‘~,11 —National T Academy v of I Sciences National Research Council B NUCLEAR SCIENCE SERIES The Radiochemistry of Zirconium and lHafnium :$-:9: CNcmLHRARY c,)) COMMITTEE ON NUCLEAR SCIENCE. :’- ‘... :. L. F.CUR=, Chuitvnan ROBLE,Y D. EVAN& ViceC~rman NationalBureauofSt.adards MassachusettsInstituteofTedmology ,,., J.A. bJUREN, Secretury WestlnghoueeElectricCorporation H. J.CURTIS G. G.MANOV BrookhavenNat.lonalLaboratory Tmmerlab,Inc. SAMUEL EPSTEIN W<.WAYNE bfIiIkE “““ CaliforniaIuetituteofTechnol~ UniversityofMichigan HERBERT GOLDSTEIN A. H. SNELL NuclearDevelopmentCorpfitionof ‘“ oak Ridge,NationalL@ho~torY knerlca E. A. UEHLING ‘H.J.GOMBERG UnlversltyofWashbgton UnlversltyofMichigan D. M. VAN PATTER E.D. KLEMA BartolResearchFoundation NorthwesternUniversity ROBERT L. PLATZMAN ArgonneNationalLaboratory LIAISON ,MEMBERS PAUL C.AEBERSOLD W. D. URRY AtomioEneqy Comdsston U. S.Air Foroe J.HOW~”?dd#fLLEN WIIiW”E: WFUGHT NationalScienceFoundation OfficeofNavalReeearoh SUBCOMMITTEE ON RADIOCHEMISTRY W. WAYNE MEINKEC Ckirnwn EARL HYDE UnlversiWof Mkhigan Unlversl&ofCdlforda (Berkeley) NATHAN BALLOU HAROLDKIRBY NavyRadologlcalDsfenaeLshoratory Moud Lahmatory GREGORY R. CHOPPIN GEORGE LEDDICOI”TE Florida-bs Universally Oak RidgeNationd Lahomtory GEORGE A. COWAN ELLIS P.STEINBERG Loe AlamosSclentlflcLaboratory ArgonneNationalLaboratory ARTHUR W. FAIRHALL PETER C. ~EVENEON UnlvereltyofWaehlngton UnlversltyofCalifornia(Livermore) HARMoN FINSTON LEO YAFFE BrookhavenNationalL@oratory McGU1 University The Radiochemistry of Zircomium and Hlafnium By ELLIS P. STEINBERG. Argonne National Laboratory Lemont, IlliM”s January1960 Subcommittee on Radiochemistry NationalAcademy ofSciences—National Research Council PrintedinUSA.Price$0.50.AvailablefromtheOfficeofTechnical Services,DepartmentofCommerce,Washington25,D.C. FOREWORD TM Subommd.tteeon Radiodmnistryis oneof a numberof subcommittees %KmlcingundertheCommitteeon NuclearSciencewithintheNetio:nalAcademy of SoUmees-NationalResearchCouncil.Itsmembersrepresentgovernment industrialandtmivsrsitylaboratoriesin theareasof nuclearchemistry andanalyticalchemis&y. TheSubcommitteehasconcerneditselfwiththoseareasof :nuclear sciencewhichinvolvetheohemist$suchas theoolleetionanddistribution of radiochwtbxilprocedurestheestablishmentof specti%ationsforradio. cthetioally-purereagamtsjtheproblemsof stockpilinguncontaminatedmateri.- .aMpthem?ailabi.lf.tyof cyclotrontimefor serviceirradiationstheplace of radicmhetistryin theundengradua%ecollegeprogmm9etc. T’Msseriesof monographshasgi”o~ outof %heneedforq-to-date eompiktionsof’radiocbtio~informationandprocedures,TheSubcommittee haseadeavox’edto presenta serieswhichwillbe of Ms&.mumuse %0 the workingscientistandwhichcontainsthelatestavailableinformation. &ch mmgraph aol.1.am%sh onevmlumethepertinentinformationrequired for~adicwhetitiworkwithan individualelementor a groupof closely relatedelements. An expwt in the radioehemistry d thepartiemlardemerit haswritten themno~aph$ f’ol.lowlmga standerdformatdevelopedby theSubccxmd.ttm. The.AtomicEnergyCommissionhas sponsoredtheprintingof thesexles. The Subconzki.ttxswis conf%ien~thesepubl.tcatfonswillbe usefulnat onlyto theradiochemistbutalsoto theresearchworkerin otherfields suchas physios,biochemistryor medicinewhowishesto useradiochmicsl techniquesto solvea specificproblem. W. WayneFMnke, Chairmen Subcommitteeon Radiochemidry iii CONTENTS 1. General Reviews of the Inorganic and Analytical Chemistry of Zrand Hf. ...1 11. General Reviews of the Radiochemistryof’Zr and Hf. 2 111. Table of Isotopes of zirconium and Hafnium . 3 Iv. Review of those Features of Zirconium and Hafnium Chemistry of Chief’Interest to Radiochemlsts . 4 v. Problems of Sample Dissolution and Interchange with Carrier. 19 VI* Counting Techniques. 20 VII.. Collection of Detailed RadiochemicalProcedures . 22 iNTRODUCTION This volume whichdealswiththeradiochemistryof zirconiumandhafniumis oneof a seriesof nmnog=phson radiochemistryof theelements.Thereis includeda review of thenuclearandchemicalfeaturesof particularinterest to themdlochemist,a discussionof problemsof dissolution of a sampleandcountingtechniques,andfinally,a collec- tionof radiochemicalproceduresfortheelementas found@ tieliterature. The seriesof monog=phawiU coverallelementsfor whichtiiochemlcalprocedunsareperttient.Plansinclude revisionof themono~ph periodicallyas newtechniquesand procedureswarremt.Thereaderis thereforeencouragedto callto theattentionof theauthoranypublishedor unpub- lishedmaterielon theradiochemistryof zirconiumandhaf- niumwhichmightbe includedIn a revisedversionof the monograph. vi I. General Reviews of the Inorganlo and Analytlaal Chemistry of Zimonlum and H4Mm. ~ Nostrand ~0., Irm. New York, 1958. Pp. 628-653, “Chemioal Elements snd their Compounds,”N. V. Sldgwlok, Word Unlverslty Press, 1950. Pp. 564-575, ‘Applied Inorganio Analysls,m W. F. Hlllebrand et al., John Wiley and Sons, Inc., New York, 1953. Chaps. 12 and 13, “Chapters In the Chemistry of the Less Familiar Elements,” B. S. Hopldns, Stlpes Publishing CO., Ohmwaign, 111., 1939. ‘Hafnium,’ Chap. IV in “Modern Advames in morganio Chemlstry,8 E. B. Maxted, Oxford University press, 1947. R. L. Barnard and R. E. Telford, Chap. 20 In “Analytloal Chemistry of the Manhattan Projeot,n C. J. Rodden, eds., HoGraw-Hill Book Co., New York, 1950. E. B. Read, OhaP. 12 In “Metallurgy of Zirconium,” B. Lumtman and F. Kerze, Jr., eds., Mo(Waw-HillBook Co., New York, 1955. tielln~s Handbuoh der Anorganlsohem Ohemle, Systems NV. 43, 8th Edition (Ve% lag Ohemle, Gmb H. Ueinhelm - Bergstrasse, 1958.) ‘Ziroonlum,”(3.I.MUler, AcademioPress (1997). ‘Reoent Advances In the Chemistry of Ziroonlum and Hafnlum,= E. M. Iarsen, J. Chem. Ed. 28, 529 (1951)0 1 Msclvent -traction in Analytical Chemistry” G. H. Morrison and H. Freiser, Wiley (1957). “Ion-Exchangersin Analytical Chendst.ry,WO. Samuelson,Wiley (1955) ● ‘Chemistry of the Metal Chelate Compounds,nA. E. Marten and M. Calvin, Prenttce-Hall(1952). 11 ● General Reviews of the Radiochemistryof Zirconium and Hafnium. No general reviews have been published. D. N. Hume pre- pared a pre13.minaryreview of the radiochemistryof some of the major fission product elements in 1945, but it was not published. Some materials from this review has been incor- porated in the following presentation. More complete information on the radiations of these isotopes and references to the original literaturemay be found in “Table of Isotopes,n D. Strominger,J. M. Hollander, and G. T. Seaborg, Revs. Mod. Phys. ~, No. 2, Part II, April 1958. 111. Table of Isotopesof Zirconiumand Haf%xium. Isotope Half-1ife Type of Decay Method of Preparation !ZP86 17 hr EC Nt p,spall.);As75(N14,3n) #7 94 fin ZrA‘(cx,n) ZP88 85 day w Ni(p,spall.) ~r89m 4.4 min It(93$%),EC(5.6~),P+(l.8~) Zr(X-ray) Z2?@ 79.3 hr EC(a75~),f3+(~25j%) Y(d,2n] 0.83 sec IT ‘Z@go(n,nl) L1X106 yr B- Nuclear fission 65 day $- Nuolear fission 17.0 hr B“ Nuclear fission .-dmin P- Nuclear fission 35 sec P- Nualear fission ~+ 112 tin Lu(p,6n) 16.0 ‘hr EC Lu(p,5n),Yb(cz,3n) ..5yl? EC Lu(p,ytj(a,xn),Ta(d,2P9n) 23.6 hr EC Lu(p 3n); Yb(a,xn) 70 day EC Hf147 (n,y) 4,8 S13C IT daughter ‘2.1 hr T.’78 19 seo IT Hf178(n,y) 5.5 hr IT Hf179(n,y) ~- Hf180 44.6 day (njy) 64 min P- W(n,a) .-. ——..— m. Review of those Features of zirconium and Hafnium Chemlst~ ● of Chief Interest to Radiochemists. 1. The Metallic State zirconium and haf%lum are diffloult to prepare as pure metals. They are very infusible and react vigorously at high temperatures with carborbo~gen, and nitrogen. When finely divided, the dry metal powders are Wophorlo and should be molatened for safe handling . In oaspaot fom and at low temperatures the metals are ve~ inert ohemloally, being attacked app??eoiablyonly by RF, aqua regla, and fused KN03. The best method of preparation of’the pure metals Is probably the van Arkel-de Boer method of reduolng the Iodides on a hot filament. Thla produces the so- oalled ●oryatal barn metal. 2. Soluble Salts l%e solution ohemlstry of ziroonfum Is not veqy well under- stood, and oonalderableoomfuslon exists in the literaturere- garding the lonlo species present in aqueous solutions. ~18 results mainly frcm the fomnatlon of collolds and the fact that ziroomlum ions undergo extensive hydrolysis and polymerization, strongly dependent on PH and conoentratlon. (1) The only Important cddation number Is #l. The nitrate, chloride, bromide, iodide, perchlorate and sulfate of zlroonium are soluble In sold solu- tlon. 3. llmoluble Salts Among the more Insoluble oompounds Is the very Insoluble -18 (~~ phosphate, ZFO(qP04)2 (K~p=2.28x10 ) which precipitates even “Zlrconlum and hafnium show a remarkable slmllarltyIn mo6t of their chemical properties,and unless otherwise noted, any statementsmade concerning one generally will apply equally well to the other. 4 . from 2@ nulfurle acid. It has’properties similar to those Of cerlc phosphate,but 16 dissolved by hydrofluorio acid. The io- date precipitates frcun8 ~HN03, and the arylsubstituted arsomteb and cupf’emate from acid solutions. The hydroxide (or hydrous oxide) 1s preolpitated with ammonia or alkali hydroxide, and a pertide with ~02 from dilute acid. Of these, only the phos- phate is soluble In exoess reagent. Barium and hydrofluorio sold give sllghtly soluble barium fluorzlrmnate of uncertain mmposl- tlon, whioh Is Insoluble in exoess fluorlde and affords a good separation frcm nlobim. The eustmrg weighing form In radloohemloal and analytical proeedure6 has been the Ignited Zr02 following preolpltatlon as ~e~l arsenate, cupfernate