E958r i C.9.. National Academy v“ of Sciences 1National Research Council NUCLEAR SCIENCE SERIES The Radiochemistry of Iridium 3“#L7 :, ,fy% COMMITTEE ON NUCLEAR SCIENCE L.F.CUR~, Chafrman ROBLEY D.EVANS,ViceChuirmun NationalBureauofStadarde MaeeachueetteInetituteofTechnology J.A.DeJUREN,Secretury WeMnghouee ElectricCorporation H.J.CURTIS W. WAYNE MEINKE BrookhavenNationalLaboratog UniversityofMichigan SAMUEL EPSTELN ROBERT L.PLAT ZMAN Callforn.laInetItuteofTechuol~ ArgonoeNationalLeboratmg HERBERT GOLDSTEIN A. H.SNELL NwlearDevelopmentCorporationof Of&RidgeNationalLaboratory America E.A.UEHLING H.JoGOMBERG Unlveret@ofWaehlngton UnlvereltyofMlcldgan D.M. VAN PATTER E.D.KLEMA BartolReeearchFoundation NorthweetarnUniveretty G.G.MANOV Tmcerleb,Inc. LIAISON MEMBERS PAUL C.AEBERSOLD W. D.URRY AtomicEne~ Commieaion U.S.AlrForce J.HOWARD MaMILLEN WILLIAM E.WRIGHT NationalscienceFoudatkon OfficeofNavalReseamh SUBCOMMIllEE ON RADIOCHEMISTRY W. WAYNE MEINKE,Chutrwaam HAROLD SURBY UnlvereityofMichtsan MoundLahoretory GREGORY R.CHOPPIN GEORGE LEDDICOTTE FlorklaStateUnlvereity OakRidgeNationalLaboratory GEORGE A.COWAN JULIAN NTELSEN LoeAlamoeSckmtlflcLaboratog Hanfod Lahoratoriee ARTHUR W. FAIRHALL ELLISP.STEINBERG UnlvereltyofWashington ArgonneNationalLaboratory JEROME HUDIS PETER C.STEVENSON Brddmven NationalLaboratory UniversityofCaltfornta(Llvemore) EARL HYDE LEO YAFFE UnlvereltyofCalifornia(Bgrkeley) McGU1 Unlvereity CONSULTANTS NATHAN BALLOU WILLIAM MARLOW Naval~iologlcalDefeneeLaboratory NationalBureauofStandamie JAMES DeVOE UntveieityofMhhigan The Radiochemistry of Iridium By D, N. SUNDERMAN and C. W. TOWNLEY Battelle Memorial Institute Columbus, Ohio M21y 1960 , OCT31 1968 Ln3RARIEs PROPERTY ..6 Subcommittee on Radiochemistry NationalAcademy ofSciences—National Research Council PrintedinUSA.Price$0.50.AvailablefromtheOfficeofTeohnical eervicea,Wxment ofCommerce,WasM@n 26,D.c. FOREWORD The Subcommittee on RadlochaMstry iB one of a number of 8UbCOmIUltkeS working under the Committee on Nuclear Science wlthln the National Academy of Sciences - National Research Council. Its members represent government, industrial, and university laboratories in the areas of nuclear chemistry and analytical chemistry. The Subcommittee has concerned Itself with those areas of nuclear science which Involve the chemist , 8UCh as the collec- tion and distribution of madiochemlcal ‘procedures,the estab- lishment of specifications for radlochemically pure reagents, availability of cyclotron time for service Irradiations, the place of mdlochemlstry In the undergraduate college program, etc. This series of monographs has grown out of the need for up-to-date compilations of radlochemical information and pro- cedures. The Subcaumlttee has endeavored to present a series whloh will be of maximum use to the working scientist and which contains the latest available Information. Each mono- graph collects in one volume the pertinent information required for radlochemical work with an individual element or a group of closely related elements. An expert In the radlochemlstry of the particular element has written the monograph, following a standard format developed by the Subcommittee. The Atomic Energy Ccmmlsslon has sponsored the printing of the series. The Subcommittee is confident the8e publications will be useful not only to the radlochemlst but also to the research worker In other fields such as Physics, biochemistry or medicine who W18heS to use mdiochemlcal-techniques to solve-a specific problem. W. Wayne Meinke, Chairman Subcommittee on Radlochemlstry Iii CONTENTS I. GeneralRetievsof the Inorganicand AnalyticalChetit~ of Itiium 1 II. GeneralEevieuaof the Radiochend.stryof hdium 1 III. Tableof Isoto@s of IndiunI 2 Iv. Reviewof ThoseFeaturesof IridiumChemistryof ChiefInterestto Radiochemiets 4 1. M3tallicjlldium 4 2. Solublesaltsof i.ndium k 3. heoluhle saltsof iridiumand p cipitationand uoprecipitation chsracteristiceof iridium 4 4* Complexions of hdium 10 5. Chelatec.mqlexeaof iridium n 6. Fktmction of the ThenoylTrMlmoroacetone(T’l@complexof iridiumtito organiceoivents u 7. &traction of iridiumtito organicaolventa u 8. Ion exchangebhatior of indiiuo 19 v. Dissolutionof MaterlalaContainingIridium 22 VI. RadicassayTechniquesfor IridiumIsotopes 23 VII. Collectionof LktalledRadiochemkalFhoceduma for Indiu.m 25 INTRODUCTION This volume which deals with the radiochemlstry of iridium is one of a series of monographs on radiochemistry of the elements. There is included a review of the nuclear and chemical features of particular interest to the radiochemist, a discussion of prob- lems of dissolution of a sample and counting techniques, and finally, a collection of ~adioche.micalprocedures for the element as found in the literature. The series of monographs will cover all elements for which radiochemi.cal procedures are “pertinent. Plans include revision oi’the monograph periodically as new techniques and procedures warrant. The reader is therefore encouraged to call to the attention of the author any published or unpublished material on the radiochemistry of indiu.mwhich might be included in a revised version of the monograph. vi The Radiochemistry of Iridium D. N. ~ end cm w. ‘lQRnlxY Batte~e Memrial Inatitute Colulrihua, Ohio May 1960 I. GENERALREVIEMSOP Tm INf)RMJCtCAND ANALYTICALCHEKCSTRYOF lNDIJJM Pp. 576-577in Vol. I of ‘AnalyticalChemist@, F. P. Treadwell, ti. ad rev. by UilliamT. Hall,JohnWley and SODS,Inc., New York,tith edition,1937. n Chapter17, pp. 7U-768 h ● InorganicChendst&, T. Moeller, JohnWley ad Sma, Inc.,New York,1952. Page 211 in ‘Solvent&traction in AnalyticalChemistr#, G. H. Morrisonand H. Freiaer,JohnWileyand Sone,Inc., New York,1957. PP. %7-405 h VO1. 5 of ‘A CoqrehensiveTreatiseon Inorganic and TheoreticalChemiat#, J. W. Mellor,Lorgmne, Green,and co., London,1924. aIndiu#, M. T. Ludwlck,Mium Corporationof Amrica, New Ymk, 1950. Pp. 461.-465in “AppliedInorganicAnalysism,W. F. Hillebmnd ati G. E. F. Ltiell, JohnUileyand Sore,Inc., New York, secondedition,1953. II. GENITW REVIJ%lSOF THE RADIOCHEKLSTRYOF INDIUM •MdioH~ separationsof lkdiunP,D. N. Sundez’m% I. B. Ackermnn, and W. W. Whim, Anal@i(xd Qmtitry 3& &O, January1959. mTheDevelopmentad Evaluationof EadiochemicalSeparation fiocedureefor Mrium, Calcium,Strontium,S~ver, and Indiu#, mm N. Sundeman,AECU-3159,February1956. 1 III. TABLE OF ISOTOPESOF INDIOM PrimazgRadiationa Isotope Half Life f Deoay G s Methcdof Preparation In107 2&~ ‘ 0.22amw MaV Cdld (d,n) #08m 0.2~6 4?07 (K, 3n) 2+ 0.330 0.637 0.88 1.05 40 min 0.637 @+ 3“5 @09m 1.3 min IT (m%). 0.658 Daughterof S&09 =1.09 4.2 m. m (94%) 0.058 AE?07(< ,h) , ~’ 0.80 (6%) 0.205 daughterof InlO~ 0.227 0;28$ 0.325’ 0.347 0.427 0:632 #Om 4.9 hrs. EC (99+ %) o.119 4#7 (<, d R’ 0.IL9 (0.6%) 0,.661 0.885 0.935 66 Edn. 0.656 A&$m( ~,n) , Cdno ~“ 2.25 (P,d 2.81 dsya EC 0.172 CdlU (p,n) 0.247 20.7mn. IT 0.155 (loo%) 0.155 Ag109{* ,n),Inu3 (n,2n) 1!5Udn. Daughterof Inu2m *3m 1.74 hrs. ~ 0.392 (100%) 0.392 D&&r of SnU3 =113 Stable(h.33%) ,. 2 III. TABLE (CONTm) Prhbmy Radiation Isotope HalfLife of Decay anmm &thod of hepam tion IT 0.192 (96.5%) 0.19’2Mev #.3 + -t~~~ EC (3.5%) O#g . #b 72 eec. /7 - ::SJ4(:9!EI] 1.30 (0.0%) InU3 + neutrone # + O.h (& : 10-%) Eo (1.9%)- #m L.5 bra. ~ 0.335 (95%) 0.335 Fiaaionproduct, # -0.83,(5%) daughterof odl-1~ #5 6xi#~. @ -0.63 Wne Exiatain nature (95.67%) =116m 54 Irdn. 0.137 (3fi) IrPb + ieutrme 0.406 (25X) 1.085 (54$ 1.271J(75X1 1.487 (~%) 2.090(25%) =116 13 sec. none $5 + neutrozm @h 1.9 bm. @ ‘“1.77.(55%) o.161 FiEShllproduct, 1.62 (23%) o.311 daughterof Cd”7 IT o.3n (225) #7 1.1 bra. /9 -0.74 =118 4s Irdn. /6 -1.5 =m 5.5 sec. d - u =119 17.5J&l. @ -2.6 =120 _ 55 sec. (#-) For nmrecoqlete infmtion on the radiatiomeof the iaotopa of indlumand for refkrenceato the ori@al literature,see ●Tableof Iaotopeam, D. Stromlngar,J. M. Hollander,and G. T. Seabcmg,Reviewsof ModernPhyeice 30, No. 2, Part II,Aprfl1958. 3 IV. REVIEWOF THOSEFEATURESOF INDIDMCHEFfLSTRXOF CHIEFINTERESTTO EUDIOCHEKCSTS 1. NetallicIhdium Mum is a relativelyrare mtal (1 x 10-5% of the earth’a crust) and is never foundin concentrateddepcsits. It vaa diaoovemd h aincores and has also been foundasfloctitidwith tungsten. one of the reaaom for interesth Imiiumchemistryis its high capturecrose-sectionfor therml mutrons whichmakesits ~eeenca in reactormaterialsundes-ble. The phgsi CS1 propartiesof iridiumare intermediatebtween those of galliumand thallium. Ihdiumhas a low maltingpetitof 156 C, a boiling pointof 450 C, and a densityof 7.20 ticc. 1% is a veryBoftand ductile mtal. In appearanceit is whiteand lustrous,reeemlilingplatinum. Iridiumis clcaelyrelatedh its chemistryto aluminum,gallium, and tlMllium. Iktalliciridiummay be preparedby electrodepositionor by thenualreductionof the oxidewith h@rogen or cartin. The mtal is slowly oxidizedin ccmtactwith air,and it b not attackedby water. l’k$tallic i.ndiumdissolvesIn acidswith likmation of hydrogenand formtion of trivdmt hdlum ions. Ths oxidationpotentialin acidicsolutionfor the In(o)- In(III)coupleis O.3hvolts. 2. SolulleSaltsof Iridium The trivalen$Ion of iridium5s the only ton sta~e in aqueous sol~tions.‘The +1 and +2 Statgssxiat as the solidhalj.des.Ths soluble saltsof tidiumincludethe c~oride, nitrate,eulfate,brcndde,icdtie, and perclilonte. 3. InsoluliLeSaltsof Iridiumand Precipitation and CoPrecipitationCharacteristicsof Iridium The commoninsolu~e saltsof Imdiumare listedin Table1. The generalreference listedin PartsI and II describethe insolublecospounds of iridiumand tlalruse in analyses. Quantitativemthods