #/lo-hydrochloric acidto a solution, and pass through it in the dark a rapid current ofair. When all the chlorine is expelled, the excess of acid is titratedwith sodium carbonate and methyl-orange. A useful paper givingthe limit of accuracy of three methods of estimating sulphide inalkali cyanide is published by T. E ~ a n . ~ 7 J. Milbauer68 statesconditions whereby sulphites may be titrated accurately with per-manganate. A. D. Mitchell and C’. Smith 69 describe a volumetricmethod for estimating sulphates, which, on the evidence they give,is trustworthy. M. J. van’t Kruys70 deals with the conditionsnecessary to ensure accuracy in the estimation of sulphates asbarium sulphate in presence of much calcium salt.G. Kernot71draws attention to the solubility of barium sulphate in solution ofsodium acetate. H. Grossmann and L. Holter 72 show that titriltion of thiocyanic acid with permanganate gives low results.K. Schroder 73 describes conditions whereby accuracy can beattained. H. Pellet 74 confirms the accuracy of Chesneau’s methodof estimating phosphorus in iron and steel and of minute quantitiesA. Gutbier and F. Falco60 Zeitsch. anorg. Chem., 1909, 63, 330 ; A., ii, 932.61 Zeikch, anal. Chew,., 1909, 48, 555 ; A., ii, 768.C2 Zeitsch. anorg. Chem., 1893, 1, 217 ; A,, 1893, ii, 195.68 Zeitsch. anal. Chem., 1909, 62, 108 ; A., ii, 434.64 Chem. Zeit., 1909, 33, 759; A., ii, 699.66 Analyst, 1909, 34, 317 ; A., ii, 701.67 J.SOC. Chem Ind., 1909,28, 10; A , , ii, 263.68 Zeitsch. anal. Chem., 1909, 48, 17 ; A., ii, 264.69 Trans., 1909, 95, 2198.70 Chem. Weekblad, 1909, 6, 735; A., ii, 939.v1 Rend. Accad. Sei. Pis. Mat, Napoli, 1909, [iii], 15, 155 ; A . , ii, 940.72 Chem. Zeit., 1909, 33, 348 ; A., ii, 449.75 Zeitsch,. ofentl. Chem., 1909, 15, 321 ; A., ii, 948 ; compare also G. Masino,Chm. Zeit., 1909 33, 1173, 1185 ; A., ii, 1058.74 Ann. Chirn. anal., 1908, 14, 7 ; A., ii, 182.65 Proc., 1909, 25, 229150 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.of phosphoric acid in general.75 Z. Romanski 76 recommends weigh-ing the molybdic precipitate in the estimation of phosphoric acidin basic slag, and he describes the necessary details.M. Ullmann 77proposes a gravimetric molybdate method of estimating phosphoricacid. F o r the estimation of small quantities of phosphoric acid,I. Pouget and D. Chouchak78 make use of the colour (yellow tobrown) produced when a solution containing an alkaloid (preferablystrychnine) is added to a solution of a phosphate in nitric acid.A. Grete79 has improved his method of titrating phosphoric acidwith molybdic acid in presence of gelatin 8O by the employment ofan ammoniacal molybdate solution. A. Gutbier and 3'. Flury*lshow that Frerichs's method of estimating tellurium 82 giveserroneous results. P. E. Browning and W. R. Flint83 describe itmethod for the separation of tellurium from selenium.H.R. Ellis 84 describes methods for the estimation of cyanamidein sodium cyanamide and " nitrolime." He finds that silvercyanamide has a composition corresponding with Ag,(CN),.Elect?-oclzemicaZ Analysis.-There is nothing of a very novelcharacter to report in this increasingly useful branch of analyticalchemistry. T. S. Price and T. C. Humphreys85 describe, with theaid of illustrations, various forms of apparatus employed in rapidmethods of electro-analysis. Their paper is of value as giving anhistorical r6sum8 of the subject. A description is given of theestimation of copper and zinc in brass. H. J. S. Sand86 hasmodified his apparatus for the rapid electrolytic separation ofmetals87 so as t o render it portable. A. Fischer88 describes anarrangement for measuring the cathode potential when using Sand'sn i e t h ~ d .~ ~ H. Filippo, jun.,90 has devised a modification of Smith'smethod of rapid electro-analy~is,~~ in which a mercury cathode is75 Ann. Report, 1908, 187.77 Seventh litter. Cong. Appl. Chena. ; Analyst, 1909, 34, 337.78 Bull. SOC. china., 1909, [iv], 5, 104 ; A., ii, 226.79 Ber., 1909, 42, 3106 ; A., ii, 936.8" B i d . , 1888, 21, 2762.s1 C'henz. News, 1909, 99, 217 ; A . , ii, 516.B2 J. pr. Chem., 1902, [ii], 66, 261 ; A., 1903, ii, 41.83 Amer. J. Sci., 1909, [iv], 28, 112 ; A., ii, 934.s4 Chem. News, 1909, 100, 154 ; A., ii, 1058.B5 J. SOC. Chem. Ind., 1909, 28, 117 ; A., ii, 342.86 Chem. Tmde J., 1909, 45, 25 ; Trans. Faraday SOC., 1909, 5, 159 ; A., 1910,S7 Ann.Beport, 1908, 194,88 Chenz. Zeit., 1909, 33, 337 ; A., ii, 521.89 Trans., 1907, 91, 373; 1908, 93, 1572.91 J. Amer. Chem. SOC., 1903, 25, 883 ; 1904, 26, 1595 ; 1905, 27, 1255, 1527 ;1907, 29, 797; A., 1903, ii, 755 ; 1905, ii, 198, 859 ; 1906, ii, 194; 1907, ii, 719.'13 Chem. Zeit., 1909, 33, 46 ; A , , ii, 182,ii, 66.Chem. Weekblnd, 1909, 6, 226 ; A., ii, 440ANALYTICAL CHEMISTRY. 151employed. It has the advantage of allowing larger volumes ofliquid to be manipulated. W. Bottger 92 describes an improvedmethod, using a mercury cathode and a helical anode. J. T.Stoddard 93 shows that cadmium, copper, nickel, silver, and zinc(and probably other metals) may be precipitated quantitativelyfrom their solutions by strong currents in substantially the sametime with the use of statiomry electrodes as when rotating elec-trodes are employed.The cathode employed was of platinum-gauzeor mercury.94 He states that with the exception of silver thecharacter of the deposited metal is scarcely affected by: the strengthof the current used; it must not exceed 1.5 amperes in the caseof silver, otherwise the deposit becomes voluminous and closes themesh. -6. Alders and A. Stahler 95 deal with the rapid electrolyticseparation and estimation of several metals as amalgams. Theapparatus consists of a flask having an injecting bottom, throughwhich are sealed three short platinum wires resting externally onit sheet of copper. An annular ring of mercury just covering theplatinum points serves as cathode, whilst the anode is a flat coilof platinum-iridium wire capable of rotation.With a current of3 to 4 amperes at 5 to 6 volts, good results are obtained in theestimation of copper, silver, and mercury as metal. J. W. Turren-tineg6 states that acheson graphite is a satisfactory substitute forplatinum in the construction of insoluble electrodes. To renderthe electrodes non-absorbent they are treated with molten paraffinwax. H. W. Gillett 97 points out that in a solution of two metalsof less potential than hydrogen, the deposition of that of higherpotential may be prevented by introducing a metal of intermediatepotential even though the voltage used be higher than that of itsdeposition potential.F. A. Gooch and F. B. Beyerg* have applied their method ofsimultaneous deposition and filtration 99 to the estimation of leadand manganese.They show Ghat in the presence of a sufficiency ofnitric acid, either metal can be deposited a t the cathode as dioxide.H. J. S. Sand 1 describes the estimation of lead electrolytically asdioxide. A. Fischer 2 states thak in the electrolytic precipitation oftin and copper by a method similar to that described by H. J. S.92 Ber., 1909, 42, 1824 ; A, ii, 619,93 J. Amer. Chem. SOC., 1909, 31, 385 ; A., ii, 347.94 Compare C1. Winkler, Ber., 1899, 32, 2192.95 E’er., 1909, 42, 2685 ; A., ii, 764.96 Seventh Inter. Cong. Appl. Chent. ; Analyst, 1909, 34, 386.97 J. Physical. Chem., 1909, 13, 336 ; A . , ii, 521.98 Amer. J. Sci., 1909, [iv], 27, 59 ; A., ii, 268.99 Ann.Report, 1908, 193.2 Zeitsch. Elektrochem., 1909, 15, 591.Chent. News, 1909, 100, 269152 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Sand3 for the separation of copper and bismuth, the tin exertsa retarding influence on the copper, necessitating a higher potential.H. J. S. Sand finds, however,4 that the copper may be precipitatedcompletely from boiling solutions at an auxiliary potential of 0.60volt, just as in the absence of tin. C. S. Tatlock5 deals with theelectrolytic estimation of nickel in ores. C. N. Otin6 points outthat in the electrolytic estimation of manganese by Engel’s method 7the deposit formed at the anode contains 7 per cent. of metallicmanganese, which may, however, be prevented by lowering thecurrent density a t the cathode or by adding ammonium sulphate(2 grams per 100 c.c.).It then has the composition of manganesedioxide after drying a t 200-220°. Addition of alcohol causes thedeposit to adhere to the anode.Employing a rotating silver anode and a, mercury cathode,J. S. Goldljaum and E. F. Smiths have succeeded in estimatingbarium or strontium in admixture with calcium with a fair degreeof accuracy by taking advantage of their respective depositionpotentials. The halogen may be estimated from the increase inweight of the anode. For the electrolytic estimation of thallium,G. W. Morden advises the use of a very dilute zinc-cadmiumamalgam instead of pure mercury as cathode in conjunction witha rotating anode.Water Analgsis.For the estimation of dissolved oxygen in water, G.B. Frank-forter, G. W. Walker, and A. D. WilhoitlO show that thecolorimetric ammoniacal cuprous chloride method of Sir W. Ramsayand Miss I. Honifrayll gives accurate results if precautions aretaken to prevent the oxidation of the cuprous solution. They haveconstructed an apparatus €or the purpose entirely of glass.W. P. Jorissen 12 finds in support of the statement of W. P. Jorissenand W. E. Ringer13 that for the estimation of dissolved oxygenin sea water, G. Romijn’s method l4 gives low results,The determination of the hardness of water by the soap methodTrans., 1907, 91, 395.Zeitsch. anal. Chem., 1909, 48, 433 ; A., ii, 766.Zeitsch. EZektroch,em., 1909, 15, 385 and 386 ; A . , ii, 703.Ber., 1895, 28, 3182; A., 1896, ii, 276 ; Zeitsch.Elekt~ochene., 1897, 3, 286,PTOC., 1909, 25, 228.305 ; A., 1898, ii, 52.8 J. Amer. Chem. Soc., 1909, 31, 900; A., ii, 763.l1 J. SOC. Chem. Ind., 1901, 20, 1071 ; A , , 1902, ii, 171.l2 Chem. Weekblad, 1909, 6, 123 ; A., ii, 343.l3 Ibid., 1906, 2, 781 ; A., 1906, ii, 490.l4 Bee. trav. Chirn., 1893, 12, 241 ; 1896, 15, 76 ; A . , 1894, ii, 28 ; 1896, ii, 579.Ibbd., 1045 ; A . , ii, 1054. lo Bid., 35 ; A., ii, 263ANALYTICAL CHEMISTRY. 153has practically been superseded by acidimetric and alkalimetricmethods, but some useful data are given by G. Piccinini.15L. Farcy16 points out that the methods of estimating nitratesdevised by G. McGowan17 and by G. Frerichsls are inaccurate inpresence of ammonium salts.During the year several authors havereferred to the well-known fact that Grandval and Lajoux's phenol-sulphonic acid method of estimating nitrates is inaccurate in thepresence of halides, and no reference need be made to these papers.An important paper on the subject has been published, however, byE. M. Chamot and D. S. Pratt,lg who bring forward evidence thatthe yellow colour produced in the cold is due to t'he nitration of-phenol-2 : 4-disulphonic acid, the compound formed being the alkaliderivative of a nitrophenolsulphonic acid. The authors are stillinvestigating the method, which has long needed placing on a soundscientific basis.According to S. Bugarszky and B. Horvath,20 the reactionI, + 5Br2 + 6H20 Z 2HI0, + lOHRris practically complete from left to right in presence of excess ofbromine, which may be boiled off without reversing the reaction.I f , after this, potassium iodide be added, the liberated iodine maybe titrated.It is stated to be a good method for the estimationof iodine in waters in presence of chlorides, bromides, ammoniumsalts, nitrates, and nitrites.Organic Chemistry.Qualit at iv e .There are a number of observations calling for notice in thisdepartment. A. Vorisek21 shows that methyl alcohol may be detectedreadily in admixture with ethyl alcohol by distilling 0.5 to 1.0C.C. of the mixture with 0.8 per cent. chromic acid and 4 to 5 C.C.of water. I n thisway 0.001 gram of methyl alcohol can be detected in 1 C.C. of ethylalcohol.G. B. Neave 22 has confirmed the Sabatier-Senderenscatalytic test for distinguishing between primary, secondary, andtertiary alcohols.23The distillate is then tested for formaldehyde.l6 Atti R. Accad. SGi. Torino, 1909, 44, 842 ; A., ii, 832.l6 Bull. SOC. chim., 1909, [iv], 5, 775 ; A., ii, 758.I7 Trans., 1891, 59, 530.Arch. Phaym., 1903, 241, 47; A., 1903, ii, 328.l9 J. Amer. Chem. SOC., 1909, 31, 922; A , , i, 641.2u Zeitsch. anorg. Chem., 1909, 63, 184; A,, ii, 932.21 J. Soe. Chem. Ind., 1909, 28, 823 ; A., ii, 834.O3 Ann. Report, 1905, 194.Analyst, 1909, 34, 346 ; A . , ii, 835154 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY,G. Denigss has published a series of papers on certain colourHe states 24 that in the resorcinol test for tartaric acid, reacttiom.I Ithe chromophore is HO*$J-T*OH and that the colour reactionvaries in intensity according ‘to the nature of the groups united tothe free affinities.He gives directions for distinguishing betweenglyceric, tartaric, and tartronic acids. Later25 he shows that themechanism of the reaction consists in the formation of aldehydesfrom these compounds, which aldehydes condense with the resorcinolor other phenol to form coloured derivatives. He describes somecolour reactions with certain phenols and opium alkaloids inpresence of sulphuric acid,26 whilst in a still later paper27 he sho’wsthat these reactions are due to methylglyoxal, and that they canbe obtained with the oxidation products of other polyhydroxy-alcohols besides glycerol.I n a further communication,2* he showsthat methylglyoxal in presence of sulphuric acid gives colourreactions with numerous organic substances. These reactions maybe made use of conversely as a test for glycerol.29 Lactic acid yieldsacetaldehyde, and glycollic acid, formaldehyde, when the respectiveacids are warmed with sulphuric acid, and colour reactionscharacteristic of these aldehydes may be applied for the detection ofthe acids.30 It is shown 3l that ally1 alcohol may be detected by thecolour reactions of its oxidation (by bromine) products-glycer-aldehyde and dihydroxyacetone-with certain alkaloids and sul-phuric acid.Dealing with the detection of various substances in foods, etc., afew papers may be referred to. E.Covelli 32 describes several colourreactions for the detection of “ abrastol ” (calcium-j3-naphthol-a-sulphonate). The reaction with nitrous acid is referred t o onp. 141. 0. Carletti 33 describes a delicate colour reaction (withsulphuric acid and alcoholic tartaric acid) for the detection of(‘ abrastol.” Pyrogallol gives the same reaction.34 A. Labat 35describes colour reactions of hydrastine, hydrastinine, and narcotinewhen these are heated with sulphuric acid and certain phenols.Oxidation of the alkaloids mentioned with permanganate producesopianic acid, colour reactions of, which with sulphuric acid and2s ]bid., 353 ; A . , i, 378. 24 Bull, SOC. chint., 1909, [iv], 5, 19 ; A . , ii, SO.26 Compt. rend., 1909, 148, 172, 282 ; A., ii, 272, 273.27 Ibid., 422 ; A ., ii, 448.28 Bull. SOC. chim., 1909, [iv], 5, 649; A., ii, 624.29 Compt. rend., 1909, 148, 570 ; A., ii, 353.Bull. Soe. chim., 1909, [iv], 5, 647 ; A., ii, 627.Boll. chim. farm., 1909, 4%, 53 ; A . , ii, 452.31 Ibid,, 878 ; A., ii, 944.3J Ibid., 1906, 6, 223 ; A., ii, 528.34 B i d . , 441 ; A . , ii, 769.35 Bull. Soc. &im., 1909, [iv], 5, 742, 743 ; A., ii, 710ANALYTICAL CHEMISTRY. 155phenols are described. SeveraJ colour reactions for the detectionof aniline are given by J. Peset.36 The detection of methylanilineand dimethylaniline in mixtures of the two is dealt with byH. Emde.37 Mlle. A. Jonescu 38 states that hydrogen peroxideconverts benzoic acid as well as ‘‘ saccharin ” 39 into salicylic acid,which may then be detected by the well-known colour reaction withferric chloride.40 The fact that iodine combines with tannin hasbeen utilised by C.Conti 41 for the detection of coal-tar colours inwines. The natural colouring matters of wine are precipitated onaddition of iodine, but not artificial colours.J. Gnezda42 describes some colour reactions of the sugars withindole derivatives. J. Ville and E. Derrien 43 show that Petten-kofer’s reactions for sucrose and Seliwanoff’s reaction for ketoses aredue to the formation of 2-hydroxy-kmethylfurfuraldehyde.S. Frankel and R. Allers44 state that adrenaline, when warmedwith iodic acid, gives a red coloration, believed to be an iodoso-derivative. To detect adrenaline in blood or extracts of organs,etc., G.Comessatti 45 centrifuges with mercuric chloride andalcohol, when, after standing for twelve t o twenty-four hours, ifadrenaline is present, a red colour appears in the supernatantliquid. K. Boas 46 succeeded in obtaining the reaction only whenthe mixture was heated. The colour reactions of adrenaline andof catechol with ferric chloride and of adrenaline with iodic acidand dichromate are, according to G. Bayert7 rendered moresensitive in presence of certain aromatic aminosulphonic acids.Certain products of the putre€action of flesh increase the delicacyof the iodine reaction; it was this fact which led Abelous, Soulie,and Toujan48 to the belief that the adrenaline increases whenputrid meat is added to minced adrenal gland. Colour reactionsof nevralteine, pyramidone, and antipyrine - are described byA. M ~ n f e r r i n o .~ ~ 0. Hamniarsten 50 describes a colour reaction ofcholic acid with hydrochloric acid.36 Zcitsch. anal. Chem., 1909, 48, 37; A., ii, 274.37 Arch. Phnrm., 1909, 247, 77; A,, ii, 275.38 .I Pharm. Chim., 1909, [vi], 29, 523; A., ii, 627.3o See Leys, Compt. rend., 1901, 132, 1056 ; A., 1901, ii, 488.40 Compare J. Pharm. Chim., 1909, [vi], 30, 16 ; A, ii, 707.41 Boll. chim. farm., 1909, 48, 295 ; A., ii, 711.42 Compt. rend., 1909, 148, 485 ; A., ii, 451.43 BUZZ. SOC. chirn., 1909, [iv], 5, 895 ; A,, ii, 946.e4 Bwchem. Zeitsch., 1909, 18, 40; A, ii, 628.45 Bed. KZin. Woch., 1909, 46, 8 ; A., ii, 628.46 Zentr. Physiol., 1909, 22, 825 ; A., ii, 628. *’ Biochem. Zeitsch., 1909, 20, 178 ; A ., ii, 839.48 Compt. rend. Xoc. Biol., 1905, 57, 301, 589.49 Boll. chim. farm., 1909, 48, 515; A., ii, 838.50 Zeitsch. physiol. Chem., 1909, 61, 495 ; A., ii, 836156 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.For the detection of peptolytic enzymes of the erepsin type,E. Abderhalden and A. Schittenhelm 51 suggest treating an alkalinesolution of glycyl-Z-tyrosine (" Peptone Roche ") with the suspectedextract. A positive result is indicated by the separation oftyrosine.Quantitatiue.Ultimate Analysis.-A convenient apparatus for indicating therate of a current of oxygen in the estimation of carbon by com-bustion is described by M. Dennstedt.52 M. Delepine 53 has deviseda boat for containing a substance undergoing combustion, whichappears to have some advantages over the ordinary form. B.Blountand A. G. Levy54 give their experience in the use of quartzcombustion tubes. Their experiments, although confined to theestimation of carbon in steel, are suggestive for organic analysis.J. A. Fries55 describes a bomb calorimeter for the determinationof the heat of combustion or for the estimation of carbon.Hydrogen may also be estimated if the bomb be lined withplatinum. A. Kleine56 has devised a modification of the Corleisflask for the estimation of carbon by the wet process, and also animproved form of soda-lime tube. E. Berl and A. G. Innes5'describe conditions wh'ereby carbon in such substances as cellulosemay be estimated accurately by the wet process.M. E. Poz~i-Escot~~describes a modification of the Von Koneck nickel crucible fororganic analysis by fusion with sodium peroxide. C. W. Bacon59has investigated Stepanoff's method of estimating halogens inorganic compounds.60 He finds that as originally described themethod gives inaccurate results, and he has therefore modified it,but the modification he proposes leaves nothing to be desired onthe score of accuracy. For the estimation of arsenic in organiccompounds, H. V. Little, E. Cahen, and G. T. Morgan61 ignitewith sodium peroxide, reduce with hydriodic acid, and titrate withiodine and starch in presence of disodium hydrogen phosphate.Estimation of Compounds and Determination of Constanto.-Themethod described by J. J. Sudborough and H.Hibberts2 for the51 Zfitsch. phyaiol. Cham., 1909, 61, 421 ; A , , ii, 840.52 Chem. Zeit., 1909, 33, 769 ; A., ii, 759.53 Bull. Soc. chim., 1909, [iv], 5, 876 ; A., ii, 937.54 Analyst, 1909, 34, 88 ; A . , ii, 346.55 J. Amer. Chem. Soc., 1909, 31, 272; A., ii, 270.ti6 Chem. Zeit., 1909, 33, 376 ; A., ii, 437.57 Ber., 1909, 42, 1305; A . , ii, 520.58 Ann. Chim. and., 1909, 14, 5; A., ii, 188.58 Chcnz. News, 1909, 99, 6; A , , ii, 179.6o Ann. Report, 1906, 212.Tram., 1909, 95, 1477, Proc.. 1904, 20, 165ANALYTICAL CHEMISTRY. 157estimation of amines is now found by the same chemists63 to beapplicable generally for the estimation of primary and secondaryamines, and of mixtures of these with tertiary amines. Accordingto Dreger,64 diphenylamine may be estimated by precipitation asthe tetrabromo-derivative (m.p. 1 0 2 O ) by adding bromine to analcoholic solution. A. Casolari 65 titrates quinol with iodine andstarch in presence of sodium hydrogen carbonate. J. C. Irvine66shows that the specific rotatory power of chitin, determined inhydrochloric acid (D 1-16), is [a]= - 1 4 . 1 O ( c = 1-75). This value,although calculated on the chitin itself, is in reality due to thehydrochloride; on allowing the solution to stand, the specificrotatory power changes to that of glucosamine hydrochloride,[ ~ ] , + 5 6 ~ . V. H. VeleyC7 finds that the affinity values of a fewalkaloids-those derived from opium-are less than 1 10-7, thevalues of the greater number being between this and 3 10-5 (thevalue of ammonia), whilst a few (for example, brucine, spartine, andcotarine) give higher values, and hence must be classed with thetetra-alkylammonium hydroxides.33. F. Howard and 0. Chick 6*have redetermined the specific rotatory powers in alcoholic solutionof cinchonamine, cinchonicine, concuscomine, cupreine, andquinicine. Unfortunately, the concentrations of the solutions arenot given. They have also determined the molecular weights andthe number of methoxyl groups in these alkaloids. I n theestimation of nicotine, G. Bertrand and M. Javillier 69 propose toisolate the base by precipitation as silicotungstate. P. A. Leveneand D. D. van Slyke7O describe methods for the separation andestimation of leucine, disoleucine, and d-valine in the products ofthe hydrolysis of proteins.Commercial Prodacts : Food and Drugs.-Instead of distilling offthe ammonia formed in the Kjeldahl process, H.G. Bennett71recommends titrating the neutralised liquid after addition offormaldehyde with standard alkaIi. A method for the estimationof small quantities of nitrogen in soils, etc., was devised byE. A. Mitscherlich in 1907, and has been modified by him and hisco-workers, P. Hem, E. Merres, and D. J. Hissink.72 I n broad63 Trans., 1909, 95, 477.64 Zeitsch. Schiess. Sprengstofw., 1909, 4, 123 ; A., ii, 708.Q Gnzzetta, 1909, 39, i, 589 ; A., ii, 769.86 Trans., 1909, 95, 564.68 J. SOC. Chem. Ind., 1909, 28, 54 ; A., i, 176.69 BUZZ. SOC. chim., 1909, [iv], 5, 241 ; A., ii, 450.'O J.Biol. Chsm., 1909, 6, 391, 419 ; A., ii, 947.7l J. SOC. Chem. Ind., 1909, 28, 291 ; A., ii, 436; cornpale Ronchkse, AnnBeport, 1907, 201.T2 See Lnndw. JahrB., 1909, 22, 631 ; Landw. Yersuchs-Stat., 1909, 70, 405 ;Chem. Weekblffid, 1909, 6, 2229 ; A., ii, 436, 614.67 m d . , 758158 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.outline the latest modification of the method is t o distil the sub-stance with Devada’s alloy and sodium hydroxide, whereby theinorganic nitrogen is converted into ammonia. The organic nitro-gen is then converted on Kjeldahl’s lines. V. Schenke73 prefers,when large quantities of nitrates are present, treating first withpotassium chlorate and sulphuric acid, and then with (( reducediron.’’ E. A. Mitscherlich 74 cites experiments showing thatSchenke’s method is inaccurate for nitrous nitrogen.75For the estimation of reducing sugars, P. Maillard 76 recommendsBonnan’s volumetric method .75 According to the evidencebrought forward, it lacks the accuracy of the Fehling methodin its most recent form, and could only be applied in the caseof small quantities of reducing sugars; it has been used chieflyin clinical practice.F. M. Litterscheid and J. Bornemann78 pro-pose t o determine the copper reduced by dextrose iodometrically(compare Litterscheid, p. 143). A somewhat similar proposal ismade for reducing sugars generally by E. Rupp andF. Lehmnnn.79 L. Eynonso shows that the influence of clarifi-cation with basic lead acetate in the analysis of sugar productsis greater on the direct polarimetric reading than on theClerget value.The influence is chiefly due to the precipitation oflxvulose by basic lead acetate.81 I n harmony with Eynon’s resultsis the observation of the writer and G. McLareh,82 that the Clergetvalue of molasses agrees, as a rule, well with the percentage ofsucrose determined by the copper method. The writer, in con-junction with L. Eynon and J. H. Lane,83 has redetermined thesolution densities of dextrose, lzvulose, and maltose. These threesugars were specially prepared in a high degree of purity for thepurpose. The specific rotatory powers of the preparations were asfollows : Dextrose, [a]; + 52*72O, (c = 10) ; laevulose, [ally - 93-83O(c = 10) ; maltose [a]’L5 + 137-72O (c = 5 .7 ) . A Jiiigerscbmid’sresorcinol method of detecting caramel in wine, spirits, etc.,84 is,according to W. Bremer and F. Sp0nnagel,~5 capable of detectingadded invert-sugar in natural honey.Among the papers published during the year on the estimationof starch, L. T. Thorne and E. H. Jeffers86 desdribe a modification7~ Chem. Zeif., 1909, 33, 712; A., ii, 699.75 Compare, however, Schenke, ibid., 203 ; A , , ii, 1051.76 Ann. Chim. anal., 1909, 14, 342; A., ii, 945.77 Compare A. J. Salm, Chem. Wcekblad, 1903, 1, 12.73 Zeitsch. angew. Chem., 1909, 22, 2423 ; A., 1910, ii, 80.79 Arch. Pharm., 1909, 247,516.80 Seventh Inter. Cong. AppI.[Chem. ; Analyst, 1909, 34, 349.81 Compare A. H. Biyan, Zeitsch. Ver. deut. Zuekerind., 1909, 1 ; A , , ii, 271.82 LOC.cit., 350.84 Zcitsch.>A’ahr. Benzusm., 1909, 17, 269.26 Seventh Inter. Cong. Appi!. Chern. ; Analyst, 1909, 34, 332.74 Ibicl., 1058 ; d., ii, 935.*3 Bid., 351.85 Ibid., 664ANALYTICAL CHEMISTRY. I59of Lintner’s method.87 M. Buisson 88 proposes to estimate starchpolarimetrically after heating for forty-five minutes with picric acidsolution.I n a useful and comprehensive paper, A. SmethamB9 gives theproximate composition of a number of new imported f eecling stuffsused as cattle food, as well as of products produced in this country.He draws attention to the great utility of the Soja bean, and thepaper may be consulted for analyses of these.90 The fact thatcertain beans (Phaseolus Zunatus) imported from Java contain acyanogenetic glucoside and an enzyme capable of splitting offhydrogen cyanide when they are steeped, has long been known.g1Smetham again calls attention to this fact,92 and also to a similardanger in the case of some kinds of manioc.F.C. Cook93 deals with Jaffe’s colorimetric estimation ofcreatinine. A. C. Chapman 94 has placed this method on a muchsounder basis, by showing that the various colour changes are duet o reduction of picric acid by creatinine, successively to a dinitro-monaminophenol (probably .the 2 : 4 : 6-derivative), mononitrodi-aminophenol (picramic acid), and triaminophennl.P. Malvezin 95 describes conditions of extracting wines with ether,whereby t3he partition of the volatile acids in that solvent isconstant.96 K.von der Heide and H. Steiner have publishedtwo useful papers on the estimation of succinic acid and of malicacid in wine.97 G. Perrin98 points out that inositol is a con-stituent of natural wines. He was, however, anticipated byMeill2~e,~g who criticises his meth0d.lA paper on the methods of examining vinegar is published byJ. Brode and W. Lange.2 Although of a preliminary nature only,the paper iq useful in indicating the degree of accuracy of severalmethods.87 Ann. Beport, 1908, 202.88 Seventh Inter. Cong. Appl. CJtcm. ; J. Soc. Chein. Ind., 1909, 28, 806.69 J. Roy. Lancashirc Agyic. SOC., 1909.90 Compare also U.S. Depart. Agric. BulZ., October, 1909 ; BdZ. Imp. blst.,91 Am. Aeport, 1906, 286.92 Compare also A. BarillB, J. Pharm.Chim, 1909, 29, 422.93 J. Amer. Chem. SOC., 1909, 31, 673 j A., ii, 709.94 Analyst, 1909, 34, 475 ; A., ii, 948.95 Gompt. rend., 1909, 148, 784 ; A , , ii, 444,97 Zeitsch. Nahr. Genzissm., 1909, 17, 291, 30’1 ; A., ii, 444, 445.O8 Ann. C’him. anal., 1909, 14, 182 ; A., ii, 624,Og J. Pharm. Chim., 1908, [vi], 28, 289.Ibid., 1909, [vi], 30, 247 ; A . , ii, 945,Arb. Kais, Ctesuad. Amt., 1909, 30, 1 ; A., ii, 366.1909, 7, 308.Compare N. Gallo, Xtaz. sper. agrar. Ital., 1909, 42, 3’1 ; A., ii, 524160 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.In the analysis of brewing materiak, H. van Laer3 has modifiedhis method of measuring the catalytic power of malt, making itmuch more rapid, whilst A. C. Chapman4 has further improvedhis cinchonine method of estimating hop tannin.W. M. Gardnerand H. H. Hodgson 5 describe an iodometric method of estimatingphenolic substances, including the tannins. E. F. Harrison 6 dealswith the diastatic power of malt extract. He recommends themethod described in the British Pharmaceutical Codex, 1907, page402, which was devised by himself and Gair. The method dis-regards Kjeldahl’s law of proportionality, in addition to which noevidence is adduced that the amount of starch converted under theconditions given is proportional to the diastatic power of the maltextract.0. Weber 7 describes a method of estimating formic acid in fruitjuices. F. Auerbach and W. Pluddemanns show that formic acidmay be estimated volumetrically by taking advantage of its reducingaction towards mercuric chloride, whilst H.Franzen and G. Grevedeal with the same principle applied gravimetrically.H. D. Richmond’s annual report on the composition of milk10gives the average composition of 17,433 authentic samples.H. S. Shrewsbury and A. W. Knappll describe a colorimetricmethod of estimating formaldehyde in milk. H. Rosset,lZ for theestimation of fluorides in foods, introduces the barium precipitateinto a leaden vessel, and heats with sulphuric acid, holding a glassdish above the fumes. He compares the degree of etching withstandards, and thus claims to make the method quantitative.For the determination of the hydrogen value in unsaturatedcompounds,13 S. Fokin14 has devised a new apparatus. A. H.Bennett 15 shows that in Walther’s method of determining citralin lemon oil16 it is advantageous to use alcoholic sodium orpotassium hydroxide instead of sodium hydrogen carbonate.17Useful physical data for the analysis of lemon, bergamot, andJ.Inst. Brewing, 1909, 15, 553.Sezenth Inter. Cong. Appl. Chem. ; Analyst, 1909, 34, 371 ; Trcms., 1909, 95,Pharm. J., 1909, [iv], 26, 388.Zeitsch. Nahr. Genussnt., 1909, 17, 194 ; A., ii, 355.Arb. Kais. Gesund. Antt, 1909, 30, 178 ; d., ii, 355.J. pr. Chem., 1909, [ii], 80, 368 ; A., ii, 1057.Ibid. , 360.1819.lo Analyst, 1909, 34, 208.l1 Bid., 12; A., ii, 192.l2 Ann. Chim. anal., 1909, 14, 365; A., ii, 933.l3 Ann. Report, 1903, 202.l5 Analyst, 1909, 34, 14 ; A., ii, 192.l6 Pharm. Zen1r.-h., 1899, 40, 621 ; A., 1900, ii, l i 3 .l7 Compare Scliimmel & Co., Reports, April, 1900.l4 Zeitsch.anal. Clem., 1909, 48, 337ANALYTlCAL CBEMISTRY. 161orange oils are given by E. Bert6 and Romeo.18 R. A. Cripps andJ. A. Brown 19 propose to determine moisture in spices by measuringthe acetylene produced by contact with calcium carbide.20 Thedifference between this and the total volatile matter gives theessential oil.T. R. Hodgson21 finds that Lasserre’s method of separatingvolatile fatty acids 22 gives results of approximate accuracy, whilsta similar conclusion is arrived a t quite independently by C. A.Keane and P. Narracott.23 Continuing his experiment^?^$t. K. Dons25 has determined the solubility in hot water and thevolatility of some of the fatty acids occurring in butter fat.Ahost interesting piece of work has been carried out by E. S. Caldwelland W. H. Hurtley.26 They have distilled butter fat, cocoanut oil,&nd their fatty acids in a cathode light vacuum. The temperaturesbf distillation differed widely from those stated by F. Krafft andH. Weilandt,27 and the conclusion is arrived at that under theseconditions a liquid has no boiling point.As usual, a large number of papers have appeared dealing withthe analysis of fats and oils, and of these a few will be referredto. H. Bull and J. C . F. Johannesen28 describe a modification ofHehner and Mitchell’s bromine addition gravimetric method ofdifferentiating fish oils. M. Tortelli29 shows that the Maurnen6thermal value of fats and oils is constant for one and the samesubstance.He has restandardised the method, and gives values€or several fats and oils. R. R. Tatlock and R. T. Thomson 30 havemade a useful study of the Polenske test in the analysis of fats andoils (insoluble volatile acids), and they find it scarcely capable ofdetecting 10 per cent. of cocoanut oil in butter, whilst it appearstrustworthy within limits of 5 per cent. for estimating cocoanutoil in margarine. L. Laband31 finds the method uncertain forbutter, but trustworthy for the detection of beef fat in lard.C. Paal and C. Amberger32 have published a most important18 Chemist and Druggist, 1909, 74 ; A!., ii, 352.19 Analyst, 1909, 34, 619.20 P. V. DuprB, ibid., 1906, 31, 213.21 Analyst, 1909, 34, 435 ; A., ii, 947.22 Ann.Inst. Pasteur, 1907, 21, 829 ; A , , 1907, ii, 991.23 Analyst, 1909, 34, 436 ; A., ii, 947.24 Ann. Report, 1908, 203.25 Zeitsch. Nahr. Gcnussm., 1903, 16, 705; A,, ii, 190.26 Trans., 1909, 95, 853. 27 Ber., 1896, 29, 1316.zj Chew. Zeit., 1909, 33, 73; A., ii, 274.29 lbid., 125, 134, 171, 184.3O J. Soc. Chem. Ind., 1909, 28, 69.31 Zeitsch. Nuhr. Genussna., 1909, 18, 289.32 Ibfd., 1909, 17, 1.REP.-VOL. VI. 162 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.paper on the metallic salts of the volatile fatty acids present inbutter fat and in cocoanut oil, and the detection of cocoanut oil inbutter. M. Monhaupt 33 has modified the Reichert-Meissl andKirschner processes, and shows that small quantities of butterfat may be detected in much cotton seed oil.I. Klimont andE. Meisels 34 point out that the fats of the goose and duck contain,like those of other domestic animals, mixed glycerides.K. Lendrich and E. Nottbohm35 have elaborated an accuratemethod of estimating caffeine in coffee. L. E. Walbum 36 hasmodified Baudin’s method of estimating cantharidin 37 so that theresults are more in accord with the more accurate method of Selfand Greenish.38 W. Lohmann 39 deals with the distinctions betweennatural and synthetic camphor ; the optical inactivity of the syn-thetic product and the presence of certain impurities are the meanssuggested. E. Deussen 40 describes methods for the estimation ofcamphor in spirit of camphor. H. C. Wood, jun.,41 has devised amethod for the assay of ergot; it depends on the ptimation ofthe (‘ resin.”A method for the estimation of combined sulphur in caoutchoucis described by T.B~dde.~2Synthetic indigo may contain bromoindigotins, and A. Binz andT. Marx43 show that when extracted with chloroform the tribromo-derivative is dissolved; a mixture of glacial acetic acid (80 vols.)and concentrated sulphuric acid (20 vols.) dissolves indigotin andbromoindigotin, but not the dibromo-derivative.Toxicological Analysis.Of the few papers classed under this head, the following appearworthy of notice. I n carrying out Gasparini’s electrolytic methodof destroying organic matter prior to testing for mineral poisons,M. Miorandi44 points out that it is advantageous to use carbonelectrodes instead of platinum, and ammonium persulphate insteadof nitric acid. The detection of minute quantities of mercury in33 Chem.Zeit., 1909, 33, 305.34 Monatsh., 1909, 30, 341 ; A., ii, 597.35 Zeitseh. Nahr. Genussm., 1909, 17, 241 ; A., ii, 449.36 Pharm. Zentr.-h., 1909, 50, 661 ; A., ii, 839.37 J. Pharm. Chim., 1888, 18, 391.a Pharm. J., 1907, [iv], 24, 324.39 Ber., 1909, 19, 222; A., ii, 525.40 Amh, Pharni., 1909, 2447, 307 ; A., ii, 770.41 Amer. J. Pharm., 1909, 81, 215.Guninti-Zcit., 1909, 23, 1143 ; A , , ii, 828.Zeits1:h. angew. Chem., 1909, 22, 1757; A., ii, 839,44 Gaxzetln, 1909, 39, i, 175; A,, ii, 342ANALYTICAL CHEMISTRY. 163urine, stomach contents, etc., is dealt with by C. Lombard0 45 andby C. S t i ~ h .~ ~C. Reichard,47 in dealing with the detection of morphine, pointsout that that alkaloid is partly converted into dehydromorphinein the animal body. W. J. Dilling4s summarises the reactions ofconiine, conhydrine, a-conhydrine, y-coniceine, and of the tri-methylpiperidine isomeric with coniine discovered by I. G u a r e s ~ h i . ~ ~I n another paper 50 he deals with the isolation of conium alkaloidsfrom animal tissues. G. Candussio 51 and U. Saporetti 52 show howa- and P-eucaine can be distinguished by their reactions withbromine and i0dine.~3Physiological.A very important paper on the isolation and estimation ofglycogen is published by E. Pfluger.54 It is shown that animalglycogen is not attacked by hot alkalis, and is best isolated byboiling a given organ with 30 per cent. potassium hydroxide.F. W. Gill and H. S. Grindley65 show by comparing the resultsof estimations of total sulphur in urine by 0. Folin’s sodiumperoxide method 56 with those obtained by the nitric acid method,that the former are low. 0. Folin57 states that his precise direc-tions have not been followed; and E. Abderhalden and C. Funk 58assert that the sodium peroxide method gives good results, Theypoint out 59 that Modrakowski 6o used sodium peroxide for thepurpose.61A. Florence62 recommends removing uric acid and creatinine byprecipitation with basic lead acetate before estimating urea in urineby the hypobromite method. Modifications of the hypobromitemethod of estimating urea are described by F. Haesler63 and by45 Arch. Farm. sperint., 1909, 7, 400 ; A., ii, 185.46 Pharm. Zcit., 1909, 54, 833 ; A., ii, 1055.47 Pharm. Zentr.-h., 1908, 49, 951 ; A., ii, 194.49 Atti 8. Accad. Sci. Torino, 1908, 43, 1095 ; A., 1908, i, 1008.50 Biochem. J., 1909, 4, 286 ; A., ii, 709.51 Boil. chim. farm., 1909, 48, 95 ; A., ii, 450,52 Ibid., 479 ; A., ii, 771.54 PJliiger’s Archiv, 1909, 129, 362 ; A., ii, 947,55 J. Amer. Chem. SOC, 1909, 31, 52; A., ii, 263.56 J. BioE. Chem., 1906, 1, 131 ; A., 1506, ii, 123.J. Amer. Chem. Soc., 1909, 31, 284 ; A., ii, 263.58 Zeatsch. physiol. Chem., 1909, 58, 331 ; A,, ii, 263.59 I b i d . , 59, 121 ; A., ii, 343.81 See also S . R. Benedict, J. Biol. Chern., 1909, 6, 363 ; A , , ii, 827 ; S. Ritson,61 Cbmpt. rend., 1909, 148, 943; A,, ii, 449.63 Chem. Zeit., 1909, 33, 110; A., ii, 275,Pharm. J., 1909, [iv], 29, 34 et seq. ; A., ii, 771.5y Compare ibid., 630 ; A,, ii, 838.Ibid., 1903, 38, 362.Biochem. J., 1909, 4, 337 ; A., ii, 827.M 164 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.A. Jolles.64 R. F. Bacon,65 for the rapid estimation of urea inurine, makes use of the facts (a) that urea yields nitrogen andcarbon dioxide on treatment with Millon's reagent, whereasammonia is unaffected, and ( b ) that both urea and ammonia yieldnitrogen when treated with alkaline hypobromite.For the estimation of glycuronic acid in urine, C. Tollens 66 pre-cipitates with ammonia, distils the precipitate with hydrochloricacid, and estimates the furfuraldehyde in the distillate as phloro-glucide. The same observer shows that the naphtha-resorcinolcolour reaction 67 may also be used as the basis of an approximatelyquantitative met hod.M. Nishi 68 states that quinine may be estimated in urine byrendering the liquid alkaline, extracting with ether, and p r ecipitating as quinine hydrogen citrate by addition of citric acid.ARTHUR R. LING.64 Zeitsch. anal. Chem., 1909, 48, 26; A, ii, 275.Philippine J. Sci., 1909, 4, 153 ; A., ii, 757.66 Zeitsch. physwl. Chem., 1909, 61, 95 ; A , ii, 836 ; compare Ber., 1907, 404513 ; A., 1908, ii, 74. 67 Ann. Aeport. 1908, 199.Arch. exp. Path. Pharm., 1909, 60, 312 ; A . , ii, 710

ISSN:0365-6217    

DOI:10.1039/AR9090600136

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

PHYSIOLOGICALCHEMISTRY.IN lastyear’sreport I alludedto the issueoftwoimportant seriesofmonographsonbiochem’lcalsubjects;duringthelasttwelvemonthsthesehavecontinuedtoappear.OneoftheseisCarlOppenheimer’s Handbuch derBiochemie ; it was intendedoriginallytocompletethisworkintwentyfasciculi,butthatnumberhasalreadybeenexceeded,andthereisnosignat presentthatthesupplyisexhausted.Theotherseriesisthatofthe BiochemicalMonographs,whichisunderthe editorshipofDrs.F. G. HopkinsandR.H.Aders Plimmer.Twomoreofthesehavebeenissued,one by Dr.S. B. Schryver on the General Characters ofthe Proteins,andthesecondbyDr.ThomasB.OsborneontheVegetableProteins,whichsupplies a long-feltgapin chemicalliterature.Inbothseriesthe subject-matterisuptodate,and one’sonlyregret,lookingtotherapidacquisitionofnewknowledge,ishowsommuchthathasbeenwrittenwithinfinitepatienceandcarewillbecomeancient history.One more newbookis worthyofmention,andthat isa,practical handbook:whichresemblesOppenheimer’sinbeingwrittenbynumerousauthors;EmilAbderhaldenisitseditor,and it willquicklyfindaplacein the library ofeverywell-equippedlaboratoryandresearcher.Theyearhasbeennoteable fortheholdinginLondonoftheCongressofAppliedChemistry,andthiseventwilllongliveinthememoryofallwhoattendedit.AtthefinalmeetingthepositionofPhysiologicalChemistrywasvindicated,andin futureit willbea separate section,insteadof,itsheretofore,a sub-sectionofOrganic Chemistry.Our section(orsub-section,as it then was)waswellattended,andonehadtheopportunityofmakingthepersonalacquaintance ofworkersfromall partsofthe globe,andofhearing themspeak.Where somany importantand interestingpaperswereread,itseemsinvidioustoselecta fewforspecialmention;the partsofthe programmewhich,however,appearedtomeasspeciallyinterestingwere(1)the seriesofpracticaldemon-strationswhichweregiveninthe newInstituteofPhysiologyatUniversityCollege;(2)theablepresentmentoftheirviewsonHandbuch deerbioehemisehen Arbeitsmethodcn166 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY,alcoholic fermentation by Drs.Harden and Young; (3) the interest-ing paper by Dr. Steudel on uric acid, to which I shall have torefer later; and (4) the important group of communications on thelipoids, which were introduced by a lucid exposition of his viewsby Professor Hans Meyer, one of the pioneers who first recognisedthe physiological importance of these substances.I n the selection of papers for more extended review, I find, onlooking up the year’s literature, not only the em,burrus des richessesto which I also referred last year, but this year I find a specialdifficulty in my task, for no new note has been struck, no greatdiscovery made, and the subjects treated are so varied and numerousthat connecting threads are hard to weave. A number of small anddisjointed details are to hand, none of them of vast importance,and at first I thought my report would dwindle down to makingan abstract of the physiological abstracts, which would not be muchmore than a catalogue of them.If this report ultimately possessesthis character, which I always endeavour to avoid, the reader mustattribute it more to the material at my disposal than to any fault ofmy own. There is an increasing tendency in some quarters topublish researches piecemeal, and driblets of what really may bean important piece of work issue month by month, and one’sattention and interest vanish, and the sequence of the story is lost,much as it is when one reads a novel issued in a monthly magazine.One can quite understand, in these strenuous days, the value of apreliminary communication in order to ensure priority, but.thatis a very different thing to what I am alluding; it really looksas if some workers are seeking fame rather by the number of papersto which their name is attached than by making solid and sureprogress by taking a little more time over their work, and finallypresenting it in more or less complete form.Having, however, delivered myself of this protest, let us nowproceed to consider the work of the year; and in so doing I shallendeavour to select subjects of general and practical interest.Proteins.The work on protein synthesis does not appear, so far as one canjudge from published papers, any further advanced that it was someyears ago when Emil Fischer first applied himself to the problem.Abderhalden and his colleagues are more concerned at present withprotein cleavage, and this is no doubt the right method of work;correct analysis must necessarily precede synthesis. It is much tobe regretted that Abderhalden is not free from reproach in referenceto what one may term the “ driblet” method of publication, forhe exhibits not only remarkable industry, but, unlike many merPHYSIOLOGICAL CHEMISTRY. 167slaves to work, he possesses ideas.One excellent specimen of a newidea is seen in the new method he has introduced of partialhydrolysis ; the distinction between proteins will probably be foundto rest not only in the kind and amount of the final cleavageproducts so much as in the way in which the individual amino-acids are linked together. For this purpose, partial hydrolysis,with a resulting yield of polypeptides, is of great utility. I n hisfirst attempt in this direction: polypeptides were separated fromthe partial hydrolysis of edestin, elastin, and keratin. One of thesecontained glutamic acid and tryptophan, another the same two sub-stances with leucine in addition, and a third, tyrosine, glycine, andleucine. From keratin a polypeptide containing cystine, glutamicacid, and tyrosine, and another containing histidine and leucinewere separated ; and from elastin, Z-leucyl-d-alanine and d-alanyl-Z-leucine were obtained.I n a later paper,3 which is one of a large number relating tothe composition of different silks (see forthcoming index), heobtained, by what he terms a, lucky accident, glycyl-Z-tyrosinedirectly from the products of the partial hydrolysis of silk.Thehydrolysis had been carried out with 70 per cent. sulphuric acida t room temperature. Similarly, two dipeptides, one of themleucyl-glycine, and the other probably glycyl-leucine, were obtainedfrom elastin.The onlookers a t the progress of our knowledge of proteinchemistry, which had its inception in Emil Fischer's remarkablework, cannot but feel that the method of partial hydrolysis isfraught with importance, and would desire that the method beworked out more thoroughly. Our feelings of satisfaction thatone of the most difficult of biochemical questions is on the way tosolution must, however, have received a set-back on reading a paperfrom the versatile pen of the veteran worker and thinker, EduardPflUger,* whose opinions are entitled to the deepest respect.Pfluger, it is true, has, or had, a theory of protein constitution,and so is not altogether unbiassed; his views on the work ofFischer, Abderhalden, and their disciples are decidedly pessimistic.H e doubts whether all this gigantic array of experiments brings usany nearer to a solution of the question of protein constitution.H e certainly points out that in their work a large portion of themolecule is still unaccounted for; and no one can deny that inthe case of the more complex proteins the cleavage productsobtained do not account for much more than half the original2 Zeitsch.physiol. Chem., 1909, 58, 373 ; A., i, 273.3 B i d . , 1909, 62; 415 ; A., i, 859.4 PJliiger's Archiv, 1909, 129, 99 ; A., i, 685168 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.molecule. Perhaps half is better than none, but the remaining halfwill undoubtedly be the more difficult one to tackle. Pfliigeradopts as the only certain test for a protein its capacity to maintainlife and enter into the composition of protoplasm; if this definitionis accepted, gelatin, protamines (many of which are poisonous),proteoses, and polypeptides must be excluded from the proteinfamily.This definition strikes one as too narrow, and toobiological; it is quite possible that members of it group may possessohemical characters in common which justify the use of a commongeneral name, and yet they may have a very different physiologicalaction. This is admitted for substances of which the chemicaluonstitution is known, and it is no great stretch of the imaginationto conceive the same to be true of substances which, like theproteins, are still in chemical darkness.Whatever may turn out t o be the ultimate value of suchanalytical work, it is certainly of minor value unless it is correct;and biochemists no doubt received another shock when a recentpaper by Levene and van Slyke appeared.These careful workersshowed that all previous methods employed for the isolation andestimation of the leucine fraction, and for the separation of itsconstituents (leucine, isoleucine, and valine), were incorrect, andthat by new and trustworthy methods the figures obtained differenormously from those given by Abderhalden. Abderhalden’s workin this direction has, of course, not been useless, but now it onlyfulfils the humble r61e of showing subsequent workers how not todo it: our knowledge of the proteins is thus delayed, for all thelaborious analyses of the leucine fraction (and possibly of otherfractions, too) will have to be repeated.Purine Metabolism.The general view now held with regard t o the origin of purinesubstances in the urine is that in mammals they arise from thecatabolism and oxidation of the main constituent of the nuclei ofcells, which is called nucleic acid.Within recent years doubts havearisen whether this statement contains the whole truth, and alsowhether the theory which has been largely deduced from experi-ments on animals can be applied without reserve to man. It isnaturally from the human point of view that the question derivesits main importance, and all that we can learn about the origin andfate of uric acid is of great practical interest. Many human illshave been attributed in the past to excess of uric acid, and someenthusiasts are inclined to regard it as the source of all our woes.Without accepting such a sweeping belief, the fact remains thatthis waste product is by no means harmless. I n man, no doubt, theJ, Biol.Chem,, 1909, 6, 391, 419, A., ii, 947PHYSIOLOGICAL CHEMISTRY. 169question is complicated by his varied diet, and some of the purinesubstances, which in health thers seems no difficulty in gettingrid of, are introduced with the food, and are of purely exogenousorigin ; thus meat contains a considerable amount of hypoxanthine,and tea and coffee account for the methylated purine derivatives ofthe urine (ax. Kriiger).G This factor is, however, fully recognisedby experimenters, and observations on man are always made ona purine-free diet if one seeks to investigate the more importantquestion of the endogenous origin of purine.Before, however, we can proceed to a systematic review of thepoint at issue, it will be necessary to allude briefly to the constitu-tion of nucleic acid, and the prevailing views regarding its decom-position in the body.Nucleic Acid.-Since the work of I.Bang and Walter Jones(described in last year's Report), it has been recognised that thereare two principal kinds of nucleic acid. One of these, now termedguanylic acid, yields, on decomposition, three products only, namely,guanine, phosphoric acid, and a pentose. The other, which maybe termed nucleic acid proper, is apparently more widely dis-tributed, and more abundant in cells generally. A t the recentCongress, to which allusion has already been made, Steudel gavethe results of his careful analyses, a,nd proposed an empiricalformula for it which differs somewhat from that advocated bySchmiedeberg last year.The following equation indicates what itis, as well as the way it splits up on decomposition with water andoxygen :C43H5703&"5P4 + 8HzO + 0, = @,H,ON, + C5HSN5 +[Nucleic acid.] [Guanine.] [Adenine.]C&&OzN2 + C,HSON, + ~C,H,~OG + 4HPO3.[Thymine.] [Cytosine.] [Sugar.] [Metaphos-phoric acid.]That is to say, the cleavage products are two amino-purine bases(guanine and adenine), two pyrimidine bases (thymine and cytosine),four molecules of a sugar of the hexose family, but not yet fullyidentified, and four molecules of metaphosphoric acid.H e also put forward tentatively his view regarding the con-stitution of the nucleic acid molecule, which may be representedroughly in the following way:OH-P- Sugar-GuanineOH-P- Sugar-AdenineOH-P- Sugar-CytosineOH-P- Sugar-ThymineBiochem. Zcitsch,, 1909, 15, 361 ; A., ii, 166,II170 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.That is, we have a chain of four atoms of phosphorus, each ofwhich is united on the one side to a hydroxyl group, and on theother to a hexose molecule; each hexose group is further united toa base, and thus the four bases enumerated above are attached tothe molecule.It is impossible to prophesy whether such a formula will standthe tests of criticism and renewed experiment, but, at any rate, wehave a working hypothesis, and one can only hope that if we havenot reached the last chapter in an interesting series of researcheswhich was initiated by Miescher many years ago, we must besomewhat near the penultimate one.The view now held with regard to the decomposition of thiscomplex molecule in metabolic processes within the body is brieflyas follows.The decomposition is accomplished by certain tissueenzymes, which have been studied in extracts of tissues and organs;their distribution varies a good deal both in different animals andin their different organs, but, speaking generally, they are mostabundant in the liver and spleen. The first t o act is callednucleuse; it liberates from nucleic acid its purine bases. The nextto come into play are called deamidising enzymes, because theyremove the amino-group ; one of them, adenase, converts adenineinto hypoxanthine (mono-oxypurine) ; the other, called guanase,converts guanine into xanthine (dioxypurine) ; finally, oxydasesstep in which transform hypoxanthine into xanthine, and xanthineinto uric acid (trioxypurine).But even that does not bring thelong list to a conclusion, for in certain organs (for example, theliver) there is a capacity to destroy the uric acid after it is formed,and so we are normally protected from a too great accumulationof this substance. What exactly happens t o the uric acid isuncertain, although it is supposed that the products of breakdownare less harmful than uric acid itself. The enzyme responsible foruric acid destruction is called the uricolytic enzyme. The uric acidwhich ultimately escapes in the urine is the undestroyed residue;the urine, however, contains a certain amount of the purine baseswhich have not been converted into uric acid.This view renders it easy to understand how too great an actionof uric acid-forming enzymes and too little activity of the uric acid-destroying enzyme may lead to a pathological condition in whichuric acid accumulates in the body.To those who have read myprevious reports, this will be an old story, but I have thought itbest to recapitulate the main data of the theory in order to pavethe way to what now follows.What we have now to consider are the weak points in the theory,for renewed experiments have shown that it is quite possible thaPHYSIOLOGICAL CHEMISTRY. 171(1) purines may arise otherwise than from the cleavage of nucleicacid, and (2) that in man the uricolytic ferment is absent fromextracts of his tissues and organs; if this is really the case, manis inferior to most other mammals in his capacity to deal withone of his enemies.Leathes7 was the first to point out that uric acid excretion isrelated in some way to muscular exercise; it is, for instance, moreabundantly eliminated during the day than during the night.Hennaway’s 8 more recent; work confirms this view. Walter Jones(working with Leonard 9), who, of course, on such a question speakswith authority, takes it as established that muscular exercise con-tributes to uric acid formation.Muscle, however, is admittedlypoor in nucleic acid, although, as is well known, it is rich inhypoxanthine; it therefore appears that not only may muscle orflesh, when used as food, increase the purine compounds in theurine exogenously, but, in a similar way, the hypoxanthine presentmay form the source of a true endogenous production of uric acid.The hypoxanthine in muscle may be spoken of as ‘‘ preformed,” andits origin is not directly connected with nuclein metabolism at all,since it occurs in the absence of adenase, an essential factor in thepassage from nucleic acid to hypoxanthine.Aders Plimmerlo gives details of a metabolism experiment on ahealthy man which casts considerable doubt on the whole theory.The subject of the experiment was fed on a meat diet, on a purine-free diet, and a purine-rich diet; also, on certain days, guanine andxanthine were added t o the diet.Scarcely any relation between thepurines given and the purines (including uric acid) found in theurine was discoverable ; he therefore considers that the prevalentopinion that the purines of the food and tissues are the sole sourceof uric acid needs revision. I f we italicise the word sole, mostphysiologists will probably agree with him, although I am doubtfulwhether many will accept without more cogent proof his alternativetheory that leucocytes in the manner of invertebrate animalsexcrete uric acid in some mysterious way without reference to themetabolism of their nuclei.The Uricolytic Enzyme.-Most interest and much work hascentred around this interesting enzyme. I t s presence has beendetermined with certainty in the majority of animals in which ithas been looked for, and is usually most abundant in the liver,although it may be present in other organs, such as the kidney.We7 J. Physiol., 2906, 35, 125, 205 ; A., 1907, ii, 114, 376.Bid., 1908, 38, 1 ; A., ii, 166.J. Biol, Cltem., 1909, 6, 453 ; A . , ii, 911.J. Physiol., 1909, 39, 98 ; A., ii, 817172 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.may take first some of the most recent experiments that supportthis view. Wiechowski,ll for instance, working with the survivingliver and kidney of dogs, finds that these organs decompose uricacid entirely, and that allantoin is one of the products of its decom-position, although probably not an abundant one, for the urinecontains mere traces.He 12 admits, however, that if uricolysisoccurs at all in human tissues, the action is extremely small ascompared with that in other animals.The uricolytic action, when present, appears t o be reversible, or,at any rate, counteracted by other enzymes; the latter view appearsto be that adopted by a group of Italian workers.13 A dog’s liverwas perfused with arterial blood containing uric acid, and it wasfound that a marked decrease of the uric acid took place; butby perfusing the same liver with blood saturated with carbondioxide, the uric acid, which had disappeared, appears again: theenzyme to which the restoration is due is stated to occur in theblood and blood-serum, but not in the blood-free liver.They thenadded to finely-minced surviving liver a large number of thedecomposition products of uric acid, but usually no formation ofuric acid occurred; the only positive result was obtained by theaddition of dialuric acid and urea.The question of uric acid destruction has also been taken upby Battelli and Stern.14 They regard it as a complex process, andthe appearance of allantoin only one of many possibilities; and theenzyme which oxidises uric acid to allantoin is named by themurkase. I t s action is most energetic in free oxygen, but, in manytissues, inhibiting substances delay its action. Uricase is absent inbirds, which is what one would anticipate; it is also absent in man.The absence of uricolysis in man is also noted by Wells and Corper,l5and by W.Jones and Miller.16 Jones and Miller started their workby searching for the uricolytic enzyme in human tissues from casesof gout. They found it absent, but this cannot be the cause ofthat disease, for they then found, in confirmation of Wiechowski,that the same is true for normal human organs. They found alsothat another member of the uric acid group of enzymes is alsol1 Arch. exp. Path. Pharm., 1909, 60, 185 ; A., ii, 329.l2 Biochem. Zeitsch., 1909, 19, 368 ; A., ii, 749.la Ascoli and Izar, Zeitsch. physiol. Chcm., 1909, 58, 529 ; A., ii, 329 ; ibid.,1909, 62, 347 ; A., ii, 909 ; Bezzola, Izar, and Preti, ibid., 1909, 62, 229, 354 ;A., ii, 1909.l4 Biochem. Zeitsch., 1909, 19, 219 ; A., ii, 749.J. Bwl. Chem., 1909, 6, 321 ; A., ii, 749 ; ibid., 6, 469 ; A., ii, 1034.Thesel6 Zeitsch. physiol. Chem., 1909, 61, 395 ; A,, ii, 821 ; see also W. Jones andobservers deal specially with fetal tissues.Wintcrnitz ibid,, 1909, 60, 180; A,, ii, 594PHY SIOLOCt ICA L CHEMISTRY‘. 173absent, namely, adenase, and this contrasts with the pig, in whichanimal, guanase is absent. In man the principal seat of uric acidformation (from guanine) is the liver, but guanase is also presentto some extent in the lung and kidney, although absent from thespleen.Differences were previously known to exist between differentanimals in the presence and distribution of the enzymes which leadto the formation of uric acid, so the absence of adenase in manis not remarkably noteworthy; the puzzling and a t presentinexplicable fact is the absence of the uricolytic enzyme in humantissues.From the evolutionary point of view, its development wouldnaturally be regarded as an important asset in the struggle forexistence. Can it be that a further development still has takenplace in man, and that so little uric acid is normally produced thatthere is no necessity to destroy it 8 I do not feel in the least inclinedto answer this question in the affirmative, and it is impossible t obe certain what is the solution of the problem until more workcasts more light upon it.A Schittenhelm’sf7 views on the matter are, however, very sug-gestive, and will make physiologists pause before they regard theaction of organ-extracts as a complete picture of actual metabolismin the body. It is quite true that the extracts of human tissuescontain no uricolytic enzyme, and often no adenase, but it isunscientific and unwise to conclude, from such results obtainedpost-mortem, that metabolism runs a similar negative course duringlife.In fact, the metabolism experiments he has performed indicatethat adenine is converted into hypoxanthine, and that the uricacid formed is in part destroyed (reappearing mainly as urea) inhuman beings.Enzymes.The specific action of enzymes is one of their most interestingproperties, and Emil Fischer’s well-known ‘‘ lock and key ” hypo-thesis furnishes 8r ready explanation for the specificity; there mustbe some relationship, for instance, between the configuration ofthe enzyme maltase and the sugar maltose on which it acts, thatenables it to unlock from their union the two molecules of hexoseof which maltose is composed; on the other hand, an absence ofsuch related configuration rendem this enzyme inoperative evenon guch closely related sugars as sucrose and lactose.There is no doubt that the various members of the large proteinfamily differ from each other a good deal more than do the threedisaccharides just mentioned ; nevertheless, from the point of viewof their susceptibility to enzymic cleavage, there is a closer simi-Zeitsch. physiol.Chem., 1909, 63, 248 ; A., 1910, ii, 62174 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.larity, as has been recently pointed out in a thoughtful essay onthe Proteins by T.Brailsford Robertson.18 All true proteins anda, large number of polypeptides are hydrolysable by trypsin, andthe great majority of them by pepsin also.The general trend of present day work on t-he enzymes is toemphasise specificity, and to seek for the agents responsible for thecleavage of comparatively simple substances. The discovery byKossel and Dakin a few years ago of arginase, an enzyme capableof hydrolytically cleaving arginine and nothing else, was thestarting point of this line of research, The discovery of creataseand creatinase, mentioned in last year’s report, is an instance ofthe same sort of work. This year we have t o add to the list, andt o chronicle the identification of salilase, which hydrolyses salicinto dextrose and saliginin, and of arbutase, which hydrolyses arbutininto quinol and dextrose.19 A glance through our monthlyabstracts will show how numerous are the papers relating toanother group of enzymes, namely, the oxydases, and it will besufficient to say in reference to this work that specificity seems asevident there as in enzymes which act hydrolytically. The newestenzyme is by no means the least interesting, as it partakes of thenature of an oxydase; it has been dubbed P-hydroxybutyrase byits discoverers, Dakin and Wakeman,20 for it is the agent responsiblein the body for the conversion of 0-hydroxybutyric acid into aceto-acetic acid.It is present in the liver cells and in aqueous extractsof the liver. Its action is increased by the addition of blood, or ofcrystallised oxyhemoglobin, which furnish readily the necessaryoxygen.The liver tissue also decomposes acetoacetates with theformation of acetone, but here the addition of blood produces noincrease in the action, which is probably what one would expect,seeing that the action is not an oxidative one.Blood Coagulation.-Here we have to deal with enzymic activityalso, and enter a field of controversy which has been comparativelyquiescent during the last few years. The work of Morawitz hadprovided, at any rate, a working hypothesis, which to a great extentexplained and harmonised previously conflicting views. Onedisturber of this placid state has been J. Mellanby,21 many of whoseexperiments do not support Morawitz’s view of the causes of bloodcoagulation.Mellanby’s theories, however, run on the same linesas those of Morawitz; the differences are those of detail concerningthe relative importance of thrombin and kinase in producingclotting, and of anti-thrombin and anti-kinase in restraining it,University of California publications in Physiology, 1909, 3, 115.W. Sigmund, Monatsh., 1909, 30, 77 ; A . i, 277.J. Physiol., 1909, 38, 28, 441 ; A , , ii, 158, 680.2o J . Biol. Chem., 1909, 6, 373 ; A . ii, 908PHYSIOLOGICAL CHEMISTRY. 175Morawitz,22 moreover, vigorously defends his own theories, and thequestion is thus in a stage not for final settlement, and one whichis mainly interesting to specialists in the subject. B. J. Colling-wood’s 23 contribution relates to the r6le of calcium in the causationof clotting; he concludes from his experiments that the bloodcarries calcium in some other way than in a state of simple solution,and that calcium ions are not essential to coagulation. The thirddisturber of the peace is L.F. RettgerF4 and his views are quiterevolutionary, for he doubts whether thrombin is an enzyme a t all;he regards the existence of a pro-enzyme as unproved, and theexistence of kinase as improbable. He looks on blood coagulationas a quantitative reaction, and probably as a mutual precipitationof two colloids, fibrinogen and thrombin. It will readily be under-stood that on this view the action of anti-thrombin, calcium salts,and decalcifying agents is interpreted on new lines, but on thisand many other points this very suggestive (but far from con-vincing) paper cannot be advantageously summarised.The wholeproblem is thus once more in the melting pot.Mechanicd Destruction of Emymes.-The mechanical precipita-tion of proteins from solution by shaking has been known for someyears, and its discoverer was W. Ramsden (1894). The destructionof enzymes by the same mechanical process is an interesting factwe owe to S. J. Meltzer and his colleagues. The announcement wasmade late in 1908F5 but the full paper26 has only just appeared,and deals principally with proteolytic enzymes. Other workers,references to whose writings arc given fully in the paper, have,however, confirmed the same statement in reference to otherenzymes.27It might be supposed that this is due to the proteins beingprecipitated and carrying down the enzymes with them, evenalthough the particles are too sinall to cause perceptible turbidity ;a second interpretation would assume that the enzyme remainsadherent to the walls of the bottle in some such way as it isadsorbed by fibrin.Such explanations do not, however, commendthemselves to Meltzer. Numerous previous experiments haveestablished that shaking is capable of fundamentally influencingbacteria, yeast, blood corpuscles, and starfish eggs, and Meltzer22 Biochem. Zeitsck., 1909, 18, 30 ; A., ii, 592.24 Amer. J. Physiol., 1909, 24, 426 ; A., ii, 680.25 Proc. Amer. Physiol. Soc., 1908, xxix, ; Amer. J. Physwl., 23; A., i, 277.26 Amer.J. Physiol., 1909, 25, 81 ; A., i, 980.27 See, for instance, H. C. Bradley, J. Biol. Chem., 1909, 6, 133 ; A , , ii, 496, inreference t o pancreatic lipase ; also Harlow and Stiles, ibid., 359 ; A,, i, 861, inreference to ptyalin.Proc. physiol. Soc., 1909, lxxix. ; J. Physiol., 38 ; A., ii, 681176 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.assumes that the nature of the destruction of enzymes is similar tothat which takes place in the destruction of living cells, and thatshaking affects a certain structure which is common to living cellsand to ferments. This, of course, may be perfectly correct, butit brings us no nearer to the real explanation of why shaking isharmful in both cases, and the terms, (( molecular disintegration ”and “ disbanding of the physiological units,” which he employs aredangerously like the blessed word Mesopotamia and othershibboleths.IJormones.Secretin.-The composition of many of the chemical messengers’of the body is still unknown.It is certainly the case for secretin,.the first substance to which the general term hormone was applied.The suggestion that it is identical with choline has been abundantlydisproved by the work of Dixon and Hami11.28 Their view regard-ing the way in which it acts on the pancreas advances ourunderstanding of the processes in which it participates. As is wellknown, there are three enzymes or potential enzymes in the pan-creatic juice, namely, trypsin, amylopsin, and steapsin (or, better,lipase) ; the two lasbnamed are present in the juice ready for actionon starch and fat respectively; the proteolytic enzyme, however,is in the condition of a pro-enzyme termed trypsinogen, and theconversion of this into the active enzyme is the work of the entero-kinase of the intestinal juice.29 The two ready formed enzymes andthe one which requires activation are present in the pancreatic cellsas mother substances, which may respectively be termed pro-trypsinogen, pro-amylopsin, and pro-steapsin.Secretin, accordingto Dixon and Hamill, acts chemically on all three, and liberatestrypsinogen in the first case, and the two active enzymes in thelast two cases. What the nature is of the chemical interactionbetween secretin and the zymogens is not known; Dixon and Hamillare inclined to regard it as combination, but Mellanby 30 has citedcertain facts which he thinks renders this view untenable.Adrenaline.-This, on the other hand, is an instance of a hormoneabout which physiologists and chemists can congratulate them-selves in having discovered the chemical constitution.31 Of its two** J.PhysioZ., 1909, 38, 314 ; A . , ii, 414.On the activation of trypsinogen by another agency, namely, calcium salts, seeB. Agrton, Quart. J. exp. Physiol., 1909, 2, 201; A . , ii, 497. On the date a twhich the digestive enzymcs appear in the human embryo, see J. Ibrahim (Biochcm.Zeitsch., 1909, 22, 24 ; A., ii, 1034).30 Proc. physiol. Soc., 1909, xi. ; J. Physiol., 39; A., ii, 683.31 On recent syntheses in the adrenaline or epinephrine series, see Tntin, Catonand Hann, Tram., 1909, 95, 2113PHYSIOLOGICAL CHEMISTRY.177isomerides, the one which occurs in nature (Z-adrenaline) is farmore powerful in its various physiological activities than thed-adrenaline. This was first shown by Cushny,32 and Cushny’s workhas been corroborated by Abderhalden and his colleagues in a seriesof papers.33 The racemic base has an intermediate power pro-portional to the amount of Z-adrenaline it contains. An interestingpoint has arisen from Abderhalden’s work in relation t o so-called‘‘ adrenaline immunity ’,; for in mice, dosage with the inactive ord-base renders these animals more resistant to the subsequentaction of the active base. This, however, was found not to hold forhigher animals, such as dogs.34Pressor Bases in Putrid Meat.-This question follows naturallyafter a consideration of adrenaline, as will be seen immediately,and is, moreover, an example of how research on the unpleasantproducts of putrefaction has been followed by practical resultswhich are not unimportant. We may take as our starting pointthe work by Abelous35 and his colleagues on the bases present inputrefying horseflesh.They did not succeed in identifying theirproduct chemically, but they showed that on injecting it into theblood stream it produces a rise of arterial blood-pressure somewhatsimilar to that caused by adrenaline. They further found a basewith the same properties in the urine, and surmised (correctly, asit turned out) that this substance is formed by putrefactiveprocesses in the intestine, from which it is absorbed, finally leavingthe body in the urine.They named it urohypertensine, and theysubsequently supported their view of its origin by discovering it inthe faxes.Quite independently of this, Dixon and Tayler found thatextracts of the placenta have a similar adrenaline-like action, andthey surmised (incorrectly, as it turned out) that it was a normalinternal secretion of the placenta, and that its use came into playduring and after delivery in causing uterine contraction. Thisbrings us to the beginning of this year, and we have now to dealwith the development of the subject during the last twelve months.Rosenheim36 showed that extracts of the placenta have no suchaction if putrefaction is excluded, and that the pressor substance,or rather substances, are products of initial putrefaction.Thea2 J. Physiol., 1908, 37, 13 ; A,, 1908, ii, 7’20 ; ibid., 1909, 38, 259;a3 Zeitsch. physiol. Chem., 1908, 58, 186, 189 ; 59, 22, 129 ; 62, 404 ; A., ii, 159,24 So far as mice are concerned, Abderhalden’s statements have been recently36 Compt. rend. Xoc. Biol., 1906, 430.313 J. PhysioZ., 1909, 38, 337 ; A,, ii, 416,REP*-VOL. VI. NA., ii, 420.333, 420, 1041.confirmed by Waterman (Zeitsch. physiol. Chem., 1909, 63 290 ; A . , 1910, ii, 59)178 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.autolytic enzymes without the aid of micro-organisms are unable tosplit off the terminal carboxyl group of the amino-acids from whichthey originate.The most active substance separated out wasidentified as p-hydroxyphenylethylamine, and the identity ofanother with isoamylamine was considered probable. I n fact, thebases are the same as those found by Barger and Walpole,37 who,on repeating Abelous’ work, were successful in discovering the com-position of his urohypertensine. The bases are derived quite simplyfrom amino-acids by the loss of carbon dioxide; isoamylamine is inthis way derived from leucine, and p-hydroxyphenylethylaminefrom tyrosine. The second is by far the more powerfulphysiologically, as perhaps one would anticipate from its closerrelationship to adrenaline.38 A third base, probably phenylethyl-amine (from phenylalanine), was separated out in smaller amount.They consider it probable that Abelous’ base is mainly isoamyl-amine.W.Bain39 then took up the subject from the clinical point ofview, and at present he has only published a preliminary accountof his investigations. He separated out the bases from normalurine, and, although they are present in such small quantities thatsufficient was not available from this source for analysis, there canbe practically no doubt, from their chemical and physiologicalproperties, that their composition is that of the two bases justmentioned. From the practical point of view of the physician, thequestion arises: Would the retention of such bases in the bodyaccount for the high blood-pressure seen in disease? And in thefew cases up to now examined, his results show that in gout andallied conditions they are scanty or even absent in the urine, andso it would appear tha,t the question must be answered in theaffirmative. But while awaiting further investigation, it is interest-ing to note that the subject has had another important practicalside issue, for Barger and Dale40 have shown that the same twobases, and especially the more powerful one, are present in extractsof ergot of rye.This explains the effect of ergot in raising arterialpressure, which previously it was difficult to attribute entirely toergotoxine. Their effect on the uterus is also marked, and so theintroduction of a pure drug has been rendered possible, and thenotorious variability of extracts of ergot need no longer be itserious difficulty.37 Proc.physiol. SOC., 1909, xxiii ; J. Physiol., 38 ; A , , ii, 254 ; J. Physiol.,1909, 38, 337 ; A., ii, 416.38 On the relative power of these and other amines, see Dixon and Dale,J. Physiol., 1909, 39, 25 ; A., ii, 688.39 Lancet, Aug. 7, 1909.40 Proc. physiol. Soc., 1909, lxvii. ; J. Physiol., 38, A, ii, 689PHYSIOLOGICAL CHEMISTRY. 179The Pineal Gland and Pituitary Body.The suprarenal gland and the thyroid are instances of theductless glands, the function of which has been elucidated by bio-chemical research; it has been shown that they produce internalsecretions which are essential for healthy life, and the method ofexperimenting with extracts of the organs has played no meanpart in the solution of their functions.It now looks as if we areon the eve of being able to chronicle the discovery of the functionof one of those little outgrowths of the brain the names of whichstand at the head of this section.The Pined Gland.-We will take this first, because it is the oneof which we know least from the physiological point of view. Itreceived its name from its resemblance in shape to a pine cone, andobtained celebrity from the fact that Descartes localised here theseat of the soul, mainly because it was the one structure in thebrain which was not paired, Recent researches by morphologistshave, however, shown that even this slender piece of evidence isincorrect. Originally the outgrowth is paired, and in some partsof the animal kingdom both outgrowths attain considerable com-plexity; one of the pair becomes developed into a median senseorgan, the so-called pineal eye, which is connected to the brainby a nerve, and which is doubtless sensitive to light, althoughcovered by skin; this is seen in certain fishes, such as the lamprey,and in a good many lizards, notably the Tuatara or Hatteria, theNew Zealand lizard.The member of the pair of outgrowths whichbecomes the pineal eye in the lamprey becomes in the lizard acomplex glandular structure called the pineal gland, and the otherone becomes the pineal eye. I n mammals, man included, the pinealeye has entirely disappeared, and the pineal gland is atrophied andcalcareous. It probably is a functionless, vestigial structure, andextracts of it produce, on injection into animals, no physiologicaleff ects.41The Pituitary Body.-This is an outgrowth from the base of thebrain, which in man weighs about half a gram, and until recentlyit also was regarded as an ancestral vestige, or a t least of but littleimportance, in spite of the fact that it possesses an elaboratestructure.It is situated in the bony depression a t the base of theskull known as the Turkish saddle (Xella turcica), and owes its nameto the view of the ancients that its function is to secrete thepituita or m-ucus of the nose.We now know that it is a structure which, like the thyroid andeuprarenal, is indispensable to life, and that it exerts its influence41 Dixon and Halliburton, Quart. J. exp. Physwl., 1909, 2, 283.N 180 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.on the metabolism of the body by the formation of an internalsecretion which contains hormones.The chief point on which weare still in ignorance is the composition of these chemicalmessengers.From the developmental point or" view it consists of two parts:one of these is nervous in origin, and is a downgrowth from thebrain in the region of the third ventricle, with which it remainsconnected by a funnel-shaped stalk known as the infundibulum;a t first this growth is hollow, and traces of the original cavity areseen in some animals, but in the majority of animals the cavityis obliterated by the growth of neuroglia. This nervous portionof the pituitary constitutes its posterior lobe, but in the adultit shows little or no true nervous structure, being made mainly ofinterstitial or neuroglial tissue.The other part of the pituitaryis an upgrowth from the mouth, which meets the nervous down-growth, and the two parts fuse together. The original connexionwith the buccal cavity is soon cut off by the completion of theroof of the mouth. This island of epithelium cells from the mouthis hollow; but as the cells multiply, the walls of the sac becomethickened, and ultimately only a cleft remains; the cells on one sideof this cleft apply themselves to the posterior lobe, which theycover and invade; this constitutes the pars intermedia; it is herethat colloid material is formed, which collects in cysts, remindingone of the colloid acini of the thyroid gland; and it is probablyowing to these cells that the posterior lobe possesses the physiologicalproperties to be immediately described ; the colloid material passesalong the remains of the cleft into the third ventricle of the brain.The rest of the buccal outgrowth is developed into the anteriorlobe proper, the largest portion of the organ; this is very vascular,and the cells, many of which are granular, possess a well-markedglandular appearance.*ZThe first investigator who recognised the importance of thepituitary was P.Marie (1885), who pointed out that the diseaseto which he gave the name of acromegaly is associated with anovergrowth of the pituitary body. This disease is a chronic one,which affects adults, and is characterised by a peculiar overgrowthof the lower jaw and of the extremities. A giant, thanks to ournursery legends, is usually regarded as an extremely powerfulperson; as a matter of fact gigantism is usually a pathologicalcondition associated with sterility and other weaknesses, and closelyallied t o acromegaly.The late Prof. Cunningham, of Edinburgh,4a These facts, as well as others relating to function, especially of the posteriorlobe, we awe to a series of papers by Schifer, Herring, and their colleagues, publishedin the first 2 volumes of the Quarterly Jozcrnul of Experimental PhysiologyPHYSIOLOGICAL CHEMISTRY. 181found in the skeletons of the giants he examined a great enlarge-ment of the sella turcica, which proved that they had largepituitaries. The question has arisen whether the condition is dueto destruction of the pituit.ary structure and consequent loss of aninternal secretion, which was the view originally advanced byMarie; or, on the other hand, the view has been advanced thatthe symptoms of gigantism and acromegaly are due to a hyper-trophic condition, in which too great a quantity of a hormoneis produced, which stimulat.es the growth of the skeletal structures.This second view is the one generally adopted to-day, first becausecomplete destruction of the organ leads to almost immediate death,secondly because feeding on pituitary does not diminish butincreases the pathological condition, and thirdly because hyper-trophy of the anterior lobe is associated normally with the growthof the skeleton in young individuals.Feeding young animals onthe anterior lobe increases their rate of growth.43 The conclusionto be drawn from this and other observations of a similar natureis that the function of the anterior lobe is related to the growth ofthe skeletal tissues, including cartilage, bone, and connective tissuein general; these effects are probably produced by hormonessecreted by the glandular cells before referred to. I n the obtainingof this knowledge, it will be noted that the method of injectingextracts has played no part; in fact, the intravascular injectionof an extract of the anterior lobe produces hardly any physiologicaleffect at all; one only notices a slight and transient fall of arterialblood-pressure, which is the usual effect produced by most tissueextracts.Quite otherwise is the history of our knowledge in reference tothe posterior lobe; this has been almost entirely elucidated from theeffects observed when extracts of this portion of the organ areinjected into the blood stream.These effects are almost certainlydue, not t o the posterior lobe proper, but to the cells of the parsintermedia which invade it and its stalk, and to the colloid materialwhich those cells produce.The first investigations of this kind were performed by Schaferand Oliver (1895) shortly after they had published their epoch-marking work on the suprarenal. They found that aqueous orsaline extracts of the pituitary were the only extracts of tissuesexcept the suprarenal which produce a rise of arterial pressure.They found that the efficacy of such extracts was not impairedby boiling, and that, although the rise of blood-pressure is producecjby constriction of peripheral vessels, there were certain points ofdetail which distinguished the action from that of adrenaline.43 See Schafer, Croonian lecture, Proc.Roy. Xoc., 1909, B, 81, 442182 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Three years later Howell, of Ealtimore, took the matter up, andascertained that the rise of pressure was entirely due t o the posteriorlobe. He also showed that the substance responsible for t.he actioncould not be adrenaline, for if a second dose is injected within acertain time the effect is not repeated; in other words, a certainamount of immunity is established which only slowly passes off.The non-existence of adrenaline in the pituitary has, since thattime, been determined by chemical tests, and within the last fewweeks H.H. Dale44 has shown another physiological differencebetween the two substances; adrenaline exerts its action bystimulating sympathetic nerve-endings, whereas pituitary extractsstimulate involuntary muscle directly. Repeated injections produceno true immunity in the sense that immune substances are developedin theSchafer and Vincent repeated Howell’s observations, and con-firmed them, and since then the action of pituitary extract instimulating other forms of involuntary muscular tissue has beennoted, and among these the pupil and the uterus may be speciallymentioned. This fact, as well as the fact that the pituitary riseof blood-pressure is of considerable duration, has led t o the intro-duction of the extract as it therapeutic agent 46; it is a little earlyto say whether the somewhat extravagant praise bestowed upon itin producing uterine contraction after delivery is really warranted.The most remarkable action which the extract has is not, however,on muscular tissue a t all, but on the kidney.I n this organ thereis vaso-dilatation instead of constriction, and an abundant flow ofurine is produced; the discovery of this is due to later work bySchafer in conjunction with Magnus and Herring. The cases ofacromegaly, in which polyuria has been described as a symptom,are really produced by an invasion of the posterior lobe.These facts, which are the result of experiments on animaIs,have now been confirmed in the case of the human pituitary,47 theposterior lobe of which alone exhibits the characteristic effects onblood-pressure and kidney.Whether other epithelial structuresbesides the kidney are stimulated has still to be discovered. Itcertainly seems a roundabout way to reach the kidney by wayof the third ventricle of the brain; still, the relationship of therenal and pituitary organs is undoubted and most marked. Schafer44 Bio-Chem. J,, 1909, 4, 427 ; A., ii, 1036.45 It would be interesting to ascertain whether Abderhalden’s adrenalineimmunity, alluded to on p. 177 of this report, is a true immunity i n this sensealso.46 See, for instance, Blair Bell, Brit.Med. J., Dec., 1909.47 Halliburton, Candler, and Sikes, Proc.physw1. SOC., 1909, sxxyii. ; J. Physiol.,38; A., ii, 417 ; Quart. J. exp. Physiol. 1909, 2, 280PHYSIOLOGICAL CHEHISTILY. 183and his colleagues attribute the actions of the extract to separatehormones, one acting on the muscular, another on the kidneytissues, but Dale is inclined to the view that it is not necessary tosuppose that more than one chemical stimulus is a t work. It shouldbe added that in Schafer’s last contribution to the subject (Croonianlecture) he has shown that both in animals and children the additionof a small and regular amount of the posterior lobe of pituitaryto their food produces an increase in the urine secreted.Finally, an important fact in the physiology of the pituit-arybody is that this organ, small though it is, is indispensable to life,and therefore should not be removed surgically in man. Paulescofound, and his results have been confirmed by Harvey Cushing, ofBaltimore, that removal of the organ in animals is invariably fatal,usually within forty-eight hours.Cushing 48 also has succeeded inaverting the fatal issue in dogs by transplanting it immediatelyafter removal into the cortex of the brain. He also observed thatmarked polyuria follows the transplantation of the entire gland,that it disappears after extirpation of the transplant, and that itdoes not follow transplantation of the posterior lobe alone; this lastfact seems to indicate some mutual relationship of the two lobesin the production of the hormone responsible for the diuretic effect.It is not yet known which part of the pituitary is essential tolife.It is almost impossible to remove one part alone, so closelyare they dovetailed into one another. It is quite possible herealso there may be a corresponding dovetailing of function.Paulesco states that the mere separation of the pars nervosa fromthe infundibulum is as fatal as the actual removal of the organ.I n view of the discovery by Herring that the secretion of the parsintermedia discharges into the infundibulum and third ventricle,this statement of Paulesco is of great interest, but it still awaitsconfirmation.Our knowledge of the chemistry of the hormones of the pituitaryis negative rather than positive.We know absolutely nothing ofthe secretion of the anterior lobe, which controls skeletal growth.But, seeing that the extract of the posterior lobe is physiologicallyactive, it is probably only a matter of time before biochemistsmake themselves acquainted with the hormone (or hormones) itcontains.We at least know that the physiologically active substances arenot protein, for the extracts can be boiled without impairing theiractivity. We further know that the pressor substance is notadrenaline for the reasons already given; and, finally, we are nowquite certain that the colloid material present is not the same4a Cushing, Crowe, and Homans, Quart. J. exper. Physiol., 1909, 2, 389184 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.material as the colloid of the thyroid gland, since it contains noiodine.The similarity in histological appearance of the two colloids gavesupport to the idea that the pituitary can act vicariously for thethyroid in cases of thyroid insufficiency. Removal of the thyroidcertainly leads to an increase in the size of the pituitary and ofthe colloid material it secretes, but extirpation of the thyroid alsomodifies the growth of many other tissues and organs in the body,and there is really no ground for the hypothesis that the two organshave any common ground of action. Disease or removal of thepituitary produces quite different effects from those observed whenthe thyroid is diseased o r removed. Injection of extracts giveswidely divergent results; and the last shred of support to the viewis now given by the demonstration of the absence of iodine in thepituitary body.Baumann, soon after his discovery of thyroiodin, looked for iodinein the pituitary with negative results. One or two observers, it istrue, have stated that they have obtained traces, but their workwill not bear close investigation. 149 found that it is entirelyabsent both in the normal human and bovine pituitary; andSimpson and Hunter 50 have obtained the same negative result insheep’s pituitaries after the thyroid gland had been extirpated.On the positive side, I can find only two researches, and thesehave both been published at present in preliminary form only.One of these is by T. B. AldrichY5l who succeeded in separating abase from the organ, from which a crystalline picrate and sulphatewere prepared. These salts had a, pressor effect,. The other is byAllers 52; he found no adrenaline and no o-dihydroxybenzenederivatives, but he attributes the pressor action to a substancewhich, like adrenaline, contains alkylated amino-nitrogen.Thus for the present we must leave this interesting subject, andalthough there is plenty of other material in the work of the yearwhich might be mentioned and is of undoubted importance, never-theless, exigencies of space compel me to close the report at thispoint.W. D. HALLIBURTON.49 Halliburton, Candler, and Sikes, Zoc. cit.gn Proc. SOC. Experim. Med. and Biology, New Yo&, 1909, 7, 11.51 Proc. Ayner. Physio2. SOC., 1907-8, xxiii ; Amar. J. PhysioZ,, 21.52 Munch. med. Woch, 56, No. 29, July, 1909

ISSN:0365-6217    

DOI:10.1039/AR9090600165

出版商:RSC    

年代:1909

数据来源: RSC

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AGRICULTURAL CHEMISTRY AND VEGETABLEPHYSIOLOGY.THE year 1909 has not. shown any marked increase or diminutionin the number of publications, but, so far as regards England a tleast, there seems to be some promise of its eventually beingregarded as a “vintage year,” on account of the publication ofRussell and Hutchinson’s paper on the function of the protozpa inthe soil, which does represent an entirely novel idea. Otherwisethere is nothing of special interest to chronicle, although in manydirections the investigations that are reported assist considerablytowards the construction of a firm and coherent theory of plantand animal nutrition.A t the International Congress of Applied Chemistry, held inLondon during the year, there was a long list of papers onAgricultural Chemistry, but it cannot be said that they resulted invery fruitful discussions.The majority of the papers consisted ofdetailed communications of interest only to specialists, and whenthe subject was of a more general character the language difficultywas a great check on free discussion.Soi I Bac t erio log y .I gave an account of some workby F. V. Darbyshire and E. J. Russell on the action of heat andof volatile antiseptics on soil, in which they had shown, in agree-ment with the observations of a number of other investigators, thatthe fertility of the soil can be very greatly increased by suchtreatment. For example, all the soils they examined, if heated toa temperature of looo for two hours, would yield twice as great acrop as the same soil untreated, when the two were afterwardscultivated under similar conditions in pots.Exposure to the vapourof carbon disulphide, chloroform, or toluene for forty-eight hours,followed by complete evapora,tion of the antiseptic, resulted in anincreased yield of about 30 per cent. Various theories have beenadvanced to account for the increased availability of the plantfood in the soil which results from. treatment of this kind.I n my Annual Report for 1907Ann. Report, 1907, 264186 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.S. U. Pickering, for example: has shown that the heating, andeven the treatment with antiseptics, are followed by a markedincrease in the amount of soluble nitrogen compounds that can beextracted from the soil, which extra available plant food he regardsas sufficient to account for the increase of crop.More generally itwas supposed that some change in the bacterial flora of the soil hadbeen effected, which resulted in a greater availability of the originalstock of nitrogen, or perhaps brought about increased fixation offree atmospheric nitrogen, but the mechanism was not clearlyunderstood. Russell and Hutchinson: working in the Rothamstedlaboratory, have arrived at another solution. They began byfinding, in common with other observers, that the treatment towhich the soil was subjected by no means effected completesterilisation. The numbers of bacteria were enormously reducedby the process if they were counted immediately afterwards, butwhen the soil was moistened and put under conditions suitablefor growth, the numbers rapidly mounted up again, and eventuallyreached a magnitude which was never attained under normal con-ditions in the untreated soil.For example, a Rothamsted soilcontained a t the outset about 7,000,000 organisms per gram, anumber which remained comparatively constant on storage ; afterheating, the number had fallen to 400 per gram; and after treatingwith toluene, to 2,600,000. Four days later, however, these smallnumbers had risen in the case of the heated soil t o over 6,000,000,after which it ceased to be possible to count the colonies; in thecase of the toluene the numbers rose to 40,000,000 in nine days.Pari passu with this increase in the number of the bacteria in thesoil came an increase in the rate at which ammonia was producedby the breakdown of the more complex carbon compounds ofnitrogen that were present in the soil.When no plants werepresent to take up this ammonia, it accumulated in the soils, becausethe bacteria which convert nitrites and nitrates had been com-pletely destroyed. It thus appeared pretty clear that the increasedfertility of the treated soils wils due to their greater power ofbreaking down the complex organic matter of the soil to the stateof ammonia, a form in which plants can assimilate nitrogen; andthis increased production of ammonia was due to an exceptionalmultiplication of the ammonia-splitting organisms which constituteso large a proportion of the normal bacterial flora of the soil. Theauthors then carried out various experiments, which showed (1) thatno stimulus could be supposed to have taken place through the treat-ment which would make the bacteria remaining in the soil moreactive; (2) that there bad been no selective destruction of organismsJ.Agric. Xci., 1908, 2, 411 ; 3, 32, Ibid., 1909, 3, 111AGRICULTURAL CHEMISTRY AND VEGETABLE PKYSIOLOGY. 187which would leave behind a population of a more active type thanthe usual mixed flora of the soil. By other steps which need notbe here set out, it became clear that the difference between thetreated and untreated soils was due to some factor in the latterwhich normally limits the number of bacteria, and therefore therate of production of ammonia, Search for this unknown factordisclosed the presence, in all soils so far examined, of numbers ofprotozoa and amoeba, which live on bacteria and keep their numbersdown to the comparatively low limit specified.The heating ortreatment with antiseptics kills off all these large organisms, butleaves unhurt some spores of the ammonia-producing bacteria,which afterwards can develop to a much greater extent than in theuntreated soil because they are freed from their normal check.The theory as it stands then assumes that, putting aside itsphysical characteristics, the fertility of a soil is determined by theactivity, or rather by the number, of its ammonia-producingbacteria, and the numl5er is kept in equilibrium by the activity ofthe protozoa for which these bacteria serve as food.Any causewhich destroys or reduces the number of the protozoa enables thebacteria to extend their territory, and so raises the fertility of thesoil. The authors have also carried out a number of collateralexperiments, which show that the direct additions of these largeorganisms will rapidly reduce the activity of various fermentingmedia, but this and other positive evidence in favour of the theoryhave not as yet been published in full. Many of Russell andHutchinson’s observations on the increase in the number of bacteriaand in ammonia production which is brought about by antisepticsare confirmed in a paper by I(. Stormer? although this author hasnot arrived a t any valid explanation of his experimental results.It will be seen that this addition to the theory of the vitalactions going on in the soil, not only serves to explain a largenumber of observations which have been accumulating for someyears past (for example, Rahn’s work on the effect of drying soil),but it is likely to lead to widespread applications in practice.Ithas always been difficult to understand why the number of bacteriain the soil was not greater, and why it varied so little with theseasons; but now we see that a limiting factor exists affected inthe same way by changes of temperature and humidity. Whatevermay be the practical outcome of Russell and Hutchinson’s work,this new point of view they have given us represents the mostnotable addition to the thedry of the soil since the publication ofHellriegel and Wilfarth’s paper on the nodule bacteria in 1886.4 Jahresber.Vereinigung nngew. Bot., 1’208, 113 ; A., ii, 608.6 A m . Beport, 1907, 265188 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Turning to some of the older questions of soil bacteriology,nitrogen fixation by means of Azotobacter continues to occupy theattention of a large number of investigators, although no speciallynovel fact has emerged during the course of the year. T. Remy6has examined the carbohydrates which will serve as sources ofenergy for the fixation of nitrogen in soils, and finds that humusis able to supply the necessary carbohydrate, so that there is alwayssome fixation taking place in any soil containing humus andcalcium carbonate.I n acid soils and in peat no fixation is goingforward. Magnesium and calcium carbonate are equally effectivebases, both of them being better than the soluble sodium andpotassium carbonates. Remy also repeated Koch’s experiments,?in which soil in psis was mixed with sugar to the extent of as muchas 2 per cent. I f these soils were then incubated for a few weeksand plants grown in them, much better crops were produced thanin the control pots where no sugar had been used. I n Remy’sexperiments the soil with sugar gained 141 milligrams of nitrogenper kilo., and this was left in compounds which soon became availablefor the plant, as shown by the growth of the ensuing crop.H. Pringsheim 8 has also been investigating the availability ofcellulose as a source of energy in nitrogen fixation, examining,however, anaerobic fermentations of Clostridium and similar organ-isms.He obtained a fixation of considerably higher quantities ofnitrogen by these organisms per gram of carbohydrate consumedthan had been observed by the previous workers with the anaerobicbacteria.One of the most interesting papers dealing with soil bacteria hasbeen contributed by M. W. Beyerinck and D. C. J. Minkman9 onthe relationship of bacteria to the formation and utilisation ofnitrous oxide. By inoculating cultures containing potassiumnitrate and organic matter with various soils and incubating themin absence of oxygen, they have picked up and identified a numberof organisms which will reduce the nitrate to nitrous oxide,nitrogen gas, and ammonia, the relative proportion of these threeproducts depending to a large extent on the concentration of thesolution.Besides identifying the denitrifying organisms originallyobserved by Gayon and Dupetit, they isolated two other organisms,which are probably the destroyers of nitrates in soil. One of theseorganisms is so active that from a good large culture a stream ofgas is evolved containing about 80 per cent. of nitrous oxide andcapable of rekindling a glowing splint presented to the orifice of6 Centr. BaEt. Par., 1909, ii, 22, 561 ; A., ii, 340.7 Ann.*Bcport, 1907, 261.8 Centr. Bakt. Par., 1909, ii, 23, 300. Ibid., 25, 30; A.: ii, 1043AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 189the exit tube.The fermentation seems so much under controlthat this might make an effective lecture table experiment. Theauthors then proceed to consider the fate of the nitrous oxide,which must always be thus arising in the soil, and show that severalorganisms can take away its oxygen to set free nitrogen. Finally,they show that in the soil there exists an organism capable ofbringing into combination a mixture of hydrogen and nitrous oxide,from which combination it derives the energy necessary to decomposecarbon dioxide and utilise the carbon for its own structure. Theexperiment is a, very simple one; a cultare solution, containing noorganic matter but the usual nutrient salts and a little sodiumbicarbonate, is inoculated with a trace of soil, and is then left incontact with the mixture of equal volumes of hydrogen and nitrousoxide. The gases slowly disappear, and at the same time theculture solution becomes covered with a thick scum formed by anorganism, the organic matter of which has been synthesised fromthe carbon of the carbon dioxide and the nitrogen of the nitrousoxide, while the necessary energy has been derived from the unionof the two gases.H.Fischer10 has examined the effect of liming the soil onthe bacteria contained therein, chiefly from the point of view ofthe behaviour of ammonium salts on soils rich in calcium carbonate.He finds, with other observers, that when either sodium nitrate orammonium sulphate is supplied to the soil, some of the nitrogenis utilised by soil bacteria and cocverted into proteins.This actionFischer finds to be increased by calcium carbonate in the case ofammonium salts, but not in the case of sodium nitrate, as indeedwould be expected from the physiological acidity of the formercompound. To this he attributes the lower manurial effect ofammoniacal nitrogen as compared with nitrate nitrogen, ratherthan to any evaporation of ammonia set free by the calciumcarbonate from the soil.A paper of considerable technical interest by S. Bieremall com-pares the various nitrogen compounds, such as nitrates, ammoniumsalts, amides, and amino-acids, as sources of nitrogen for thecultivation of soil organisms, the experiments being made both withpure cultures and a mixed inoculation with ordinary soil.Thesesources of nitrogen are also combined with different carbohydratesand other sources of carbon, and although no general conclusionscan be drawn from the results, the worker who desires to make upthe most suitable medium for the cultivation of particular organismsmay there find much information of value.lo Landw. VcrszdLs-Stat, 1909, 70, 335 ; A., ii, 602.l1 Cent. Bukt. Par., 1909, ii, 23, 672 ; A., ii, 692190 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY,R. W. Stigell12 reports a series of experiments on the influenceof heavy inoculations of various common putrefactive bacteria, suchas B. megatherium, B. subtilis, B. pyocyalzeus, on the germinationof seeds and the development of young roots. The author foundthat the bacteria had but a sniall and irregular effect on the plantsat any stage in their development, in spite of the numbers of thebacteria in the medium.Soil Physics.A.Miintz and H. Gaudechon 13 have given us very elegant demon-stration of some points in the behaviour of soluble salts, like sodiumnitrate, when applied as fertilisers to the soil. Taking boxes offairly dry soil, they introduced here and there on the surface acrystal of sodium nitrate, and observed that after a time a moistspot grew round the crystal, marked by a change of colour inthe soil. This moist spot was formed by water which had beendrawn by the salt from the surrounding soil. The salt itselfdissolved, but did not diffuse laterally outside the area of themoist spot.Similarly, in wet soil, the crystals formed a zone ofdissolved salt round them, but diffusion either laterally or verticallywas extremely slow, and did not extend more than 2.5 cm. in sixdays. When the boxes were further exposed to fine rain, the saltswere carried vertically downwards with very little lateral diffusion,forming very steep-sided cones of soil within which the salt couldbe traced. The authors conclude that very little movement ofsoluble manurial salts takes place in the soil by diffusion. TheRothamsted experiments afford a number of interesting illustrationson this point. For example, on the grass field, the effect of anapplication of 550 lb. per acre per annum of sodium nitrate forthe last fifty-three years does not extend a foot over the boundaryline of the plot, the change in the character of the herbage beingquite sharp and decided a t the edge of the plot.The question of the nature of clay, and the flocculation ofsuspensions of such fine particles, continues to attract a good dealof investigations, but I cannot see that the subject is beingmaterially advanced.The experimental facts remain much as theywere summarised in 1907,14 and the explanations offered are onlyverbal. W. Funk15 powdered felspar very finely and obtained acolloidal suspension when it was mixed with water ; a t the same timechemical change had taken place, as was shown by the fact thatthe water became alkaline. When the water contained carbonl2 Cent. Bakt. Par., 1909, ii, 23, 727.l3 Cotnpt.rend., 1909, 148, 253 ; A., ii, 259.l4 Ann. Beport, 1907, 269.l5 Zeitsch. axgew. Chem., 1909, 22, 145; A . , ii, 146AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 191dioxide, the attack on the felspar was greater, but there was lesstendency to form a colloid suspension. P. Rohlaad16 has alsoexamined the nature of the substances forming suspensions in water.He tried powdered talc, alumina, ultramarine, calcium carbonate,calcium sulphate, felspar, etc., with water, but found that onlythose materials formed true suspensions which react with water t oproduce colloidal substances. It will be noticed that these resultssimply confirm the conclusions reached by Morison and Hall1’ in1907.E. Blanck 18 has investigated the effect of a mixture of calciumcarbonate or lime on the physical properties of the soil.He findsthat calcium carbonate increases the percolation through the soil,but not its power of capillary lifting, whilst i t diminishes its water-holding capacity. Lime, on the contrary, increases the water-holding capacity, but diminishes the capillary uplift and thepercolation. These observations also are explicable by the differencein the flocculating power of calcium bicarbonate and calciumhydrate observed by Morison and Hall (Zoc. cit.).I n continuation of their work on the organic substances containedin soil, which were discussed in my last report, Schreiner andShorey l9 have isolated another crystalline substance from theorganic matter of soil. By extraction with alcohol and ether of aclay soil containing more than 16 per cent.of organic matter and0.5 per cent. of nitrogen, they obtained a cholesterol-like substanceof the empirical composition C2,H,,0, to which they have giventhe name of agrosterol, because it gives Liebermann’s cholesterolreaction. Its significance in the behaviour of the soil is not yetapparent.The question of the function of roots in rendering the mineralmatter of the soil available for plant food has always been a matterof discussion ; latterly the increased solution has been generallycredited t o the carbon dioxide excreted by the roots. E. A.Mitscherlich20 has now shown that an artificial increase in theamount of carbon dioxide in the soil is followed by no increasein production. The roots and the decay of organic matter normallyproduce sufficient carbon dioxide to give the soil water its maximumsolvent action, so that 8 does not become more effective whenan excess of carbon dioxide is added artificially. a.Haselhoff 21 also investigated the weathering power of roots byl6 Zeitsch. angew. Chcm., 1909, 22, 931 ; A . , ii, 474.l7 Ann. Report, 1907, 269.l8 Landzu. Jahrb., 1909, 38, 715, 863.l9 J. dmer. Chem. Soc., 1909, 31, 116 ; A . , i, 152.2o Landw. Jahrb., 1910, 39, 157.Landw. Yersuchs-Slat., 1909, 70, 53; A., ii, 259192 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.allowing plants to grow in vessels filled with coarsely powderedrocks of various kinds. He examined their contents after severalyears, and found that leguminous plants were more effective thancereals, both in growing under such conditions and in reducing therock to a state of very fine particles.Chemistry of the Growing Plant.I n the papers of this year less attention seems to have been paidto assimilation than to respiration, on which a good deal of interest-ing work has been reported.P. B. Jensen 22 has been investigatingthe intramolecular respiration of seedlings under anaerobic con-ditions, and this he regards as identical with the process ofalcoholic fermentation. He fixes on dihydroxyacetone as theintermediate product that is first formed from dextrose, and findsthat it yields carbon dioxide and water under the action of oxydasein normal respiration, but carbon dioxide and alcohol under theaction of one of the zymase enzymes In absence of oxygen.I n many respects, Jensen’s conclusions are confirmed byS.Kostytscheff,23 who does not regard alcohol as a normal productin respiration, because it cannot be transformed by any of theenzymes present into carbon dioxide. He considers that alcoholis produced by a special action in the absence of oxygen fromsome intermediate product, which would agree with the dihydroxy-acetone postulated by Jensen. J. White24 has examined cerealseeds of various ages to ascertain if any connexion exists betweenthe retention of vitality and the presence in the seeds of still activeenzymes. Seeds of wheat, barley, oats, maize, and rye would rarelygerminate when more than ten years old, but even after twentyyears the author found in them diastatic, fibrin-digesting, andereptic ferments retaining their activity.No relation could betraced between the vitality of the seeds and the persistence of theenzymes, nor did the addition of enzymes enable any of the other-wise non-germinable seeds to germinate.The author then studied the respiration processes in seeds, andfound that many of them gave off carbon dioxide in considerablequantity immediately after harvesting, but that the gaseousexchange ceased as soon as the seeds had become moderatelydesiccated. The author considers that dry seeds, when stored, ‘arenot respiring, and in this respect agrees with other observers. Itis, however, difficult to believe that the. action is entirely suspended,22 Ber.Dezct. hot. Gcs., 1908, 26a, 666 ; A., i, 172.28 Biochem. Zeitsch., 1908, 15, 164 ; A., ii, 173 ; Ber. Dezct. bot, Qes., 1908, 26a,24 Proc. Boy. SOL, 1909, B, 81, 417.665 ; A., ii, 84AGRICULTURAL CHEMlSTRY AKD VEGETABLE PHYSIOLOGY. 193although one can see reasons for supposing that it must be SO slowas t o be almost beyond the possibility of measurement.B. Schulze and J. Schiitz 25 have been examining the diurnal andseasonal variations in the composition of the leaves of various plantsand trees. They find that the diurnal migration, not only of thecarbohydrates, but also of nitrogenous compounds and ash is wellmarked, there being an accumulation during the daylight, followedby a depletion in the night. The seasonal variation gives rise t oa maximum richness of the leaf about June, after which the pro-portions of nitrogen and valuable ash constituents fall off steadily,there being a very considerable withdrawal of nutrient materialbefore the leaf is allowed to fall.Otto and Kooper26 have also published a paper in which theyarrive a t the same conclusions, although their investigation dealtwith only the nitrogenous compounds in the leaf.The question of whether higher plants are capable of utilisingany compounds of nitrogen other than the nitrates has again beeninvestigated by H.B. Hutchinson and N. H. J. Miller.27 Theysucceeded in growing wheat and peas in water cultures under sterileconditions, so that neither nitrification nor other bacterial changescould take place in the nutrient supplied. The plants grewnormally when supplied with nitrogen only in the form ofammonium salts, and such plants always contained higher per-centages of nitrogen than those grown with sodium nitrate undersimilar conditions.In view of the absence of nitrification in acidsoils and the rapid growth of the plants in soil that has been partlysterilised, in which nitrification has also been shown to be suspended(see page 185), it is important to notice that certain differencesshow themselves in the habit of plants feeding directly on ammonia,for example, an increased percentage of nitrogen in the dry matter,a darker colour of the leaf, and a dwarfer habit. These differencesmay even be seen on the Rothamsted plots in the open, as thoughthe nitrification of the ammonium salts were not complete eventhere.Stoklasa and Ernest 28 have returned to the question of the acidsecretions from roots.They found that in water cultures in whichaeration was defective, the roots of oats, maize, and buckwheat didsecrete small amounts of formic and acetic acids. The roots ofbarley, however, gave rise to very little of these products; withbetter aeration the acids were completely oxidised to carbon dioxide,25 Landw. Versuchs-Stat., 1909, 71, 299.2G Landw. Jahrb., 1910, 39, 168.27 J. Agric. Sci., 1909, 3, 179 ; A., ii, 923.23 Jahrb. wiss. Bot., 1908, 46, 55 ; A,, ii, 256.REP.-VOL. VI. 194 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.and in no case were mineral acids observed.The carbon dioxideproduced in twenty-four hours from the roots varied from 60 to130 milligrams per gram of dry matter, and when the plants wereset to grow in powdered gneiss or basalt, nitrogen only beingsupplied, the extent of growth was found to correspond with thepower of the plant to excrete carbon dioxide from its roots, showingthat a plant’s attack on the insoluble minerals of the soil is entirelydue to the carbon dioxide excreted from the root.The chemistry of the wheat grain has excited continued attention,T. B. Wood and W. B. Hardy29 have dealt further with thechanges in the physical character of gluten when in equilibriumwith dilute solutions of acids and alkalis. I n his former paper,3OWood had shown that the gluten of wheat flour loses all consistencywhen suspended in weak acid of a strength below a certain criticalconcentration.For different acids, this critical concentrationshowed no relation to the conductivity of the solution. Thecohesion of the gluten was restored by the addition of salts (elec-trolytes) in small quantities. The authors have now measured therate of transport of the particles of the hydrosol of gluten in auniform electric field, which gives a means of measuring the potentialdifference between the water face and the protein face of eachparticle of the hydrosol. The curve obtained for such potentialdifferences with various concentrations of acid agrees in form withthose expressing the effects of salts on the cohesion of the gluten,whence the authors concIude that the hydrosol of gluten consistsof particles surrounded by an electric double layer, on the potentialdifference between which and the solute the physical state of thecolloid depends.H. J.von Liebig31 has examined the sugars in wheat flour, inwhich he finds 1 to 1.5 per cent. of sucrose and 0.1 to 0.4 percent. of dextrose. I n the dough the reducing sugars increase up to4 or 5 per cent. through the formation of maltose, but the sucrosesuffers a small loss. I n the dough fermentation, the maltose rapidlydiminishes. The author has also measured the diastatic power ofvarious flours, but finds them only from 1/3 to 1 / 7 of Lintner’sscale, the largest numbers being obtained with coarse, dark flour.W. E. Brenchley and A.D. Hal132 have studied the progressivechanges in the composition of the grain of wheat during itsformation and ripening. These authors distinguished three stages-the formation of the pericarp, the filling of the endosperm, andthe ripening process. The material forming the pericarp contains alarger proportion of nitrogen in the dry matter, and a smaller30 Ann. Report, 1907, 273.32 J. Agric. Sci., 1909, 3, 195.29 Proc. Roy. Soc., 1909, B, 81, 38; A., i, 341.31 Landw. Jahrb., 1909,38, 251AGRlCULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 195proportion of phosphoric acid in the ash, than does the endospermmaterial. As soon as the endosperm begins to fill, the plant movesinto it material which is practically uniform in composition, at allstages, early and late, in the filling.There appears to be nojustification for the opinion usually held that the proteins aremoved in first and the carbohydrates later. The ripening processis in the main one of desiccation, although there is some changefrom non-protein to protein. The authors incidentally show thatboth the nutrition and assimilation of the plant continue to amuch later date than has been usually supposed. The total amountof dry matter, nitrogen, and ash in the plant increases to within afortnight of harvest. I n a separate paper, W. E. Brenchley33discusses the accompanying changes in the structure of the grainfrom the date of fertilisation onwards.I n a communication to the International Congress, which hassince been reprinted, J.A. Le Clerc and J. F. Breazeale 34 describesome experiments to show that annual plants, like wheat, oats, andother cereals, lose considerable quantities of their inorganic con-stituents through washing by rain. Many previous observers havenoticed that the total amount of nitrogen and ash constituents ina plant shows some diminution before the plant finally ripens, andthis has been variously attributed to mechanical losses through thefall of dead leaves, etc., or to a physiological excretion by theroots into the soil again. Le Clerc and Breazeale reject the sup-position that there is any physiological excretion from the roots,because all the migrations traceable during the growth andmaturation of the plant take place from below upwards towardsthe flowering head.They do find, hoyever, that it is possiblet,o extract. by water considerable proportions, particularly of potashand phosphoric acid, from the plant, the losses being greater theolder the tissue that is washed, and greatest of all when the tissueis dead. The authors consider that their experiments have con-siderable bearing on the total amount of plant food removed fromthe soil by crops growing in the open, and on such matters asthe richness in mineral constituents of hay, etc., which has beensubjected to rain either before or after cutting. It is certainlyoften noticeable that when corn crops have stood long in shockand have been much rained on after cutting, there is a notice-able increased vigour of growth in the next crop on the spots onwhich the stocks had been standing.A.J. Brown35 has published a further paper on the permeable33 Ann. of Botany, 1909, 23, 117.34 Year Book of the Dept. of AgTic. (U.S.A.), 1908, p. 389.a5 Pro. Roy. Soc., 1909, B, 81, 82; A., ii, 386.0 196 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.membrane existing in the testa of liarley seeds, which permits watert o pass into the endosperm, but stops certain other substances. Forinstance, barley seeds will absorb water from hydrochloric andsulphuric acids, but not the acids themselves, whereas acetic, pro-pionic, formic, and trichloroacetic acids will pass through themembrane. The membrane is impervious to most dissolved salts,but mercuric chloride and cyanide will pass; sucrose, dextrose, andglycerol are atrested by the membrane, but ethyl alcohol, ethylacetate, and acetone pass through, as also does iodine dissolved inpotassium iodide. I n none of these cases is there any destructionof the membrane prior to the passage of the selected material.In an interesting paper on the effect of anaxthetics and of coldon plants, L.Guignard 36 finds that these agents bring about inter-action between such glucosides and ferments as are present in theleaf. For example, the leaves of crucifers, when strongly chilled orexposed to the vapour of chloroform, give rise t o mustard oil.Leaves of Gaultheria procumbens give rise to methyl salicylate,whilst cyanogenetic plants form hydrocyanic acid. Probably theseobservations could be extended to throw some light on the well-known processes of hastening the flowering of plants by etherisationand chilling; they may be compared with the observations ofMuller-Thurgau that potatoes become sweet during frost becausethe enzyme processes producing sugar continue their action, whereasrespiration, which destroys sugar, is suspended.E.Schulze and C. Godet 37 have contributed a paper on the carbo-hydrates of plants, which is valuable to workers on plant materials,but is unsuited for abstraction.Manures and Manuring.Attention is still chiefly fixed on the two new fertilisers obtainedby the fixation of atmospheric nitrogen-calcium cyanamide andcalcium nitrate, both of which are now becoming regular articlesof commerce.A new arc for the more economic production ofnitric oxide was brilliantly demonstrated at one of the Londonmeetings of the International Congress of Applied Chemistry, andthis modification is to be operated by the present producers ofcalcium nitrate. As regards the fertilisers themselves, little thatis novel can be gathered from the reports of the very large numberof experiments that have been made with them; calcium nitrategenerally proves to be as effective as sodium nitrate-nitrogen fornitrogen-whilst cyanamide falls more into line with ammoniumsulphate. Some discussion still goes on as to the exact nature of36 Conzpt. rend., 1909, 149, 91 ; A., ii, 823.57 Zeitsch. physlsiol. Chern., 1909, 61, 279 ; A., ii, 824AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY.197the decomposition experienced by calcium cyanamide in the soil,whilst rather contradictory results are reported as to its actionon seedlings and young plants. For example, A. Muntz andP. Nottin38 find no bad results even when the cyanamide is sownwith the seed or applied as a top dressing, whereas H. von Feilitzen39observed injurious effects when the fertiliser and seed were sownat the same time, but not when seeding took place a fortnight aftersowing the manure. Von Feilitzen sets down the injurious actionto calcium carbide contained in the cyanamide, an impurity whichhas latterly been removed before the fertiliser is sold. Muntz andNottin found in a series of pot experiment.s that the cyanamidenitrifies almost as rapidly as ammonium sulphate, although withlarge quantities there is some delay in starting the action.Among phosphatic fertilisers, C.G. T. Morison 40 has been study-ing the amount of free lime in basic slag, and found, instead of thelarge amount usually expected, only from 5.29 down to 1.28 percent. in the samples he examined. After trying various methodsfor the estimation of the free lime, the author obtained the bestresults by extracting the finely ground slag with cold water freefrom carbon dioxide, and titrating the extract.J. Rendrick 41 has also made a number of determinations of thelime in basic slag by extraction with water, a solution of sugar,and a solution of ammonium chloride respectively. Extraction withwater yielded the lowest results, ranging from 0.5 to 2 per cent.inthe freshly ground samples examined. Hendrick also showed thatthe slags contain 15 to 20 per cent. of lime so loosely combined thatit will liberate ammonia when distilled with a solution of ammoniumsulphate. Probably the basic slag made in the earlier years ofthe industry contained a greater proportion of free lime, just as itwas generally less rich in phosphoric acid.Morison also discusses the nature of the phosphoric acid compoundin basic slag, and from analyses of the crystals obtained fromunground cinder, and from the solubility of the slag and ofthe crystals in weak solvents, he concludes that the compoundis (CaO),,FeO,Pz0,,SiOZ, instead of the (CaO),,P,O, usuallydescribed. This agrees with some previously published analyses ofStead, who also failed to find crystals of tetrabasic phosphate oflime in most of the slags he examined.The compound in questionforms pale green or blue needle-shaped crystals in the cinder.S. U. Pickering42 has continued his studies of fungicides andDciit. landw. Prcsse, 1909, 36, 327 ; A . , ii, 430.38 Comnpt. rend., 1908, 147, 902 ; A . , ii, 88.40 J. d g ~ i ~ . S L Y 1909, 3, 161.41 J. Soc. CJ~cnz. Ind., 1909. 28, 775.42 J. Agric. Sci., 1909, 3, 171298 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.similar substances, and has succeeded in clearing up the mysterieswhich have long clung about the substance known as “Bordeauxmixture,” mysteries due to theoretical discussions based on in-sufficient knowledge or imperfect analyses.The author has alreadyshown 43 that with an excess of lime, as used in the ordinary recipefor Bordeaux mixture, a precipitate of the composition lOCuO,SO,is formed, whereas when a strictly limited amount of lime is addedto the copper sulphate solution, by employing lime-water instead ofmilk of lime, the compound 4Cu0,S03 can be obtained. The fungi-cidal action of Bordeaux mixture is due to the gradual liberationof copper sulphate by the action of atmospheric carbon dioxideon the basic salt, and Pickering shows that carbon dioxide mayliberate 25 per cent. of the copper from the latter salt, but only10 per cent.. from the former. He found that secondary reactionsincrease the quantity of soluble copper up to 40 per cent.of thecopper in the salt precipitated by lime-water, and about 25 percent. of the copper in the ordinary basic salt, but the latter amountis not attained in practice because of the protective action of thelime which is also present alongside. As the lime has also to becarbonated before the copper salt is attacked, it has a furtherinjurious effect by delaying the action of the fungicide. Finally,the calcium carbonate produced has its own precipitating action onthe copper salt, so that the fungicidal power of the salt precipitatedby lime-water is altogether about twelve times greater than that ofthe same amount of copper in ordinary Bordeaux mixture; it is alsomuch speedier in action.A new method of estimating nitrates is described by A.Kleibe1-,~4in which stannous chloride is employed to reduce the nitrate tothe state of ammonia; 0.5 gram of the nitrate is placed in a750-1000 C.C. flask with 5 grams of stannous chloride, 4 to 5 gramsof iron filings, 15 C.C. of strong hydrochloric acid, and 7.5 C.C. ofwater, the mixture being digested for a quarter of an hour on thewater-bath.Chemistry of Animal 1Yutrition.I n this subject work continues to be very active on the part ofthe pure physiologists; eventually their work will be applied toagricultural problems, but until the whole question of proteinhydrolysis and re-formation in the body has been cleared up nogreat advance is likely to be made in the feeding of animals onscientific principles.The evidence as t o the specific character of the proteins of eachanimal that had already been obtained from the experiments of43 Trans., 1907, 91, 198%44 Chcm.Zcit., 1909, 33, 479 ; A., ii, 517AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 199Miss Willcock and Hopkins 45 has been strengthened by further workreported this year. V. Henriques,46 experimenting with rats, foundthat nitrogen equilibrium could not be maintained when zeinwas the only nitrogen compound fed, although the loss of body-nitrogen was less than on an entirely nitrogen-free diet. Gliadin,which contains tryptophan but not lysine, maintains nitrogenequilibrium, and can even lead to storage of nitrogen. E.Abderhalden 47 also fed dogs on the cleavage products of casein fromwhich the &tryptophan had been removed.Thereupon they lostbody-nitrogen, but the equilibrium was maintained when either theunaltered cleavage products were fed or tryptophan was separatelyadded. While all these papers point to the necessity of thetryptophan group in building up the proteins contained in theorganism, they go further, and show that no complete under-standing of the peculiarities of animal nutrition is possibleuntil we have a full record of the syntheses of both animaland vegetable proteins. On this latter point Osborne, Leaven-worth, and Brantlecht 48 rather abandon the hope of determiningthe monoamino-acids accurately, and would differentiate theproteins by separating the hexone bases, which can be obtainedquantitatively.They give results for about twenty-four vegetableproteins; histidine was present in all to the extent of about 2.5per cent., lysine was absent from the gliadins but present inthe proteins from leguminous seeds. Arginine varied from 1 to 14per cent., being least in oil seeds, but most abundant in cereals.The discussion continues of the part played by non-protein nitro-gen compounds in nutrition. Morgen, Beger, and Westhausser 49fed milch cows on diets in which the non-protein compounds ofmalt, extract of grass, asparagine, ammonium acetate and tartratewere compared with protein. The authors conclude that the con-version of these substances into digestible proteins in the intestineby the action of bacteria can hardly be regarded as proved.Although of much less value than proteins, they will do sqme ofthe work of the latter bodies, not so much by enabling the proteinsto be better utilised, as by themselves carrying out some of theirfunctions, although they are probably not converted into materialsavailable for the making of meat or flesh.W. Thaer5O fed sheepwith hay and various quantities of protein, asparagine, molasses,etc., and found that the nitrogen of the molasses was but little45 Ann. Rcport, 1907, 276.46 Zeitsch. physiol. Chem., 1909, 60, 105 ; A . , ii, 594.47 I b X , 61, 194 ; A., ii, 327, 817."' Landtv. Vemcchs-Stat., 1909, 71, 1.Anzer. J. Physiol., 1908, 23, 180 ; A . , i, 72,16kl., 70, 413 ; if., ii, 605200 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.utilised, the asparagine somewhat more so. The inorganic elementsof nutrition have attracted more attention than usual, especiallythe phosphorus compounds. Hart, McCollum, and Fuller 51 findthat animals become unhealthy when the phosphorus in the rationfalls below a certain limit; increased amounts result in largerskeletal growth. Nuclein, lecithin, and phytin gave no betterresults than inorganic phosphates, although there was no evidenceof synthesis in the body of organic from inorganic phosphoruscompounds. E. Koch,52 on the contrary, found that inorganic andnon-protein phosphorus compounds are not utilised in repairingphosphorus waste, except perhaps when phosphorus starvation wassetting in. From the practical point of view, H. Ingle53 showsthat most of the foods, such as oat hay, mealies, and bran, usedfor horses in South Africa are deficient in lime rather than inphosphoric acid, and possess a very low Ca0,P205 ratio. The authorconnects this badly balanced diet with the prevalence of a disease,osteoperosis, characterised by an exceptional weakening of thebones, which causes considerable mortality in parts of the colony.Ingle recommends the use of leguminous fodders, such as lucernehay, t o provide a greater amount of lime in the diet, instead ofthe bone meal which is often employed, because in the latter thelime is already combined wihh phosphoric acid. Certain pasturesand particular parts of the country have always been famous forraising horses with good bone, but there has been no scientificinvestigation of the causes.A. D. HALL.51 Amer. J. PJhysiol,, 1909, 23, 246 ; A., ii, 161.59 St. Petersb. Aled. Woch., 1906, 400 ; A . , ii, 162.53 J. Agrlc. Sci. 1909, 3, 22

ISSN:0365-6217    

DOI:10.1039/AR9090600185

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY.IN the two years which have elapsed since the publication of theReport on the Progress of Mineralogical Chemistry during 1907,a great deal of work has been done, much of it of a highly specialisedcharacter. An attempt will now be made to classify it under theheadings eniployed in previous issues of this Report, special stressbeing laid on investigations of general interest.General and I'hysical Chemistry of Minerals.LMinerat Gels.-" great deal of attention has of late been paidto the investigation of the colloidal substances which may beconveniently termed gels. Thus H. Stremme 1 has studied artificialprecipitates of alumina and silica, and has come to the conclusionthat the natural amorphous " hydrated silicates," such as allophane,halloysite, and montmorillonite, are to be regarded, not its definitecompounds, but as mixtures of gels of alumina and silicic acid.This suggestion has been followed up by F.Cornu,2 who hasattempted a classification of such substances found in Nature underthe headings : hydroxide gels, carbonate, sulphate, molybdate,uranate, phosphate, arsenate, and antimonate gels, silicate gels,and organic gels. The silicate gels can be further subdivided intogroups, such as the chrysocolla group, the gymnite group, etc.Cornu sees in gels the typical products of the normal products ofweathering. He points out that it is useless to attempt to givedefinite chemical formuh to such substances, and he thinks itprobable that many amorphous minerals to which names andformulze have been assigned will, in the future, prove t o be mixtures.It is, however, to be noted that the compositions of many gels agreefairly closely wit.h those of the corresponding crystalline substances.has continued his researchesinto the part played by water in a number of crystalline hydratedsilicates.His experiments have led him to give the formulaCcntr. Min., 1908, 622, 661.Ibid., 1909, 324 ; Zeitsch. Chcm. Ind. Kolloide, 1909, 4, 15, 187; A,, 3909,Hydrated Silicates.-F. Zamboniniii, 222, 409.3 Rend. Accad. #ci. 2%. Mat. Papoli, 1908, [iii], 14, 148 ; A . , ii, 154202 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Zn2(ZnOH)2$i,07,H,0 to hemimorphite. Pyrosmalite he regardsas a metasilicate, (SiO,),[R(OH),Cl],H,.Thaumasite isCaSi0,,CaC0,,CaS0,,15H20. Cordierite and catapleite do notcontain any water of constitution, whiIe sepiolite is derived froman acid, H,Si,O,, and has the formula Mg2Si,08,nHz0.Mutual Relations of Fused Silicates.-In the Report for 1906 anaccount was given of the exceedingly valuable investigations of thecompounds of lime and magnesia with silica made in theGeophysical Laboratory a t Washington. This work has since beenextended to mixtures containing all three components,4 and thestudy of the compounds of alumina with silica, lime, and magnesiahas also been begun.5 Both sets of investigations have led toresults of the greatest interest and importance. In the first place,it has been shown that CaSiO, and MgSiO, both exhibit enantio-tropy.The a-form of the former, pseudo-wollastonite, is unknownin Nature. The &form is wollastonite, and inversion takes placeabout 1 1 9 0 O . The &form of MgSiO, occurs in meteorites. A tabout 1365O it changes into an ortho-rhombic form distinct fromenstatite, and unknown in Nature. The two silicates form but onestable compound, CaSiO,,MgXiO,, identical with diopside. It meltsat 1380°, and good crystals can be got from molten calcium chloride.A eutectic occurs between diopside and pseudo-wollastonite, con-taining about 60 per cent. of the former, and melting a t 1348O. Asecond eutectic, containing 68 per cent. of magnesium silicate, hasalso been observed. Six solid solutions appear in the system, butonly two contain more than a small quantity of the minor com-ponent.These are a solution of diopside, to the extent of 17 percent., in wollastonite, and a solution of magnesium silicate indiopside, the latter taking up about 60 per cent. of its own weightof MgSiO,. The study of the alumina-silica series has shown thatthere is but one compound, AkSiO,, stable in contact with themelt. This is sillimanite (fibrolite). Andalusite and cyanitechange into silliinamite whcn heated above 1300O. Magnesia alsoforms but one compound with alumina, namely, MgO,Al,O,. Lime,on the other hand, forms four compounds with alumina, namely,3Ca0,A120, ; 5Ca!o,3A1203, melting a t 1 3 8 7 O ; Ca0,A1203, meltinga t 1587O; and 3Ca0,5Al20,. The first and the last have no truemelting point.The two compounds 5Ca0,3AI20, and 3Ca0,5A120,have an unstable form each, while 3CaO,Al,O, and probably3Ca0,5A1,03 are unstable a t the melting point. A study of theternary system CaO-A120,Si0, is in progress.The problems presented by the diopside (CaMgSi,O,)-hedenbergiteE. T. Allen and W. P. White, with optical study by F. E. Wright rtnd E. S.E. S. Shepherd and G . A. Rankin, ibid., 28, 293 ; A., ii, 1015.Larsen, Amer. J. Sci., 1909, [iv], 27, 1 ; A., ii, 247MlNERA LOG ICAL CHEMISTRY. 203(CaFeSi,O,) series of minerals have also been attacked in a some-what diff crent manner by V. Posch1.6. Hedenbergite, chalybite,magnesia, calcium carbonate, and silica were melted together indifferent proportions. The physical properties of the products,with the exception of the density, were found to vary continuouslywith the composition, Enstatite and diopside form an iso-dimorphous series.Somewhat similar results were obtained in theolivine group. A good deal of similar work has also been under-taken by other members of Doelter’s school. Mixtures of oligoclasewith enstatite or augite have been examined by M. Schmidt.’ Thefreezing-point curves of mixtures of nepheline with zegirite orlabradorite and of labradorite with diopside have been plotted byE. Dittler,s and the order of separation in these cases found to bein harmony with Rosenbusch’s rule, while mixtures of elaolite andanorthite, as well as those of augite, with labradorite and olivineor magnetite have been studied by IT. Schleimer.9Synthetical studies of the potassium alurnino-silicates have beenmade by Z.TVeyberg,lo who has prepared crystalline compounds ofthe formula: K,Al2SiO6 and K,A1,Si,O8 respectively. Attempfk toobtain similar compounds containing chromium were unsuccessful.Constitution of SiZicates.-In order to throw light on the con-stitution of the natural silicates, Tschermak decomposes purematerial with hydrochloric acid a t low temperatures, and, afterwashing the silicic acid set free, allows it to dry in the air. A tfirst, evaporation of the excess of water alone takes place, but ata certain stage of the process dehydration of the acid begins. Thispoint is determined by weighing the gel of silicic acid at frequentintervals ; when the losses corresponding with equal intervals oftime are plotted, the point where dehydration of the acid beginsis shown by a discontinuity in the curve.By igniting the gel, thecomposition corresponding with the point of discontinuity can beascertained, and the particular silicic acid determined of which themineral under investigation is taken to be the salt. This methodhas been subjected t o adverse criticism by van Bemmelen 11 and by0. Miigge.I2 The latter takes objection t o it on the grounds (1)that Tschermak’s results can in many cases be satisfied by morethan one acid; (2) that the point of discontinuity of the curve islargely dependent on the temperature a t which drying takes place;Tsch. Min. iMitt., 1908, 26, 413 ; A., 1908, ii, 400.7 Jdirb. -%?in.Gcil-Bd., 1909, 27, 604 ; A . , ii, 590.8 Monatsh., 1908, 29, 1037 ; d., ii, 47. !I JaA7.b. J t i n . , 1908, ii, 1.lo Ccntr. illin., 1908, 326, 395, 519 ; d., 1903, ii, 697, 857.l1 Zeitsch. nnorg. Chcin., 1908, 59, 225; 1909, 62, 1 ; A . , 1908, ii, 838 ;l2 Ccntr. Min., 1908, 129, 325 ; A., 1908, ii, 277, 688.1909, ii, 234204 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.(3) that it is uncertain whether the acid set free from the mineralis really the acid of which the mineral is the salt, especially inthose cases in which the temperature of decomposition is high;(4) that doubt exists as to how far the acid set free remains stableduring the conditions of drying. He supports this criticism byobservations made on the gel prepared from natrolite.I n reply,Tschermak13 states that his method rests on two hypotheses: first,that the acid set free is the acid from which the salt is derived,and, second, that the process of drying takes place in two distinctstages-evaporation of excess of water, followed by dehydration ofthe acid. These hypotheses may safely be regarded as tenable untilfacts contradictory of them are recorded. Up to the present thishas not been the case. Any apparent ambiguity which arises ininterpreting the results can quickly be resolved by considering theempirical formula of the mineral from which the acid is obtained,when one of two or three possible acids will be seen to be muchthe more probable. Thus, in the case of the acid made from albite,the water percentage is consistent with any one of the followingf ormuke : H4Si;O12, H6Si&,, H,Sil1026, or H,Si,O,.Considerationof the empirical formula of albite, NaAlXi,O,, shows that H2Si,0,(H,Si@,-H,O) is much the most probable.Colour of Minerals.-The cause of the often brilliant coloursexhibited by natural crystals of substances, which in the pure stateare colourless, has given rise of late to a great deal of dis-cussion. There appears to be a general consensus of opinion thatthe colouring matter, whatever it may be, is present in solidsolution, but as to its exact nature widely different opinions havebeen held. On the one hand, we find those who think that thecolour is due to small quantities of organic matter contained inthe crystals. They base their belief mainly on the ease with whichheat often destroys the colour, and on the fact that small quantitiesof organic matter or of carbon dioxide and water are given offwhen the substances are heated in air.On the other hand, we findthose who admit no connexion between colour and the presenceof organic matter, but believe in the inorganic nature of thepigment. Since the colouring matter appears in many cases toform but a smdl fraction of a per cent. of the substance, it is a tbest very difficult, and often quite impossible, to get satisfactorychemical evidence of its existence. And in our present state ofknowledge it is easier to speculate on the cause of the phenomenathan to give any convincing explanation of the facts observed. Auseful summary of the literature of the subject has been recentlypublished by K.Simon,14 and on the experimental side he has13 Centr. $fin., 1908, 225 ; A . , 1908, ii, 490.; Zeitsch. nirorg. Chent., 1909, 63, 230 ;A., ii, 884. Jahrb. Jlin. Beil.-Bd., 1908, 26, 249 ; A . , 1908, ii, 954MINERALOGlCAL CHEMISTRY. 205tried the effect of heating amethyst, smoky quartz, tourmaline,topaz, and zircon in hydrogen and oxygen gases. He finds that thecolour, which disappears on heating, can often be restored byexposing the minerals to radium radiations or even to direct sun-light. He declares for the inorganic origin of the pigments, butadmits that their nature is as yet unknown. Experiments of asomewhat similar kind have been made by W. Hermann,l5 whoheated borax glasses, coloured by various oxides, under the sameconditions for comparison.The results indicate that the coloursof zircon, corundum, spinel, epidote, and beryl are due to oxideof iron, while chromium and manganese, with iron, cause colorationin green zircon, garnet, and tourmaline. In other cases thepresence of organic matter introduces complications. Similar con-clusions as to €he importance of iron, chromium, and manganeseas colouring agents have been reached by C. Doelter from anextensive study of the action of radium radiations and of Rontgenand ultra-violet rays on miaerals.16 Experiments on the action ofradium in changing the colours of minerals have also been conductedby D. Berthelot,l7 F. Bordas,ls S. Meyer,lg and R.Brauns,20 while0. Miigge2l has paid special attention to the curious phenomenaknown as pleochroic halos. No individual case offers greaterdifficulties, or has been more discussed, than that of rock salt.z2Among the many conflicting views as to the nature of the deepblue colour, that which regards it as due to metallic sodium hasmet with increasing recognition of late,23 owing mainly to the workof Siedentopf. It has, however, been justly pointed out that,although fragments of salt can be coloured blue by exposure tosodium vapour, yet such fragments possess very different propertiesto those of the natural mi11eral.~4 The colour of the latter can bedestroyed a t a temperature of 275O, while the former remain blueat 400O.Mineral A n d y ses .Apart altogether from assays of ores and of minerals of economicimportance made for purely technical purposes, a very large numberof complete analyses of minerals of all kinds have been publishedMonatsh., 1908, 29, 1145 ; 1909,30, 179 ; Zeitsch.CJbcm. Incl. Kolloidc, 1909,lb Zeitsch. anorg. C’hem., 1908, 60, 369 ; A., ii, 56.4, 188 ; A., ii, 109, 363, 409 ; Cesatr. Min., 1909, 232.l7 compt. rend., 1907, 145, 818 ; A , , 1908, ii, 8.l8 ]bid., 800, 874; A . , 1908, ii, 8, 9.l9 Physikal. Zeitsch., 1909, 10, 483; A., ii, 716.2o Centr. Min., 1909, 721.21 Ibid., 65, 113, 142.23 I?. Corm, Centr. A l i v . , 1909, 336.24 G. Spezia, ibid., 398 ; A . , ii, 675.22 See Ann. Report, 1906, 324206 ANNUAL REPORTS ON TEE PROGRESS OF CHEMISTRY.during the past two years.I n the space a t our disposal it isimpossible to refer i;o them all, even if it were necessary, or desirable,so to do. All that will be attempted, therefore, will be to callattention to those among them which throw light on the com-position of rare or imperfectly investigated species, or which havebeen made with special care on material of which the crystallo-graphic and optical characters have also been determined.A damit e.-Brilliant ortho-rhombic crystals(a : b : c =0*9736 : 1 : 0.7013)found in cavities in zinciferous limonite at Monte Valerio,Tuscany, have the formula Zn(ZnOH)AsO,. 25A esc?bynite.-A specimen from Hitter0 has a composition whichmay be represented by the formula:2(2Ce20,,3Ti02),4(ThO2,TiO2),Y2(Cb03)~,3(CaO,Ti~~),3Fe(CbO3)2,Z'e(TaO3),,6TiO2.The columbic acid obtained from this mineral, and most carefullypurified from titanic and tantalic acids, has properties which suggestthat it contains some unknown substance.26AZstonite.-A very thorough investigation of the properties ofthis mineral has been made by S.Kre~tz,~7 who finds that, althoughthe most important constants agree very nearly with those calcu-lated on the supposition that it is an isomorphous mixture of thecarbonates of barium and calcium, yet nevertheless undeniabledifferences exist. The percentage composition of the crystals fromAlston Moor was found to be as follows : CaCO,, 31.40; BaCO,,62.46 ; SrCO,, 6.05 ; which may also be expressed as 93*32CaBaC206,6-05SrC03, 0.53BaC0,.The crystallographic and optical con-stants of the crystals are: system, ortho-rhonibic; a : b : e =0*582(7) : 1 : 0*719(5). Principal refractive indices for sodium light:Amphibole Group-Since the publication two years ago ofPenfield and Stanley's highly important work on this complex anddifficult group (Annual Report, 1907, p. 289), several valuablepapers have appeared. Among these we may notice, in the firstplace, a long memoir in which S. Kreutz 28 gives detailed informationas to the optical constmts and chemical composition of griineritefrom La MalliBre, tremolite from Switzerland, actinolite fromZillerthal, richterite from Lgngban, hornblende from Russell, NewYork, pargasitk from Pargas, and basaltic hornblende from Lukow.I n spite of much careful work, he has only succeeded in tracing2j P.Aloisi, Proc. verb. Soc. Toscana Xci. Hat., 1907, 17, 4 ; A., ii, 587.26 G. P. Tschernik, Bull. Acad. Sci. St. Pe'tersbozcrg, 1908, 4, 389 ; A., 190827 Bull. Acad. Xci. CT~COW, 1909, 771.28 Sitzungsber. K. Akad. Wiss. l'ien., 1908, 117, (i), 877; A,, ii, 154.c~=1-5261, p=1-671(0), y=1*671(7).ii, 399MINERALOGICAL CHEMISTRY. 207a connexion between composition and optical properties in theactinolite-tremolite series, where general relations similar to thoseestablished by Wulfing for the diopside-hedenbergite series ofpyroxenes appear to hold good. I n other cases there is no obviousrelation between the colour or strength of double refraction andthe amount of iron present, and it seems probable that the effect ofvariation in the amount of certain components, for example, FeOor A1,0, is not the same in all members of the group.Whenceit follows that such components cannot be present as simple silicates,such as FeSiO, or Al,Si,O,. There is, however, a connexion betweenabsorption and dispersion, the latter increasing rapidly in theneighbourhood of the region of absorption. Another importantinvestigation is due to Washington and who have com-pared the composition of a black basaltic amphibole from the islandof Linosa with that of a very similar mineral described fromGreenland under the name kaersutite. Both minerals are highlytitaniferous, the chief difference between them being that in theLinosa amphibole, iron is present mainly in the ferric condition,whereas in the specimen from Kaersut, ferrous iron predominates.The proper interpretation of the analytical results is doubtful, butthey appear t o be consistent with the metasilicate formula ofPenfield and Stanley.This formula is also in harmony with theresults of an analysis of actinolite from Rhode IsIand.30 On theother hand, a careful investigation31 of a variety of glaucophane,known as rhodusite, in which alumina is nearly completely replacedby ferric oxide, leads to the conclusion that this substance isto be regarded as an isomorphous mixture of the two molecules,Na$’e,Si*O,, and (Mg,Fe,H2,Ca,Mn)Si03, in the ratio 1 to 5, a resultnot in keeping with the formula proposed by Penfield and Stanley.The rhodusite examined came from the neighbourhood of theAsskys River in the Minussinsk district, Siberia, and consisted ofgreyish-blue, st-rongly pleochroic fibres.The optical constants andcomposition of hornblendes from the island of Coll, Eebrides, andfrom Chester (Mass.) have been determined by Duparc and Pearce.32A pophyZZite.-An elaborate study of the crystals found in geodesin Melaphyr on the lower Tersja, a tributary of the Tomj river,has been made by P i l i p e n k ~ . ~ ~SiO,. Fe,03. CaO. K20. F. N. H,O. Total.The composition is as follows:52.12 0.26 24.56 5‘23 1-73 0.02 16-63 100-5529 Amer. J. Sci., 1908, [iv], 26, 187; A., 1908, ii, 863.30 B. L. Johnson and C. H. Warren, ibid., 25, 1 ; A., 1908, ii, 202.31 W. Iskull, Zeitseh.Kryst. Min., 1908, 44, 370 ; A., 1908, ii, 401,32 Bull. SOC. franc. Min., 1908, 31, 116 ; A., ii, 60.m Am. Ge‘oZ. Hin. Buss., 1908, 10, 200208 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Dehydration follows the same course as observed by Hersch.A rgyrodite.-Analyses of material found in the Werner collectionat Freiberg 34 and of a specimen from Bolivia 35 both support theformula, Ag,GeS,, proposed by Penfield. It has been suggested thatthis may be written in the form 3R;S,R;RIVS3 to bring out ananalogy with the formula 3R~S,R111R111S3 of tetrahydrite.Bauxite.-A great many specimens have been analysed byH. Arsandaux,36 who finds that on heating the mineral with stronghydrochloric acid on the water-bath, all the iron is extracted, whilenearly the whole of the alumina remains in the insoluble residue.Examination of the residue leads to the conclusion that the amountof water associated with the aluminz is independent of the amountof iron present, and may be expressed approximately by the formulaA1203,H20.Analyses of this mineral have also been published byR. Lachman,37 and the theory of its formation discussed.Bertraa~~te.-Crystals from the Altai Mountains have beenexamined by Pilipenk0.37~. Their composition agrees fairly wellwith the formula H2G1,Si2O9.Brosternite.-This name was applied by P. Poni in 1900 to certainmanganites of manganese and ferrous iron of variable compositionoccurring in crystalline schists near Brosteni, in Roumania. Thesedeposits have recently been the subject of detailed study byV.C. Bu$ureanu.a He concludes that the brostenites are the resultof the oxidation of a carbonate of composition 5MnC03,FeC03,and belong to the four following types: R0,2Mn02,2H20;R0,3Mn02,2H20 ; R0,3MnO2,3H20 ; and R0,5Mn02,H20.The manganese ore of the Queluz district, Brazil, appears to havehad a somewhat similar origin, for 0. A. Derby39 finds that it hasbeen derived from a rock consisting largely of manganese carbonate,his first impression that it was derived from the weathering of arock rich in manganese garnet having proved incorrect. Themanganese deposits of India have been exhaustively studied byL. L. Fermor,4O who has embodied his results in an elaboratememoir. He has observed several new minerals in these deposits(see juddite, sitaparite, and vredenburgite).Curlosite.-The substance to which this name was given was foundaccompanying benitoite in California, and was a t first believed to34 F.Kolbeck, Centr. Min., 1908, 331 ; A., 1908, ii, 703.35 v. M. Goldschmidt, Zeitsch. Xryst. Min., 1908, 45, 548 ; A , , ii, 58.36 Compt. rend., 1909, 148, 936, 1115 ; A , ii, 490, 587.37 Zeitsch. prakt. Geol., 1908,16, 353.3 7 ~ Bull. Acad. Sei. St. Pdtersbourg, 1909, 1116 ; A , 1910, ii, 48.38 Ann. Sci. Univ. Jassy, 1908, 5, 87 ; 1909, 6, 7 ; A., 1908, ii, 955; 1909, ii, 745.39 Arner J. Sci., 1908, [iv], 25, 213 ; A., 1908, ii, 506.40 Mem. Geol. Xurv. India, 1909, 37, pp. 1-610MINERALOGICAL CHEMISTRY. 209be a new mineral. It has proved, however, on further examinationto be identical with neptunite.41 In composition the material fromCalifornia is very similar to that from Greenland, but rather lessmanganese and more calcium and magnesium are present in theformer.The formula is R ~ R ~ T i S i 4 0 1 2 , where R1=Na and K,and RII=Fe, Cay Mg, and Mn.CldoiwmnganokaZit e.-A new analysis agrees approximately withthe formula 4KC1,MnC12.42 The mineral is rhombohedra1(a : c = 1 : 0*5801), not monoclinic as stated by Lacroix. Thecrystals are pale yellow, highly deliquescent rhombohedra. Theindex of refraction is about 1-59, and the birefringence very low.A good uniaxial interference figure was observed in a section cutperpendicular to the trigonal axis of the rhombohedron.C7~ZornatrokaZite.-Further investigation has shown this substanceto be merely an intimate mixture of the chlorides of potassium andsodium .43Conicl~aZcite.-Minute indistinct cryst.als of this rare mineralhave been found lining cavities in copper ore a t Maya-Tass, in theProvince of Akmolinsk, Western Siberia.44 The optical characterspoint to ortho-rhombic symmetry.The composition is as follows :As,O,. P,O,. CuO. CaO. Fe,O,. MgO. H,O. Total.36-40 1.30 31.55 23.10 0.40 1-90 5.15 99-80ConneZZite.-Our knowledge of the composition of this very raremineral has depended hitherto on an analysis made by Penfield ofa very small quantity. The recent discovery of a specimen a tBisbee, Arizona, has enabled C. Palache and H. E. Merwin 45 tomake a fresh examination of the substance.They conclude thatthe formula is Cu22C14S02,,20H20, a, result which differs consider-ably from Penfield's formula CUl,(C1,0H),S016,15H20.Coronadite.-L. L. Fermor 46 has pointed out. that this mineralmay be regarded as a salt of the same hypothetical acid, H4Mn0,,from which hollandite and psilomelane are derived, and assigns toit the formula Mn21Pb6R511(Mn05)16.CossyTi,te.-This mineral is a variety of aenigmatite, found insmall crystals weathered out of the pantellerite of the island ofPantelleria. It has recently been the subject of an exhaustivestudy by J. S0ellner.~7 The symmetry is anorthic, and the constants41 W. M. Bradley, Amer. J. Sci., 1909, [iv], 28, 25 ; A., ii, 815.42 H. J. Johnston-Lavis and L. J. Spencer, Min.Mag., 1908, 15, 54 ; A., 1908,44 L. Michel, Rull. SOC. franc. Min., 1909, 32, 50 ; A , , ii, 491.45 Amw. J. Xci., 1909, [iv], 28, 537 ; A., 1910, ii, 47.JG h'ee. b'eol. Surv. India, 1908, 36, 295 ; A . , ii, 153.47 Zeituch. Kryst. Nin., 1909, 46, 518 ; A . , ii, 814.ii, 395. 43 Ilrid.REP.-VOL. VZ. 210 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.as follows: a : b : c =0*66856 : 1 : 0.35173; a=9O043’, P=102°30’,y=90°18+’. The angle between the good cleavages, 110: lT0, is66O16’.It is pointed out that cossyrite, zenigmatite, and rhonite may beregarded as a group of isomorphous minerals intermediate betweenthe pyroxenes and the amphiboles.CTpoZite.-F. Cornu48 has suggested that the change of systemwhich Nacken has observed to take place between 550° and 570° isdue to the formation of a cubic substance isomorphous withcr yolithionite.Dadwrite.-Rough, corroded crystals from Maharitra, Mada-gascar, have been shown to possess the ordinary formula,Ca0,B20,,2Si02.49BplsanaZyte.-The small, iron-black crystals found in the granularlimestone from the neighbourhood of Vogtsburg (Kaiserstuhl i / Br)were for long regarded as perowskite, but since A.Knop detected inthem considerable quantities of columbium and czesium, they havebeen considered as constituting a separate species under the namedysanalyte. The correctness of this conclusion has been challengedby 0. Hauser,50 who holds that the substance is merely perowskitecontaminated by enclosures. Analysis of selected crystals gave thefollowing results :The analytical results may be expressed by the formula(H2)2 (N+)3 ( FeI1,Mn, Mg, C a) 15 (FeIIIA1) 2 ( Si,Ti) 22067-TiO,. SiO,.Cb,O,. Ce,O,. FeO. CaO. MnO. Na,O. Total.50.93 2’21 4-86 2‘80 9-22 25-60 0.23 4‘37 100.22DatoZite.-The composition of a specimen analysed by J.Fromrne51 agrees very well with the formula, Ca(BOH)Si04, if itbe assumed that. a little of the boron is replaced by aluminium.Fic7LteZite.-Crystals from a peat bog at Borkovic, Bohemia, havebeen shown to belong to the hemimorphic class of the obliquesystem.52 Analysis gave the formula C18H32, a result confirmed bymolecular weight determinations.Felspar Group.-It has long been known that analyses of thepotash felspar orthoclase, KA1Si30,, made on pure, apparentlyhomogeneous material, often show the presence of sodium andsometimes of calcium as well.I n explanation it has been assumedthat these elements are contained in albite or anorthite, presenteither in isomorphous or mechanical mixture. The problem offeredby such orthoclases has recently received a good deal of attention.48 Cen‘entr. Min., 1908, 546 ; A., 1908, ii, 955.49 A. Lacroix, Bull. Sac. frang. Min., 1908, 31, 315 ; A . , ii, 812.50 Zeitsch. anorg. Chem., 1908, 60, 237 ; A., ii, 60.51 Tsch. Min. Mitt., 1909, 28, 312.62 F. Plzjkand V. Rosickf, Zcitsch. Kryst. Min., 1908,44, 332 ; A , , 1908, ii, 395MINERALOGICAL CHEMISTRY. 211The analytical work of Barbier and Prost53 tends to show thatsodium is not present as albite, but as a monoclinic sodium silicateisomorphous with orthoclase.A similar conclusion has been reachedby Schwantke 54 as regards calcium, for he attributes its presence tothe hypothetical molecule CaA1,Si6OI6. He has pointed out that theexistence of stilbite, (Ca,Na+12Si6016, 6H20, lends support to theidea that such a molecule is possible. On this view the intergrowthof plagioclase and quartz, probably derived from alteration oforthoclase and known as myrmekite, can be explained as due tothe conversion of CaAl2Si6OI6 into CaA1,Si208 with separation ofsilica. The problem has also been attacked by melting togethersynthetical preparations of orthoclase and anorthite, and of ortho-clase and plagioclase.55 It has been found that orthoclase is onlymiscible to a very slight extent with anorthite.With plagioclasethe tendency to form mixed crystals is greater, and increases withthe amount of albite substance present. I n both cases zonedcrystals are formed, the centre being rich in calcium, whilethe edges concain much potassium. Pure orthoclase does notcrystallise out of the mixture. This case of mixed crystallisationapparently conforms to type I V of Retgers,56 in which the com-ponents are isodimorphous, and a considerable gap exists.The distinction between orthoclase and microcline made by DesCloizeaux on optical grounds has been the subject of it chemicalstudy by P. Barbier.s7 He finds that small quantities of lithiumor of rubidium or of both these elements invariably occur inorthoclase, but are not found in microcline.I n this he sees afundamental chemical difference between the two minerals, a viewin which he is supported by F. Gonnard.58 The crystallographicconstants of good crystals of pure albite from South Greenland havebeen determined by Dreyer and Goldschmidt .59 Minute crystals ofandesine from Monte Palmas, Sardinia, have been shown byF. Millosevich6* to possess properties in harmony with a positionin the plagioclase series between Ab,An and Ab,An2. An interest-ing illustration of the application of the methods of physicalchemistry to the study of a rock is to be found in Vogt's paper 61 ona labradorite-norite from the Lofoten Islands.bY Bull. SOC. chim., 1908, [iv], 3, 894 ; A., 1905, ii, 363.54 Ccntr.Ji'in., 1909, 311 ; A . , ii, 558.55 E. Dittler, zbid., 663.5G Zcitsch. physiknl. Chent., 1889, 3, 552.57 Compt. rend., 1908, 146, 1330 : A . , 1908, ii, 704.58 Bull. Soc. franq. Min., 1908, 31, 303.59 Ll.lcddelelseromGronland, 1907, 34, 1 ; A., 1908, ii, 116.6o Alti 22. Accad. Lincei, 1909, [Y], 18, i, 22 ; A . , ii, 248.Quart. J. Gcol. SOC., 1909, 65, 81 ; A., ii, 678.P 212 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.G~,u~inite.-This species occurs in small, yellow crystals in thesanidine bombs of Montc Somma, and was described in 1857 byGuiscardi as an orthorhombic calcium titano-silicate. Rebuffatsubsequently gave it the formula2 (Na,K),O ,8Ca0,5 (AI,Fe,Ce),O,,lO SiO,.As a recent examination of the crystals proved them to be anorthicwith the angles and optical characters of hiortdahlite, a new analysiswas undertaken by G.T. Prior, with the result that the identitywith hiortdahlite was completely proved, the formula of the mineralbeing SCaSiO,,[ Ca (F,O H)] NaZ r 0,.62Gedrite.-Sheaves of long, narrow crystals of this aluminousvariety of anthophyllite have been found abundantly in amphibolitein Ontario.63 The mineral has a clove-brown colour, and exhibitscharacteristic pleochroism. Its composition is very similar to thatof a specimen from GBdres in the Pyrenees, and may be representedby a formula of the type given by Rammelsberg: 4RSi03,A1,0,,where R= Mg, Fe, H,.Gehlenite occurs as a contact mineral near the junction ofaltered limestone and intrusive basic diorite in the Velardefiadistrict of Durango, Mexico.Crystals were not observed, butF. E. Wright64 was able to establish the identity of the mineralby its physical characters. The substance has a fair basal cleavage,and is uniaxial : w = 1.6, w - E = 0.0055. The composition cannotbe expressed by any simple formula, but is similar to that of otherspecimens from Monzoni, Falkirk, and Clarence, the mineral beingessentially a calcium aluminium silicate.Hutchettite.-A crystalline substance, possessing optical charac-ters suggestive of orthorhombic symmetry, has been found in nestsin Cretaceous marl near C~acow.~5 It appears to be a paraffin ofthe formula C38Ri8.Hopeit e.-The brilliant crystals which occur associated withvanadinite on a bone-breccia in a cavern in the zinc and lead oreat Broken Hill, Rhodesia, are found on optical examination toconsist of an intimate interlamination of two modifications whichdiffer in density, optical character, and the rate a t which theylose water on heating, but possess the same chemical composition,agreeing with the formula Zn,P20,,4H,0.L. J. Spencer66 pro-poses t o call these two modifications a-hopeite and P-hopeite respec-62 F. Zambonini, J f i n . Mag., 1909, 15, 247 ; A., ii, 677.63 N. N. Evans and J. A. Bancroft, Amer. J. Xci., 1908, [iv], 25, 509 ; A., 1908,64 Amer. J. Sci., 1908, [iv], 26, 545 ; 'A., ii, 62.65 J. A. Morozewiez, Bull. Acad. Sci. Cracow, 1908, 1067 ; A . , ii, 409.66 Dlin. Mag., 1908, 15, 1 ; A . , 1908, ii, 397.ii, 604MINERALOGICAL CHEMISTRY.213tively. His observations and conclusions have recently beensubjected to some criticism by G. Ces2~ro.~~HortonoZite.-This rare species has been discovered in veinstraversing an ultrabasic olivine rock at Rhode Island.68 I n com-position it. resembles closely the material from Munroe, Orange CO.,N.J., analysed by Penfield and Forbes.Hydrated Calcium Carbonate.-P. N. Tschirwinsky 69 has re-cently reviewed our knowledge of the hydrated forms of calciumcarbonate. He rega,rds only three of these as definitely established,namely, CaC0,,3H20 ; CaC0,,5H20 ; and CsCO,,GH,O. The firsttwo occur as minerals, and may be termed trihydrocalcite andpentahydrocalcite respectively (compare Ann. Report, 1906, 307).ZZvaite.--A specimen from Elba, examined by Tschermak’smethod, gave results indicating that it was derived from thediorthosilicic acid, H6Si,0,.70 The formula is therefore written(FeO),Fe,(FeOH),( Si207)2.Janosite.-Some time ago R.Scharizer 71 suggested that themineral janosite asserted by Weinschenk and Toborffy to beidentical with copiapite might really be a mixture of copiapite,Fe4S,0,,,18H2O, with ferric tetrasulphate, Fe,S40,,,9H20. He hassince found that fresh experiments support this conclusion. Hebelieves, moreover, that it is necessary to distinguish betweenordinary or a-copiapite, (HO),Fe,(S0,),,17H20, and another similarsubstance which he calls P-copiapite, (HO)Fe,( SO,),,l 3H20, andwhich is possibly identical with Rammelsberg’s misy.KaoZinite.-The white product resulting from the weathering ofquartz-porphyry in the neighbourhood of Halle has been analysedby V.Selle,72 who has also determined the composition of theportion insoluble in concentrated sulphuric acid. He concludesthat mica was the first product of the alteration of the felspar inthe rock, and that it was subsequently converted into kaolinite.I n the Halle district the decomposed porphyries are richest inkaolinite near the surf ace, and minerals of pneumatolytic originare absent. It may therefore be deduced that the formation ofkaolinite is dependent on the ordinary processes of weathering..Xr6hnkite.-Large, oblique crystals from Chili have beenexamined by Palache and Warren.7X They have the usual formulaCu S0,,Na2S0,,2H;0.67 Ball.Acnd. roy. Belg., 1909, 567 ; A., ii, i 4 5 .Gs B. L. Johnson and C. H. Warren, Ayncr. J. Xci., 1908, [iv], 25, 35 ; A, 1908,7u E. Baschierj, Proc. verb. SOC. Tosenna Sci. AT&, 1907, 16, 49 ; A,, ii, 589.71 Zeitsch. Eryst. Afin., 1909, 46, 427 ; A., ii, 587.72 Zcils. Naturu:., 1907, 79, 321 ; A., ii, 6 3 .7ra Amer. J. Sci., 1908, [iv], 26, 342 ; d., 1908, ii, 1047,ii, 202. 69 Zeitsch. Icryst. d f k , 1909, 46, 302 ; A , , ii, 4922J.4 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Mangano-tantaJite.-Large masses of this mineral have beenfound in pegmatite-veins in the Wodgina tin-field, Western Aus-tralia. A specimen analysed by Simpsqn was found to contain68-65 per cent. Ta205, 15-11 per cent. Cb;O,, and 14.15 per cent.Heymacite.-Native anhydrous tungstic acid, WO,, and ahydrated form, W0,,2H20, have been described under the namesof tungstite and meymacite by Silliman and Carnot respectively.No analysis of Silliman’s mineral has been published, and thematerial examined by Carnot was so impure that the formulaassigned to it can only be regarded as uncertain.The study ofsimilar specimens found near Salerno in British Columbia has ledWalker74 to the conclusion that tungstite and meymacite areidentical, and that the true formula for the mineral is W0,,H20.He suggests that the name tungstite should be retained. Thematerial from Salerno has resulted from the alteration ofwolframite. As it was not found possible to obtain a pure speci-men for analysis by mechanical means, advantage was taken ofthe solubility of the mineral in ammonia and dilute soda.Afterdeducting insoluble impurities, the results were in harmony withthe formula given above.Mimetite.-Two varieties of this mineral, one yellow and theother white or colourless, are found in the cupriferous strata ofSardinia.75 They vary slightly in chlorine content, and exhibit acorresponding variation in the value of the angle 1011: 0001, thenumbers being 40°4’ for the yellow crystals which contain 2.30per cent. of chlorine, and 39O52’ for the white crystals with 2.44 percent. of chlorine.Monazite.-Yellow crystals from Carolina have been analysed byG. P. Tschernik,76 and the question of the condition in whichthorium exists in the mineral has been discussed by 0.Kress andF. J. M e t ~ g e r . ~ ~ The thorium has been held to be present assilicate (thorite or orangite), or as phosphate, or in both theseforms. To throw light on the problem, Kress and Metzger havedetermined the percentages of thoria, quartz, silicate silica, andtotal silica in a very large number of specimens. As they findthat in general the silica available for combination with the thoriais in defect, they conclude that the thorium is not present assilicate. This conclusion was confirmed by microscopical examina-~ ~ 0 . 7 373 A. G . Maitland, Bull. geol. S’urvcy Westcriz Ae6slrnlia, 23, 65 ; A . , ii, 59.74 Anacr. J. Sci., 1908, 25, 305; A . , 1908, ii, 507.75 A. Serm, &ti h’. Accnd. Lincei, 1909, [v], 18, i, 361 ; A ., ii, 492.76 B161Z. Acnd. Xci. Xt. P&tersbo?wg, 1908, 243 ; A . , 1908, ii, 302.77 J. Ainw. Chcm. Soe., 1909, 31, 640 ; A., ii, 588MlNERALOUICAL CHEMISTRY. 21 5tion, which showed that the silicate present in monazite is quitedifferent t o thorite, and is very likely a felspar.Morinite is an alteration product of amblygonite, and occurs insmall, oblique crystals with tin-ore a t Montebras (Creuse).7* Itscomposition is represented by the formula3A1P04,Na&CP04,3CaF,,8H,0,which, expressed in the form (A1F)3N~H(P04)3,(CaF)3P04,8H~0,shows in the first molecule a relation to amblygonite,[Al(F,OH)](Li,Na)PO,.NepheZine.-J. A. Morozewicz 79 has found that nepheline iscompletely soluble in N /4-hydrochloric acid, and that enclosedimpurities may thus be readily separated..Taking advantage o€this fact, he ha.s analysed three specimens of elzolite from theMariupol district, Sea of AZOV, an elzeolite from Mias, Urals,and two sets of crystals from Vesuvius. I n all the ratio(A1,Fe),O3 : (N%,K,,Ca)O = 1 : 1, but the ratio (SiTi)O, : (Al,Fe),O,varies from 2-11 : 1 to 2-21 : 1. The ratio K,O: (N+lO+ CaO)varies from 1 : 4.06 to 1 : 5.6, being usually 1 : 4.4. These results,considered in connexion with earlier work, lead to the conclusionthat sodium and potassium do not replace one another iso-morphously, but that most analyses may be represented as com-binations of the molecule K,A12Si,0,, with 4, 44, 5, or 5& moleculesof Na,Al,Si,O,.Nephrite.-Analyses of a series of specimens of New Zealand" greenstone," selected to illustrate the variation of composition withcolour, have been published by A.M. Finlayson.80Nontronite.-Pseudomorphs of nontronite after wollastonite arefound in the copper mines at Aranzazfi, near Concepcih del Oro,in Mexico.81 They have been formed by the action on wollastoriiteof iron sulphate derived from the alteration of copper pyrites.The formula H,Fe,Si,O,, has been deduced from an analysis ofthe purified material. This differs considerably from the formula,H4Fe,Si20g, proposed by Weinschenk for nontronite from nearPassau.Oncosine is a compact variety of niuscovite, which swells LIP andintumesces when heated. A specimen has recently been analysedby G. Piolti.*20rthite.-Well-developed crystals from the Radautal have been7s A.Carnot and A. Lacroix, BUZZ. Svc. frnnp. Hin., 1908, 31, 149; A.,is Bull. Acnd. Sci. Cracozu, 1907, 958 ; A . , 1908, ii, 201.so Quart. J. geol. Soc., 1909, 65, 351 ; A., ii, 901.81 A. Bergeat, Centr. Xin., 1909, 161; A., ii, 411.B2 Atti R. Acead. Sci, Torino, 1909, &&, 743 ; A., ii, 813.ii, 55216 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY,measured and analysed by J. Fromme.83 I n addition to the usualconstituents, the specimen contained small quantities of yttriumand glucinum. A formula of the general type,H20,4R0,3R203,6 S?02,expresses the results fairly well. A full account of the analyticalmethods employed will be found in the original paper.Pdigorskite Group.-A number of somewhat ill-defined minerals,such as ‘‘ mountain leather,” have been grouped together underthis name.An elaborate critical discussion of the available datahas led A. Fersmann 84 to divide the group into the seven followingclasses : (1) paramontmorillite of the general compositionH,,A1,Si~0,7 ; (2) a-paligorskite, H32Mg2A14Si,,046 ; (3) 8-paligor-skite, HzoMg2A12Si,0,, ; (4) a-pilolite, H28Mg4A12Silo04, ; (5)P-pilolite, H36Mg6A12Si,30,3 ; (6) parasepiolite, H3Mg,Si3012 ; (7)ferruginous paligorskite.Pahierite.-Although the analytical results agree best with theformula 4PbS04,3[(K,Na),S04], there is some reason to believe 85that the true formula is PbS04,(K,Na),S04.Peridot.-Good crystals from St. John’s Island (Zebirget), in theRed Sea, have been analysed by J.Couyat.86 His results are verysimilar to those recorded by Stromeyer for oriental peridot. Theindices of refraction (sodium light) are : a = 1.6546 ; P = 1.6706 ;y=1*6898, values which agree closely with those obtained byZim6nyi.PZumosite.-A felted aggregate of dark steel-grey fibres fromFelsobsnya has been analysed by J. Loczka.87 The materialexamined appeared to be free from stibnite and iron pyrites. Theformula deduced is 4PbS,FeS,3Sb2S3, but the results obtained agreebest with the formula 7(Pb4/5, F ~ I , ~ ) S , ~ S ~ ~ S ~ , given by Spencer andPrior to jamesonite, of which mineral plumosite is merely a variety.Pyromorphite.--Crystals from British Columbia have been thesubject of careful chemical and crystallographic examination by0.Bowles.88 Two varieties are distinguished, which differ in colourand to a slight extent in composition also. A comparative studyofl specimens from various localities has also been made byR. Brauns.89 Dark brown crystals from Agidienberg of normalcomposition have been found by him to have the axial ratioa : c = l : 0.72926.83 Tsch. Min. Mitt., 1909, 28, 318.84 Bull. Acad. Sci. Xt. Pdtersbourg, 1908, 637 ; A . , 1908, ii, 603.85 A. Lacroix, Bull. SOC. franc. Min., 1908, 31, 260 ; A., ii, 57,SG Bull. SOC. franc. Afin., 1908, 31, 344 ; A . , ii, 813.87 Ann. M w e i Nat. Htmgarici, 1908, 6, 586 ; A . , ii, 153.8D Ccntr. Min,, 1909, 257 ; A , , ii, 492.Amer. J. Sci., 1909, [iv]. 28, 40 ; d., ii, 900MINERALOGICAL CHEMISTRY.217PyrochZore.-The results of analysis of octahedral crystals fromthe Caucasus may be expressed 90 in the form Y203,Cb20,+2(2Ca0,Cb20,), 2Ca(CbO,I2, 4 Fe(CbO,),, Mg(CbO,),, 2(Ca0,Ti02), 4NaF.Quartz.-In 1890 Le Chatelier made the very important andinteresting observation that quartz undergoes a reversible changea t about 570O. This change is manifested by a sudden alterationin the coefficient of expansion, in the circular polarisation, and inthe birefringence. The phenomenon was subsequently investigatedfrom the crystallographic side by 0. MuggeFl who, from a studyof the etched figures, came to the conclusion that the form ofquartz stable below 570°, and termed by him a-quartz, belongedto a different type of symmetry to the form stable above 570°,so-called /3-quartz.These two forms have recently been the subjectof detailed examination by Wright. and Larsen,92 who place thetransition temperature at 575O +_ 2O. They einphasise the fact,pointed out by Mugge, that quartz which has been heated above5750 possesses properties, notably a peculiar twin structure, whichenable it to be distinguished from quartz which has never reachedthis temperature. On the possibility of this discrimination theybase the use of quar€z as a kind of “geological thermometer,” anddiscuss its application to the elucidation of the past history ofvarious rocks, their geberal conclusion being that vein and geodequartzes and certain large pegmatite quartz masses and pegmatiteveins were formed below 575O, while graphic and granite pegmatitesand granites and porphyry quartzes were in all probability formedabove that temperature.The relations between quartz, chalcedony, and opal have beenstudied by H.Leitmeier.93 Specimens of the three minerals wereheated with a 50 per cent. solution of potassium hydroxide at 80°for five hours, and from their behaviour under these conditionsthe conclusion was drawn that quartz and chalcedony are varietiesof the same species.Rhodieite.-Our knowledge of the composition of this rare boratehas hitherto been confined to an analysis made by Damour. Therecent discovery of the mineral in Madagascar has providedmaterial for a fresh investigation.”* The results lead to theformula 6B203,3A1203,4G10,4(Li,K,Na,H)20.Rhthite.-The composition of large, black crystals analysed byPisani 03n may be expressed by the formula(Na~K~H)2Ca,(Fe~Mg) ,,(AI,Fe) 16, ( Si,Ti)21090.Do G. P.Tschernik, Bull. Acnd. Sci. X t . Pdembourg, 1909, 365 ; A . , ii, 411.Dl Jnhrh. Min. Festbnnd, 1907, 181 ; A . , 1908, ii, 302.y2 d m r . J. Sci., 1909, [iv], 27, 421.93b A . Lacroix, Bull. Soc. franc. Min., 1909, 32, 325 ; A , , 1910, ii, 49.93 Ccntr. illin., 1908, 632; A . , 1908, ii, 954,A Lacroix, Compt. rcnd., 1909, 149, 896 ; A., 1910, ii, 46218 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Reyerite.-A scaly zeolitic mineral from Niakornat, in Green-land, has been identified with reyerite {see Ann. Report, 1907, 288)by 0. B. Boeggild.94 The composition of the rhombohedra1 crystalsmay be expressed by the formula 2Ca0,3Si0,,1&HZ0 orH,Ca,( SiO&,+H,O.RutiZe.-Small crystals from Vaux (RhGne), which wereapparently quite free- from inclusions, were found t o contain 1.75per cent.of oxide of tin.95 This observation is interesting onaccount of the isomorphous replacement of titanium by tin.8assoZite.-If steam is passed over tourmaline at a high tem-perature and then condensed, it is found to contain traces of boricacid. This fact has been adduced by R. Nasinig6 in support ofthe theory that sassolite is derived from tourmaline. His viewshave, however, been criticised by G. D’A~hiardi.~’Soda Nitre.-The results of analyses of several samples of Chilisaltpetre show that all contain iodate, and some, perchlorate.98 Thesamples rich in sodium nitrate contain potassium nitrate as well,and also small amounts of chromate.8tephanite.-Some remarkably fine crystals from Arizpe, Mexico,have been described by W.E. Ford.99 The formula 5Ag,S,Sb,S3is in good agreement with the analytical results.Striiverite.-In a detailed account of the analysis of this mineral,Prior 1 has discussed the difficulties which attend the separationof columbic, tantalic, and titanic acids, and has shown that theusual gravimetric methods bring out the percentage of titaniumconsiderably too high. I n the light of these results he re-examinedthe ilmenorutile from the Ilmen Mountains, and from Evje, inNorway, and found, on estimating the titanium colorimetrically,that his view was correct.These determinations, together withtwo new analyses, of which the first was made on a specimenfrom the Ilmen Mountains, and the second on one fromIveland in Norway, correspond approximately with the formulaFeO,Cb20,,5TiO2, with possibly some admixture of FeTiO, orFeTiZO,, and thus exhibit analogy to the formula assigned tostriiverite, FeO(Ta,Cb),0,,4Ti02, a substance of similar crystallineform. His conclusion is that striiverite and ilmenorutile may bestbe represented as solid solutions of the rutile (TiO,TiO,) andtapiolite or mossite (Fe[(Ta,Cb)O&) molecules, the former name94 Mcddelelscr om Groi land, 1908, 34, 93 ; A., 1908, ii, 399.95 G. Friedcl and Grandjean, Rzcll. Soc. fmnq. Min., 1909, 32, 52 ; A., ii, 491.1)6 Atti R.Accnd. Lincei, 1908, [v], 17, ii, 43 ; A . , 1908, ii, 862.97 Ibid., 238 ; A., 1908, ii, 955.9* F. W. Dafeit, Monatsh., 1908, 29, 235 ; A . , 1908, ii, 60399 Amer. J. Sci., 1908, [iv], 25, 244 ; A., 1908, ii, 505.G, T. Prior and F. Zambonini, Min. Mag., 1908, 25, 78; A., 1908, ii, 398MINERALOGICAL CHEMISTRY. 219being appropriate for those rich in tantalic acid, whilst thelatter may be kept for those in which columbic acid pre-dominates.Vesuvianite.-A number of specimens have been tested for boronby Wherry and Chapin.2 The largest amount was found in thecrystals from the Wilui river in Siberia. The authors draw atten-tion to the fact that the amount of ferric iron present is alwayssmall, never exceeding 5 per cent., and they sugges!" that thisindicates that only part of the aluminium is basic, most of it,together with the boron, playing the part of an acid. To giveexpression to this view, Clarke's formula for vesuvianite,R,I'Ca,Al,( Si'04)6(RI1=H2, K,, N+, Mg, Ca, Fe, Mn, and also AlOH and A1F withFeIII, MnIII, or B replacing some of the Al), may be written in theform Ca7(RI1A1O2),( SiO,),( SiO,), or Ca7R1'(RI1A10,) ( Si04),( SO3),.Warwickite.-Minute slender crystals, showing characteristiccopper-red reflections on the cleavage surfaces, occur in a meta-morphic limestone in contact with granite a t Amity, New York.Spinel and magnetite are intimately associated with the mineral,and if it be assumed that the alumina and ferric oxide found onanalysis are due to t'hese substances, and allowance be made incalculating the results, the formula 3(Mg,Fe)0,Ti0,,B,03 or(Mg,Fe),TiB,O, is arrived at.This differs somewhat from theformula 6Mg0,Fe0,2Ti02,3B,03 hitherto accepted for thespecies.3TVhezaeZZite.-Large %win crystals of this rare mineral haverecently been discovered associated with ankerite and barytes in afault breccia in a coal mine near Schlan, in Bohemia. The crystals,which have been fully dcscribed,4 have the composition CaC,O,,H,O.Allied to whewellite is an oxalate of calcium, called thierschitc,investigated by Liebig in 1853. It was found as an incrustationon the marbIe columns of the Parthenon, and its formation appearsto have been due to the action of thallophytes on the marble. Anincrustation of similar origin has recently been described fromlimestone on the south bank of the Krym,?TiohZerite.-Yellow prisms examined by G.P. Tschernik 5 havea composition approximately expressed by the formula :Zr,Cb2Ca,,Na,F3Si,,042.Xenotime.-A crystal of this mineral, resembling a cube, beinga combination of the basal plane with a tetragonal prism, has been'3 J. Amcr. Chenz. SIX, 1908, 30, 1654 ; A . , ii, 57.Awcr. J. SLL, 1909, [iv], 27, 179 ; A . , ii, 247.F. Slavik, B d l . Intern. Acad. Sci. Bohdme, 1908, 13 ; A., ii, 154.Bzdl. Acad. Sci. Xt. Pktcrsbowg, 1909, 903 ; A ? , ii, 1028220 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.found with good crystals of phenacite in pegmatite a t San Migueldc Piracicaba, in Minas Geraes.6P,O,. Y,03, &c.Al,O,+G1,0,. SiO,. Total.33.21 62.62 3.05 1’41 100 *29The composition is as follows :Zeolite Group.-S. J. Thugutt 7 believes that the amount ofwater held by zeolites depends on the size of their particles aswell as on the pressure of aqueous vapour in the surroundingatmosphere, and on the period of time the material remains incontact with that atmosphere. He finds that zeolites in a fine stateof division give off more water on ignition than if they have onlybeen coarsely powdered. Apophyllite, on the other hand, loseswater when ground. The composition of good crystals of natrolite,from Leitmeritz, with which some of his experiments were made,is represented by the formula Na2A12Si,0,,,2H,0. The state ofhydration of a number of zeolites has also been examined byE.Lijwenstein,s using van Bemmelen’s method. The specimenswere kept a t 2 5 O over sulphuric acid of known dilution and vapourpressure, and the loss in weight and water content was determinedafter equilibrium had been reached. It was found that the vapourpressure of chabazite, heulandite, and stilbite varies continuouslywith the water content, the crystals remaining clear. The zeolitesof Montresta, Sardinia, previously examined to some extent byRimatori, have also been investigated by L. Pelacanig and byJ. Deprat.lo The former has analysed chabazite, the latter stilbite,and both have studied T~eulandite and nzesolite. Pelacani regardsmesolite as an isomorphous mixture of scolecite and natrolite. Hehas observed that when chabazite is slowly heated to 350° the ratea t which water is given off diminishes as the temperature rises,while for mesolite the reverse is true. Chabazite which has beenheated to 350° will reabsorb water, rapidly and completely. Onthe other hand, in the case of mesolite, reabsorption is slow andpartial. Chabazite which has been heated to redness will reabsorbabout one-fourth of the total water emitted, mesolite treatedsimilarly absorbs none a t all.A specimen of heulandite, possessingthe abnormal value of 4 7 O for the prism angle 110 : 150, has beenanalysed by A. Serra.loi His results lead to the formula(Ca,Mg,Na,K)O,Al2O3,SiO2,5H,O. Analyses of heulundite and ofstilbite have also been published by B. Mauritz.11 The p7ziZZipsiteE.Hussak, Cedr. Min., 1909, 268 ; A., ii, 492.Centr. Nin., 1909, 677 ; A . , ii, 1027.8 Zeitsch. anorg. Chcm., 1909, 63, 69 ; A., ii, 736.dtti R. Accad. Lincci, 1908, [v], 17, ii, 66 ; A . , 1908, ii, 864.l’) Bull. h’oc. f r a y . Nin., 1908, 31, 181 ; A., ii, 61.10a Atti R Accad. Lincci, 1909, [v], 18, ii, 348 ; A , , 1910, ii, 48.l1 Am. Mzcsei. Nat. Ht~ngnrici, 1908, 6, 537MINERALOGICAL CHEMISTRY. 221found in minute crystals in the basalt of Mont Simiouse, Loire,I2can be represented as RAl,Si5O,,,5H;O (R = Ca., K, Na). A detailedinvestigation of the zeolite, called poonaldit e, which occurs asso-ciated with apophyllite and stilbite near Poonah, and which hasusually been classed with scolecite, has shown that it crystallisesin the anorthic system, has the formula:(N~A1,Si30,,,2H20) + 2(CaA1,Si30,,,3H20),and is identical with mesoZite.13New Minerals.Many new minerals have been described during the past twoyears.Of those which exhibit well-defined physical and chemicalcharacters, alamosite, hillebrandite, rinneite, spurrite, andvilliaumite are among the most interesting. Of the rest, some,owing to lack of suitable material, have not as yet been determinedwith any great precision, while others owe their inclusion in ourchronicle solely to the too prevalent tendency to assign new namest o substances which are only varieties of well-known species. I nthe brief resume which follows, the species are arranged alpha-betically.A Zaite.-Hydrated vanadium oxide occurs in blood-red, mossymasses of composition V,O,,H,O in mines close to the Alai Moun-tains and South of Andijan, Siberia.l*AZamosite.-This interesting mineral is lead metasilicate,PbSiO,. It forms snow-white, radiating, fibrous, spheroidal aggre-gates, with here and there minute, colourless crystals, where singlefibres have been free to develop between the spheroids.StudyI5of six of these crystals proved the system to be monoclinic,a : b : c=1*375 : 1 : 0.924. P=84OlO’. The crystals are elongatedalong the axis of symmetry, and exhibit a good cleavage per-pendicular to this axis. The optic axes lie in the plane ofsymmetry. The crystallographic characters show analogies withthose of wollastonite. The mineral was found near Alamos,Sonora, Mexico. A crystalline substance of the same compositionhas been obtained by S.Hilpert and P. Weiller16 in their studyof the freezing-point curve of mixtures of lead oxide and silica.The artificial substance is said to crystallise in either the ortho-rhombic or monoclinic system, and its density, 6.36, is somewhatless than that of the mineral, 6.488.l2 P. Barbier, Bull. SOC. Chirn., 1908, [iv], 3, 822; A., 1908, ii, 956 j andF. Gonnard, Bull. SOC. franq. Min., 1908, 31, 269 ; A., ii, 63.l3 H. L. Bowman, E n . Alag., 1909,15, 216 ; A., ii, 677.l4 I<. A. Nenadkevitsch, Bull. Acad. Sci. St. Ptftersbozrrg, 1909, 185 ; A., ii, 411.l6 C. Palache and H. E. Merwin, Amer. J. Sci., 1909, [iv], 27, 399 ; A., ii, 676.l6 Bcr., 1909, 42, 2969 ; A., ii, 890222 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Aloisiite is a a amorphous hydrosilicate of a type very poor insilica. It occurs intimately mixed with calcium carbonate in thetufa of Fort Portal, Uganda.17 I t s composition correspondsapproximately with the formula (R’zR’’)4Si06, where R’ = Na,Hand R“=Fe, Ca, Mg.Anophorite is a variety of alkaline hornblende found in theshonkinite rock of Katzenbuckel.It exhibits pleochroism simiIarto that of the mineral termed cataphorite by Brogger, from which,however, it differs in chemical composition and in optical orientation.Analysis gave the following results 18 :SiO,. TiO,. A1,0,, Fe,Os. FeO. MnO. MgO. CaO. Na,O. K,O. H,O.49-79 5-37 1.98 7-54 9.18 0-36 11-59 3-16 7-92 1.85 1.52A rizonite.-This mineral occurs in pegmatite near Hackberry,Arizona, associated.with gadolinite, to which it is somewhat similarin outward appearance. Examination19 of a single, rough, im-perfect crystal has led to the conclusion that the system is probablymonoclinic. There is no cleavage. The density is 4.25. Themineral is dark steel-grey in colour, and opaque in the mass, butthe edges of very thin fragments transmit a deep red light(p>1*84). It is not magnetic. The mineral is completely decom-posed by hot concentrated sulphuric acid, and on analysis provedto be ferric metatitanate, Fez03,3TiOz. This compound has nothitherto been observed in Nature, but i t seems probable that aniserine described by Rammelsberg,20 and also a titanic iron sandfrom Brazil examined by J.B. Mackint.osh,21 contain it mixed withferrous titanate.Bityite.-Small, yellowish-white, hexagonal prisms, with perfectbasal cleavage, are found in pegmatite a t Maharitra, Madagascar.Optical examination shows that the crystals are pseudo-hexagonal.D = 3-05. The composition may be represented asfollows : 1 OSi0,,8A1,03,5~ (Ca,Gl, Mg )O, 14 ( Li,Na,K),0,7Hz0, but asthe water is only expelled a t a very high temperature, the formulamay be written more simply thus : 7(R’,O + RN0),4A1,0,,5Si0,,and the mineral may be regarded as a basic orthosilicate relatedto staurolite and kornerupine.22Brugnat eZZite.-Flesh-red laminz, resembling mica, and exhibit-ing good cleavage and pearly lustre, are found associated withasbestos, aragonite, magnesite, artinite, and brucite in Valp = 1*62-1*64.l7 L.Colomba, Alti 22. Accnd. Lincei, 1908, [v], 17, ii, 233 ; A . , 1908, ii, 956.W. B’reudenberg, Mitth. d. Bad. gcol. Landesanstalt, 1908, 6, 47.C. Palmer, Anzer. J. Sci., 1909, [iv], 28, 353; A., ii, 1026.2o Pogg. Ann., 1858, 104, 532.21 Amer. J. Sci., 1885, [iii], 29, 342.22 A. Lncroix, Coinp,t. r e i d . , 1908, 146, 1367; A . , 1908, ii, 705MINERALOGICAL CHEMISTRY. 223Malenco.23 The analytical results are satisfactorily represented bythe formula MgC0,,5Mg(OH),,Fe(OH)3,4H2Q.Chomitite.-The name has been given to a mineral isolated fromthe sand of some of the streams descending from the KopaonikMountains, Servia.24 It occurs as minute, shining crystals, whichhave the formula Fe,O,Cr,O,.A magnet placed a t varying dis-tances from the sand extracts from it dull crystals resemblingmagnetite in appearance, but which contain chromium in increasingproportion.DeEorenzite.-Black, orthorhombic crystals of a strongly radio-active mineral resembling polycrase in habit occur in the pegmatiteof Craveggia, Piedmont 25; a : b : c = 0.3375 : 1 : 0.3412 ; D = 4.7.The analytical results may be expressed by the formula:In composition the mineral is therefore closer to yttrocrasite thanto polycrase.HalZerite.-This name has been suggested for a mica resemblingmuscovite in appearance, found a t Mesvres, near Autun, and whichproved on analysis to be a lithium-bearing variety of soda-micawithout fluorine.26Hillebrandite. - A well-defined mineral of the formulaCa&IiQ,,€f2O has been observed a t the Terneras mine, Velardeiia,Mexico, associated with yellow garnet and wollastonite, near thejunction of altered limestone and intrusive basic diorite. It isfibrous in structure, but the optical characters suggest ortho-rhombic symmetry.The mean refractive index is about 1.61. Thebirefringence, weak to medium. The axial angle is medium, withstrong dispersion, giving rise t o abnormal blue interference tints.The mineral readily dissolves in hydrochloric acid with separationof some silica, and is slowly decomposed by water.HuZsite.-Along the margin of the granite intrusives of theextreme western part of the Seward Peninsula, intense pneumato-lytic contact metamorphism has taken place, notably in the neigh-bourhood of Brooks Mountain, and it considerable variety ofminerals has been developed.28 Among these a black, lustrous,opaque mineral is found, which somewhat resembles magnetite inappearance. It always occurs in crystals, and is associated withvesuvianite, magnetite, and brown garnet in a matrix of calcite.23 E.Artini, Atti 3. Accad. Lincci, 1909, [v], 18, i, 3 ; A . , ii, 247.24 M. Z. Jovitschitsch, nlonatsh., 1909, 30, 39 ; A . , ii, 246.25 F. Zambonini, Zeitsch. Kryst. Alin., 1908, 45, 76 ; A . , 1908, ii, 604.26 P. Barbier, Compt. rend., 1908,146, 1220 ; A., 1908, ii, 604.27 F. E. Wright, Amer. J. Sci., 1908, [iv], 26, 551 ; A., ii, 62.2* A, Knopf aud W. T. Schaller, ibid., 25, 323 ; A . , 1908, ii, 5072244 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Unfortunately the crystals do not lend themselves to exact measure-ment, but they probably belong to the orthorhombic system.There is a good prismatic cleavage, and the substance reacts stronglyfor boron.It is usually magnetic, owing to the presence ofmagnetite in intimate admixture. This association renders thedetermination of its composition difficult, but analyses of carefullyselected material lead to the formula 7(Fe,~lg)0,Fe203,H20,4B203.Juddite.-This name has been given by L. L. FermorZ9 to amanganiferous amphibole which is found associated with blanforditea t K&charw&hi, in the NBgpur district. The mineral, which hasnot as yet been fully examined, is characterised by its remarkablepleochroism.Leesbergh-This name was given by L.Blum3O to a white,chalky mineral from the Victor iron-mine in Lorraine. It wassupposed to have the formula 2MgC0,,CaCO3, but W. Bruhns hasshown that the composition is not constant, and regards it as amixture with calcite or dolomite of a mineral allied to hydro-magnesite, 3MgC03,Mg(OH),,3H20.Linosite.-The propriety of assigning this name to a variety ofhornblende found in the island of Linosa, off the coast of Tunis,has been discussed by H. S. Washington and F. E. Wright.31 I nview of the uncertainty of our knowledge as to the true chemicalcomposition and relations of the hornblendes, they prefer for thepresent to class it with kaersutite rather than to constitute it aseparate variety.Loaisite.-A mineral discovered in Marmato by Boussingaulthas been assigned this name by R.L. Codazzi32 in a description ofthe minerals of Colombia. The published analysis agrees closelywith the composition of scorodite, Fe203,As20,,4H20, of which thesubstance may possibly prove to be a variety.NatrochaZcite.-This interesting and well-defined species has acomposition 33 expressed by the formulaIt is found in the mining district of Chuquicamata, Antofagasta,Chile, where it occurs as bright emerald-green crystals of acutepyramidal habit, belonging to the monoclinic system :a : b : c = 1.423 : 1 : 1.214; /3=61°174’; D=2*33.There is a good cleavage parallel to 001.Na~S04~Cu4(0H)2(S04)2~2H~0*The optic axes lie in the29 Bet. geol.$ 2 6 ~ ~ . India, 1908, 37, 199 ; A., ii, 491.so i W t . geol. Landesanst. Elsass-Lothingen, 1908, 6 , 303 ; A., 1908, ii, 703.32 Centr. Nin., 1908, 183.33 C. Palachc and C. I-I. Warren, Arner. J. Sci., 1908, [iv], 26, 345 ; d . , 1908,Arne?.. J. Sci., 1908, [iv], 26, 210 ; A., 1908, ii, 863.ii, 1047MlNERALOGlCAL CHEMISTRY. 225plane of symmetry, and the acute bisectrix is inclined at 1 2 O tothe crystallographic axis cf in the acute angle P . The indices ofrefraction and optic axis angle for sodium light are as follows:a = 1.6491 ; f l = 1.6555 ; y = 1.7143. 2V = 36O52’. The axes arestrongly dispersed, the angle for blue being about 3O greater thanfor yellow.0stwaZdite.-It has recently been pointed out by F. Cornu 34 thatcarbon, sulphur, gold, silver, and many metallic sulphides occurin Nature as hydrogels, and he proposes to give the above nameto (‘ buttermilk silver,” which he regards as the hydrogel form ofsilver chloride.Pwigeite is a boron mineral related to ludgwigite and hulsite, and,like the latter, occurs at Brooks Mountain, Alaska.35 The coal-black, lustrous, rather soft material is seen under the microscopeto be composed of hair-like needles, but the system of crystallisat~ioncannot be determined.It resembles hulsite (see p. 223) in beingreadily soluble in hydrochloric and hydrofluoric acids, and inreacting strongly for boron. Analyses are consistent with theformula 6 (Fe,Mg) 0,Fe,03,H,0,3B203.Paratooite.-The name has been applied to certain phosphaticmaterials which probably represent the remains of a deposit ofbird-guano found a t Elder Rock, in an arid district near Paratoorailway siding in South Australia.36 Two types may be distin-guished. The first occurs in yellow, encrusting masses, and isoptically isotropic. The second consists of an aggregate of small,yellowish-brown, birefringent globules.The latter has a composi-tion approximating to that of beraunite, whilst the former isessentially a hydrated phosphate of aluminium, ferric iron, andmagnesium.1’Zancheite.-A blue copper silicate, forming botryoidal massesor fibrous veins in limestone, is found associated with dioptase a tMindouli, French Congo?’ The fibres are optically biaxial andpositive. The composition is 5H20,15Cu0,12Si0,, which may bewritten in the form H,(CUOH),CU,(S~O~)~~. The water is onlyexpelled at a red heat.PZumboniobite.-Under this name has been described a mineralresembling samarskite in composition, but containing lead.38 Itoccurs in dark brown to black, imperfectly crystalline mau Qses, asso-34 Zeitsch.Chcm. Ind. Kolloide, 1909, 4, 187 ; A., ii, 409.35 A. Knolif and W. T. Schaller, Amer. J. Sci., 1908, [iv), 25, 330 ; A . , 1908,36 D. Mawson and W. T. Cooke, Trans. Roy. SOC. South Austyalin, 1907, 81, 65 ;37 A. Lacroix, Compt. rend., 1908, 146, 722 ; A., 1908, ii, 508.38 0. Haiiser and L. Finckh, Her., 1909, 42, 20iO ; A., ii, 676.ii, 507.A., 1908, ii, 397.REP.-VOL. VI. 226 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.ciated with pitchblende, in the mica mines a t Morogoro, UluguruMountains, German East Africa.Its density is 4.801 to 4.813,and the approximate percentages of its most important constituentsare: Cb,O, 46, UO, 13.7, Y;03 14.5, PbO 7, FeO 6, and €I,O 6.It also contains small quantities of TiO,, SnO,, MnO, and CaO.Rinneit e.-The mineral occurs in crystalline, lenticular masses ofsome size, intercalated in rock salt beds, and associated with sylvine,in a mine a t Nordhausen.39 Analysis of pure material has shownthat the substance is a triple salt of the formula FeCl2,3KC1,NaC1,the whole of the iron being present in the ferrous state. A smallpart of the chlorine is replaced by bromine. The salt slowlyoxidises in air, and cannot be recrystallised from water, but froma study of the solubility data of the salt and its components, theconditions for its artificial formation have been ascertained.Thewell-marked cleavage in three directions a t 60° in the same zone,and the definite uniaxial interference figure suggest that it belongst o the hexagonal system, a conclusion verified by the examinationof measurable crystals from Hildesheim, which have been describedby 0. Schneider,40 and their isomorphism with salts of the typeK4CdC1, fully established.Risorite.-The substance described in 1907 as a new yttriumcolumbium mineral from Risor, in Norway,41 has been the subjectof further examination, and shown to be a definite species.42 Newanalyses confirm those previously given. The mineral is isotropic,exhibits considerable &radioactivity, and may be regarded as anisomorphous mixture of fergusonite wibh metatitanates.Rizopatronite.-A name used for the vanadium sulphide foundat Minasragra, Peru.43 It is to be regarded as a synonym ofpatronite, the mineral being called after Antenor Rizo-Patrona, thediscoverer of the ore (compare Ann.Beport, 1907, 302).Rosasit e.-Compact, light green, mammillated masses occursparingly a t the mines of Rosas, in Sardinia,44 associated withmalachite and aurichalcite. The composition is approximatelyrepresented by the formula 2Cu0,3CuC03,5ZnC03.Spurrite.-The interes€ of this mineral centres chiefly in itsremarkable composition, 2Ca&0,,CaC03. No crystals have beenobserved, but the optical characters, twinning, cleavage, and etchedXJ H.E. Boeke, Jahrb. &Tin., 1909, 2, 19; also Centr. Min., 1909, 72, and40 Centr. Min,, 1909, 603.41 Awn,. Report, 1907, 288.42 0. Hauscr, Zeitsch. anorg. Chem., 1908, 60, 230 ; A,, ii, 60.43 J. J. Bravo, Chcrn. Zentr., 1908, i, 1793 ; from Ocslerr. Zeitsch, Berg.44 D. Lovisato, Atti R, Accad. Lincei, 1908, [v], 1'7, ii, 723 ; A,, ii, 246,Sitzungsber. K. Akad. Wiss. Berlin, 1909, 24, 632 ; A., ii, 153 and 582.Hiittenwesen, 1908, 56, 166 ; A., 1908, ii, 703MINERALOGICAL CHEMISTRY, 227figures indicate monoclinic symmetry.45 The index of refraction Pis approximately 1.674, and the birefringence is high. The mineraleffervesces in dilute hydrochloric acid, and dissolves readily withseparation of gelatinous silica. It occurs in granular masses marthe junction of altered limestone and intrusive basic diorite in theVelardefiia district, Mexico (compare hillebrandite, p. 223).Attempts to prepare this substance synthetically have not as yetbeen successful.Sitaparite.-A dark bronze-grey mineral is found at SitapAr, inthe Chhindwiira district, India, which a t first sight closely resemblesvredenburgite (see p.ZZS), but is distinguished from it by itsfeeble magnetic properties, vredenburgite being strongly magnetic.46The composition may be expressed by the formula9Mn,0,,4Fe203,Mn02,3Ca0.S t eEZerit e.-A new zeolite of the formula CaAI,Si70,,,7H20 hasbeen found in one of the Aleutian I~lands.~7 It crystallises in theortho-rhombic system.TarameZZite.-This mineral is found in the granular limestone ofCandoglia (Val Toce).48 It occurs in radiating aggregates or inthin, irregular veins penetrating magnetite or pyrites. It exhibitsone good cleavage, is brownish-red in colour, has a high refractiveindex 0 1 - 7 4 ) , and is biaxial.It is exceedingly pleochroic. Thesystem of crystallisation is not quite certain, but is probably ortho-rhombic. The results of an analysis made on a small quantity ofmaterial agree fairly well with the formula Ba,Fe”Fe”’4Si10031,and the mineral may be regarded as a basic salt of a polymerideof met asilicic acid, B a4Fe (Fe” ’0) Fe, ( SO,)l’uwmawite.-This name has been given to a dark green mineralfound in fragments in the jadeite quarry at Tawmaw, UpperB~rrna.~g The optical characters and composition indicate thatii is a chromiferous epidote:SiO,.A120,. Cr20,. Fe20,. CaO. H20. Total.37‘92 12.83 11-16 9‘93 25.35 2.38 99.57Turanite is a copper vanadate, 5Cu0,V20,,2H20, found inspongy masses or in radio-spheroidal aggregates in mines situatenear the Alai Mountains, Siberia.50UI~Zigite.--This mineral resembles perovskite in appearance, andwas at first mistaken for it.51 It occurs in black, glistening46 F. E. Wright, Amer. J. Sei., 1908, [iv], 26, 547 ; A., ii, 62.Q6 L. L. Formor, Bec. geol. Surv. India, 1908, 37, 207; A., ii, 491.47 J. A. Morozewicz, BUZZ. Acad. Sei. Cracow, 1909, 344; A , , ii, 1028.4E E. Tncconi, Atti R. Aecad. Lincei, 1908, [v], 17, i, 810 ; A , , 1908, ii, 863.49 A. W. G. Bleeck, Bee.geol. Sum. India, 1908, 36, 254 ; A , , ii, 412.6O Ii. A. Nenadkevitsch, Bull, Acad. Sci. St. Pktersbozcrg, 1909, 185 j A., ii, 411,61 0, Hauser, Zeitsch. anorg. C‘hem,, 1909, 63, 340 ; A,, ii, 901.Q 228 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.octahedra in a nepheline rock from East Africa. Analysis showsthat it is an aluminous zirkelite, in which titanium predominatesover zirconium, the formula being Ca(Zr,Ti)O,,Al(Ti,Al)O,.Vashegyite forms compact, dull, white masses, and is found insome abundance at the iron mine of Vashegy, Hungary.52 Itsformula is 4A1,03,3P20,,30H~0. It is associated with diadochite(a sulphatophosphate of iron) and with another substance of theformula 3Al2O3(Fe2O3),2P2O,,17H2O.ViZZiaumite.-This name has been given to sodium fluorideoccurring as a primary constituent of the nepheline syenite of theIsland of Ruma, Los Islands, off the west coast of Africa.53 It isspecially characterised by its crimson colour, strong pleochroism,very low refractive index (n = 1.327), and weak birefringence.Itcrystallises in the tetragonal system, but is pseudo-cubic, with threeperfect cleavages a t right angles. It is distributed in spots throughthe rock, from which water extracts some 0.35 per cent. of solublesalts, consisting in the main of sodium fluoride. The mineralcontains traces of potassium, calcium, and possibly of zirconium.Manganese, to which it was thought the colour might be due, couldnot be detected.It hasbeen described by W. I. Vernadsky,54 who concludes from a studyof the best analyses that the beryls as a class have the compositionzGlA12Si40,2,yA, where A is GlH,SiO,, G1Si03( ?), Cs2Si03, Li,Si03,or N+SiO,.Vredelzburgite is perhaps the most interesting of several newminerals recently described by L. L.Fermor,55 from the manganesedeposits of India. It is dull steel-grey in colour, with metalliclustre. The well-marked octahedral cleavages suggest either cubicor tetragonal symmetry. A striking property is its strong magnet-ism, often polar in character, and equal to that of magnetite. Thesimplest formula is 3Mn~O4,2Fe2O3, but if the iron is present asFe304, two analyses give the formula: 2Mnz0,,3(Mn,Fe),0, and7Mn2O3,8(Mn,Fe),0, respectively.I n addition to the above new minerals, two other species, as yetunnamed, may claim our attention.The first 56 of these is aphosphate of iron, possibly derived from viviaaite, which has beenfound with trona, thenardite, and gypsum in clay about 300kilometres north-east of Lake Tchad. The composition of thisVorobyevite is a variety of beryl containing msium.52 K. ZimBnyi, Zeitsch. Kryst. Mi%, 1909, 47, 53 ; A . , ii, 900.53 A. Lacroix, Compt. reibd., 1908, 146, 213 ; A., 1908, ii, 200.b4 Bd1. h a d . Sci. St. Pdtersbourg, 1908, 975 ; A., 1908, ii, 965,65 Rec. geol. Swv. Jndia, 1908, 37, 199 ; A . , ii, 491.66 G , Garde, Compt. rend., 1909, 148, 1616 ; A . , ii, 676MINERALOGICAL CHEMISTRY. 229phosphate does not agree exactly with that of any known mineral,and is as follows:P,O,.Fe,O,. A1,0,. CaO. H,O. Resid. Total.33-30 44-20 1'50 2-28 20'47 0.75 99.5The second57 is a nickel mineral, believed to be new, from sandejected from Vesuvius during the eruption of April, 1906.Me t eo Tit es.The constituents of a number of meteorites have been analysedduring the past two years, and some work of more general interest.has also appeared. I n the firs€ place, we may notice that L. Fletcher58has shown that a compound of iron and nickel of the formulaFe,Ni, possibly exists in meteorites. He was led to this conclusionby finding that when the nickel-iron of Zomba was repeatedlyextracted with a solution of mercuric ammonium chloride, a gradualenrichment of the residue in nickel was brought about; a resultwhich may be explained by the existence of a compound Fe,Ni,,containing 38.5 per cent.of nickel. A similar substance seems t ooccur in the iron meteorites of Youndegin and Sacramento.W. Tassin59 has made the curious observation that the Alleganmeteorite contains oldhamite, CaS, apparently distributed throughits ground mass in a very finely divided state. This constituentcannot be detected with the microscope, but certain portions ofthe stone evolve hydrogen sulphide freely when treated wi'th anacid, and the powder, after removal of magnetic particles, wasfound to contain 16.66 per cent. of calcium sulphide. The sameauthor has also investigated the composition of the chromite fre-quently contained in meteorites.60 Analyses of specimens isolatedfrom various meteorites has shown that the typical chromite com-position is exceptional, but that all conform to the type RO,R,O,with variable amounts of aluminium and magnesium.The struc-ture of meteoric iron has been discussed a t some length byFraenkel and Tammann.61 They point out that a typical specimenof such an iron consists of kamacite, taenite, and a mixture ofthese known as plessite. When meteoric iron is heated without accessof air, the kamacite first changes into granular crystals, and thenthe taenite begins to disappear. This change takes place even a ttemperatures so low as 420°, but proceeds rapidly a t high tem-peratures. On comparing the magnetic properties of nickel-iron57 Casoria, Ann. R. Scuoln Super. Agrie. Portiei, 1907, 7 ; A ., ii, 155.68 Mi%. Hag., 1908, 15, 147 ; A., ii, 65."'Proc. U.S. National Museum, 1908, 34, 433 ; A., 1908, ii, 956.MI Ibid., 685.61 Zeitseh, anorg. Chem., 1008, 60, 416; A , , ii, 157230 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.alloys with those of meteoric iron, it was found that both lose theirmagnetic properties at about the same temperature, but thevariation in individual pieces of meteoric iron is too great for anyvery accurate comparison to be made. Attempts to prepare anartificial meteoric iron led to no definite result.Among individual meteorites we may notice the following.Tektit es.-Fragments of a substance called moldavite, closelyresembling green bottle glass in appearance, have been found atvarious localities in Bohemia. They possess a peculiar externalstructure, and their nature and origin have given rise to muchspeculation. The view that they are artificial ha.s been widelyheld, but in the last few years a theory propounded by F. E. Suesshas made some headway. According to Suess, moldavite and sub-stances of a somewhat similar nature found in Australia areto be regarded as meteorites of a peculiar kind, the so-calledtektites. Of late t.his question has again been hotly debated.A study of two specimens recently found at Kuttenberg has ledWeinschenk62 to declare himself an adherent of the meteorictheory. On the other hand, A. Rzehak63 believes that thesespecimens are artificial, a view in which he is supported by Suess.64The latter, however, still holds to the meteoric theory of the originof moldavite, and finds strong confirmation of its truth in theproperties of a meteorite of glassy nature recently described byE ic hs t ad t .Aimworth.-A coarse octahedrite found in the winter 1906-7near Ainsworth, in Brown County, Nebraska.66CaZon DiubZo.-Specimens consisting of a nucleus of iron sur-rounded by iron shale have been described.67 The nucleus consistsof schreibersite, cohenite, kamacite, taenite, and olivine, of whichall except the kamacite have been analysed.Cold BokkeueZd.-The fractured surface of a specimen of thismeteorite, kept since 1865 in the Indian Museum at Calcutta, hasbecome covered with a growth of crystals of alunogen.68St. Christophe-la-Chartreuse.-This stone fell in 1841, and hasrecently been the subject of detailed study by A. Lacroix.69 It isa grey chondrite, consisting chiefly of olivine and hypersthene. Italso contains considerable quantities of nickel-iron, felspar, andti2 Centr. Min., 1908, 737 ; 1909, 545.64 Ibid., 1909, 462.65 &ol. F6rm F6rh.widl, 1908. 30, h e f t 5..63 Ibid., 1909, 452.E. E. Howell a n d TV. T a s h , Amer. J. SGL, 1903, [iv], 25, 105 ; A., 1908,67 G. P. Mxrill and W. Twin, Sntit7uoninn MisceZl. Cbllectioizs, 1907, 50, 203 ;63 &I. Stuart, Rec. qcol. Xirrv. Iwlia, 1908, 37, 2, 224.ii, 204.A., ii, 591.Bull. SOC. Sci. N d . dc ~’OLCCS~, Fransc, 1906, [ii], 6, 81 ; d., ii, 248MINERALOGICAL CHEMISTRY. 231troilite, and smaller amounts of diopside and chromite. A mono-clinic pyroxene similar to rhombic pyroxene in composition is alsopresent. This substance, which is referred to as clinohypersthene,appears to have crystallised out from the fused rhombic pyroxene,and is identical with the magnesia-pyroxene prepared artificially.8ckufstadt.-This stone was supposed by C. Klein to be theunique representative of a group of meteorites containing leucite ;there seems, however, to be good reason for believing that it ismerely a piece of leucite-basanite lava from V e s u v i u ~ . ~ ~T~’iZZiu~natozun.-This meteorite is a typical octahedrite of mediumcoarseness.71 Ilamacite, taenite, and plessite are present, withhere and there nodules of troilite, some of which enclose car-bonaceous matter, and are usually bounded by a thin line ofschreibersite.I n conclusion, attention must be called to the recent issue of a,second Appendix to the sixth edition of Dana’s System ofMineralogy,” making this invaluable work complete up to thebeginning of the year 1909.A. HUTCHINSON.70 M. Belowsky, Cmtr. Afin., 1909, 289 ; A., ii, 592.71 E. E. Howell and W. Tassin, Amer. J. Sci., 1908, [iv], 25, 49 ; A., 1908,ii, 20

ISSN:0365-6217    

DOI:10.1039/AR9090600201

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

RA .DIOACTIVITY .Ia-Rays.IN previous Reports the evidence has been given for the conclusionthat the a-radiation from radioactive substances is due to theexpulsion of positively charged particles of atomic dimensions witha velocity of the order of about one-fifteenth that of light. Theinitial velocity of expulsion is the same for all the a-particles of anyone type of radioactive matter, but differs, within somewhat narrowlimits, for the different types. The mass, however, is identical inall cases, and is 2n times that of hydrogen, where n is the numberof atomic charges carried by the a-particle, which may be comparedwith the valency of an ion in electrolysis. Methods have nowbeen developed which have enabled the number of a-particlesexpelled from a radioactive substance to be directly counted, andthese have established that n=2.The atomic weight, therefore, ofthe a-particle is 4. Other evidence has proved directly the identityof the a-particle with the helium atom, a result long indirectlyforeshadowed. The theory of probability applied to radioactivechanges leads to the conclusion that, when the numbers of atomsdifhtegrating in unit time is few, variations from the averagenumber may be anticipated, inversely proportional in magnitude tothe square root of that number. Such rapid variations in theintensity of a-radiation, and therefore of the ionisation, from aconstant source, in part observed unwittingly,3 in part sought fordeliberately make themselves apparent, especially when theionisation currents of two separate similar preparations are balancedagainst each other. Complete balance is never so attained, theindicating instrument showing perpetual excursions on either sideof the zero position.This phenomenon has now been thoroughly~ t u d i e d , ~ and found to be due to real variations in the rate of1 This report corers the years 1908 and 1909.E. von Schweidler, Beibl. Ann. Physik., 1907, 31, 356.H. L. Bronson, PhiZ. Mag., 1906, [vi], 11, 143.I<. W. F. Kohlrausch, Sitxungsber. K. Akad. Wiss. Wien, 1906, 115, (iia), 673.E. Meyer and E. Regener, Ann. Physik, 1903, [iv], 25, 757 ; H, Geiger, Phil.Mag., 1908, [vi], 15, 539RADIOACTIVITY. 233expulsion of a-particles, which have been shown, although the resulthas been subject to some criticism,6 to follow the law deduced fromthe theory of probability.Two independent methods have been now developed which aresufficiently sensitive to enable the effect; of a single a-particle to berecorded.The first 7 makes use of the scintillations produced inzinc sulphide, the discontinuity of which in the spinthariscope haslong been known. A definite small portion of the zinc sulphidescreen, faintly illuminated to assist in focussing, is viewed through amicroscope of suitable aperture and magnification, so that thepicture appears in not less than its natural brightness. Underthese conditions, for which the original paper may be profitablyconsulted, the number of scintillations in the field of vision canreadily be counted, when the intensity of the source is such thatthey do not exceed more than one every few seconds. I n the secondmethod,8 which is less simple, but offers more guarantee that allthe a-particles expelled are counted, the ionisation in the gasproduced by the a-particle is magnified by the application of apotential at the electrodes so great that the gas is near the breaking-down point a t which a disruptive discharge would pass.I n thesecircumstances the ions produced themselves become ionising agencies-the negative ions more readily than the positive-by virtue ofthe kinetic energy acquired under the field, and produce freshions in their path by collisions. The field is adjusted so that onlythe negative ions so ionise, and the magnification of the effect isthen large but not infinite, the energy of the a-particles, as it were,merely pulling the trigger whereby a much larger quantity of theenergy of the electric field is released.Fields of the order of 1000volts per cm., and a gas pressure of about 5 cm., were employed.The a-rays from a powerful source traverse an exhausted tubeseveral metres in length, and pass through a minute aperturealong the axis of the detecting chamber, which consists of a narrowcylinder, connected to the high voltage battery, carrying a, centralelectrode connected with the electrometer. The arrival of eacha-particle causes the electrometer needle to move with a suddenjerk, after which, by means of a suitable “ air resistance,” itautomatically returns again to zero.The number of jerks-usuallyadjusted to one every few seconds-gives the number of a-particlesentering the detecting chamber. From geometrical considerations,the total number expelled from the source can thus be deduced.N. Campbell, PTOC. Carnb. Phil. Soc., 1909, 15, 117.7 E. Regener, Bcr. Deut. physikal. Ges., 1908, 78.8 E. Rutherford and H. Geiger, Proc. Roy. Soe., 1908, 81, A, 141 ; A . , 1908,ii, 555234 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.In this way, it was found that 3.4 x 1010 a-particles are expelled persecond froin the radium-C in equilibrium with 1 gram of radium.This fundamental constant will be termed Q. Each of the firstfour a-ray changes of radium give the same number of a-particle~.~Hence this number holds equally for radium itself, the emanation,and radium-A, the total number per second from 1 gram of radiumin equilibrium 10 being therefore 1.36 x 1010 per second.Takingthe limit of detection of minute quantities of radium by theemanation test as 10-12 gram,11 it follows that this correspondswith the expulsion of only one a-particle every 100 seconds, and,indeed, the von Schweidler variation is easily detectable by theirregular motion of the gold-leaf in such measurements.A comparison of the results of the electric and scintillationmethods showed that both gave the same result, so that undersuitable conditions each a-particle produces a scintillation. Thisbeing the case, it is probable that the scintillation method, onaccount of its simplicity, will be widely employed, and will supplantthe electric method almost completely.The electric and fluorescence methods have, since the aboveaccount was written, been supplemented by a third, depending onthe photographic action of the a-rays.It has been shown that eachhalide grain in the film struck by an a-particle is rendered capableof development, and the method appears to consist in countingthe number of opaque grains in the film by means of a microscope.It is claimed that it is applicable to very weak sources by the useof very long exposures, and to a-particles of very short range.12From the total positive charge carried by the a-particles froma known mass of radium, the individual charge on each a-particlewas deduced to be 9 .3 ~ 10-1O E.S.U.13 This is between two andthree times the previously accepted value of the single atomiccharge, 3.4 x 10-lo, but there is now good reason for believing thatthe older determinations, by the well-known cloud method, gavetoo low a value, and that 4.65 x 10-10, or one-half of the charge onthe a-particle, is nearer the truth. More recent determinations by thecloud method 1* have given 4.65, whilst the study of the Brownianmovement in liquids15 has given 4.1. By the aid of the ultra,microscope, the same constant has also been determined for theAnn. Report, 1905, 296.lo Compare ibid., 295 (line 8 from bottom).l2 S. Kinoshita, Royal SOC. Meeting, 9/12/09 (abstract only available).l3 2. Rutherford and H. Geiger, Proc. Roy. Soc., 1908, 81, A, 162 ; A,, 1908,ii, 794.l4 Millikan and Begeman, Physical Aev., 1908, 197 ; R.A. Millikan, Phil. Mag.,,1910, [vi], 19, 209.F. Soddy, Phil. Mag., 1909, [vi], 18, 851 ; A . , 1910, ii, 10.l5 J. Purrin, An7~ Chim. Phys., 1909, [yiii], 18, 1RADIOACTIVITY. 235charged fine dust produced in a gas by the arc between metallicelectrodes,l6 and found to be 4.6. From Planck’s theory ofradiation, the value 4.69 has been found. There is thus a con-siderable body of evidence that the a-particle carries two atomiccharges, and the value of its atomic mass is therefore 4. Dividing thefarad by the new value of the atomic charge leads to the resultthat there are 6-22 x 1023 atoms in one gram of hydrogen. The periodof average life of radium, since the atomic weight is known, can bededuced from the number of atoms in one gram and the number ofa-particles expelled per second, on the assumption that only onea-particle is expelled per atom disintegrating.The value so found(2560 years) agrees so well with the best determinations that it maynow be considered definitely proved that only one a-particle is soexpelled. The theoretical volume of emanation in equilibrium withone gram of radium, on the assumption that one molecule of mon-atomic emanation results from one atom of radium disintegrating, is0.585 cu. mm. at N.T.P., whereas the theoretical rate of productionof helium, four atoms of helium resulting from each atom of radiumdisintegrating, is 158 cu. mm. per year. The theoretical heatingeffect of the a-particles from one gram of radium is 113 gram cal. perhour.These fundamental quantities, calculated from the value of&, are all so completely borne out by experiment, that no doubtremains of the essential accuracy of the underlying assumptions.The identity of the a-particle with helium has also been provedin the most complete manner.18 The emanation from 140 milligramsof radium was stored in exceedingly thin-walled glass tubes sur-rounded by an outer exhausted jacket. The tubes were proved tobe perfectly gas-tight and impervious to the passage of ordinarygaseous helium, but their thickness was less than the range of thea-particle in glass, so that practically all the a-particles expelledfrom the enclosed emanation penetrated, with diminished velocity,the glass walls of the tube.The presence of helium in the outersurrounding jacket was tested for by filling it with mercury andcompressing its contents into a tiny spectrum tube. I n this waythe passage of helium in the form of a-particles through the gas-tight glass tube was decisively shown. As is to be expected, thea-particles, owing to their velocity of projection, bury themselves toa slight depth in the wall of the outer jacket, and an appreciabletime is taken for the helium to diffuse out. By wrapping lead foilround similar thin tubes, filled with emanation, and not surroundedby a jacket but left exposed to the air, and subsequently melting thel6 F. Ehrenhaft, Physikal, Zeitaeh., 1909, 10, 308.l7 Compare also M.Moulin, Le Radium, 1909, 6, 164.l8 E. Rutherford a d T. Boyds, PhiL Mag., 1909, [vi], 17, 281 ; A., ii, 203236 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.lead in a charcoal vacuum, it was proved that the lead retainssome of the helium it receives during its bombardment witha-particles. The same lead not so treated gave no helium whenmelted. This removes the last possible objection that the heliumwas in the glass all the time and merely liberated by the action ofthe a-particles.I n view of the simplicity and directness of the radium series ofchanges, each successive a-ray disintegration giving one atom ofhelium from each atom undergoing disintegration, it might be con-cluded that other a-ray changes would be similar. It is, however,in the highest degree significant that this does not appear to bethe case.The relative ionisation given by the emanation and theactive deposit of thorium and actinium respectively l9 is in eachcase such as would result if twice as many a-particles were givenoff in the change of the emanation as in the change of the activedeposit. As there is conclusive indirect evidencez0 that in thechange of the thorium active deposit two a-particles of differentrange are emitted, probably in consecutive changes so rapid thatthey still defy analysis, i t appears that four a-particles at leastmust result from one atom of thorium emanation on disintegration.So far, the a-rays of the active deposit of actinium have beenconsidered homogeneous, and due to actinium-23, but anomalies inthe a-ray range curves have now been observed 21 for this case also,and a similar explanation to that for the thorium active deposithas been suggested.Here, however, the difference in the rangescan only amount to a few millimetres of air, and the matter is notso definite. I f the explanation is correct, the actinium emanationmust also give a t least four a-particles. The case of uranium, whichappears to give two a-particles, will be again referred to. Thenumber of ions (presumably pairs of ions are referred to) producedby the a-particle of radium-C during its whole range in air hasbeen redetermined 22 on the new data to be 2-37 x lo5. The specificionisation a t each point of the range has been determined.A t theend of the range this diminishes very rapidly, but still not abso-lutely abruptly. The data obtained allows the number in the caseof any other a-particle of different range to be calculated. Theestimation of small quantities of radium by means of the saturationionisation current in air a t low pressure, using a small part onlyD f the range of the a-particles, is suggested.The scattering of the a-particles in passage through air andl9 H. L. Bronson, Phil. Mag., 1908, [vi], 16, 291; A., 1908, ii, 792.21 Mlle. L. Blanquies, Compt. rend., 1909, 148, 1753 ; Le Radium, .1909, 6, 230 ;22 H. Geiger, Proc. Roy. Soe., 1909, 82, A, 358.Ann,. Report, 1906, 342.d., ii, 634RADIOACTIVITY. 237metals 23 has been reexamined by the scintillation meth0d.~4 I n agood vacuum there is no scattering, but a single gold leaf issufficient to cause notable scattering of the beam.It has also beenestablished25 that a diffuse reflection of a-rays occurs from theincident surface of a metal struck by a-rays, which is the greaterthe greater the atomic weight of the metal. Gold returns abouttwenty times as many a-particles as aluminium. I n one experizpentwith platinum, about 1 in 8000 of the a-particles was reflected.The effect attains a maximum very quickly when the thickness ofthe reflector is increased, about half the maximum being attainedby a thickness equivalent to only 2 mm. of air. Further searchfor any indication of the a-particle after it has passed its criticaldistance a t which ionisation ceases26 has resulted in failure. Ithas been shown that the positive charge transported by the particlesand the secondary emission of electrons produced on impact cannotbe detected beyond the critical distance.27 It appears certain thatthe a-particle is quite suddenly stopped at the end of its detectablepath, and becomes an ordinary atom of helium, but its kineticenergy a t this point is still considerable, and may possibly furnisha source necessary for any process of atomic synthesis.28It is known that the heavier metals absorb the a-rays morestrongly at the end of their path than initially.29 The “ a i requivalent ” of the metal, or thickness of air equivalent to it giventhickness of metal, increases as the range increases.Paper andsimilar substances have air equivalents independent of the range,but in hydrogen the “ hydrogen equivalent ” increases for thesesubstances as with the metals.The effects are cases of a generallaw that if the stopping power of any substance is taken as thestandard, the relative stopping powers of substances of greateratomic weight than the standard increase as the range of thea-particle increases, while for substances of less atomic weight thanthe standard the converse is true.30The phenomenon of “ initial recombination ” 31 shown exclusivelyby the ionisation produced by a-rays has received an elegantAnn. Beport, 1906, 335.24 H. Geiger, Proc. Roy. SQC., 1908, 81, A, 174 ; A!., 1908, ii, 795.zj H. Geiger and E. Marsden, Proc. Roy. SOC., 1909, 82, A , 495 ; A ., ii, 782.2(i Ann. Report, 1906, 335,E. Aschkinass, Ann. Physik, 19OS, [iv], 27, 377 ; A . , 1908, ii, 920 ;W. Duane, Amer. J. Sci., 1908, [iv], 26, 464 ; Con@. rend., 1908, 146, 958 and1089 ; A . , 1908, ii, 553, 554.28 Compare W. H. Bragg, Presidential Address : AzcstrnZian ASSOC., 1909.29 Ann. Report, 1907, 312.30 T. S. Taylor, Amer. J. Sci., 1908, [iv], 26, 169 ; A., 1908, ii, 7 8 3 ; Phil.in Ann. Report, 1906, 338.Mag., 1909, [vi], 18, 604 : A . , ii, 850 ; Physical Rev., 1909, 28. 4652.38 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRI’.explanation. The a-particle leaves behind in its flight a longcolumn of ions of cross section corresponding with that of thea-particle. Thus, in air a t atmospheric pressure, the passage ofan a-particle will leave about l o 5 pairs of ions crowded into 3 cm.length of one of t-hese narrow columns.The real concentration ofthe ions in these columns is far greater than the average concentra-tion for the whole gas, and recombination is favoured. Even avery intense electric field acting normally to the trajectories of therays cannot completely prevent recombination, whereas it has beenfound that if the field acts at right angles to the trajectories thesaturation current is far more readily and completely 0btained.3~This seems to render unnecessary the earlier view that the ionsgenerated from one atom were caught and prevented from escapingby other atoms in the same molecule.P-Rays.As is well known, the ratio elm of the charge to the mass of thej3-particle diminishes rapidly as the velocity (9) of the particleapproaches that of light, and this has been generally explained bythe increase in the (purely electromagnetic) mass of the electronat high velocity.The variation of e / n z with v for the B-particlesof radium has been redeterminedB with great accuracy, and thevarious mathematical equations which have been proposed ontheoretical grounds t o express the law of variation have been thussubjected to experimental test. A grain of pure radium fluoridewas placed in the centre of two parallel circular plates, 0.25 mm.apart, electrically charged to opposite sign. A photographic filmon the inside of a cylinder coaxial with the plates and of twicetheir diameter received the trace of the deflected rays.A magneticfield acted in the direction parallel to one diameter of the plates.Thus it was ensured that only those rays escaped and reachedthe film for which the electrostatic deviation inside the platesexactly balanced the electromagnetic deviation. After the rays hadescaped from the parallel plates, the magnetic force alone operated.I f a is the angle between the direction of the rays and that ofthe magnetic field, and H and F are the strengths of the magneticand electric fields respectively,, 17= - or, in words, each pointon the photbgraphic trace corresponds with rays of a definite knownvelocity, fixed by the conditions of the experiment. The deviationof the trace at each point from the plane of the parallel plates32 M.Moulin, Compt. rend., 1909, 148, 1757; Le &dium, 1908, 5, 136;A., 1908, ii, 921.33 A. H. Buchcrer, Php8lsikaL Zeitsch., 1008, 9, 755.H sin aThe theory is ascribed to M. LangeviRADIOACTIVITY. 239thus gives the magnetic deflection of homogeneous rays of knownvelocity, and so the variation of e./m with velocity is determined.As a result, it was established that e/mo=1.705 x 107, where morepresents the mass a t low speeds, and e/m=e/m,(l -P2)%, where Pis the ratio of the velocity of the particle to that of light. Thisis the Lorentz theoretical equation, and its experimental proofappears also t o have important metaphysical consequences inestablishing the Lorentz-Einstein principle of relativity.Measurements 34 of the amount.of negative electricity transportedin a high vacuum from the bare active deposit of radium have ledto the ccnclusion that as many electrons are emitted in the changeof radium-@ as in that of radium-C, and that for each a-particlefrom the latter there must be at least 20 and probably 50 electronsemitted. The electric and magnetic deflection of these electronsshows, however, that most of them move with the relatively feeblevelocity of less than 4 x 108 cm. per second. They would thuspossess very little penetrating power, and must be due to rays ofhhe 6 type, rather than to true penetrating P-rays. Over thedistance of 0.5 mm. in air from the bare surface, however, theyproduce intense ionisation, comparable with that produced by thea-particles of radium-C.This perhaps explains the probablyerroneous statement that radium-B emits a-particles.35With reference to the true &particles emitted by radium-C, otherexperiments 36 have indicated that probably only one, or possiblytwo P-particles are emitted for each a-particle. The negative chargecommunicated in a high vacuum to an insulated brass cylinder,connected to an electzometer, from a glass tube, of wall thickness0.078 mm., containing radium emanation, placed inside thecylinder, corresponded with 3.7 x 1O1O B-particles per second (referredto 1 gram of radium), assuming the charge on each particle to be4 . 6 ' 7 ~ 10-lo E.S.U. Corrections for a small proportion of the@-particles of radium-C absorbed in the glass, and also for a smallproportion of those from radium-B able to get through, gave thenumber 5.0 x 101O (for radium-C alone).This correction involves,however, the unproved assumption that the total number of&particles expelled from radium-B is equal to that from radium-C,and is therefore preliminary.34 W. Duane, Le Eadium, 1908, 5, 71 ; Asner. J. Sci., 1908, [iv], 26, 1 ;A,, 1908, ii, 748 ; E. Aschkinass, Ann. Xeport, 1907, 315 ; Ann. Physik, 1908,[iv], 27, 377 ; A., 1908, ii, 920.35 Ann. Beport, 1906, 346 and 34T ; F. A. Harvey. PhysikaZ. Zeitsch., 1909, 10,46 ; A., ii, 203 (also Physical XGV., 1909) ; H. L. Eronson, Ph2/sikaZ. Zeitsch., 1909,10, 393 ; A,, ii, 634.W. Makower, Phil. illng., 1909, [vi], 17, 171 ; A., ii, 204 ; Brit.Ass, Xep.,1908, 601240 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.A fundamentally important consequence of the same experimentsis the proof that the number of &particles penetrating successivethicknesses of matter is reduced according to the same exponentiallaw as when the absorption is determined in the usual way bymeasuring the ionisation the emergent particles can produce. Thewhole question of the nature of the P-rays, whether homogeneousor heterogeneous as regards velocity, and the exact meaning to beattached to their “ absorption ” in passage through matter,37 is, inspite of numerous researches, still in a highly controversial state, andwould scarcely repay very detailed discussion at the present stage.I n the first place, it has been established38 that in passagethrough matter far more of the P-rays are scattered out of theiroriginal direction than are completely stopped, and relatively verythin screens-0.01 cm.of aluminium, or 0.002 cm. of gold-com-pletely scatter a pencil of &rays in all directions. Scattering alonecan be represented by an exponential equation with a numerical“ coefficient of scattering,” which is for all substances about thirteentimes greater than the true coefficient of absorption. This easyscattering is one of the many difficulties which make any exacttheory of the nature of the absorption of P-rays difficult to establish.I n the second place, it appears that the so-called absorption-coefficient is very much influenced by relatively small differences invelocit,y.Thus, comparing the ,&radiations of uranium-X andradium-E2, the absorption-coefficients in aluminium are respectively14 and 40 (cm.)-I, whereas the velocities are, according to newdeterminations,39 2.76 x 1O1O and 2.31 x 1010 cm. per second. Recentwork to be considered has shown that if single @-ray products aredealt with, the absorption tends to be in almost all cases purelyexponential, and since it is known that the number of &particlesis exponentially diminished, it follows that the velocity of theemergent particles is not altered by their passage through matter,for a diminution in velocity far too small to be directly detectedby magnetic deflection methods would have a large influence inincreasing the absorption-coefficient.Revolutionary conclusions, itis true, as to the heterogeneity of 6-rays and their linear ratherthan exponential absorption by matter have been recently putforward, but it remains very open to question whether the methodsemployed were refined enough to bear such an interpretation.4037 For a fnll discussion of the alternative possibilities at issue, see Ann. Xcport,1907, 315.38 J. A. Crowther, Proe. Boy. XOC., 1908, 80, A, 186 ; A., 1908, ii, 247 ; ProC.Cnmb. Phit. SOC,, 1909, 15, 273 ; J. P. V. Madsen, Phil. May., 1909 [vi], 18,909 ; A, 1910, ii, 7.40 W. Wilson, Proc. Roy. SOC., 1909, 82, A, 612 ; 0. Hahn and L. Meitner,Phpsiknt. Zeitsch., 1909, 10, 948; A., 1910, ii, 8 ; W. Wilson, ibid., 1910, 11, 101.39 H. W. Sahmidt, Physiknl.Zeitsch., 1908, 9, 6RADIOACTIVITY. 24 1A working theory has been put forward, which, although almostcertainly not rigidly true, has proved extraordinarily fruitful of newdiscoveries, according to which only one type of &radiation is givenout in each disintegration, and this radiation is strictly homogeneousas regards velocity and is absorbed by matter according to a purelyexponential law. Departures of the 8-ray absorption curves fromthis law indicate complexity of the B-rays, due to their beingderived from more than one disintegration product.41 I n order toavoid, as far as possible, complications due to " secondary " brays,aluminium is used as the absorbing material in taking the absorp-tion curves, and the diameter of the electroscope is large comparedwith that of the pencil of rays to include also scattered radiation.I n these circumstances, according to this theory, if the absorptioncurve of the /3-rays is not exponential, a complex disintegration ofmore than one &ray product is indicated, and in many cases wherenew B-ray products have been indicated in this way, they havesubsequently been found to exist, and have been separated by newmethods.It may be remarked in passing, however, that such atrue exponential absorption applies a t best only over a limitedrange. Thus, the penetrating P-radiation of uranium-X, from thefirst regarded as an example of homogeneous B-radiation, and forwhich even now no evidence of complexity has been advanced, isnot exponentially absorbed by a.luminium in any circumstances,the absorption-coefficient increasing continually and regularly tonearly three times the initial value before the rays are allabsorbed.42 The advocates of the theory seem disposed to regardall such phenomena as due to unsuitable conditions of measure-ment, but it is to be noted that they have never yet shown a trueexponential absorption curve except over a short range.It seemsas though the B-particle probably does suffer some reduction invelocity in passage through matter, accounting for this change ofthe absorption-coefficient, although this diminution may well be toosmall to be detected directly by magnetic measurements.43It has also been found impossible completely to deviate theP-rays of either uranium or radium by magnetic fields several timesas strong as is sufficient to deviate the great majority of the rays,and a very small proportion of the &rays in each case seem topossess velocities very nearly indeed approaching that of lightitself.44 Nevertheless, if has been established for a great numberof single &ray products that pure exponential absorption of the41 0.Hahn and L. Meitner, Physikal. Zeitsch., 19OS, 9, 321 ; A . , 1908, ii, 452.42 .M. Levin, ibib., 1907, 8, 585 ; A,, 1907, ii, 836.u H. W. Schmidt, ibid., 1909, 10, 929 ; A . , 1910, ii, 7.44 F. Soddy, Phi?. May., 1909, [vij, 18, 858 ; A., 1910, ii, 10.REP,-VOL. V1. 242 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Thorium-D ............ 0 '4410'434 Uranium-x { o.012Radium.................. 0.022............Radium-& ............ 0'162Radioactinurn ......... 0 -04Actinium-A less than 0 -04Actinium-C.. ............ 0.24y-Rays.A great impetus has been given to the study of the y-rays fromthe physical standpoint by the tlieory46 that they also, like theP-rays, consist in the emission of discrete particles, rather than ofpulses or waves of electromagnetic character similar to light. Thetheory, which is known as the neutral-pair theory, in that thediscrete y-particle is supposed to consist of an electrically neutralcouplet composed of one negative and one, still itself unknown,positive electron, has hardly been seriously opposed so far as they-rays themselves are concerned.It is its further extension to the45 0. Hahn and L. Meitner, PhysiknZ. Zeitsch., 1908, 9, 321, 649 and 697;A., 1908, ii, 452, 920, 1007 ; 1909, 10, 697 and 741 ; A., ii, 849, 954 ; 0. Hnhn,ibid., 1908, 9, 2 4 6 ; A . , 1908, ii, 484.48 Ann, Beport, 1907, 3211tADIOACTIVITY. 243X-rays, and ultimately possibly even to light itself, that has arousedopposition, and it is not difficult to foresee that the growth of thetheory threatens to reopen fundamentzl questions of the natureof electromagnetic radiations in general and to modify the oldundulatory theory, so as to bring it more into harmony with themodern views as to the discrete nature of the electric charge. Afull consideration of the general question would be manifestlyimpossible here.The y-rays only can be considered, although, asalready remarked, this is to confine the evidence mainly t o the sidein favour of the newer theory. It is recognised that the y-rays,directly, produce little, if any, detectable action. Their ionisationand other effects have been traced, a t least mainly, to the secondaryP-rays, into which they are in part transformed in passage throughmatter. On the new view a certain proportion of the neutral pairsis broken up on impact with atoms, the negative partner beingliberated as a detectable &particle. The main evidence in favourof the theory is that the y-ray possesses momentum in the directionof its propagation. The secondary P-particles they generate move a tfirst mainly in the direction of the original beam, whereas onthe older pulse theory no such asymmetry is to be anticipated.Theconsequence is that there exists great disproportionslity in theamount of secondary &radiation from the incident and emergentfaces of a plate traversed normally by a pencil of y-radiation. Itis easy to tell from this, without otherwise knowing, in whichdirection the y-ray is moving, whilst on the older pulse theory thiswould be impossible.47 A tendency €rom this point of view is toregard the P- and y-radiation as mutually convertible in theirpassage through matter. The production of secondary y-rays fromP-rays has, however, not hitherto been observed,4* although theexistence of a feeble secondary y-radiation produced by y-rays hasnow been well established.49 The interdependence of the primaryP- and y-radiation is questioned also on account of the great relativepoverty in y-rays, as compared t o P-rays, shown by uranium ascontrasted with radium.50 Experiments on intensely active pre-parations of uranium-X, prepared from large quantities of uranium,have shown that the y-rays possess, contrary to prior statements,only sIightly less penetrating power than those from radium,61 but47 W.H. Bragg and J. P. V. Madsen, Phil. Mag., 1908, [vi], 15, 663 ; A., 1908,ii, 556 ; 16, 918 ; A., ii, 112.48 H. Stnrke, Ber. Dcut. physikal. Ges., 1908, 10, 267; A., 1908, ii, 341.49 R. D. Kleeman, Phil Mag., 1908, [vi], 15, 639 ; A., 1908, ii, 553 ; A. S. Eve,ibid., 16, 224 ; A., 1908, ii, 795 ; ibid., 1909, 18, 275 ; A ., ii, 7 8 3 ; J. P. V.Madsen, ibid., 17, 423 ; A., ii, 365.50 F. Soddy and A. S. Russell, Phil. Mag., 1909, [vi], 18, 620 ; A., ii, 851.Compare Ann. Beport, 1906, 352.R 244 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.in proportion to the @-radiation they are over sixty times lesspowerful. The y-rays are shown, with suitable methods of measure-ments, to be exponentially absorbed by matter (after a certaininitial thickness), the absorption-coefficient having been redeter-mined for both radium and uranium y-rays for a number ofsubstances and shown to be nearly proportional to the density.Certain fruitful sources of confusion in previous measurements withregard to the numerical value of these coefficients have been clearedU P .A second and perhaps more essential modification brought aboutby the new theory concerns the source of energy of the secondaryj3- or cathode-radiation produced by y-rays and X-rays respectively,in that it is ascribed to the energy of the primary beam, ratherthan to the internal energy of the atoms subjected to the radiation.The effects dealt with are in general complicated, more than onetype of secondary radiation being produced.I n the first place,the velocity of a part of the secondary &rays produced by y-raysappears to approximate to the velocity of the primaryThis is in favour of the view that the p- and y-rays are mutuallyconvertible. I n the second place, there is a tendency to explainthe variations of secondary radiation with the atomic weight ofthe radiator,53 without recourse to the view that any specificsecondary radiation is emitted by the atoms of the radiator.54An earlier view, that the primary radiation acted as the triggerto release a certain internal store of energy from the atom in theform of secondary P-radiation, travelling with a velocity dependenton the nature of the atom rather than on that of the primarybeam, is on its trial.It appears rather as if the character of theprimary beam, and not at all that. of the atom, decided the natureof the secondary radiation.Thermo-Radioactivity .The heat evolution of more than 1 gram of radium chloride,containing 0.7951 gram of radium (element) as determined byatomic weight estimations, has been redetermined.The conditionswere somewhat indefinite as regards the proportion of the energyof the penetrating radiations converted into heat, the rays having topenetrate 1 mm. of glass and 5 mm. of copper before escaping fromthe calorimeter, so that all the P-radiation and a small part of they-radiation would be absorbed. The result was that 1 gram of52 K. Ij. Kleeman, Proc. Roy, Xoc., 1909, 82, A, 128 ; A , , ii, 364.53 Anw. Report, 1906, 350 ; 1907, 318.64 W. H. Bragg and J. Y. V. Madsen, Phil. Nag., 1908, [vi], 16, 602; A., 1908,ii, 921 ; J. P. V. Madsen, zbzd., 1909, 18, 909; A, 1910, ii, 7RADIOACTIVITY. 243radium (element), in equilibrium with its products as far asradium-C, generates 118.0 gram-calories per hour. The uncertaintyattaching to the amount of the products radium-I) to radium-P inthe preparation was not greater than 1 / 2 per cent.55A real advance in the measurement of minute evolutions of heatfrom radioactive preparations appears to have been made in theconstruction of a calorimeter capable of measuring the evolution of0.001 gram-calorie per hour.56 The apparatus consisted of twosimilar exhausted vessels, half full of ether, connected from belowthe ether-level by a capillary gauge containing a gas bubble, themotion of which was observed. The evolution of heat is recorded bythe rise in the vapour pressure of the ether surrounding the pre-paration.The whole was elaborately insulated from externalthermal influences, and the preparation to be tested was placedinside one of the vessels, together with a Peltier couple of iron-nickel, which was cooled by the passage of a current to neutraliseexactly the heat evolved from the radioactive preparation.A pre-liminary determination with 0.8 milligram of radium chl >ride gave120 calories per gram of radium per hour. A radio-thcriuin pre-paration gave 0.025 cal. per hour, which was of the same order asthat from radium of similar activity. A polonium preparation gave0.0117 cal. per hour. I n the latter case, it was calculated that a,quantity of radium giving the same ionisation current as thepolonium would have given 0.011, so the result is favourable to theview that the heat disengaged is almost entirely due t o the kineticenergy of the a-particles expelled.A determination of the heat generated by thorium oxide hasgiven as the result that 1 gram, in equilibrium with its productsof disintegration, gives 2.1 x 10-5 calories per hour, which is3.2 x 106 times less than that given by radium in equilibrium.57Experiments have also been made on pitchblende, but final resultsare not yet to hand.58 The earlier observation that the absorp-tion of X-rays in lead produces more heat than in zinc has now beendefinitely shown to be erroneous.59.55 E.v. Schweidler and V. F. Hess, Sitzzmgsbzr. K. Akad. Wiss. Wien, 1908,117,(iia), 879.5(i W. Duane, Compt. rend., 1909, 148, 1448 and 1665 ; A , , ii, 534, 637.57 G. B. Pegram and N. W. Webb, Physical Rev., 1908, 27,18.58 Compare J. Joly, Radioactivity and Geology, p.11 ; H. H. Poole, Phil. Mag.,The result is considerably higher than is t o be anticipated69 Ann. Report, 1906, 351 ; H. A. Burnstead, Phil, Mag., 1908, [vi], 15, 432 ;1910, [vi], 19, 314.from the simple disintegration theory.A., 1908, ii, 342246 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Recoil of Disint egration Products.When an atom of mass of the order of 200 expels an a-particleof mass 4 with a velocity of the order of 2 x lo9 cm. per second, itfollows, if the expulsion obeys ordinary mechanical laws, that theproduct of the disintegrat.ion must recoil with a velocity of theorder of 4 x 107 cm. per second in the direction opposite to thatof the expelled a-particle. Conclusive evidence of this recoil hasnow been obtained, and the phenomenon, in addition, has beenthe means of adding an extremely valuable new method for theseparation of radioactive products, too difficult to be effected byordinary chemical and physical processes.In the last Report,attention was directed to the feeble residual activity left after theactive deposit of actinium produced by the actinium emanationcompletely decays, which was described as one of the most interest-ing radioactive phenomena of the time.60With very active preparations of radio-actinium this activityhas been further studied, and it has been shown to be due toactinium-X, which is the parent rather than the product of theactive deposit. Now actinium-X is not volatile even at a red-heat.The residual activity is completely prevented when the actiniumpreparation is wrapped in tissue paper, which allows the emanationto go through, and the ordinary active deposit of actinium to beformed without hindrance. Actinium-X, free from its parent radio-actinium, does not show the residual activity, although, of course,it generates emanation, and produces the ordinary active deposit.The explanation is that it is only produced by nascent actinium-X,which recoils from the actinium preparation at the molllent of itsformation from radio-actinium by the expulsion of the a- andP-particles.61It is found that a negative charge on the plate being madeactive increases greatly the amount of recoiled actinium-X collected.I n the case of a long known similar phenomenon with radium-B,62which is not '' volatile '' in the ordinary sense, but appears so atthe moment of its formation from radium4 by expulsion of ana-particle, the recoil explanation had already been suggested. Thiscase and many others63 has been reinvestigated, and been foundparallel t o that of actinium-X, the amount of radium-B collectedbeing greatly assisted if the collecting surf ace is negatively chargedwith respect to the active deposit.It appears that the recoiledAnn. Report, 1907, 328.G1 0. Hahn, Physikal. Zeitsch.. 1909, 10, 81 ; A., ii, 206.G2 Miss Brooks, see Riitherford's Badioaetivity, 2nd edition, p. 392.63 0. Hahn and L. Meitner, Ber. Dezct. ph9sikaZ. Ges., 1909, 11, 55RADIOACTIVITY. 247product of disintegration carries a positive charge, as it has beenfound to do in other cases. I n the actinium active deposit itself,it is known that the first substance, actinium-A (half-period, thirty-six minutes), only expels feeble '&radiation and no a-radiation,whereas the product, actinium-B, expels an a-particle (possibly twoin rapid succession) 64 in its rapid change (half-period, 2-15 minutes)into actinium-C.This latter substance, which had been discoveredshortly before these experiments, as it is separated from a solution ofthe active deposit by adsorption with charcoal and finely dividedmetals,65 gives only the penetrating P- and y-rays of actinium, andhas a half-period of 5.1 minutes. It was found that pureactinium-C, decaying exponentially to zero with a period of 5.1minutes, and giving only P- and y-raaiation, could be obtained byexposing a negatively charged surface in the neighbourhood of theactive deposit.I n suitable circumstances, more than half thetheoretical production of pure actinium-C could be got in this way.In these rapid successive changes the new method of separation isa most powerful new weapon of attack. Changes too rapid for anyother process to be of service can thus be detected. The next resultwzts new. Thorium-A (half-period, 10.6 hours) gives no a-particlewhereas the product thorium (B and C) (half-period, 60.4 minutes 66gives two of different range, and it was previously thought theP- and y-rays also. The recoil method, however, yielded from thethorium active deposit an entirely new product, called thorium-D,giving only the B- and y-rays, decaying exponentially to zero withhalf-period 3.1 minutes.It gave no a-rays on decaying, and hencemust follow thorium (B and C) in the series. The absorption curvesof the thorium-D P-rays are identical with those of the morepenetrating of the two types given by the thorium active deposit.An independent set of similar experiments, carried out with acondensed film of radium emanation in a vacuum,67 showed thatradium-A, -B, and -C recoiled from tmhe emanation. No electricfield was employed in these experiments, and it was found thatthe amount recoiled varied inversely as the square of the distance,and was very markedly diminished by the presence of air or othergases. The air absorbed the products recoiled exponentially, andin one case, under 0.44 mm.pressure with 6.5 cm. of path, halfwas absorbed by the air. Hydrogen was found to absorb therecoil products far more than air in proportion t o its density.In both sets of investigation it was established that the expulsionof the P-particle by itself produces a detectable recoil of the6.1 Conipare Mlle. Blanquies, p. 236.G5 0. Hahn and L. Meitner, Phylsikal. Zeitsch., 1908, 9, 649 ; A., 1908, ii, 920.66 Ann. Beport, 1906, 342.67 S. Russ aid W. Makower, Proc. Roy. Soc., 1909, 82, A, 205 ; A , , ii, 455248 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.product, which is far smaller than that produced by the a-particle.Thus, the active deposit of radium, after being left long enoughfor the rapidly changing a-ray substance, radium-A, completely todisintegrate, exposed in a vacuum gave a recoil product- of radium-Calone, which could only be due to the P-particle expelled in thechange of radium-B. Further investigations have established thatradium-(? itself gives a new rapidly decaying recoil product.68 Thecomplex nature of radium-C has already been adumbrated onseveral grounds.69 I n addition to the evidence drawn from thevery penetrating character of the a-radiation, which indicates afar more rapidly changing product than that ascribed to radium47(half-period, 19 minutes), and to the discrepancies between thecalculated periods of radium-D, the substance gives a complex/3-radiation not exponentially absorbed by aluminium (comparep.240). Recoil experiments with pure radium4 itself, separatedby chemical methods from a solution of the active deposit ofradium, gave products decaying very rapidly, with a half-periodof from 1 to 2.5 minutes. Only very feeble recoil effects wereobtained, indicating that radium-C, gives &rays and no a-rays.The recoil product, radium-C,, gave a-rays, and decayed ex-ponentially with a period of about two minutes.There is thus evidence that radium4 is complex and consistsof two rapidly succeeding products, whilst three are suggested.The results so far, however, are not very conclusive. The newmethod may perhaps also apply to cases like radium-P, to determinewhether i t is the true end-product of the series. There is littledoubt that the new method may serve to throw light on problemscapable of being attacked in no other ~ a y .7 ~ There is some evidencethat radium-P gives a recoil product which carries a positivecharge, and is detectable thereby. I f so, a method may exist forthe recognition of t.he final end-product of the series, even althoughit is completely non-radioactive. Even the determination of theatomic weight by measurements of the magnetic and electricdeflexion of the charged particle is not entirely out of the ques-tion.Influence of Temperature on Radioactive Change.This subject has been left in an unsatisfactory stake in previousreports, and, in spite of further researches, still remains unsettled,a real conflict existing in the experimental results of differentworkers, and even of the same workers in different experiments.gs 0.Hahn and 1,. Meitncr, Physiknt. Zcitsch., 1909, 10, 697 ; A., ii, 849.69 Ann. Repod, 1907, 312 and 338.70 J. C. McLennan, Nature, 1909, 80. 490 ; compare also E. Aschkinass,A m . Physik, 1908, [iv], 27, 377 ; A . , 1908, ii, 920RADIOACTIVITY. 249Many of the results already recorded 71 have been independentlyconfirmed.72 The P- and y-activity of radium-C from a quartz tubecontaining the radium active deposit has now been measured duringthe actual heating. Soon after heating to llOOo or 1200°, a decaymore rapid than the normal occurred, gradually becoming normalas the heating was maintained. On cooling, the decay was a t firstless than, but increased to, the normal.Disturbances due tounequal volat.ilisation of the products and to the permeability ofthe tube a t high temperature appear to have been eliminated.With the emanation itself in the quartz tube, a rapid increase atfirst was always observed. I n the first experiments, cooling broughtthe activity below the normal, and the activity then graduallyincreased to the normal. I n later experiments, however, thisincrease was not observed. This was attributed to non-homogeneityof the emanation, for which some other as yet incomplete evidenceexists, the consideration of which may profitably be postponed.73With the hard y-rays little change was observed. It is concludedthat the changes both of the emanation and radium-A areaccelerated by rise of temperature.Other investigators continueto deny any effect of t e r n p e r a t ~ r e . ~ ~ The changes, in any case, aresmall, but the evidence in their favour cannot be altogether ignored.The question remains an open one.Helium and Ultimate Disintegration Products.A measurement of the rate of production of helium from 0.07gram of radium chloride, by absorbing condensable gases in charcoalcooled in liquid air (sometimes in liquid hydrogen), and measuringthe increase in the amount of residual gas in a compression gauge,gave 0.37 cu. mm. of helium per gram of radium per day, whichis very nearly the theoretical value (compare p. 235).75 Theradium was heated to 450° before the measurements, and thepurity of the gas measured as helium was established.The pro-duction of infinitesimal quantities of helium from uranium andthorium has been established by direct experiments with largequantities of materials by means of the calcium absorption process,which ensures that the helium could not have been of atmospheric71 Ann. Report, 1907, 336.72 W . Engler, Ann. Pltysik, 1908, [iv], 26. 518 ; A., 1908, ii, 650.73 Compare also Rutherford and Tuomikoski, IlIcm. Mnnchester Phil. A'oc. , 1909,53, xii. ; A., ii, 456 ; Rutherford, Phil. Mag., [vi], 1909, 17, 723 ; d., ii, 456 ;A, Debierne: Compt. rend., 1909, 148, 1264 ; A . , ii, 534.74 H. W. Schmidt, Physikal. Zeitsch., 1908, 9, 113 ; A., 1908, ii, 141 ; Makowerand Russ (controversial against the latter), ibid., 250 ; A., 1908, ii, 449 ; H.W.Schmidt and P. Cermak, ibid., S16.75 Sir J! Dewar, Proc. Roy. Soc., 1908, 81, A, 280 ; A,, 1908, ii, 921250 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.origin. The amount produced in both cases is of the same orderas the theoretical. I n the uranium experiments it spectroscopicestimation of the rate of production agreed with the theoreticalon the assumption that each atom of uranium disintegrating givesone, not two, atoms of helium, but the estimate is necessarily aminimum 0ne.76 The amount corresponds with only 11 cu. mm.per thousand kilograms of uranium per year.Attempts have been made to use the amount of helium con-tained in common rocks and minerals as a criterion of theirgeological age. Except in the one definite case of beryl, whichcontains a marked amount of helium and practically no radioactivematter, and possibly of the saline minerals, such as carnallite, theamounts of helium correspond roughly with what is to be expectedfrom the amount of uranium (measured as radium) and thorium.77It has been established, however, that under laboratory conditionsthe rate of escape of helium, even from dense, compact mineralslike thorianite, far exceeds the possible rate of production, so thatthe primitive natural conditions must have been more favourableto the retention of helium.78 This escape, of course, would in-validate the estimation of geological age, making it too low.However, the most recent results with hzmatites of variousgeological horizons, from Oligocene to Devonian, indicate ages fargreater than are usually ascribed by geolcgists.79 Still more recentresults with zircons of geological ages from Tertiary to Archean,indicate a very close agreement between the age and the ratio ofhelium to radioactive matter.Doubt has been thrown on theexistence of argon in zirconium minerals, such as malacone, exceptin spectroscopic quantities.8O Doubt has also been thrown on thepossibility of lead being the ultimate product of the uraniumdisintegration,*l owing to- the absence (less than 0.01 per cent.) oflead in a fine crystal of autunite (hydrated uranium calciumphosphate). Independent spectroscopic examination of anotherspecimen of this mineral, it is true, and on Cornish tobernite(hydrated uranium copper phosphate), showed lead as the only76 F.Soddy, Phil. Mag., 1908, [vi], 16, 513; A . , 1908, ii, 921 ; Physikal.Zeitsch., 1909, 10, 4 1 ; A., ii, 207 ; Proc. PJqs. Soc., 1909, 178.77 It. J. Strutt, Proc. Roy. SOC., 1908, 80, A, 572 ; 81, A, 272 and278 ; A.,1908,ii, 649, 922, 923; J. W. Waters, Phil. Nuq., 1909, [vi], 18, 677 ; A., ii, 848.78 R. J. Strutt, Proc. Boy. Soc., 1909, 82, A, 166 ; A , , ii, 457 ; J. A. Gray,ibid., 301 ; A., ii, 570.79 R. J. Strutt, ibid., 1909, 83, A, 97 ; A., 1910, ii, 9 ; ibid., meetingof 9/12/09, abstract only available.so R. J. Strutt, ibid., 1908, 80, A, 572 ; A., 1908, ii, 649 ; C . F.Hogley, Phil. Mag., 1909, [vi], 18, 672 ; A . , ii, 884 ; A. von Antropoff, Zeitsclt.Elektrochem., 1908, 14, 585 ; A . , 1908, ii, 943.81 W.Marckwald and B. Keetman, Ber., 1908, 41, 49 ; A., 1908, ii, 144RADIOACTIVITY. 251important foreign constituent. The quantity in the first case was,however, only such as would be formed theoretically in 10,000years.g2 The mineral must either be of extremely recent formation,or lead cannot be the ultimate product. With regard to theultimate product of the thorium series, the active deposit ofthorium appears to decay away completely, leaving no feebleresidual activity, and the unknown product of the last knownmember, thorium-D, if not entirely stable, must possess a lifeperiod of a t least two million years.83 I n this research the periodsof thorium-A and -23 were redetermined very accurately, and foundto be 10.605 hours and 60.4 minutes respectively.The Radioactive Emanations.Physical Properties of Rudium Emanation.-Several workers nowhaving a considerable fraction of a gram of pure radium, manyinvest.igations have been carried out on the properties of pureradium emanation.The volume of the emanation in equilibriumwith 1 gram of radium has been found to be almost exactly thattheoretically deduced (p. 235) on the aasumption that one mon-atomic molecule of emanation results per atom of radium dis-integrating, the most trustworthy measurements agreeing in givingabout 0.58 to 0.6 cu. mm. at N.T.P. Tho initial rapid contractionof volume of freshly separated emanation, although not entirelyexplained, has been traced to impurities, which have in no casebeen entirely eliminated.The measurements have therefore beentaken of the minimum volume reached after a few hours. Theamount of emanation measured has been compared by y-raymeasurements with a standard radium preparation.84 The volumeof emanation has been proved to be proportional to its y-activity,independently of the time of its accumulation.On this infinitesimal quantity of gas, determinations have beenmade of the spectrum, vapour pressure, boiling point, freezingpoint, critical temperature, critical pressure, and the density ofthe liquid. The spectrum 85 is now fairly well known, having beenphotographed both with the prism and grating with sufficientlyconcordant results. An unexplained fact is the presence of xenon84 J. A. Gray, Phil. Mag., 1909, [vi], 18, 816 and 937 ; A., ii, 956.83 I?.v. Leich, S’itzunysber. K. Aknd. Wiss. Wien., 1907, 116, (iia), 1443.84 E. Rutherford, Phil. Mag., 1908, [vi], 16, 300 ; A . , 1908, ii, 791 ; R. W. Grayand Sir W. Rainsay, Trans., 1909, 95, 1073 ; A. Debierne, Compt. rend., 1909,148,1264 ; A., ii, 534.85 E. Rutherford and T. Royds, Phil. Nay., 1908, [vi], 16, 313 ; A . , 1908, ii, 787 ;T. Royds, ibid.. 1909, [vi], 17, 202 ; A . , ii, 206 ; A. T. Cameron and Sir W.Ramsay, Proc. a y . SOC., 1908, 81, A, 210 ; A . , 1908, ii, 786 ; T. Royds, ibid.,1909, 82, A, 22; A., ii, 287 ; H. E. Watson, ibid., 1909, 83, A, 50 ; A., ii, 954252 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.in the emanation spectrum on one occasion, for which no sourcehas been suggested.The vapour-pressure curve of the emanationhas been plotked in one set of investigations from 500 mm., 202'6OAbs. (solid) to 47,450 mm., 377*50° Abs. (critical temperature), thefreezing point being given a t - 71O.86 The liquid emanationobserved in a microscope is described as a t first colourless andtransparent like water, but as its temperature is reduced it ceasest o transmit light, and on further cooling with liquid air the solidemanation glows with great brilliancy, a t first like a small steel-bluearc lamp, whilst a t a still lower temperature the glow is a brilliantorange-red. From a comparison of its boiling point, critical tem-perature, and critical pressure with those of the other inert gases,it was concluded that the atomic weight of the emanation was176.The theoretical value, on the assumption that only ana-particle is expelled in the production of the emanation fromradium, is 222.5, which has also been advocated from the samedata on other grounds.87 Both numbers would fit in the PeriodicTable equally well. Before this evidence from the physical con-stants can be considered beyond criticism, it would be of interestto have similar measurements carried out with 0.1 cu. mm. ofxenon, krypton, and argon.DifJzcsion-Coefficie.nts.-The coefficients of diffusion of all threeemanations have been redetermined with considerable accuracy, butthe deduction therefrom of the molecular weight of the emanationappears to be beset with uncertainty. I n the first place, the effectof a charge on the molecule, which a t least initially it may reason-ably be supposed to have, has been considered to be a disturbingfactor sufficient completely to vitiate the method and to give toolow values for the molecular weight.88 Possibly another disturbingfactor, which also would apply mainly to the short-lived emanations,is the effect of recoil, causing the emanation molecule at first tomove more rapidly than that of a8n ordinary gas of similar molecularweight and temperature.For the long-lived radium emanation,however, one would not expect either objection to apply, unless,indeed, the emanation molecule has its charge maintained by theions in the gas. It has been suggested that fresh evidence mightbe obtained from a comparison of the thermal conductivities ofthe emanation and the heavier argon gases at very low pressure,89a6 R.W. Gray and Sir W. Ramcay, Zoc. cit. ; compare also E. Rutherford, Phil.Mao., 1909, [vi], 17, 723 ; A . , ii, 456.G. Rudorf, Zeitsch. EZektrochcm., 1909, 15, 749 ; A . , ii, 954.s8 Sir J. J. Thonison, Camb. Phil. Society's Meeting, 8/11/09. Abstract only sofar available.8y F. Soddy and A. J. Berry, Royal SOC. Meet,ing, 9/12/09 ; F. Soddy, Nature,1611 2/09RADIOACTIVITP. 253which have been shown with argon and neon t o agree fairly wellwith the values calculated from the kinetic theory.The most notable experimental advance with the radiumemanation has been the direct comparison of its velocity of diffusionin hydrogen through asbestos plugs with that of mercury vapoura t 250° and 275O.This is the first time direct comparison hasbeen made with a monatomic gas of similar molecular weight.g*The coefficients of diffusion of the emanation at the two tem-peratures were 0.0341 and 0.0376, as compared with 0.0370 and0.0407 for mercury. On the assumption that the molecular weightsare proportional to the squares of the diff usion-coefficients, themolecular weight of the emanation is 234.5. Another determina-tion 91 in air at the ordinary temperature has been made by Curieand Danne’s original method, with improvements, by measuring theexponential escape of emanation from a bulb provided with along, narrow tube. This gave the coefficient of diffusion 0.1015 atN.T.P. I f the same law holds for the emanation as for hydrogen,water, and carbon dioxide, the molecular weight would be between70 and 100, but no monatomic gas seems to have had Its coefficientof diffusion so measured. The coefficient of diffusion of the actiniumemanation has been deduced from the exponential decrease, withheight, of the active deposit on a vertical wire in a, long cylinder,at the bottom of which an actinium preparation was spread.92 Alsothe rate of diffusion of actinium and thorium emanations havebeen compared by the same method.93 I n the first investigationthe coefficient was determined in air at various pressures, and incarbon dioxide and hydrogen. It was found that the ratios ofthe diffusion-coefficients in air to those in hydrogen and carbondioxide respectively were the same for the actinium emanation asfor ether, alcohol, water, etc.It was concluded that the molecularweight must be about 70 whatever the conditions uncier whichdiffusion is measured. I n the second investigation, the valuesfound for the actinium emanation agreed well with those calculatedby Graham’s law from the diffusion-coefficients in air when diffusionwas carried out in hydrogen, carbon dioxide, sulphur dioxide, andargon. The actinium emanation coefficient was 1-19 times thatof the thorium emanation (in air a t 76*cm.), and it was concludedthat the molecular weight of the thorium emanation is 1.42 timesthat of actinium. This question of the molecular weights of theemanation is thus still far from settled, and is one of the greatestimportance in the present state of t.he subject.yo P.B. Perkins, An~er. J. Xci., 1908, [iv], 25, 461 ; A., 1908, ii, 552.91 L. Chaumont, Le Radium, 1909, 6, 106 ; A . , ii, 781.C. Bruhat, Contpt. rend., 1909, 148, 629 ; Lc Iladium, 1909, 6, 67 ;A., ii, 300. 93 S. BUSS, Phil. Nag., 1909, [vi], 17, 412 ; A., ii, 36625% ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Condensation.-An interesting, but somewhat incomplete, investi-gation 94 has shown that whereas the temperature of condensationof the radium emanation in tubes of copper, iron, tin, and silver isabout the same (- 155O) as that originally found, in glass the tem-perature is about 20° lower. I n silvered glass the temperature waslittlc, if any, higher than in ordinary glass.This may explain thedifferences between the initial experiments, in which it was foundthat the temperature of condensation (in metal tubes) wasextremely sharp, and those of a large number of later investigators(working with glass apparatus), who have found that by continuedpumping some emanation can be continuously extracted evenwhen it is kept at liquid-air temperature. Investigations have alsobeen carried out on the absorption of the emanations by charcoaland other porous materials.95 Not much hitherto has been knownof the condensation of the actinium emanation, as its rapid decay(to 1 / 2 per cent. in 30 seconds) makes the experimental workdifficult. A very complete and careful comparison96 has now beenmade between its behaviour at low temperature and that of thethorium emanation, with the notable result that the two emanationsare so completely alike as regards their condensation that theycan barely be distinguished.This is unexpected in view of largedifference in molecular weight indicated by diffusion experiments.At -120° both emanations begin to condense, and condensationis complete a t -150O. I f anything, the actinium emanation isslightly the more volatile. The disengagement of the emanationfrom radium-barium chloride and fluoride has been further studiedin great detail. I n the case of the former, the temporaryminimum of emanating power passed through a t 920°, 2 5 O belowthe melting point, has been associated with a point of polymorphictransf~rmation.~~ Radium salts precipitated along with hydratesof the rare earths have a very strong emanating power in the coldin the dry state, as in the case of the actinium preparations.98The great loss of emanation from dry radium bromide in the cold,as compared, for example, with radium chloride, is perhaps to beascribed to the greater spontaneous instability of the bromide,and its rapid conversion into hydroxide and carbonate by the actionof the air.The Question of Transmutational Reactions Produced b y the94 A .Laborde, Le Radium, 1909, 6, 289; A., ii, 634.95 Compare also E. Henriot, ibid., 1908, 5, 41 ; A., 1908, ii, 651 ; R. W.y6 S. Kinoshita, ihid., 1908, [vi], 16, 121 ; A , , 1908, ii, 652.97 Ann. Report, 1907, 332 ; L. Kolowrat, Le Radium, 1909, 6, 321 ; A, 1910,98 H.Herschfinkel, Compt. rei?d., 1909, 149, 276; A., ii, 714.Boyle, Phil. Mag., 1909, [vi], 17, 374. (See A., 1908, ii, 1005.)ii, 91RADIOACTIVITY. 255Radium Emanation.-The experiments on the presence of neon withhelium in the gases produced by the action of radium emanationupon liquid water99 have been repeated by the original investiga-tors, who conclude that they furnish conclusive evidence of the firstobserved case of transmutation.1 I n the experiment described, theanalysis given showed that nearly 0.3 C.C. of nitrogen gas waspresent. Other workers have carried out similar experiments,and obtained in four out of five experiments no indication of neonin the helium produced. It was found that when 1/10 C.C.ofair was added to the helium, and the gas again subjected to coldcharcoal, the neon spectrum could be clearly seen. I n the fifthexperiment neon was observed, which was ascribed to atmosphericorigin through air leakage.2 The presence of lithium in salts ofcopper, subjected to the action of the radium emanation, was notobserved in a series of independent experiments carried out withvery carefully purified materials in platinum vessels.3 It wasshown that water originally free from lithium, after standing inglass vessels for a short time, contained it in detectable quantities.The presence of lithium in opaque and transparent fused quartz wasalso detected. The occurrence of lithium in radioactive mineralshas been examined. Lithium in spectroscopic quantity was foundin all, but no relation existed between the amount of lithiumand that of copper.Autunite contains no copper, and carnotitebut little copper, and relatively much lithium.4 Experiments todetect lithium after the direct action of the rays and emanationof radium on salts of copper and gold have given negative r e ~ u l t s . ~The formation of considerable quantities of carbon dioxide by theaction of carbon dioxide-ffee radium emanation on solutions ofhydrofluosilicic acid, titanium sulphate, zirconium nitrate, thoriumnitrate, and lead chlorate, and its absence in similar experimentswith mercurous nitrate, has been interpreted on the view that theelements of the carbon group are degraded into carbon by theaction of the emanation, the more readily (except lead) the higherthe atomic weight of the element.6 From the thorium solution, 2.9milligrams of carbon, as carbon dioxide, wcre obtained per cu. mm.of emanation employed.99 Ann, Beport, 1907, 335.Sir W.Ranisay aiid A. T. Cameron, Trans., 1908, 93, 992.E. Rutherford and T. Roycts, PJd. Mag., 1908, [vi], 16, 812 ; A., 1908,Mme. Curie and Mlle. Gleditsch, Compt. rend., 1908, 147, 345 ; A., 1908,Mlle. Gleditsch, ibid., 146, 331 ; A., 1908, ii, 246 ; Sir W. Ramsay andE. P. Perman, Tram., 1908, 93, 1775.Sir W. Ranisay and F. L. Usher, Ber., 1909, 42, 2930; A., ii, 860,ii, 1006.ii, 793.A. T. Cameron, ibid., 456 ; A . , 1908, ii, 247256 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The Radioactive Decomposition of Water and Various Gases.For six or seven years the source of the excess of hydrogenalways present in the electrolytic gas evolved in the radioactivedecomposition of water has remained unaccounted for, but muchfresh light has recently been thrown on the question.Contrary t oearlier observations, the decomposition of water by the penetratingrays only of a considerable quantity of radium has been observed.'After the first three days, for some months, a steady evolution ofgas occurred, followed by a slow progressive diminution in therate of production. The steady evolution was 0.115 C.C. per dayper gram of radium, which is about 1 per cent. of the amountevolved from radium in solution. On testing the gas, it was foundto be pure hydrogen, and an amount of hydrogen peroxide wasfound in the water nearly corresponding with the equation:It is calculated that rather more than 0.01 per cent.of the totalenergy evolved by the radium can be utilised in this reaction.No such effect was observed for X-rays, but ultraviolet light froma quartz mercury vapour lamp brings about the same reaction.This is in conformity with the observation that hydrogen peroxideis found in greater amou:it in snow and rain during the daytimethan a t night, and that it is not found in dew.An unaccountable cessation in the normal evolution of hydrogenand oxygen from a solution containing more than 0.2 gram ofradium has been recorded. After some months of normal gasevolution, very little gas was generated for two months, and thenthe normal rate of evolution (25 C.C.per week) was resumed andmaintained.8 As a result of a long series of experiments on thechemical action of the radium emanation on water, mixtures ofhydrogen and oxygen, both moist and dry, oxides of carbon,hydrogen chloride, ammonia, and mixtures of nitrogen and hydro-gen, it was found that the general law could be formulatedthat each molecule of emanation disintegrating produces a definiteeffect. The volume changes in the gases brought about by thepresence of a definite quantity of emanation proceed exponentiallywith the time, the constant, for the average of all the experiments,being the same as that of the decay of the radium emanati~n.~Liquid water is decomposed, whereas the mixed gases, hydrogenA.Debierne, Compt. rend., 1909, 148, 7 0 3 ; Le Radium, 1909, 6, 65;A., ii, 364 ; M. Keinbaum, Conapt. rend., 1909, 148, 705 ; 149, 116 and 273 ; LeUadizmm, 1909, 6, 225 ; A . , ii, 364, 714, 717.2H,O = H,O, + H, - 90,000 calories.13. W. Gray and Sir W. Ramsay, Trans., 1909, 95, 1073.Sir If'. Ramsay and A. T. Cameron, ibid., 1908, 93, 966 ; compaie also(See A , , ii, 778.) H. Herschfinkel, Le IZadium, 1909, 6, 228RADIOACTIVITY. 257and oxygen, in presence of phosphoric oxide are recombined.Carbon dioxide is decomposed with deposition of carbon andformation of carbon monoxide, whilst the latter gas also depositscarbon and forms carbon dioxide and some oxygen. Hydrogenchloride and ammonia are decomposed into their constituents,whilst mixtures of nitrogen and hydrogen contract in presence offused calcium chloride, which absorbs ammonia.A t 130° mixturesof hydrogen and oxygen recombine, whereas the reverse changewith steam did not appear to take place. The general actionof radioactive substance in causing chemical combination appearsto be well explained by dissociation of molecular aggregates, andthe temporary formation of free atoms, rendering the substancesextremely reactive, as in the so-called nascent state. This greatchemical reactivity of otherwise inert substances in presence of theradioactive materials has always to be remembered in the inter-pretation of their actions,The Active Deposits.The conditions of the deposition of the active deposit, with andwithout the action of electric fields, and of gravity1° have beenexamined in great detail.The amount of active deposit attractedto the negative electrode in the radium emanation varies with thevoltage in a, manner closely analogous to the ionisation currentthrough the gas, indicating that the specific velocity and coefficientof recombination is of the same order of magnitude forthe active matter as for the ions in the gas. Hence thepractically important result follows that to get the maximumdeposition a voltage sufficient to produce saturation in the gasis necessary in each case.11 Without the action of an electricfield or gravity, by working with vertical parallel plates a t varyingdistances apart, a maximum distance apart exists beyond whichthe amount of active deposit does not increase, indicating thatthe time taken for the particles to diffuse to the plates exceeds theirperiod of average life.This limiting distance apart, however, isattained at a distance twelve times less than indicated by theoreticalconsiderations, as though the particles of the active products wereaggregations very much larger than single molecules.12 It hasbeen established that radium-A is absent from that part of theactive deposit falling under gravity, the time taken in f allizlgteing greater than the short life-period of this substance. Thiswas done very neatly by exposing two horizontal superimposedlo Ann. Report, 1907, 336.11 H. W. Schmidt, Physsikal. Zeitsch., 1908, 9, 184.l2 A.Debierne, Le Radium, 1909, 6, 97.REP.-VOL. VI. 258 ANNUAL REPORTS ON THE PROGLtESS OF CHEMIS'J'11Z7.plates to the emanation, and then, after the removal ofthe plates from bhe emanation, balancing the ionising currentfrom the under surPace of the upper plate against that due tothe upper surface of the lower plate. The net effect was due tothe gravity-deposited activity alone, and its decay curve showedno rapid initial drop characteristic of radium-A .I3 By finding themaximum distance between the plates beyond which the gravity-deposited activity did not further increase, the time of fall and,from Stokes' law, the size of the falling particle were estimated.I n moisture-laden air, the size found was much greater than indry, and reached diameters from 150 to 280 pp, which is wellwithin the region of ultramicroscopic vision.Supporting thisinference, the formation of persistent mists has been observedin flasks containing moist, but not necessarily saturated, airilluminated by the arc. These last sometimes over a month, andgradually disappear as the emanation decays. They have beentraced to chemical actions, such as the formation of oxides ofnitrogen from the air, and the oxidation of sulphur from india-rubber stoppers, and are especially dense in chemically reactivegases such as chlorine.14 The results seem to have a bearing on theimportance of radioactivity in producing meteorological phenomena.By experiments on the activity deposited on rods immersed in theemanation a t various temperatures, it has been found that at 900°neither radium-A nor -B will deposit, whereas radium-C will, and,since the deposition under these conditions is uninfluenced by theelectric field, it is concluded that radium8 is not charged a t themoment of its formation from radium-B.The followingvolatilisation points are given : radium-A, 900° ; radium-B, GOOo ;radium-C, l2OOO.15 A full comparison of the behaviour of theactive deposits from the three emanations in an electric fieldin gases a t various pressures has been carried out.16 The con-clusion is come to that some of the particles of the activedeposit carry negative charges, for, especially in the case ofactinium, some of the deposit is attracted t o the positive electrode.It appears that the sign of the charge on the particle depends tosome extent on the number of collisions made with the gas moleculesand may be either positive or negative.Recoil phenomena probablyplay a part in the interpretation of some of the observed effects.l3 L. Wertenstein, Compt. rend., 1909, 149, 268 ; A . , ii, 713.l4 Mm3. Curie, ibLd., 1908, 147, 379 ; A . , 1908, ii, 797 ; H. Ilcrschfinkel,l5 W. Makower, Le Badi.unz, 1909, 6, 50.l6 S. RUSS, Phil. Nag., 1908, [vi], 15, 601 and 737 ; A , , 1908, ii, 651, 556 ;Lc Badium, 1909, 6, 228.W. T. Kennedy, ihicl., 1909, [vi], 18, '744; A . , ii, 955RADIOACTIVITY 259The Uranium-Rudium DisZnt egration Series.Uranium MineraZs.-A valuable set of measurements, giving therelative a-ray ionisation due to each member of the uranium-radium disintegration in equilibrium in radioactive minerals, interms of that given by the parent substance, uranium, as unity, isembodied in the following table l7:Uranium.................... 1.00 Radium-R .................. 0.04 (a)Ionium ................... 0 -34 Radium-C .................. 0.91Radium emailation ...... 0 62 1 Actinium and products.. 0.28Radium-A ................. 0 '54Radium ..................... 0 '45 i Radium-P ................ 0.46Total activity ...... 4-64 times uraniumOmitting radium-B, the activity of which is due to very softP-rays, the actinium products, and uranium itself, the numbers arein good agreement, considering the ranges of the various a-particlesexpelled, with what is to be expected if each product gives onea-particle per atom disintegrating.But the results indicate clearlythat uranium gives slightly more effect than would be the casei f two a-particles were expelled. It is not impossible that inuranium two a-ray changes may succeed each other too rapidly foranalysis. But as the range of the a-particles of uranium is low,this is not very probable. It is more likely, if two successivechanges are really involved, that complete chemical similaritybetween the uranium and its product has hitherto prevented theirseparate identification (compare footnote, p. 262). Be that as itmay, the result bears out in a most striking manner the atomicweight relations existing between uranium and radium, for thedifference of 12 units indicates that three a-particles are expelledin the course of the transformation.Since ionium, the directparent of radium, gives an a-particle, this requirement is entirelysatisfied.I n the case of actinium and its products, for which the data arerather uncertain owing to the difficulties in completely separatingit from the mineral, it is clear the result is quite exceptional. I nthe actinium series, four successive changes, possibly five, in whicha-particles of average range are expelled, are known to occur.This result is the chief reason for considering actinium to be notin the main uranium-radium series, but in a branch or subsidiaryseries from uranium. The results would be consistent if out ofabout every eight atoms of uranium disintegrating seven producedradium and one actinium. The hypothesis has been put forward 18B.Boltwood, Amer. J. Sci., 1808, [iv], 25, 269 ; A., 1908, ii, 454 ; H. N.McCoy and W. H. Ross, J. Anaer. Cheen. Soc., 1907, 29, 1698 ; A . , 1908, ii, 80.la H. N. McCoy and W. H. Iioss, ibid., 1698; A., 1908,1ii, 8 0 ; F. Socldy,Phil. Mag., 1909, Lvi], 18, 739 ; A., ii, 952.s 260 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.that the same atom may disintegrate in more than one way, eachmode obeying the simple law independently of the other modeof disintegration. This would be extremely difficult to establishby experiment, for were one type of rays (say a-rays) given out inone mode of disintegration and another (say &rays) in another,each radiation would decay with the same period, which would bethe sum of two separate periods.The same fixed proportion would,however, exist between the amounts of products of the two modesof disintegration as existed between the reciprocals of the separateperiods, Thus, if a t one point in the disintegration series, one ofthe products disintegrated in dual fashion, the period of the onemode in which actinium was the product being about seven timesthe period of the other mode which gave rise to radium, the knownrelations between actinium, radium, and uranium would receive aneasy explarfation.Doubt has been cast upon the complete constancy of ratio betweenthe quantities of radium and uranium in minerals.19 This ratiohas been redetermined by separating the two constituentschemically.For autunite a relatively smaller number (2.85), andfor thorianite a relatively larger number (4*19), was obtained thanthe value for Joachimsthal pitchblende, which agreed with theaccepted value ( 3 . 5 8 ~ 10-7). It appears that the ratio is thehigher the older the mineral, although the differences are not great.It would be interesting t o have also measurements of the radium,for comparison, in the same minerals not subjected to any chemicalprocesses of separation.It is to be noted that the anomalous uranium-free radiummineral from Issy l’Eveque, the radium of which appears to havebeen derived from a distant uranium-lode by the action of per-colating water, has its activity, which in the lump exceeds that ofpure pitchblende, entirely confined to the surf ace.Acids dissolvedoff practically all the activity, but hardly any of the mineralitself .20As convenient standards of radioactivity have been suggestedfilms of pure uranium oxide, U,O, (about 0.7 gram, spreaduniformly over a circular plate 7 cm. in diameter by means ofchloroform), for which the a-activity is the maximum. The totala-activity of 1 gram of uranium, that is, the activity in a prac-tically infinitely thin film, if no absorption occurred in the sub-stance or its support, is equal to that of 796 sq. cm. of such afilm. The saturation current per sq. cm. of surface of these filmsl9 Mlle. Gleditsch, Compt. rend., 1909, 148, 1451 ; 149, 267 ; Le Radium, 1909,6, 165 ; A., ii, 533, 714.H.N. McCoy and W. H. Ross, J. Amcr. Chern. Soc., 1907, 29, 1698;1., 1908, ii, 80RADIOACTIVITY. 261is 5-79x10-13 ampere. They can thus be used to calibrate thereadings of electroscopes in absolute measure. The a-activity ofpure radium, free from products, is given as 1.3 x lo6 times thatof equal weight of uranium.21The manufacturers’ designation of the activity of radium pre-parations, as so many million times uranium, are meaningless andmisleading. The best method is to compare the y-activity of aknown weight of the radium sample against a known weight of itstandard preparation, under identical conditions, both preparationshaving been kept sealed up in glass tubes (provided with platinumwires sealed through) for at least a month.The purity of theprimary standard should be checked by atomic weight estimations,or by the rate of evolution of heat. The ready spontaneousdecomposition of radium bromide must be borne in mind.22 Aspecimen initially of 0.5 gram of pure radium bromide, as preparedby the maker, was found on delivery to weigh only 0.388 gram,and to be partly insoluble in water, but soluble in hydrobromicacid with evolution of carbon dioxide and gain of weight. After-wards for some months the solution evolved bromine and relativelylittle oxygen. Then the evolution of bromine stopped, and thenormal evolution of electrolytic gas began.Badio-uraniumc-The separation of a new substance, acting asthe direct parent of uranium-X, and therefore intermediatebetween it and uranium, has been described.23 In preparinguranium-X from a large quantity of uranyl nitrate, it was noticedthat in one preparation the activity due to uranium-X hadincreased ten times on keeping.From this preparation uranium-Xwas separated, decaying at its normal rate, while the remaindergenerated a fresh amount of uranium-X. Very little of the sub-stance so far has been separated, and it must resemble uranium inchemical nature very closely. The evidence, so far as it goes, isclear, but further confirmation must be awaited before theexistence of the body can be regarded as established. There is noevidence whether or no it gives any specific radiation.Uranium-X.-The repeated separation of uranium-X producedfrom a very large quantity of uranyl nitrate, in order to obtainevidence as to the nature of the product of its disintegration, hasgiven results difficult to interpret on the view that this substanceis intermediate between uranium and radium in the dibintegrationseries. Were uranium-X the direct parent of ionium (which in21 H.N. McCoy and G. C. Ashman, Amer. J. Sci., 1908, [iv], 26, 521 ;2J Sir W. Ranisay, Sitrzmgsbcr. hF. Aknd. Wiss. W i e n . , 1908, 117, (iia), 943 ;J. Danue, Comnpl. Tend., 1909, 148, 337 ; LeBadiwu, 1909, 6, 42 ; A., ii, 288.A . , ii, 148.Jfonatsh., 1908, 29, 1013 ; A., ii, 7262 ANNUAL REPORTS ON THE PROGRESS OF CHEMTSTRY.turn is the direct parent of radium and gives out a-rays duringthe transformation), it is to be expected that as its P-radiationdecayed, a very feeble a-radiation, due to the ionium produced,would grow.By deviating the &radiation as much as possible ina strong magnetic field and working in hydrogen, experiments havebeen made which would suffice to detect such a growth if it hadoccurred at the rate indicated by theory, and these experimentshave given a negative result.24 Although still incomplete, theyraise the question whether uranium-X is not, in the actiniumrather than in the radium series.The absorption of uranium-X by charcoal has shown that, forany one initial concentra.tion of uranium-X, the ratio of theconcentration in the solution and in the charcoal, when equilibriumis attained, is a constant independent of the mass of the charcoalemployed.25 This is analogous to Henry’s Law for the solutionof gases in liquids.A remarkable point seems to be that theabsorption is dependent upon the presence of unknown impuritiesin the solution, and is completely prevented by a trace of thoriumsulphate.26Parent of Radiuml.--The growth of radium in solutions of largequantities of purified uranyl nitrate has now been established totake place, and it is found to proceed at a rate proportional tothe square of the time. This indicates that there can exist onlyone intermediate substance in the uranium-radium series, having alife-period which is long compared with the time of the experi-m e n t ~ . ~ ~ The period of average life of this substance, which isalready known to be ionium, is calculated from these experiments tobe 18,500 years as a maximum.If, however, there exist new inter-mediate substances in the series, of lifeperiod comparable with thetime of the experiments (four years), of which there is someevidence, the calculated period referred t o would be reduced.28Intensely active preparations of ionium have now been prepared24 F. Soddy, Phil. Mag., 1909, [vi], 18, 858 ; A., 1910, ii, 10.25 A. Bitzel, Zeikch. physikal. Chcm., 1909, 67, 725 ; Le Radizcm, 1909, 6, 342 ;26 Compare B. Szilird, Compt. rend., 1909, 149, 113 ; A., ii, 715.27 I t may be remarked that the existence of a direct intermediate product sochemically alike to the parent that its full equilibrium quantity in the latter is neverdirninished by any chemical operation, which is of courae always probable, is notconsidered in this and all similar deductions.The two successive substances wouldact always together exactly as one substance, and it is in this sense the deduction isto be read. On the other hand, if the two substances are not consecutive but areseparated by an intermediate substauce chemically dissimilar, as in the thoriumseries, the complete chemical similarity is no insuperable barrier to their separateidentification.as F. Soddy, Phil. Mag., 1908, [vi], 16, 632; A., 1908, ii, 919 ; 1909, 18, 846 ;A., 1910, ii, 10.A . , ii, 851R A ~ I O A C ~ ~ ~ V I ~ I ' Y . 263both by the method of adding a little thorium to the mineral andseparating out the thorium and ionium together,29 and by pre-cipitating the rare earths in the mineral with hydrofluoric acidin strongly acid solution.30 It has also been prepared in thetechnical production of radium from pitchblende residues.31 Thepoverty of the latter in ionium led to the belief that it mightbe almost entirely separated, during manufacture, with theuranium, but the latter investigation shows that a t least some iscontained in the non-uranium residues.One estimate gives 20 percent. of the full equilibrium amount. It has been established thationium gives a-rays of range 2.8 cm. in air. But it does notgive @-rays, previous observations to the contrary32 being due tothe presence of uranium-X. Ionium possesses all the good qualitieswhich have made polonium preparations of value in experimentalwork, with the added advantage that its activity is practicallyconstant. The production of radium from these preparations hasbeen proceeding at a constant rake since observations began, whichis additional evidence of the extended period of life of ionium.Radium-Detailed accounts of the methods employed in thetechnical production of radium have been published, but the prin-ciples are identical with the original ones worked out byDebierne.33 It has been shown that no radioactive matter is lostduring the roasting, or in the liquors from the precipitations.34A new and very direct method for the determination of the periodof average life of radium has been worked 0 ~ t , 3 5 depending on thecomplete separation of the full equilibrium amount of ioniumpresent in a mineral and the measurement of the fraction of theequilibrium amount of radium it generates per year.Thereciprocal of this fraction is the period of average life of radium.The accuracy of the method is independent of errors in the radiumstandards employed, and depends only on the completeness ofthe separation of all the ionium in the mineral. The valueascribed by this method to the period of average life was 2874years, or for the period of half-change about 2000 years. This,which is necessarily, if anything, too high rather than too low,29 B. Boltwood, Amer. J. Xci., 1908, [iv], 25, 365; A., 1908, ii, 455.so B. Kectman, Ja7zrb. Akzdionlltiv. Elektronik, 1909, 6, 2 6 5 ; d., ii, 852 ;3 l S. Meyer and E. von Schweicllhr, Wiener Anzciger.Sitxung., 11/6/09,33 Ann. Report, 1907, 330.$3 L. Haitinger und I(. Ulrich, Sitzu?zgsber. h7. Akud. Wiss. FYieiL, 1908,117, (iin),619 ; Nonatsh., 1908, 29, 485 ; A . , 1908, ii, 857 ; H. l'aweck, Zeitsclz. Elektrochem.,1908, 14, 619; A., 1908, ii, 917.34 J. $t6p, Oesterr. Zeitsch. Bery. Iliittenwescn, 1909, 57, 155 and 173 ; A , , ii, 635.35 B. Boltwood, Amer. J. Sci., 1908, [iv], 25, 493 ; A., 1903, ii, 551,W. Markwald and B. Keetman, Ber., 1908, 41, 49 ; A., 1908, ii, 144264 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.is about 12 per cent. greater than the value deduced from themethod of counting the number of a-particles expelled.The spectroscopic dat.a, from which the high value of 257.8 hadbeen assigned to the atomic weight of radium, have been held tobe capable of a different interpretation. The earlier value is basedon a relation which is shown not to be exact for the case ofthe known atomic weights of the other elements in the alkaline-earth family.By means of a new interpolation formula whichtakes into account these differences, the experimentally found value226.5 has been deduced from the same data.35A. Obviously thespectroscopic evidence is of little weight.Thorium.Further work on the B-rays of rnesothorium36 has shown thatthe latter substance consists of two successive products, for whichthe names thorium-1 and thorium-2 are suggested, the nextproduct, radio-thorium, being, with this nomenclature, thorium-3.Starting from meso-thorium freed from radio-thorium by repeatedpurification, and precipitating in the solution a little addedzirconium by means of ammonia, the precipitate contains thorium-2,possessing a &radiation which decays exponentially to zero insome hours, whilst the filtrate yields a substance (thorium-1) givingat first no P-rays, but regenerating them exponentially with thesame period as that at which the B-radiation of the first pre-paration decays.The period of half-change is given as 6.2 hours.The series now runs:Meso-thorium./----------/-- 7Thorium (a-rays) -+ Thorium-1 (rayless) -+ Thorium-2 (&rays) -+5.5 years. 6.2 hoursRadio-thorium.2 years.Thorium3 (a-rays) -+ Thorium-X, etc.The half-period of radio-thorium (737 days) is obtained by directob~ervation,~~ and from it and the curves of the variation ofactivity of freshly-made thorium preparations with time, that ofmeso-thorium (thorium-1) is deduced to be 5.5 years.38 Of thetotal a-activity of thorium in equilibrium with all its products, ithas been deduced very neatly that 11 per cent.is due to thorium35a W. Marsliall Watts, Phil. Xaq., 1909, [vi], 18, 411 ; A . , ii, 780.36 Ann. Report, 1907, 326 ; 0. Hahii, Physikal. Zcitsch., 1908, 9, 245 and 246 ;37 An?&. Rcport, 1907, 324.38 H. X. McCoy arid W. €1. ROSS, J. Anzcr. Chem. SOC., 1907, 29, 1709 ;A., 1908, ii, 454.A , , 1908, ii, 81 ; 0. Hahn, Phgsikal. Zeilsch., 1908, 9, 392; A . , 1909, ii, 557RADIOACTIVITY. 265itself, 20 per cent. to radio-thorium, and 69 per cent.to thorium-Xand later products. The total a-activity of 1 gram is 1009 timesthat of 1 sq. cm. of the standard film of uranium oxide alreadydescribed.A tmospheric and Natural Radioactivity.The amount of radium emanation in the atmosphere has beendetermined by condensation in charcoal a t the ordinary tempera-ture,39 by condensation at liquid air temperature in metal tubes,40and in other ways.41 The amount varies widely in different localitiesand for the same place with atmospheric conditions, and is of theorder of the equilibrium amount from 10-11 to 10-1O gram ofradium per cubic metre of air. It is insufficient to cause more thana small part of the natural ionisation in the air, which is ascribedmainly to the penetrating radiation from radioactive elements inthe earth’s surface.42 The radium emanation has been detected inthe atmosphere by means of its active deposit a t great heights,up t o 3000 metres, by the use of free balloons.43A number of investigations have shown that the thoriumemanation.plays a large part in producing the active deposit fromthe atmosphere, and that thorium is an agent in terrestrial radio-activity of importance comparable with uranium.I n Rome44 andManchester 45 the equilibrium quantity of active deposit on anegatively charged wire after long exposure to the atmospherewas found to be mainly due to thorium. I n New Haven (Con-necticut) and California46 the proportion is rather less, while a thigh places in the Alps little thorium could be detected.47 Theproportion probably depends somewhat on the potential to whichthe wire is charged.For Manchester it has been calculated that1.4 times more thorium than uranium atoms break up per second inthe earth’s crust, so that there must, be seven times more thoriumpresent than uranium. Direct methods for the determination ofthorium in common rocks have been worked 0 ~ t . 4 8 The Vesuvian89 J. Satterly, Phil. Mag., 1908, [vi], 16, 584; A . , 1908, ii, 918 ; A. S. Eve,ibid., 622 ; A . , 1908, ii, 919.40 G. C. Ashman, Anzer. J. Sci., 1908, [iv], 26, 119 ; A . , 1908, ii, 913.41 W. Wilson, Phil. .Nag., 1909, [vi], 17, 216 ; A., ii, 205.42 K. KUM, Physikal. Zcitsch., 1909, 10, 834; Th. Wulf, ibid., 997.43 S. Flmming, ibid., 1908, 9, 801 ; A., ii, 7.44 G.A. Blanc, ibid., 295 ; A., 1908, ii, 452.45 W. Wilson, Phil. Nag., 1909, [vi], 17, 321 ; A., ii, 202.46 H. Dadourian, Le Radium, 1908, 5, 102 ; A . , 1908, ii; 453 ; F. A. Harvey,47 A. Gockel and Th. Wulf, ibid., 1908, 9, 907 ; A . , ii, 109.48 G . A. Blanc, Le Iladiuyn, 1909, 6 , 306; Phzl. Mag., 1909, [vi], 18, 146 ;J. Joly, ibid., 1909, [vi], 17, 760 ; 18, 140, A . , ii, 458, 635 ; R. J. Strntt, Proc.109. Soc., 1909, 83, A, 97; A., 1910, ii, 9.Physikal. Zeitsch., 1909, 10, 4 6 ; A., ii, 203266 ANNUAL REPORTS ON THE PROGRESS OF CWEMISTEY.lavas appear unusually rich both in thorium and radium. Fifty-one rocks from t.he St. Gothard Tunnel show on the average abouttwo-thirds as much thorium as uranium (calculated from theradium).I n the soil of Rome 1-45 x 10-5 gram of thorium pergram was found, and larger quantities in syenites and granites.As an agent in the production of natural radioactivity, and inquestions connected with the heat of the interior and undergroundtemperature gradients, the importance of thorium appears co-equalwith that of the uranium-radium series. On the important ques-tion as to the amount of radium in the ocean, considerablediscrepancies exist in the results of different workers, and discussionmay be deferred.49 The amount is extremely small, although inthe aggregate it must total a very large quantity.Reference may be made to a work where the main geologicalbearings of radioactivity have been fully discussed,50 which rendersit the less necessary to deal with them in detail here.Potassium.A number of investigations have left no doubt as to the existenceof it specific feeble &activity from salts of potassium, which inall probability is a specific property of the element.51 Rubidiumhas also been shown to possess a distinctive B-activity far lesspenetrating than that of potassium.52 The value of h/cl(cm.)-lof the potassium &ray is given as 8, showing that it is only alittle less penetrating than the radiation of uranium-X. For therubidium radiation the value is 53. The activity of very thicklayers of potassium salts is slightly greater than that of rubidium,but the specific activity of the latter, allowing for its greaterabsorption, must be seven times as great as the former. Allattempts to concentrate the activity seem to have failed.sz*V a riozcs .Three other notable results may be briefly mentioned. Thespeed of crystallisation of superfused droplets of pure sulphur,49 J. Joly, Phil. Mag., 1908, [vi], 15, 385 ; 16, 190 ; A,, 1908, ii, 246, 649 ;1999, 18, 396 ; A., ii, 780 ; A. 5. Eve, ibid., 102 ; A . , ii, 633 ; W. Knoche,Physikal. Zeitsch., 1909, 10, 157 ; A . , ii, 287.50 J. Joly, Radioactivity and Geology.61 J. C. McLennan and W. T. Kennedy, Pld. iWccg., 1908, [vi], 16, 377 ; A.. 1903,ii, 750 ; M. Levin and R. Ruer, Physikal. Zeitsch , 1908, 9,245 ; A., 1908, ii, 448 ;W. W. Strong, Physical REV., 1909, 29, 170; compare A., ii, 715; E. Henriot,Compt. rend., 1909, 148, 910 ; A., ii, 458 ; E. Henriot and G. Vavoii, ibid., 149,30 ; A . , ii, 635 ; E. H. Biichner, Proc. I(: Akad. FVetensch. Anisladam, 1909, 12,154 ; A., ii, 779.Constable and Co., 1909.52 N. Campbell, Proc. Camb. Phil. SOC., 1909, 15, 11 ; A., ii, 288.5% Compare, however, E. Ebler, Chem. Zeit., 1908, 32, 812RADIOACTIVITY. 267under the microscope, has been found to be increased by the8-rays of radium, whereas X-rays produced no effect. The effectis possibly to be associated with the charge carried by theThe pleochroic halo in certain minerals has been associated withthe a-rays of embedded granules of radioactive minerals producingchanges in colour in the surrounding matrix. The radius of thesehalos corresponds closely with the range of the a-particle in themineral.54 I n this way visual evidence has been obtained ofquantities of radioactive matter only just within the range of themost sensitive electrical methods. A sensitive micro-balance on anew principle has been constructed capable of detecting changes inthe weight (of an otherwise small constant load) if greater than4 x 10-9 gram, which it is proposed to attempt to employ infollowing the weight changes in radioactive matter due to dis-integration.55 The balance, in the first place, is a gravity balanceof the ordinary type, entirely constructed of fused quartz, thebeam weighing less than 0.5 gram, carrying on one end ascounterpoise a sealed quartz bulb containing a known amount ofair. Balance is effected by varying the external pressure of theair in the balance case. Accordingly, as the external pressure isless or greater t.han that of the air in the bulb, the latter representsa small positive or negative weight of easily determinable amount.The pressure of the air in the balance case is adjusted until thebeam remains at zero position.FREDERICK SODDY.53 L. Frischauer, Conzpt. rend., 1909, 148, 1261 ; Le Iiadi~m, 1909, 6, 161;44 J. Joly, P?d, Mag., 1907, [vi], 13, 381 ; 0. Miigge, Cenlr. Min., 1907, 397 ;65 B. D. Steele slid K. Grant, Proc. Roy. SOL, 1909, 82, A, 580 ; A., ii, 876.A., ii, 532.1909, 65, 113, and 143 ; A., ii, 286

ISSN:0365-6217    

DOI:10.1039/AR9090600232

出版商:RSC    

年代:1909

数据来源: RSC

摘要:

INDEX OF AUTEO RS' NAMES.Ahderhalden, E., 86, 156, 162, 167, 177,Acree, I;. F., 66.Ahrle, H., 51.Alherda van Ekenstein, W., 83, 123.Alcock, Miss M., 95.Alders, H., 151.Aldrich, T. B., 184.Alefeld, E., 148.Allen, E. T., 202.Allers, R., 155, 184.Allmand, A. J., 47.Aloisi, P., 206.Amherger, C., 161.Angeli, A., 79.Angelucci, O., 34.Antropoff, A. von, 250.Applebey, M. P., 23.Archibald, E. H., 28.Armstrong, H. E., 12.Arndt, K., 24.Arsandaux, H., 208.Artini, E., 228.Aschltinass, E., 237, 239, 248.Ascoli, M., 172.Ashman, G. C., 261, 265.Asriel, M., 70.Aten, A. IT. W., 26.Auerbach, F., 160.Auld, S. J. M., 138.Auwers, Ti., 73.Ayrton, H . , 176.Baborovskf, G., 47.Bacon, C. W., 156.Bacon, R. F., 164.Baeyer, A . von, 66.Bain, Miss A.M., 110, 112.Bain, W., 178.Raker, H. B., 43.Ball, W. C., 146.Bamberger, E., 98.Bancroft, J. A., 212.Barbier, P., 211, 221, 223,199.Barger, G . , 88, 106, 107, 178.13ari118, A., 159.Rarrett, W. H., 47.Barrow, F., 127.Barrowcliff, M. , 103.Bartell, P. E., 13.Raschieri, E., 213,Battelli, F., 172.Baud, E., 14.Baudisch, O., 82, 98.Raner, W., 72.Baume, G . , 14, 38.Raxter, G. P., 38.Bayer, G., 155.Beckniann, E., 51.Begeman, 234.Reger, C., 199.Bell, 13., 182.Belowsky, M., 231.Rernmelen, J. M. van, 203.Rendixsohn, K., 50.Renedict, S. R., 163.Bennett, A. H., 160.Bennett, H. G., 157.Reretta, A., 142.Bereza, S., 83.Rergeat, A., 215.Bergh, G. F., 78.Berkeley, Earl of, 6, 7, 9.Berl, E., 156.Berry, A.J., 252.Bert&, E., 161.I:erthelot, D., 205.Bertrand, G., 123, 157.Resson, A., 48.Best, S. R., 101.Bevan, E. J., 82.Beyer, F. B., 151.Beyerinck, 31. W., 188.Bezzola, C., 172.Ridot, 140.Uierema, S., 189.Bigelow, 8. L., 13.Biilmann, E., 133270 INDEX OF AUTHORS' NAMES.Bingham, E. C., 18.Binz, A., 162.Birch, W. C., 144.Black, J. A., 142.Blair, A. A,, 148.Blaise, E. E., 90.Blanc, G., 92, 93.BIanc, G. A., 265.Hlanck, E., 191.Ulanksma, J. J., 69, 83, 123.Blanquies, Mlle. L., 236.Ulceck, A. W. G., 227.Blount, B., 156.Hloxam, W. P., 105.Blum, L., 224.Boas, K., 155.Bodenstein, M., 16.Boeggild, 0. B., 218.Boeke, H. E., 226.Biittcher, K., 106.Bottcher, W., 50.Bijttger, W., 151.Boltwood, B., 259, 263.Bone, W.A., 42.Bonnett, F., 2.Borchardt, L., 88.Rordas, F., 205.Borelli, V., 146.Bornemann, J., 158.Bosart, L. W,, jun., 137.Bose, E., 18, 125.Bosworth, R. S., 142.Bougault, J., 87.Bourdier, L., 87.Bouveault, L., 92, 93.Rowles, O., 216.Bowman, H. L., 221.Boyle, R. W., 254.Bradley, H. C., 175.Bradley, W. M., 209.Bragg, W. H., 237, 243, 244.Urandenburg, R., 146.Brantlecht, C. A., 199.Braun, J. von, 87.Hrauns, R., 205, 216.Bravo, J. J., 226.Bray, U'. C., 140.Breazede, J. F., 195.Bremer, W., 158.Brenchley, W. E., 194, 195.Bridgman, P. W., 5.Brillouin, M., 17.Brink, P. N., 2.Brode, J., 159.Bronson, H. L., 282, 236, 239.Brown, A. J,, 10, 195.Brown, J. A., 161.Browne, A. W., 49.Browning, P.E., 29, 146, 150.Bruhat, C., 253.Bruhns, W., 224.Brunck, O., 137.Bruneau, P,, 123.Bryan, A. H., 158.Bryiiildsen, A., 137.Bucherer, A. H., 238.Bucherer, N. T., 97, 100.Budde, T., 162.Hiichner, E. H., 266.13ugarszky, S., 153.Biiisson, M., 159.Hull, H., 161,Bumstead, H. A., 245.Burgstaller, A., 149.Burt, P. P., 36.Burton, C. V., 6.I<usch, M., 148.Rutterfield, W. J. A, 139.Bulurranu, V. C., 208.Byk, A., 113.Cahen, E., 143, 156.Cain, J. C., 94.Caldwell, K. S., 161.Cameron, A. T., 251, 255, 256.Campbell, N., 233, 266.Campo, A. del, 140.Candler, J. P., 182, 184.Candiissio, G., 163.Carletti, O., 154.Carnot, A., 215.Caro, N., 102.Casolari, A., 157.Casoria, 229.Caspar, C., 71.Caton, F.W., 106, 176.Cerniak, P., 249.CesLo, G., 213.Chamot, E. M., 153.Chapin, W. H., 219.Chapman, A. C . , i59, 160.Chapman, D. I,., 49, 52.Chardin, D. A., 125.Charpy, G., 53.Chattaway, F. D., 97, 98, 102.Cliaumont, L., 253.Chemische Fabrik Grunau Landslioff &Chick, O., 148, 157.Chouchak, D., 150.Ciusa, R., 64.Clarke, H. 'l'., 63.Clarke, L., 138.Clough, G. W., 120.Codazzi, R. L., 224.Coffetti, G., 143.Cohen, E., 4, 13, 45.Colin, A., 97.Collett, E., 147.Collingwood, B. J., 175.Colomba, L., 222.Conianducci, E., 41.Meyer A&.-Ges., 77INDEX OFCoinessatti, G. , 155.Commelin, J. W., 13.Conti, C., 155.Cook, F. C., 159.Cooke, W. T., 225.Cornu, F., 201, 205, 210, 225.Corper, H. J., 172.Coste, J. H., 140.Cotton, A., 113.Couyat, J., 216.Covelli, E., 140, 141, 154.Coward, H.F., 42.Cripps, R. A., 161.Cross, C. F., 82.Crossley, A. W., 88.Crowe, S. J., 183.Crowther, J. A., 240.Curie, Xadainc B l . , 255, 258.Cnshing, H., 183.Cusliny, A. K., 177.D’Achiardi, G., 218.Dadouriaii, H., 265.Dufert, Y. W., 218.Dalrin, H. D., 174.Dale, H. H., 178, 182.Ddlimore, P. B., 140.Danne, J., 261.DauvB, 140.Davies, H., 131.Davies, S. H., 139.Davis, R. 0. E., 137.Dawon, H. M., 26.lkbierne, A., 249, 251, 256, 257.Decker, H., 68.Degcns, P. K., 16.Delbridge, T. G., 65.Delbriick, I<., 82.D e l E l h ~ , &I., 156.l)enham, H G., 27.Denhnm, W. S., 70.I)enig&s, G., 154.I)ennstedt, hl., 156.Deprat, J., 220.Derby, 0.A., 208.Uerrieii, E., 155.Desha, L. J., 136.Deusseo, E., 162.Den-ar, Sir J., 249.Dilling, W. J., 163.Dirnroth, O., 72.Dittler, E., 203, 211.Dixon, H. B., 41, 42.Dixon, TV. E., 176, 178, 179.Dobson, Miss M. E., 89.Doeltcr, C., 205.Donnan, F. G., 68.Dons, K. K., 161.Donovaii, W., 145.Dorogi, S., 99.Doughty, H. W., 109,AUTHORS’ NAMES. 271Dreger, W., 157.Dreyer, C., 211.Drouginine, G., 113.Duane, W., 237, 239, 245.Dudy, F., 137.Dumas, H. N., 142.Dunlop, J. C. M., 90Dunn, F. P., 134.Dunstan, A. E., 20.Duparc, L , 207.Dupertliuis, H., 22.Dntoit, P., 22, 28.Ebler, E., 140, 266.Eclrardt, M., 147.Edgar, G., 144, 147.Egerton, A. C. G., 35.Khreuhalt, F. , 235.Rhrlich, F., 116.Eichvi.cde, H., 89.Einhorn, A., 79.Eisenlohr, F., 73.Ellis, H. R., 150.Emde, H., 63, 155.Eiuerson, W. H., 142.Endeinann, H., 148.Engeland, K., 87.Engler, C., 103.Eugler, W., 249.Erlenmeyer, E., jun., 133.Ernest, J., 193.Evans, N. N., 212.Eve, A. S., 243.Everatt, R. W., 125.Everest, A. E., 112.Ewati, T., 149.Eynon, L., 158.Fake, F., 149.Fnlk, li. G., 57.Farcy, L., 153.Feilitzen, H. von, 197.Feist, K., 113.Fenton, H. J . H., 83,Fermor, L. L., 208, 209, 221, 227, 228.Ferna, J., 89.Ferstnann, A., 216.Fichter, F., 53.Filippo, H., jun., 150.Finckh, L., 225.Findlay, A, 19, 20, 117.Finkelstein, Mlle. M. , 104.Yinlayson, A. M., 215.E’ischer, A., 150, 151.Fischer, E., SO, 82, S i , 118, 119, 121,Bischer, F., 50.Fischer, H., 189.Fisher, K., 118.Fiske, A.H., 138.Flatau, E., 125.122, 125272 INDEX OFFhwitzky, F. M., 15.Flemming, S., 265.Fletcher, L., 229.Flint, W. R., 39, 150.Florence, A., 163.Flurscheim, B., 57, 60.Flury, F., 150.Fluss, G., 36.Folrin, S., 160.Folin, 0.) 163.Foote, H. W., 16, 25.Ford, W. E., 218.Forster, M. O., 71, 72, 96, 127, 134.Fournier, L., 48.Fox, J. J., 142.FrSnkel, S., 155.Fraenkel, W., 229.Frankforter, G. B., 152.Frankland, P. F., 127.Franklin, E. C., 29.Franzen, H., 45, 180.Fraschina, C. , 138.Fraser, E., 78.Freudenberg, W., 222.Freund, M. , 104.Freundler, P., 113.Frey, W., 16.Friedel, G., 218Friedlander, P., 105.Friedrich, G., 103.Friend, J. A. N., 144.Fries, J. A., 156.Frischauer, L., 267.Fritsch, R., 138.Fromme, J., 210, 216.Fuller, J.G., 200.Funk, C., 163.Funk, W., 190.Gabriel, S, 90.Gadaskin, D. I)., 138.Gage, R. B., 145.Galletly, J. C., 142.Gallo, N., 159.Gams, A., 104.Ganghofer, A., 148.Garde, G., 228.Gardner, W. M., 160.Gamier, M., 137.Gandechon, H., 190.Gay, L., 14.Geiger, H., 239, 233, 234, 236, 237.Gerhardt, C., 136.Gernez, D., 44.Gerngross, O., 87.Genim, J., 77.Gessler, A., 24.Gibbs, H. D., 29.Giles, W. B., 147.Gill, F. W., 137, 163.Gillett, H. W., 151.AUTHORS’ NAMES.Girsewaid, C. von, 48.Glascock, B. L., 39.Gleditsch, Mlle. E., 255, 260.Gmelin, A,, 84.Gnezda, J., 155.Gockel, h., 265.Godet, C., 196.Goldbaum, J. d., 152.Goldschmidt, H., 69, 70.Goldschmidt, V.M., 208, 211.Gomberg, M., 66.Gonnard, F., 211, 221.Gooch, F. A., 142, 143, 151.Goodwin, H. M., 24.Goutal, E., 148.Grandjean, 218.Grant, K., 267.Gray, J. A., 250, 251.Gray, R. W., 36, 251, 252, 256.Graziani, F., 74.Greaves, R. II., 143.Green, A. G., 100.Green, W. H., 23.Gregory, A. IT., 147.Grete, A, 150.Greve, G., 160.Grindley, H. S., 137, 163.Grossmnnn, H., 102, 128, 145, 149.Guignard, L., 196.Guinchant, J., 15.Gutbier, A., 148, 149, 150.Gutmann, A., 109.Guye, P. A., 36, 37, 44, 113.Gyr, E., 28.Haavardsholm, O., 137.Haesler, F., 163.Hahn, O., 240, 241, 242, 246, 247, 248Haitinger, L., 263.Hall, A. D., 194.Halliburton, W. D., 179, 182, 184.Hamill, P., 176.Harnmarsten, O., 155.Handa, M., 141.Hann, A.C. O., 106, 176.Hanriot, M., 81, 123.Hansen, C., 136.Hantzsch, A., 67, 68, 94.Hardy, W. H., 194.Harlow, h1. M., 175.Harries, C. D., 62.Harrison, E. F., 160.Harrison, Miss J. P., 18.Hart, E. B., 200.Hartley, E. G. J., 6, 7, 9.Hartley, H., 23, 46.Hartmann, W., 77.Harvey, F. A., 239, 265.Harwood, H. F., 147.Haselhoff, E., 191.264INDEX OFHasenbgumer, J., 13.Hauenstein, E., 51.Hauser, O., 146, 210, 225, 226, 227.Haworth, W. N., 118.Heide, K. von der, 138, 159.Heiduschka, A., 108.Henderson, G. G., 142.Hendrick, J., 197.Henriot, E., 254, 266.Henriqnes, V., 199.Herman, 139.Herrnimn, W., 116, 205.Herschfinkel, H., 254, 256, 258.Herz, P., 157.Herzig, J., 107.Herzog, J., 79.Hes, A., 148.Hess, H., 85.Hess, V.F., 245.ITibbert, Miss E., 145, 147.Hihbert, G. S., 89.Hibbert, H., 70, 75, 156.Hickmnns, Miss E. M., 117.Hicks, W. L., 74.Hildcbrand, J. € I . , 39, 136.Hilditch, T. P., 125, 126.Hilpert, S., 221.Hissink, D. J., 157.Hodpon, H. H., 160.Hodgson, T. R., 161.Hofniann, K. A., 49.Hogley, C. P., 250.Holter, L., 149.Holland, W. W., 5.Holt, A., jun., 17, 40.Homans, J., 183.Horvath, R., 158.Howa~d, 13. F., 148, 157.Howell, E. E., 230, 281.Howwjanz, S., 78.Hudson, C. S., 124.Huqonnenq. L., 86.Humphreys, T. C., 150.Hundeshagen, F., 146.Hunter, A, 184.Hurtley, W. H., 161.Hussak, E., 220.Hntchinsoii, H. B., 186, 193.Hynd, A., 81.Ibrahini, J., 176.Iljin, L. F., 107.Ingle, H., 200.Innes, A. G., 156.Inouye, K., 45.Ipatieff, W.PIT., 1, 77.Irvine, J. C., 81, 157,Isherwood, P. C. C., 67.Iskiill, W., 207.Issaias, B., 67.Izar, G., 172.KEP.-VOL. VI,AUTHORS’ NAMES, 273Jaboulay, E., 147.Jackson, C. L., 138.Jacobson, P., 96.Jakowkin, A. A., 13.Jannasch, P., 147.Jaubert, G. F., 46.Javillier, If., 157.Jeffers, E. H., 158.Jeffery, J. H., 145.Jensen, P. R., 192Jessup, A. C., 35.Jessup, A. E., 35.Jilke, W., 147.Johannesen, J. C. F., 161.John, W. E. von, 147.Johnson, R. I,., 207, 213.Johnson, F. M. G., 14.Johnston, J., 23.Johnston-Lavis, H. J., 209.Jolles, h., 164.Joly, J . , 265, 266, 267.Jones, G., 2.Jones, G. C., 145.Jones, H. C., 22, 32.Jones, H. O., 125, 132.Jones, W., 171, 172.Jones, W. J., 73, 149.Jonescu, Mlle.A., 155.Jorissen, W. P., 152.Jovitschitsch, M. Z., 223.Jowett, H. A. D., 103.Kahlenberg, L., 13.Kairn, H., 102.Kalmus, H. T., 24.Karczag, L., 122.Tiatayama, M., 16.Kay, F. W., 116.Keane, C. A., 161.Keetnian B., 250, 263.Kemmerich, W., 67.Kennaway, E. L , 171.Kennedy, W. T., 258, 266.Kernbaum, M., 256.Kernot, G., 149.Kilpi, S., 143.Kinoshita, S., 234, 254.Kipping, F. S., 62, 114, 115, 130, 131,Kleeman, R. D., 243, 244.Kleiber, A., 148, 198.Kleine, A., 156.Klimont, I., 162.Knapp, A. W., 160.Knecht, E., 147, 149.Kiioche, W., 266.Knopf, A., 323, 225.Knorre, G. von, 139.Knox, J., 143, 144.Koch, E., 200.Koehl:r, A,, 90.132.274 INDEX OF AUTHORS’ NAMES.Konig, J., 13.Koepsel, A., 139.Korber, F., 3.Koetschau, R., 62.Kohlrausch, K.W. F., 232.Kohnstamm, P., 4.Kolbeck, F., 208.Kolowrat, L., 254,Roninck, L. L. de, 145.Iiooper, W. D., 193.Korczyfiski, A., 67.JCossel, A . , 87.Kostytscheff, S. , 192.Krassa, P., 54.Kress, O., 214.Kreutz, S., 206.Krieble, V. I<., 118.hriiger, M., 169.Kruys, 112. J. yan’t, 149.Kubinsky, J . , 83.Kubli, H., 100.Kiirz, I<., 265.I<uzma, 13 , 47.Kuzma, G., 47.Laband, L., 161.Labat, A, 154.Laborde, A., 254.Lachman, R., 208.Lacroix, A., 210, 215, 216,225, 228, 230.Ladenburg, A ., 1 1 6.Laer, H. van, 160.Landecker, I f . , 147.Lane, J. H., 158.Lange, W., 169.Langheld, K., 88.Larsen, E. S., 202, 217.Leavenwortli, C. S., 199.I,ebeau, P., 48.Le Chatclier, H., 15.Le Clerc, J.A., 195.Lchalleur, J. P., 147.Lehmann, F., 158.Leitmcier, H., 217.Lemaire, P., 140.I,enioult, P., 139.Lendrich, K., 162.Lenger, W., 50.Lenher, V., 38.Leonard, V. N.; 171.Lerch, F. von, 251.Le Suenr, H. R., 90, 122.Levallois, 92.Levene, P. A., 157, 168.Levin, M., 241, 266.Levy, A. G., 156.Lewis, S . J., 146.Lewkowitsch, J., 138.Liebermann, C., 133.Liebig, H. J. von, 194.217, 222,Ling, A. R., 158.Litterscheid, F. M., 143, 158.Little, H. V., 156.Loczka, J., 216.Lob, W., 82.Loffler, K., 102, 103.Lowenstein, E., 220.Lijwinger, B., 148.Lohmann, W., 162.Lomhardo, O., 163.LovBn, J. M., 122.Lovisato, D., 226.Lowry, T. M., 128.Liining, 0,, 148.Luff, €3. D. W., 130, 132.Lux, P., 3 i .rAllllci, v.i i . , 70.Rllnag, R., 11 6 .RlcCay, L. W., 143.McCoy, H. N., 259, 260, 261, 264.iVcDon:ild, I). P., 129.IShIiitosh, I)., 14.RlcKre, R. H., 102.JlcKcnxie, A., 113, 120.Itlackintosh, J. E., 222.Rlclnren, G., 158.RlacLaurin, J. S., 145.McLcllan, 6. G., 139.I1IcLeniiaii, J. C., 248, 266.A7acMalton, 1’. S., 52.hlcMillan, A . , 130.Madsen, J . 1’. V. , 240, 243, 244.Makin, E. G., 22.Mai, J., 139.Mailey, R. D., 24.Mailhe, A , 76.Maillard, P., 158.Naitlmd, A. G., 214.illaliower, W., 239, 247, 249, 258.hlelvezin, P., 138, 159.Marclietti, G., 79.Rlarckwald, W., 117, 1?2, 250, 263,Marko, D., 116.Marle, E. R., 148.Marsden, E., 237.Martin, F., 55.Martin, N. h., 25,Marx, T., 162.Masing, G., 46.Masino, G., 149.Matignon, C ., 15.Matsui, M., 10s.Mauritz, B., 220.Mnuthner, F., 78.Mawson, D., 225.Mayer, 0. von, 45.Meisels, E., 162.hleiseiiheimer, J., 131,McCollunr, E \’., 200IXDEX OF AUTHORS’ NAMES. 27 5Meitner, L., 240, 241, 242, 246, 247,RIeldrum, A. N., 89.Mellaiiby, J., 174, 176.Rleltzer, S. J., 175.Meneghini, D., 54.hlenzies, A. W. C., 21.Merling, G., SB.RIerres, E., 157.Merrill, G. P., 230.Merriman, R. W., 138.Merwin, H. E., 209, 221.Metzger, F. J., 146, 147, 214.Meyer, K., 232.RIeyer, K., 144.Meyer, I<. H., 64.Meyer, S., 205, 263.Meyer, W., 131.Michael, A., 69, 70, 75.hlichel, L., 209.Milbauer, J., 149.Rlilier, J. K. 172.Miller, Rl., 83.Miller, N. H. J., 19:;.hlilliltaii, R.A., 234.Rlillosevich, F., 211.Mills, W. H., 110, 112.RIinkman, D. C. J., 188.Rliorandi, &I., 162.iVitchel1, A. D., 140.Mitscherlich, E. A, 157, 158, 191.Rloir, J., 35.Monferrino, A., 155.Monhaupt, M., 162.Monten, F., 3.Montgomerie, H. H., 129.Morawitz, P., 175.Rlorden, G. W., 152.Morel, A., 86.Morgan, G. T., 95, 143, 156.Morgen, A., 199.Morison, C. G. T., 197.Rlorozewicz, J. A, 212, 215, 227Morse, H. N., 5.Moulin, &I., 235, 238.Mugge, O., 203, 205, 217, 267.nIiiller, H. A, 113.Miiller, R., 96.Muller, W. J., 146.Mdntz, A., 190, 197.Muir, 31. M. P., 53.Narracott, P., 161.Nasiiii, R., 318.Neave, G. B., 153.Nelson, J. M., 57.Nenadkevitsch, K. h., 221, 227.Nernst, W., 141.Nesmjeloff, V., 139.Bey, F., 132.Nishi, M., 164.Nolda, E., 117.248.Nottbohni, E., 162.Nottin, P., 197.Noyes, A. A . , 31.Oddo, B., 142.Oechslin, K. J., 70.Oechsner de Coniuck, W., 52.Olivari, F., 40.Olizy, R., 23.Oppenheini, P., 104.Orloff, E. I., 77.Orndorff, W. R., 65, 142.Orton, I<. J. P., 69, 73, 149.Osborne, T. B., 199.Ost, H., 83.Ostroniisslensky, I. von, 110, 114.Otin, C. N., 152.Otto, It., 193.Paal, C., 77, 148, 161.Padoa, hf., 74.Palache, C., 209, 213, 221, 224.Palmer, C., 222.Palmer, H. E., 146.Panajotom, G., 144.Pannain, E., 142.Parker, H. G., 137.Patrick, 111. A., 28.Patterson, T. S., 129, 1SO.Yaweck, II., 263.Prarce, J?., 207.Pechiiiann, H. von, 72.Pedrina, S., 40.Pegram, G. B., 245.Pelacani, L., 220.Pellet, H., 149.Pellini, G., 40, 54.Perkin, A.G., 105, 106.Perkin, W. H., jun., 89, 90, 110, 111,Perkins, P. B., 253.Pernian, E. P., 255.Perrin, G., 159.Perrin, J., 234.Perrot, F. L., 38.Peeet, J., 140, 155.PAliger, E., 163, 167.Philippe, L. H., 133.Phillips, H. E. W., 21.Yiccinini, G., 153.Pickard, R. H., 122.Pickering, S. U., 186, 197.Pickles, S. S., 138.Pictet, A., 104.Picton, N., 67.Pilipenko, P. P., 208.Piolti, G., 215.Pisani, F., 217.Plimmer, R. H. A., 171.Pluddemann, W. , 160.Plzak, F., 210.11s.T 276 INDEX OF AUTHORS’ NAMES.Pijschl, V., 203.Pollok, J. H., 140.l’oole, 11. H., 245.l’ooth, P., 148.Posiicr, T., 62.l’ostiiia, S., 13.1’0x2-Escot, &I. E., 141, 145, 156.I’ratt, D.S., 153.l’reti, L., 172.l’reuiier. G., 16, 17.l’rice, 1’. S., 150.l’ringsheini, H., 188.Prior, G. T., 212, 218.l’ritzc, M., 145.l’rost, A., 211.l’rud’honinie, If., 97.l’ynian, F. L., 103, 104.Ralle, P., 103.liafh, E., 145.Eanisay, Sir IFT., 33, 34, 851, 253, 355,256, 261.Rankin, G. d., 202.Bappeport, H., 28.Baschig, F., 49.Rasl<e, li., 122.Itaucrt, D., 18.R&y, I-’. C., 50.Read, J., 115.Record, F., 138.Recoura, A., 47.Regener, E., 232, 233.Reichnrd, C., 163.Reid, E. E., 137.Ritzel, A., 262.ltemfrey, P., 68.Rcmy, T., 188.Renner, V., 107.lienouf, Miss K,, 88.Eettger, L. F., 175.Rewald, B., 116.Reynolds, J. E., 48.Richards, T. W., 2.Richaud, A., 140.Itichmond, H. D., 160.Biedel, A., 62.Riesenfeld, E.H., 52.Riess, M., 148.Ritson, S., 163.Robertson, !r. E., 174.Robinson, F., 83.Rohde, K., 62.Rohland, P., 191.Eohner, F., 53.Romanski, Z., 150.Romeo, 161.Rorive, F., 82.Itosenhain, W., 15.Rosenheini, O., 177.l’olJe, w. J., 110, 111, 114, 115.Pouwt, I., 150.Rosenmund, li. IT., 106.Rosenthaler, L., 113.Itosickf, V., 210,Ross, W. H., 259, 260, ‘264.ltosset, H., 160.Xoth, K., 77.Hothmund, V., 1.29.Royds, T., 235, 251, 255.Rndorf, G., 252.Ruer, R., 266.Rupe, H., 126.Rupert, F. F., 13, 49.Xupp, E., 158.Riiss, S., 247, 249, 253, 258.Russell, A. S., 243.liussell, E. J., 156.ltutherfoul, E., 233, 234, 235, ‘240,Wzehak, A,, 230.Sabatier: I’., 76.Salway, A. H., 62, 115.Sand, €1.J. S., 150, 151, 152.Sailin, A., 148.Saporetti, U., 163.Satterly, J., 265.Schaefer, E. A., 1S2, 183.Schaller, W. T., 223, 225.Schsrizer, B., 213.Scheiber, J., 134.Scheibler, H., 119, 121.Schenke, V., 158.Scheuer, O., 37.Schittenhelin, A., 156, 173.Schleimer, H., 203.Schlenk, W., 64.Schmidt, H. W., 240, 241, 249,.257,Schmidt, J., 78, 80.Schmidt, &I., 203.Schmidt, M. R., 22.Schneider, 0 ., 226.Schneider, W., 68, 103.Scholtz, M., 132.8choor1, N., 140.Schreiner, O., 191.Schroeder, J., 138.Schrijder, K., 149.Schroeter, G., 71.Schiitz, J., 193.Schulte, W., 144.Schulz, X., 62.Schulze, R., 193.Schulze, E., 196.Schupp, W., 16, 17.Schwantke, A., 21 1.Schweidler, E, von, 232, 245, 263.Scott, A., 37, 38.Sebelien, J., 137.Selle, V., 213.Scmmler, F.W., 79, 98.Seniper, L., 84.251, 255INDEX OF AUTHORS’ NAMES. 277Senderens, J. P,. , i G .Senier, A., 75.Scntcr, G., 20, 70.Scrra, A., 214, 220.Shcptiearcl, F. G., 75.Sliepher(1, E. S., 202.Shcttrrly, P. P., 49.Sclkoff, s. w., 22.Shol.ey, E. c., 191.Slirc\vshury, I I. s., 1 GO.Shiikoii’, A. A., 80.Siegfried, 14. , i s .Qigitiiinil, W., 174.Sikcs, A. \Ir., 182, 184.Sikorsky, S. , 125.Sinion, Ti., 204.Sinionscn, J. L. , 90.Simpson, S., 184.Sinnige, 1,. R., 4.Skita, h., 77, 89.Slaglv, E. A., GG.Slatoi; A., 70.Slavfli, F., 219.Slykc, I). D. van, 157, 168.Smct, G. (ley 139.S~iietham, A., 159.Sniilcs, S., 63.Smiriioff, \V. A,, 11s.Sniith, A., 21.Smith, Miss A.I?., 69.Smith, C., 149.Smith, E. F., 152.Smith, E. R., 16.Sinith, W. R., 46.Smits, A., 13, 15.Snelling, W. O., 137.Soddy, P., 234, 241, 243, 250, 252, 259,Soellner, J., 209.S~rensen, S. P. L., 141.Spencer, J. F., 139.Spencer, L. J., 209, 212.Spezia, G., 205.Sponnagel, F., 158,Stahler, A., 148, 149, 151.Staudinger, IL, 79, 83.Starke, H., 243.Steele, B. D., 267.Steiner, H., 159.Steingroever, J., 87.&6p, J., 263.Stephenson, J., 7.Stern, Illlle. L., 172.Steudel, H., 169.Stich, C., 163.Stigell, R. W., 190.Stiles, P. G., 175.Stobbe, H., 65, 75.Stock, A., 50.Stockmnnn, H. , 79.Stoddard, J. T., 151.262.Stijrmer, K., 197.Stoeimer, R., 71, 75.Stoklasa, J., 193.Stollk, R., 72.Straus, Fa, 62.Stremme, 1% , 201.Strong, W.W., 266.Strutt, It. J., 250, 26.5.Stuart, M., 230.Stnll, w. N., 2.Sudborongh, J . J., 156.Suess, F. E., 230.Rurgunoff, N. J., 46.Sutherland, E. C., 148.Swett, 0. D., 137.Szilkrcl, D., 262.Taeconi, E., 227.Tammann, G., 2, 46, 229.Tanatatr, S., 54.Tassin, W., 229, 230, 231.Tatlock, C. S., 152.Tatlock, It. It., 161.Tnylor, C. E., 147.Taylor, 1’. S., 23i.Tliacr, W., 199.Thicle, J., 95.Thole, F. J3., 20.Thomas, E. M., 23.Thomas, I?., 105.Thomas, J., 109.Thomson, D., 129.Thomson, Sir J. J., 252.Thornson, R. T., 161.Thorne, L. T., 158.Thornlcy, T., 127.Thorpe, J. F., 101.Thorpe, Sir T. E., 37, 141.Threlfall, R., 2.Thugutt, S. J., 220.Tichwinsky, M. M., 138.Tilden, Sir W. A., 34.Tilley, G.S., 38.Timmermans, J., 4.Tinkler, C. I<., 68.Titherley, A. W., 74.Tollens, B., 82.Tollens, C., 164.Tortelli, M., 161.Townsend, J. S., 43.Traube, BI., 82.Trautmann, W., 147.Tsakalotos, D. E., 20, 44.Tschermak, G., 203, 204.Tschernik, G. P., 206, 214, 217, 219.Tschiiikin, M., 147.Tschirwinsky, P. N., 213.Tschitschibabin, A. E., 66.Tschugaeff, L., 129.Tschunke, R., 103.Tucker, P. A,, 15278 INDEX OF AUTHORS' NAMES,Tuomikoski, U., 249.Turncr, B. FL, 28.Turrentine, J. W., 151.Tutin, F., 103, 106, 176.Twiss, D. F., 70.Udby, O., 70.Ullmann, M., 150.Ulpiani, C., 101.Ulrich, I<., 263.Usher, P. L., 34, 255.Vaubel, W., 143.Vavon, G., 266.Vegard, I,., 9.Veley, V. H., 97, 103, 157.Vernadsky, W. I., 228.Ville, J., 155.Vodden, L., 49.Vogt, J. H. L., 211.Voldere, G. de, 139.Vorisek, A., 153.Vries, H. J. F. de, 137.MTaJe, J., 138.Wagner, E., 5.Wakeman, A. J., 174.Walhuin, L. E., 162.Walker, G. W., 152.Walker, J. W., 118, 125.Walker, T. L., 214.Wallach, O., 91, 93, 94, 110, 111.Walpole, G. S., 106, 138, 178.Ward, If. L.. 143.Warren, C. H., 207, 213, 224.Washbnrn, E. W., 32.Washington, H. S., 207, 224.Waternian, N., 177.Watt.rs, J. W., 250.Watson, H. E., 251.Watts, W. M., 264.Webb, H. W., 245.Weber, O., 160.Wedekind, E., 83,131, 132, 146.Wedekind, O., 132.Wegelius, H., 143.'Wegscheider, R., 31, 32.Weichhold, O., 118.Weiller, P., 221.Weimcrs, F., 113.Weinschenk, A, 230.Weiss, F., S7.Weiss, L., 147.Welde, R., 89.Wells, H. G., 172.Wendel, A., 116.Werehowsky, W., 1Werner, A., 64.Wertenstein, L., 258.Westhausscr, F., 199.Wcsthoff, F., 83.Wctzel, J., 136.Weyberg, Z., 203.Wherry, E. T., 219.Whitc, G. F., 32.White, J., 192.White, W. I'., 202.\Vidmenn, 1;. l'., SO.Wiechowski, W,, 172.Wiclnnd, H., 71, 84, 85, 95.Wilhoit, A. D., 152.Wilkiil, J. If., 142.Wilks, W. A. R., 140.Willers, F. A , 125.Willstattcr, R , 51, 99, 100 108.Wilson, W., 240, 265.Wintcrnitz, M. C., 172.Wirth, T., 108, 146.Witt, 0. N., 96.Wbliler, L., 16, 5 5 .WdNing, I€., 137.Wohl, A, 116.Wolokitin, A., 45.Wood, H. C., j t m , 162.Wood, T. E., 194.Wren, H., 118, 121.Wright, F. E., 202, 207, 212, 217, 223224, 227.Wunsch, D. F. S., 102.Wuite, J. P., 15.Wulf, T., 265.Yates, J., 122.Zachariades, N., 37.Zambonini, F., 201, 212, 218, 223.Zedtwitz, A., 49.ZemplBn, G., 87, 122.Zerewitiiififl, T.. 68.ZimBnyi, K., 228

ISSN:0365-6217    

DOI:10.1039/AR9090600269

出版商:RSC    

年代:1909

数据来源: RSC