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NAS-NS-3061 RA OF BISMUTH NUCLEARSCIENCE SERIES National Academy of Sciences - National Research Council Published by Technical Information Center ENERGY RESEARCH AND DEVELOPMENT ADMINISTRATION COMMITTEE ON NUCLEAR SCIENCE John Huizenga, Chairman, Nuclear WrUcture Re=arch Laboratory Thomas A. Tombrello, Vice Chairman, California institute of T=hnology C. K. Reed, Executive SecretarNyet,ional Academy of Sciences Lowell M. Bollinger, Argonne Nationel Laboratow Peggy Dyer, UnivarsiW of Washington Rusaall Heath, Aerojet Nuclear Co., Inc. Roy K. Middlaton, University of Pennsylvania 1:Lon Morgan, Columbie Scientific Industries G. Davis O’Kelley, Oek Ridge National Laboratow G. C. Phillips, Rice University Henry N. Wagner, Jr., The Johns Hopkins Medial Institutions Joseph Wen~, Brookhaven National Laboratory Sheldon’ Wolff, University of California Chien-Shiung Wu, Columbia Univar?@ Alexander Zuckar, Oak Ridga National Laborato~ Liaison Members William S. Rodney, National science Foundation George L. ROWS, Energy Research and Development Admini-ration SUBCOMMITTEE ON RAD1OCHEMISTRY G. Davis O’Kelley, Chairmsrr, Oak Ridge National Laboratory Glen E. Gordon, UnivwsiW of Maryler& ‘“- ,-. Rolfa H. Hw*r, Rutgers Univemity John A. Miskel, Lawrence Livermore LaboratoW Harold A. O’Brien, Jr., Los Alamos Scientific Laboratory Richard W. Perkins. Bettafle Pacific Northwest Laboratories Andrew F. Stehney, Argonne National Laboratory Kurt Wotfsbarg, Los Alanros Scientific Laboratow LiaisonMembers ~ John L. Burnatte, Energy Research and Davelopmant Administration FTed Findeis, National Scienca Foundation i.,.~.. Radiochemistry of Bismuth Kashinath S. Bhatki TataInstitutoefFundamental Research Homi Bhabha Road,Bombay 400005 and Bhabha Atomic ResearchC-entre Trornbay,Bombay 400085 (India) Prepared for Subcommittee on Radiochemistry National Academy of Sciences - Natiorial Research Council IssuanceDate:September 1977 Published by Technical 1nform,ation center ENERGY RESEARCH AND DEVELOPMENT ADMINISTRATION Price$4.75.Availablefrom: NationalTechnicalInformationservice U.S.DepartmentofCommerce SpringfieldV,irginia22161 Printed in the United States of Anmrh ERDA TArrical Informution Center, Oak Ridge, Ten~ 1977 Foreword The Subcommittee on Radiochemistryisone ofanumber ofsubcommitteesworkingunderthe Committee on Nuclear Science of the NationalResearchCouncil.Itsmembers represent government, industriala,nd universitylaboratoriesin the areasof nuclearchemistryand analyticaclhemistry. The Subcommittee has concerneditselwfiththoseareasofnuclearsciencewhich involve the chemist,wch as the collectionand distributionof rediochemicalprocedures,the radiochemicalpurityof reagents,radiochemistryinenvironmentalscienceq nd in nuclear medicine,andtheroleofradiochemistryincollegeand universi~programs. Thisseriesof monographs hasgrown out of the need forcompilationsofradiochemical information,procedures,and techniques,The Subcommittee hasendeavoredtopresentaseries thatwillbe of maximum useto theworking scientistE.ach monograph presentspertinent informationrequiredforradiochemicalwork with an individualelementorwitha specialized technique. Expertsintheparticularradiochemicaltechniquehavewrittenthemonographs.The Energy Rewarch and Development Administrationhassponsoredtheprintingoftheseries. The Subcommittee isconfidentthesepublicationswillbe usefulnotonlytoradiochemists butal= toresearchworkersinotherfieldssuchasphysics,biochemistry,ormedicinewho wish touseradiochemicaltechniquestosolvespecificproblems. G.DavisO’Kelley,Chairman Subcommittee on RadioChemistry ,,. ., iii Preface -Thisreport on the radlochemistryof bismuth has been preparedas one of aseries of monographson the radiochemistryof the elementsunder the sponsorshipof the Subcoinnitteeon Radlochemistryof the Comnitteeon Nuclear Scienceswithin the National ResearchCouncil. Includedherein Is a reviewof the nuclearand chemicalfeaturesof par- ticularinterestto the radiochemfst,a discussionof Importantanalytical proceduressuch as precipitation, solventextraction,ion exchange,paper chromatography,electroanalyticalseparations,volatilization,etc., together with gravimetrlc,volumetric,and photometricmethods and a discussionon problemsof dissolutionof a sample. Also includedare variousradioactivity countingtechniquesand a collectionof radiochemicalproceduresfor bismuth as found In the literature. The informationcontainedin this report is Intendedprimarilyfor a radiochemist,but the increasinginterestof the so-calledradlochemistin problems involvlngmineral, meteorological,biologicaland environmental samplesand the continuinguse of radiochemlcaltechniquesby biologists, biochemist:,analytical,organicand physical chemistshas caused a rather broad definitionof radiochemistryto be taken. It is hoped that this report will be of use to workers in these diverse fields,while at the same time keep- ing reasonablyaccessiblethe data needed by workers desiringto make simple, fast separationsof bismuthfrom some other radioelements. The literaturesearchwas completedaround the middle of 1973. It is hoped that the bibliographyIs sufficientlyextensiveto serve the needs of the radiochemist,but it is to be expectedthat Importantreferences were omitted. Notificationof such omissionsof publishedor unpublished materialor new techniquesfor incluslonin futurerevisionsof this monograph WOU1d be much appreciatedby the author. K. S. Bhatki Bc+nbayI,ndia March, 1976 iv Foreword iii Preface iv Contents v I. GeneralReferenceson the Chemistryof Bismuth 1 A. Inorganicand AnalyticalChemistry 1 B. Radiochemistry 1 II. Isotopesof Bismuth 3 III. Reviewof the Chemistryof Bismuth 10 A. MetallicBismuth 10 B. ChemicalPropertiesof Bismuth 11 c. BismuthCompounds 12 1. Solubleand insolublesalts of bismuthand gravimetriccompounds 12 2. The bismuthylcompounds 15 3. Organiccompoundsof bismuth 16 4. Sununaryof the propertiesof bismuthcompounds 18 D. Precipitationand Coprecipitation 23 1. Coprec~pitationof Bismuth 23 2. Precipitationof bismuth 25 E. BismuthComplex Ionsand Chelates 29 F. AnalyticalDeterminationsOther than Gravimetric 29 1. Volumetricmethods 29 2. Colori,metricand SpectrophotometricMethods 38 3. 2-Pyridylazocompounds 44 G. SolventExtraction 46 v 1. Ion associationsystems 49 2, Chdlatesystems 50 H. Ion Exchange 58 1. Cationexchange 60 2. Anion exchange 68 3. Chelatingresin 70 I. Chromatography 71 1. Paperchromatography 72 : 2. Separations 74 3. Reversedphase extractionchromatographyor partition 79 chromatography J. Electrochmlcal Techniques 82 1. Electrolyticmethods 83 2. Potentiometrictitrations 86 3. Amperometry 86 4. Polarographicanalysis 89 K. NeutronActivation 91 L. Atanic AbsorptionSpectrometry 93 M. Vacuum Evaporation 95 N. The Ring Oven Technique 95 O. Substoichiometryin BismuthAnalysis 99 IV. Dissolutionof BismuthSamples 100 v. CountingTechniques 101 VI. CollectedRadiochenicalProcedures 105 References 129 vi Radiochemiatry of Bismuth KashinathS. Bhatkl Tata Instituteof FundamentalResearchpBombay-5 and BhabhaAtcnnicResearchCentre,Trombay (India) I. GENERALREFERENCESON THE CHEMISTRYOF BISMUTH A, Inorganicand AnalyticalChemistry 1. The AmericanSociety for Metals,MetalsHandbook,Chapmanand Hall, London, 1971. 2. Basolo,F. and Pearson,R. G., Mechanismsof Inorgan~cReactions. 2nd edition,John Wiley and Sons, New York, 196/. 3. Busev,A. I., Tiptsova,V. G. and Ivanov,V. M., “Bismuth”,in Handbookof theAnalyticalChemistryofRARE ELEMENTS. (Translated by Schmorak,J.) Ann Arb,or-HumphreySciencePublishers, London, 1970. 4. Fritz,J. S., “Bismuth”,in Treatiseon AnalyticalChemistry. Kolthoff,I. M. and Elving,P. Section A. IntersciencePublishers,New”Yo;k~”l;6~’14;:175.p 5. Lingane,J. J., AnalyticalChemistryof SelectedMetallicElements. ReinholdPublishingCorporation,New York, 1966. 6. McGraw-HillEncyclopediaof Scienceand Technolo “Bismuth”,in Vo1. 2> PP. Z68-ZIU. McGraw-HillBook 7. Miller,E. A., “Originand Distributionof the Elements”,in L. H. Ahrens, (cd.)PergamonPress,Oxford, 1970. 8. Morries,P., “Bismuth”,in ComprehensiveAnalyticalChemistry, Wilson, C. L. and Wilson, D. C* PP. 26b-Z/6s ElsevlerPublishingCo.,Amste;d~,si96+ 9. Templeton,D. H. and Bassett,L. G., “Phosphorus,Arsenic,Antimony and Bismuth”,pp. 321-338,In C. J. Rodden (cd.)Anal tical Chemistryof the ManhattanProject,McGraw-HillB+o,o., hew York, lYtLI. 10. Wilson,C. L. and Wilson,D. W.. (eds.) ComprehensiveAnalytical Chemistry,Vol. 11.C: “ElectricalMethods,PhysicalSeparation Methods”, lsevierl%blishing Co., Amsterdam,1971. B. Radiochemistry 1. Bagnall,K. W.. “The Chemistryof Polonium”,in Advances in InorganicChemistryand Radiochemistry, vol. 4, ~cademic Press, New York, 1962. 1 2. Figgins,P. E., “The Radlochemistryof Polonium”NationalAcademy of Sciences- NationalResearchCouncilReportNAS-NS-3037,(1961). 3. Fritz,J. S., “Bismuth”,Ames LaboratoryReport IS-232,(Oct.1960), Ames, Iowa. 4. Gibson,W. M., “The Radiochemistryof Lead”,NationalAcademy of Sciences- NationalResearchCouncilReportNAS-NS-3040(1961). 5. Haissinsky,M., and Adloff,J. P., RadiochemicalSurveyof the Elements,ElsevierPublishingCo., New York,~ 6. Kirby,H. W. and Salutsky,M. L., “The Radiochemistryof Radium”, NationalAcademyof Sciences- NationalResearchCouncilReport, NAS-NS-3057(1964). 7. Lange, R. C., “TheAnalyticalChemistryof Polonium”,in Anal tical * -#Y;;;;~~e;.;ti~ !4%” ‘. ‘. ‘eds.)’“ 8. McKay, H. A. C,”,Principlesof Radiochemistry,Butterworths,London, 1971.