放射化学系列-碲的放射化学(英文)

. (L22&QJv?k) 1“ National Academy ‘ v of Sciences National Research Council m NUCLEAR SCIENCE SERIES The Radiochemistry of Tellurium i COMMITTEE ON NUCLEAR SCIENCE L. F.CURTISS,Chaiwzan ROBLEY D. EVANS, Vice Chairman NationalBureauofStandards MassachusettsInstituteofTechnology J.A. DeJUREN, Secrefa~y WestinghouseElectricCorporation C.J.BORKOWSKI J.W. IRVINE,JR. Oak RidgeNationalLaboratory MassachusettsInstituteofTechnology ROBERT G. COCHRAN TexasAgriculturalandMechanical College SAMUEL EPSTEIN CaliforniaInstituteofTechnology U. FANO NationalBureauofStandards HERBERT GOLDSTEIN NuclearDevelopmentCorporationof America E. D. KLEMA NorthwesternUniversity W. WAYNE MEINKE UniversityofMichigan J.J.NICKSON MemorialHospital,New York ROBERT L. PLATZMAN Laboratoirede ChimiePhysique D. M. VAN PATTER BartolResearchFoundation LIAISON MEMBERS PAUL C. AEBERSOLD CHARLES K. REED AtomicEnergyCommission U. S.Air Force J.HOWARD McMILLEN WILLIAM E.WRIGHT NationalScienceFoundation OfficeofNavalResearch SUBCOMMITTEE ON RADIOCHEMISTRY W. WAYNE ME INKE,Chairman HAROLD KIRBY UniversityofMichigan Mound Laboratory GREGORY R. CHOPPIN GEORGE LEDDICOTTE FloridaStateUniversity Oak RidgeNationalLaboratory GEORGE A. COWAN Los Alamos ScientificLaboratory ARTHUR W. FAIRHALL universityofWashington JEROME HUDIS BrookhavenNationalLaboratory EARL HYDE UniversityofCalifornia(Berkeley) JULIAN NIELSEN HanfordLaboratories ELLIS P.STEINBERG ArgonneNationalLaboratory PETER C. STEVENSON UniversityofCalifornia(Livermore) LEO YAFFE McGillUniversity CONSLJLTANTS NATHAN BALLOU JAMES DeVOE NavalRadiologicalDefenseLaboratory UniversityofMichigan WILLIAM MARLOW NationalBureauofStandards CHEMSTRY The Radiochemistry of Tellurium G. W. LEDDICOTTE Oak Ridge National Laboratory Oak Ridge, Tennessee ImmnceDate:July1961 Subcommittee on Radiochemistry NationalAcademy of Sciences—National Research Council PrfntedinUSA.Price$0.50.AvaIlnblefromtheOfficeofTechnical Rervicea,DeparbnentofCommerce,Washington25.D.C. FOREWORD The Subcommittee on Radlochemistrv ~s one of a number of subcommittees working under the Commlt{ee on Nuclear science within 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, such as the collec-” tion and distribution of radiochemical procedures, the estab- lishment of specifications for radiochemically pure reagents, availability of cyclotron time for service irradiations, the place of radiochemistry in the undergraduate college program, etc. This series of monographs has grown out of the need for up-to-date compilations of radiochemical Information and pro- cedures. The Subcommittee has endeavored to present a series which will be of maximum use to the worktig scientist and which contatis the latest available tiformation. Each mono- graph collects in one volume the pertinent information required for radiochemical work with am individual element or a group of closely related elements; An expert in the radiochemistry of the particular element has written the monograph, following a standard format developed by the Subconmlttee. The Atomic Energy Commission has sponsored the printing of the ,series, The Subcommittee is confident these publications will be useful not only to the radlochemist but also to the research worker h other fields such as physics, biochemistry or medicine who wishes to use radiochemical techniques to solve a specific problem. W. Wayne Meinke, Chalman Subcommittee on Radiochemistry .,.111 INTRODUCTION This volume which deals wfth the radlochemlstry of tellurium is one of a series of monographs on radiochemfstry of the elements. There 16 included a review of the nuclear and chemical features of particular Interest to the radlochemist, a discussion of prob– lems of dissolution of a sample and counting techniques, and finally, a collection of radlochemlcal procedures for the element as found in the literature. The series of monographs will ‘cover all elements for which radiochemical procedures are pertinent. Plans Include revision of 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 tellurlum which might be included In a revised version of the monograph. iv CONTENTS 1. GeneralReferenceson the Inorganicand Analytical Chemistryof Tellurium . . . . . .-. . . . . . . ...1 II. RadioactiveNuclidea of Tellurium . . . . . . . . . . 1 III, The Chemistryof Tellurium and Its Application to the Radiochemistryof the Tellurium Rsdionucliiies.. . . . . . . . . . . . . . . . . . . . 2 A. The 1. 2. B. The 1. 2. 3. 4. 2 General Chemistryof Tellufium . . . . Metallic Tell@um . . . . . . . . . . The Compoundsof Tellurium . . . . . . a. The Oxide, Oxyacid, and Oxyhslide Cosqmunddof Tellurium . . . . . . b. Halogen Compoundsof Tellurium . . C. HydrogenCcsspoundsof Tellurium. . d. The Sulfur C!ompomds . . . . . . . e. U1 Compoundsof Tellurium . . . AnalyticalChemistq of Tellurium . . Separationby Precipitation . . . . . Separationby Volatility . . . . . . . Separationsby Electmlysia . . . . . Separationsby SolventExtraction . . a. Ion AssociationSystems . . . . . b. Chelate Complex Systems . . . . . Separationsby Ion Exchange . . . . . Separationsby Paper Chromatography . . . . . . . . . : . . . .,5 . . . . 8 . . . . 9 . . . . 10 . . . . 10 . . . . 10 . . . . u. . . . . 12 . . . . 14 . . . . 14 . . . . 15 . . . . 15 . . . . 16 . . . . 16 . . . . 17 Iv. Dissolutionof Samples ContainingTellurium . . . . . 18 v. Safety Frac*ices .’..... . . . . . . . . . . ...19 m. bunting Techniquesfor the Tellurium ,Radionuclides. . . . . . . . . . . . . . . . . ...19 VII. Collectionof DetailedRadiochemicalProcedures for the TelluriumBeilionuclides. . . . . . . . . . . 20 v . The Radiochemistry of Tellurium G. W. LEDDICOTTE Oak Ridge Nationul Laboratory* Oak Ridge, T@m.essee I. GENERAL RITERENCESON ‘THEINORGANICAND ANALYTICAL-STRY OF TELLURIUM 1. 2. 3. 4. 5. 6, 7. Remy, H., Treatise on Inorg@c Chefietw, Volume 1, p. 741-’7s2, Elsevier,Amsterdam (1956). Kleinberg,J., Argerslnger,W. J., Jr., and Griswold,E., Inorganic Chemistry,p. 434-455,Heath, Boston (19&l). Hillebrand,W. F., Iu.ndell,G. E. F., Bright, H. A. and Hoffman, J. L., Applied InorganicAnalysis,John Wiley and Sons, New york, 1958. Wilson, C. L. and Wilson, D. W., ComprehensiveAnalyticalChem- istry, Elsevier,Amsterdam,1959. Sienko,M. J. and Plane, R. A., Chemistry,McGraw-Hill,New York, 1957. Chexlot,G. and Bezler, D., QuantitativeInorganicAnalysis, John Wiley emd Sons, New York, 1957. Sldgwick,N. V., The ChemicalElements and Their Compounds, Unlver8ityPress, Oxford, 1951. II. RADIOACNYE NUCIZDES OF TEILURIUM The radioactivenuclides of tellurlumthat are of interestin the radiochemistryof telluriumare given in Table I. This table has been compiled’frominformationappearingin reprts by Strominger,et al., (1) and by Hughes and Harvey.(2) *@crated for U. S. Atomic lherm Comnissionby Union Carbide Corporation. 1 Teble I. The radioactiveNuclhieaof Tellurium Radio- nuclide Te118 Tellg ~121m Te121 Te12@ Te125m Te127m Te127 Te12gm Te129 Te131m Te131 Tel& Te133m Te133 Te134 Half- life 6.0 d 4.5 d 154 d 17 d 104 d *d 115 d 9.3 h 33.5 d 72 III 30 h 24.8 m 77.7 ~ 63 m 2m 44 m Mode of Ec EC IT EC IT IT IT ~-(only) IT P-, 7 IT P-, 7 P-, 7 IT P-, 7 B- Energy of Rwiiation,Mev y: 1.6 7: 0.082, 0.213 7: 0.5(%, 0.573 7: 0.W5, 0.159 7: 0.110, 0.0353 7: 0.9885 p-: 0.7 7: 0.106 p-: 1.8 y: 0.3, 0.8 7: 0.17’7 B-: 2.0, 1.4 p-: 0.22 7: 0.4 P-: 2.4, 1.7 7: 0.6, 1.0 Producedby Sb-d-5n Sb-d-4n Te-n-y, Sn-c+n, Sb-d-2n, Sb-p-n ~ Telam , d IU1, Sb-d-2n, Sb-p-n Te-n-y, Sb-d-2n ‘I&n-y, d Sb125 ‘e-n-y’ ‘-d-p’ 1-n-p127Uranium fission,d Sb Te-n-y, Te-d-p, Te-n-2n, ~-;LQ7~~~*ssion,J Te-n-y, Te-d-p, Te-n-2n, Te-y-n, Uranium fission Te-n-y, Te-d-p, Te-y-n, Te-n-2n, Uranium fission, Thorium fission,d Te”~, d Sb~9 Te-G , !Ihoriumfission, ?d Sb13 Uranium fission,d Sb133 d Te1331n Thorium fission III. THE -STRY OF ~AND ITS APPLICATIONTO THE RADIOCHR41STRY OF THE TELTUR17JhiRADIONUCLIDES %diochetistry is probablybest describedas being m aualysistech- nique used prinw’llyeither (1) to assist in obtaininga pure radionuclide in some form so that an absolutemeasureM nt of its radioactivity,radia- tion energies and ha~-life canbe made, or (2) to determinethe amount of a particularradioelementin a radionuclidemixture, or (3) to complete a radioactivationanalysis specific stable element in be- u6ed to detenuinethe concentrationof a a lwrticular.sample material. b order to be 2 an aid in accompllahlngany one of the above interests,radiochemktry umally considem the Isolatlonof the deeired rtiionuclldeby either carrieror carrier-freeseparationmethods. Generally,carriermethods are used mat frequentlyin radlochemi~try. They involve the addition of a SM1l mount of inactive stable element to a solution of the irradiatedmaterial to serve aa a carrier of the redio- nuclide of that element through the separationmethod. In carrier-free separations,i.e., zadiochemicaltechulquesused mostly for abaolute rdio- activltymeasurements, it is requiredthat the radtoelementbe isolated in a manner capable of givfng either no amunt or a minimal amount of stable element in the final form to be used In the radioactivitymeasurements. In most instances,analyticalrtiiochemistzyis dependentupon more conventionalideas in analyticalchemistm Involvingseparationsby such methods as precipitation,solvent extraction,chrcmmtography,volatiliz- tion, and/or electrolysisand the subsequent”presentationof the isolated redioelementin a form suitablefor a messurement of the redioelenmtns radioactltity. One major differenceexistsbetween carfier radiochemistg and mQ& conventionaltechniquesin that it is not always necessaryto re- cover completelythe added amount of carrier element, since a radiochemlcal analysisis desi~d to assure that the atoms of a radioactiveelement ,, achieve an isotopic state with the atoms of the inactive element, and any loss of the radioactivespecies is proportionalto the “loss”of carrier dting the separationprocess. Calorimetric,polarographicand similar analysis techniquesare seldom used in radiochemistry,becauee they do not separatethe desired redionuclide from contaminants(eitherradioactiveor stable) h the mixture being anal- yzed. However, some of the developmentsused In these analysistechniques may be useful in rediochemistry. The informationthat follows genemlly describesthe chemicalbehavior of telluriumand its compunds. Many of these reactionshave been used or 3 can be ueed in devlslng mdlocheunic@ analyel~methods for the tellurium redlonucllde13. More detailed hfo-tion cm the Inorganicand analytical Chembtly of thla Oectlon mxlomph. tellurium can be obtainedeither frm the ~ferences cited in or from the geneml re&rences given“inSection I of this J A. me GeMml Ch&iatry of Telltiulu Telhriun iE leas widely distz5bk.edtpea selemlum;however, It is mre C&b&l memgated in sp6cificmbel=il depoeitm. Its chief mlnemle m“ heekite, A+lk, altaiti,,PbTe,coloradoite,Hg!K, and silver-goldh~tides, sum ae Sylvanite,-4. Wutium abo is found b its native State end m combinatim with oxygen, e.g. telluriumocher, Te02. It also is found mixed with mJYur ead t3elenim. An hprknt ore of telhriti is ~ te, Which 1s a mixtureof lead, golA,copper, silver, aud 6mtimny suM?ltiEand telluz5des. TeIiurium 18 mmt often ricovere~from the ande slhes of copper re- fining d from the mineml, nagyaglte. !l%eaematerialsare ueually decom- posed by boill& with a mixture of cuncentre.ted&chloric and nil&c acide. Folhwlng an evaporationto dryneaB,the remidue iB diaaolved,in mchloric acid - * t@JutiuuIPrecipikted by meana of SUU dioxide. If seleniumand tellurium are cti”ined in tl&I mixture, they can be sepaka%ed . by boiling the miiture with S~C acid. b thiB process,tellu2#umin precipitatedae Te02 and the seiknium,ae selenite,is transfonuedto aele- nloue acid uhi@ rendm In eolution. 1. hkxalllc Tellurium ‘Ielluriummtd Is isomm@oue with grey crystallineselenium. It is silver white aud ~” a metal~c lueter. It is very btittle and cen h pwdered eaeily. When telluriumla ~aited frcm solutionby the reduc- titi of tellurouaacid with sulfwoua acid, it Is”obtainedea a vohdnoue brown powder, or “emrpboua” telltium. Tellurlm metel will burn when heated in air,and it will combine. energeticallywith,the halogena and mny nmtala. However,unlike selenium, .. 4 . it till not combtnedirectlywith hydrogen. It will not dissolve h non- oxidizlngacids,but it is soluble in concentratedsulfuficacid, nitric acid and cauBtic all&is. Q 2. The Compoundsof Tellutium Tellurium,like selenium,can form compoundshaving oxidationstates Of -2> +4, and +6. A +2 oxide, TeO, exists and will form TeC12 in cold hydrochloricacid, but vhen heated it decomposesInto free telluriumand a -!-4complex chloride. (Lather 3) reports.that the followingoxldation- reduction’potentialsexist for tellurium: a) In Acid Solution H2Te ~ Te ~ Te02 ~ H6Te06 b) In Base Solution 1.14 ~ 0.57 ~. -- Te-- — — 3 ~ ~04-- . Tellurium (like selenium and sulfur) reacts with other elements in a ., manner Bhilar to oxygen. However, it will not coubinedi~ctly with sele- nium or sulfurbut will form mixed crystalswith them. The oxides, the chloridesand the fluoridesare the umst stable compoundsof tellurium. The acids and salts derived from the dioxidesare also stable. Tellurium (like seleniwn)is electronegativelybivalent towardshydro- gen and the metals. In its electropositivebehavior, telluriumexhibits a valence of +4 In its ccmpoundformationwith mofitelements. An excep- tion exists In its combinationwith fluorine;here 3 valence date of +6 exists. In general,the compoundsof telluriumare analogousto those of suMur and selenium;the principaldifferenceis that they have a lower stabilitythan the sulfur and selenium compounds. The meet tiportamtcompoundsformed by selenium include oxides,~ acid8, mqhal ides, halide Compound=hys drogen compoundsand alkyls. Table II lists the more import-t of these compoundsand @ves Informationabout their solublllties. 5 Table II. Volubilityof TelluriumC-unds Compound Formula Water SolubiUty Acids H6Te06.4H20 Salublein cold water H6Te06 Solublein cold.andhot water (H2~04)x TeBr4.HBr-5H20 H2Te0 3 Bromides TeBr2 Chlofides TeBr4 TeC12 TeClh Slightlysolublein cold water; solublein hot water. llecompo~es Slightlysoluble in cold water; decomposesin hot water Ikcompmea Decompoaea Dscompmea kcomposes.slightly Volubilityin Other Solvents Solublein alkalisand dilute acids; slightly solublein strcmgacib, insolublein alcohol. Solublein alkalisand acids; insolublein alcohol. Solublein alcohol; slightlysolublein KOH. Solublein NaOH and acids; slightlysolublein NH40H; . insolublein alcohol. Decomposesin NsOH; slightlysolublein min- eral scidOsmltartulc acid. E!alublein NaOH; mineral acids and tartaricacids. Lkcon&ses in NaOHj slightly solublein mineral acids and tartaricacid. Solublein HC1, benzene, alcohol,chlorofonu,and CC14; insolubleIuCS2. Fluorldea Iodldes Oxides sulfides Metal-organica TeF4 DecolrcposeB TeF6 Ikcomposefi Te12 TeIh TeO Te02 TeO 3 TeS03 Tes2 ‘ CH#e. Insoluble Slightlysolublein cold Water; decompose in hot Insoluble Insoluble Insoluble Eecorapmes bBOluble SlightlysolubleIn cola water Soluble InsolubleIn cold water; elightly8oluble In hot water. Insoluble Decompose in acids and alkalis. LkdubleIn HI, alkalis, and NH40H. Solublein HCIJ dilute acids,H2S04 emNaOH. SolubleinHCl, KNO and alkalis;inaoluble~NH40H. Decomposesin cone.HC1; solublein hot KOH; insol- uble in acids and alcohol. Solublein H2S04. Solublein alkalineBul- fideB; insolubleIn acids. SolubleIn alcoholand ether. Solublein alcoholand ether. Solublein chloroformand benzene Insoluble a) The Oxide, Oxyacid and @halide Compunds of Tellufium The nmst stable oxide of tellurium,tellurium dioxide,Te02, is formed eitherby the ccmihustionof telluriumor by oxidizingtelluriumwith cold concentratednitric acid. The crystalstructureof Te02 resemblesthat of ’02’ Pbo2 and MgF2. It is usually colorlessand till turn yellow when heated. It melts and vapfizes at an incipientred heat and will solidify frmn the melt in rhombic needleO. It is only spwdngly soluble in water but will dissolve in concentmtedetrong acids smd concentrated.sdAall hydroxides. In its reactionwith water~ it forma tellurousacid, H#eo3. Tellurouaacid cannotbe obtdned in the pure state because it has a tendency to fozm high-molecularcomplexesas it loies water. If the water is driven off at high tempe=tures, Te02 will be formed. The correspu3ing salts of tellurousacid are the te~tites, which, fi their s~lest fomn, M21Te03, resemble sulfitesand normal selenites. Colorless;water.soluble alkall telluritesalts are formed if Te02 is fused with alkali hydroxides, or carbonates,or if it is put into solutionwith causticalkaliB: H#03 (like seleniousacid, H2Se03) canbe oxidizedwith strong oxi- dizing agentS like chlorineor bromine to produce telluric acid, H6Te06. The anhytides of telluricacid correspondto the sdfuric acid anhydrides. The water contentof telluricacid differs from sdf’uricacid and the o@inary telluric acid, orthotelluricacid, has the fonuula H6Te06-4H20. The salts of telluric acid ere the tellurates. Telluric acid is a very weak acid, and its volubilityin water is quite high. As a rule, only a portion of the hydrogen atoms of telluric acid can be replacedby metals to fomn tellurates;however, some metil tellmtes, such as As6Te06 and Hg3!l@06,inuhich all of the hydrogen atoms are replaced,are known. Other acid anhydridemoleculescaube lidsed to the oxygen atoms of telluricacid to form heteropolpcids like H6[T@(OOMO03)a and H6[T40-W03)6]. Orthotelluricacid, = it is heated, loses water and if the temperatw= ‘cc* w“j ye~~ te~mim trloxide,M 3’ will be fomed. Te03 is 8 prtially soluble in water and when heated at red heat, It lose8 oxygen md is transformedInto TeO “.2 Allotellurlcacid Is producedwhen ortho- telluricacid”is heated to its melting point in a sealed tube. It is fomned as a colorlesssyrup mass that is miscible with water. Unllke ortbotelltic acid, Its water solutlonaare distinctlyacid in reaction. Upon standbg” a solutionor allotellurlcacid slowly reverts to orthotellurlcacid. Tellurium does not form oxyhalide ccsupoundsas do sulfm and selenium. b) ~O@ ~ of Tellurium Telluriumforma blvalent and quadrivalentc~ with bromine and chlorine. It forma both qusdrlvalentand hexavalentcompmnds with tluokine and a tetravalentcompouudwith iodine. Monohalidecompoundsof tellurium do not exist. ‘l?elluriumdichloride,!kC~, canbe pre~d by a direct cmination of the elementsor by the reactionbetween Tec14 and el=ntal te~~~. Telluriumdibromide,TeBr2, IS fo=dby heat- ~Br4. me tet-ides, TeC14, TeBr4, and Te14 are formed by a direct combinationof the elements. !JS1lUIZI.UI.11tetmfluoride, TeF4, Is pre~by heating telluriumhetiluorlde, t 180° in the presence of elementaltellurium. All of the telluriumTeF6, a tetmhalldes, except TeC14, are thermallyunstable. TeBr4 wI1l dissociate above its boiling point (414°)into TeBr2 and Br2; m14 when heated ab~e 100° will decomposeinto the elements;TsF4 will USPrOPOfiiOnate ab~ l~” to form elementaltelhmhzm and TeF6. All of the tellurlwmtetm- halldes react tith water to form Te02 (or the correspondingacid} and the ha~de acid. !CeUu