放射化学系列-锇的放射化学(英文)

c-.~ --!National.... Academy --,2; ofZa Sciences National Research v Council NUCLEAR SCIENCE SERIES The Radiochemistry of Osmium .. ...- .=. . m COMMlllEE ON NUCLEAR SCIENCE J. W.IRVIN&“= LIAISONMEMBERS PAUL C. ~ ~lLEEED Ammlo ~ CaInllnti u.o.Air?Orm J.~ABD ~m WmLUH E.wmoET Ndmd~~ -of Ndmmamh SUBCOMMllTEEON RADI-EMISTRY W. WAYNE ~, ~ m HmE ml- ofm- mh9rRlQ d -mia mrkmlay) NAW- ~ JUIJANNmLaEN Nmml Bdlolo@omlIXmn ~ry E** UbmmrlOm mumoRY a C!EOPPIN Q.DA= O’KELLET F’10ri&~ tlbiwrd~ W IU~ N-MI hho~ GxmE A.cmAN H_Im P.NmmBERG Lw Alms EdmUf10Idmramry ArPnw Ndmal L~q ARTHUR W. FADUALL PETER C.~EVEN~- univorsi*ofw~~ L~nrmllyofCdbndn (Uml-lmrm J~ mJDm DUANE N.SUNDERMAN ~mm Natlamlti~ BumiieMmmrid hlmuraa CONSULTANTS ~1 M. CLARK J-W. WD?CHE8THI RaindaarPOiymdmlcIMUw Mnm -~ budnueoiieohm~ . . The Radiochemistry of Osmium G. W. LEDDICOTTE Oak R@ge National Laboratory Oak Ridge, Tennessee . . . Ootchr 1901 R.lWS PROFERT.Y Subcommittee tm Radiochemietry Naticmal Academy d 8ciencee-Nat.imal Research Camcil . .——- . . PrinbdinUeA. Prlce$O.W.Avmlldle&mntbs OMaaf Taclmld Ekrvimn,~~t alCaQmaroe,Wm~ 2S,D.C. FOREWORD The Subcommittee on Radlochemlstry is one of a number of subcommittees working under the Committee on Nuclear Science wlthln the National Academy of Sciences - National Research council . Its members represent govenunent, Industrial, and university laboratorlea In the areas of nuclear chemistry and analytical chemistry. The Subcommittee has concerned ltBelf with those areas of nuclear science which Involve the chemist, such as the collec- tion and distribution of radlochemlcal procedure, the estab- lishment of speclflcatlons for availability of cyclotron time place of radlochemlstry In the etc. This series of monographs radlochehcally p~e reagentB, for service irradiations, the undergraduate college program, has grown out of the need for up-to-date compllatton’a of %adlochemlcal Infomatlon and pro- cedures. The Subcommittee has endeavored to present a serlea which will be of mexlmum use to the”working scientist and which contains the latest available Information. Each mono- graph collects In one volume the pertinent Information required for radlochemlcal work with an individual element or a group of closely related elementB. An expert In the radlochetistry of the particular element has written the monograph, followlng a standard format developed by the Subconmlttee. The Atomic Energy Commlsslon has sponsored the prlnttig of the series. The Subcommittee Is confident these publications wI1l be useful not only to the radlochemlst but also to the research worker h other fields such as physics, biochemistry or medlclne who wishes to use radlochemlcal techniques to solve a specific problem. W. Wayne Melnke, Chairman Subcommittee on Radiochemlstry Iii INTRODUCTION This volume which deals with the radlochemlstry of osmium Is one of a series of monographs on radlochemistry of the ele- ments.. There is Included a review of the nuclear and chemical features of particular interest to the radiochemist, a“discus- sion of problems of dissolution of a sample snd counting tech- niques, and finally, a collection of radiochemical 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 publinhed or unpublished material on the radiochemistry of osmium which might be included in a revised version of the monograph. iv I. II. III. Iv. v. VI. VII. CONTENTS General Reference8 on the Inorganic and Analytical Chemistry ofomium... . . . . . . . . . . . . . . . . . . . RadioactiveNuclidesof Osmium. . . . . . . . . . . . . . . . The Chemistryof Osmium and ItsApplicationto the Radiochemist~ of the Osmium Redionuclides . . . . . . . . . . A. The Gene@ Chemist~ofOsmium. . . . . . . . . . . . . . 1. MetallicOstim. . . . . . . . . . . . . . . . . . . . 2. ‘lTne :: ;: CoIzpound.sof osmium. . . . .“. . . . . . . . . . . Tne OxideCompmmdeofOsmium. . . . . . . . . . . The HalideCompcundsofOsmium . . . . . . . . . . MiscellaneousCompmmis of Osmium.. . . , . . . . The ComplexCmgp3uudsof Osmium.. . . . . . . . . B. The Analytical Chemistry of Osmium . 1. SeparationBy Precipiktion. . . 2. Separation By Volatilization . . 3. Seramt ion BY Solvent Extraction i. &togx-apily Dissolution of S.mples Safety Practices . . . Separation . . . Contitiing Osmium ,., . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Counting ‘Techniquesfor the Radioactive Osmium Isotopes. . . . Rediochemical.Procedures for the Osmium Radionuclldes. . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . 1 1 2 3 4 4 4 4 5“ 5 6 7 -r 8 9 9 10 10 11 18 v The Radiochemistry of Osmium G. W. LEDDICOTTE Oak Ridge National Laboratory Oak Ridge, Temws$ee I. GENERALREFERENCESON TsE INORGANICAND ANALYTICALCHEMLSTRYOF OSMIUM. Sidgwick,N. V., The Chemical Elements and Their Compounds, p. 145&@8, Oxford Unlversity Press, London, 1950. Kleinberg, J., Argerslnger, V. J., and Griswold, E., Inoretic chaEtFy, P. 565-X, Heath,ms~n (19@. Renry,H., Treatise on Inorganic Chemdatry,Volume I, p. 342-3>1,Elstier, hsterdsm 71956). Beamish, F. E., “A CriticalReviewof MethodaFor Isolating and Separating The Six Platlnum Metals,” Talanta ~, p. 1-35 (1960). , Scott, W. w., ~t~ hkthOdS Of “ChetiCd MySiE, VO1- 1, pp. 7U?-7’26, Van Nostmnd, Nev York, 1939. Hlllebrand,W. F,, Luudell, G. E; F., Bright, H. A., smi Hoffman, J. I., Applied Inorganic Analysis, John Wiley, New York, 1953. II. Redden, C. J., Analytical chemistry of the Manhattan Project, pp. 3-159, @3 aui 491-493, McGraw-Hfll, New York, (1950). Schoeller,W. R,, and Pcwell,A. R., Tne Analysisof Minerals and Ores of The Rarer Elements, 3rd Fd., Gtiffin, London, 1955. RADIOACTIVE NUC_ OF OSMIUM The radionuclideE of osmium that are of interest to the tiiocheudst given in Table I. The Information tabulated IS ~imil= to that appearing compilationsby Strmlinger;”et al, (1) and by Hughes and Harvey:’) ‘Operated for U. S. Atomic Fhergy Commission by UnionC=bide Corporation. a-e Ill 1 III. ueed THE CHEMIS~ OF OSMIUM AND ITS APPLICATIONTO THE RADICKHEMISTRY OF THE OSMIUMRADIONUCIJDES. RadiochemlBtryla probablybest deBcribedas beingan analysistechnique primarily(1)to assistin obtalnlnga pure rdiOnUclide of BorneBpecific element In a suit-ableform HO “thatan absolute mesaurement of Its radioactivity, radiation energies, and half-life can be made, or (2) ta deterdna the amount of radioactivityof a particular radioelement in a radionucl-idemixture, or (3) to complete a radioactivationanalysis being used to determine the stable ele- ment concentration ROaio- Nucllde 08182 ~H183 0s185 ~~186n OSlgh #Qln Oslglm 0J91 0s193 Hdf- Iife ii a particularsamplemateriaL. b orderto be an aid in TABLE I IWE ~10’~NE iUWIiES OF OSMTUM l.fodeof w Ener~ of Radlatlon 24.o h EC 7 0.510 L2.O h Flc y 0.3, 1..6 97 ~ EC y 0.648, 0.878 8 x 10-1o a ~ 7 0.137 6h IT 7 0.03’ 9.5m IT 7 0.039, 0.187, 0.359, O.*, 0.614 14 h IT ““7 o.07k 16 d P- p- 0.143 7 0.L71J 0.L29 31 h B- 0- 1.1 Produced By Re-p-kn Re-p-3n Re-d-2n, Re-p-n Os-n-7 Daughter Re186. kughter 12 d Ir189 Daughter 3 h Irlx Oi-n-y Oa-n-7, Os-d-p, Os-y-n Os-n-y, Os-d-p, Ir-d-2p ; 0.066 accomplishing any one of the abwe interestB, radiochemiat~ usualLy considers the isolation of the desired mdionuclide by either carrier or carrier-free separation methods. ,. Generally, “carrier”methodB are uBed nmat frequently In radlochemistry. They involve the addition of a Bmdl .a?rwuntof inactive stable element to a solution of the irradiatednmteriaL to serve as a carrier of the radionuclide of that element through the Reparationmethod. ‘Tarrier-free”ae.parations ., .. conno~ that no carrier is added. These radlochemicaltechnique are used “2 6ilverf gold, Iron, and nickel. It is usually obtained from these base materiale by a reduction proceaE. 1. Metallic osmium Metilic osmium is a gray, brittle metkl ness. It haE.a denBity of 22.7anda melting form, it Ie”tisoluble in acids; however, in fuming HN03 forming osmium tetroxide, when possessing a considemble hard- point of 2700° c. h a compact finely divided,”it is soluble 0s0~, which is hi@ly volatile. 2. The CompoundE of 08mdum Oeudum can form compounds havlgg oxidation etates of +2, +3, +4, +6, ~ A.(3) me Os@ Iom,are un6table in acid. Such groups as Cl-, Br-, N02-, -- dNH- +3 +4c204 ‘ rm, en 3 forg complex ionE yith 08 and 06 . Ions of 0s+8, such aa perperosuclcacid,F$OSO, can existin hydrochloricacid. In ‘3 and 0s3+alkelineeolutiom, 0s can form oxideor,hydratedoxideccm.- pounde. Many omnatee are known, although the trioxide of 08+6 ham not been i601ated. Owqyl compounds are -so known;,however, they readily de- c-ose in acid solution. These compounds can be deac~bed in the follmdng manner: a. The Oxide Compounds of Oenlium. oa+4 is the mst stable oxidation fitateof osmium. Its binary compounds include ostium (IV) oxide, 0E102. It is usually obtiined as a black or brown powder from a chemical reaction between osmium metal and osmium tetroxide, 0s04. ,It is inert towards water and acids d h~gen till easily reduce it to the metal. When heated in air, it’is convetied to the tetroxide. A hydrate form, 0a02.2~0, can be prcduced if a 8olution of the tetroxide is reduced. OB~um tetroxide, OeOb, is uBualJ.yproduced by heating powdered osmium metal in air to about 200° or by oxidizing osmium metal or its compoundswith ‘ot Concent=ted ~3 ‘r %!s04” It iE colorless,volatile,and poisonous. It is only slightly soluble in water but extremely soluble in nonaasociated organic solvents such “~ cblorofomn. It 18 a strong &dlzing agent and is frequently’usedin specific organic oxidatlonso b.’”The Halide Compmlnds of osmium. 0s+4 forms binary fluorine, chlorine, and icdine. An inccmrpletefluorination 4 .. compoundswith Of powdeked OSUWUM ~ti WIII form the tetrafluoride,OaFb, and the hexafluoride, 0aF6. Osmium tetrachloride,OsClk, is obtained by uniting chlorine and osmium metal at temperatures of 650-7000. It is a black volatile material which will slowly dissolve in water to produce a yellow eolution and deposit 0s02. Osmium iodide, 0e14, is formed by evapcnating a solution of the hydrated dioxide with hydriodic acid. Osmium dichloride, 0sC12, ie formed by heating the trichloride, OSC1 , 3. in a vacuum to W“. It is tisoluble in water and does not react with HC1 and H2S04. Oemium trichloride,0sC13, is formed by the chlorinationof osmium metal at temperatures above 700°. It is hydroscopic and dissolves redly ,in water to yield weakly acidic solubione. c. Mi.scellaneoueC +2Ompounds of Osmiuml. 08 can combine direct~at high temperatureswith SUEur, selenium, and tellurium to form the sulfide, selenlde, and telluride compounds. They are inert to alAalies and to mcmt acids but can be converted to the tetroxide by hot concentratedHN03. 08+6 forms a blnmy compound, 0sP2, when elemental osmium and phosphorus are com- bined at temperate above ~“. Os~um phosphide is a non-volatile grayish substance that does not react with aclde or alkalie. Other compounds of the 0s+4 ‘3 and Oe,0s, +0 statea are usually complex. d. The Complex Compounds of Osmium. 0S+4 forma many complex compoundEI, most of which are anionic. Many of these complexes contati sulfite, halogen, or halogen-Oulfitogroups. ~ical of the sulfitoand the tied compounds are +J~ tY7XB,M#s(so3)6 and qpc14(903)4. The SUlfito group communds reeult from the reaction of sodlumbistiate on Na6~a02(S03)~ .5H20. The reactione of suk?ltes and blsu~ites upon hexacbloroosmate (IV) compaunds pro- b duce the tied Chloroaulfitocomplexes. The halo complexes usuaUy have the form M2[OsCl~. ~ed hexa-halo compounds of such types as ~~sC15Br] and M2[OeC13Br J are usually fomed by the reduction of aqueous solutions of osmium tetroxide, containing the appropriate alkali metal salt, tith etb.amol. 0S+6 forms numerous complexes. These include the oemates, ~OB04; the - derivatives,~ fh02X~ ; the OXY-OSULY1 salts, M2[Os03X~ and the nitrilohalldea,MIOsNX~ or Iv$@X~. The osmatecompoundsare usually obtained either by fusing metallic osmium with mixtures of alkali metal 5 hydroxideand ~t=tis or by the %duction of osmiumtetmoildein a~ine nolutlon!?ithethanol. The = complexes - Contauling cl, CN, N02, SO , 3 or C204 groupi3- are,prepared by reacting the tet~ide with materials con- tating theee ~ups. The cyano complexes are inert to acids; the other complexes are rapidly decomposedby water. ~lOrO, M&j bro~i and oxalato groups are usually contained iu the oxy-08my1 cOUtpleXes.The nitro c-lexes are the moat stable M C= be formed in the treatment of aqueous osmium tetroxide with dkalimetal nitrites. l’heDltriloNlides canbe +8produced by.reacting hydrohalic acids @th the Oe complexes known as the oami~tes, M lj3B031j. ThI.osmiamates are formed by reacting concentrated NHkOH with WaIIIl,strongly alkaline solutions of the tetroxide. The nitrilo- halides dissolve and rapidly decompeae in water. Fluoro complexes of the compositionM2~s04F~ have been formedby reacting satumted solutions of,alkali metal fluoride tith osmium (VIII) tetroxfde. These complexes readily diaeolve in water and deconpse in air. Hydroxo ccnuplexes,such as lf2[OaOh(OH)~ are fomed by adding saturated solu- tions of alkali to equeous solutions of the tetroxide. 0B+2 forms hexocyeao complexes of the compositionM4[OS(CN)~by adding alkalicyanidesto a eolutionof .osmlumtetroxide.Nitrosylderivatives, JM2[os(@x , ~d suMito CQUdS , Such 2S M+(SO)4 are d-so lfn~. ~ the nitmxo compounds, C1-,.Br-, or I- ~PS complete the complex. Hexahalo complexes of’0s+3 are Imcnin; however, the purity of such com- pounds k not been well established. “AmncLnecomplexes u-e lmown for 0s+4, 0s+3 , and CM*. These compmunds are usually formed by the reaction of other complex compoundswith amonia. B. The Analytical Chemistq Oi”osdum Osmiom, like all of the other platin~ metals, is usually determined (4J~)FO~C acid, scdiualfO=tegravlmetticallyas the metal. d hydrogen will reduce it to the metallic etate, and it can be displaced from solution with ztic, alumlnum, or magneslummetd pwdere. Other organic ~agents, such as thionalde, strychnine sulfate, thiourea, or thiazole, can be used to precipitate oemiummetil. (6,7) 6 GilcJmiBt@) and Beamlsh(9) have reviewed many of the methods that can be used to isolate and separate osmium and the other platinum metals from other elements and from each other. Many of these met~s canbe usedby a radlochemiet in his work with the osmium r~ionuclide~. 1. SeparationBy Precipitation Omium, like all of the other platinum metals, can be separated from moat of the other chemical elments by aaturatlu”an acid eolution with hydrogen sulfide.(k, 10) ~=nt~ ~Uch ss Bilver, copper, cadmium, me.rcW, iridium,germanium, tin, lead, arsenic, antimony, bismuth, molybdenum, aelenlum, tellurium, and rhenium can Intetiere in this separation. Aqua regia till readily dissolve osmium sulifide.(4) Talmini=d Ss&ria(ll) report that the volubility of osndum eulfide in alkaline solution is adequate enough to separate osmiw from many other elementm. osmium (as well as the other platinum metals) can be sepamted from such baae metals as gold, copper, and zinc by digesting any of Its chloro COIWOm in a Solutim of aod.i~ titrite in order to convert the osmium to a sohible nitrite complex.(12) The base metils can then be removed from the dxture by behg precipitated ae oxldea or hydrated oxides. 0s+4 ~ the other platlnum metals can also be sepamted from gold by precipitating gold from an acid solution with such reagente as femous sulfate,(13) sulfur dioxide}4) oxalic acid~4) hydroqulnone\’4) tetraethyl~tiw chloride,’15) and sodium nitrite.(16) 2. Sepam tion By Volatilization Omium canbe readily oxidized to 0s+8 and the formation of the volatile octavalentoxide has been used most frequently to eeparate osmium from all of the other platinum mtala (except ruthenium) and other chemical elements. Tenant first used an oxidizing fusion and a distillationprocess Involting nitric acid. Gilchrist(18)later showed that osmium couldbe rapidly distilled from a hexabrcnnos~te solution by the use of a 10$ HN03 oolution. However, in the aaqe investigation,it was shown that i%e distillation of hexachlorosmate ,. solutions with nitric acid took a much longer time to complete than distil,la- . (19-23) ‘ion ‘ith ‘2”4” Various modifications of this distillationtechnique exist. 7 The volatile osmium tetroxide can be collected and absorbed in receiting liquids (18) 6NHC1.Thioma .90h-such as hydrochloric acid-sulfur dioxiae solution, (24) tion~20’25) 3C@ hydrogen peroxide, _or 6 N sodium hydroxide.(26,27) Osmium (as well as ruthenium) u be eeparated from other elements by a perchlonlc acid distillation of the cblorosalts.(24) Westland and Beamiah(13) have also used a method in which osmium was removed from a chloride solutionby a distillationat 115° Wth a g202 - H2S04 ~tme. The tetroxide wa~ abaorbed either in a 40% BBr solution or In a 5$ solution of thiourea in ethanol- hydrocblorlc acid (1:1). Sepsmtione of osmium from other elements by the use of aqua regia distillationsare also recorded.(9) The separation of osmium from ruthenium usually occur~ in nm6t of these distillations, Whenever the oxides of both elements are volatilized, 8s in the hydrogen peroxide method of Westland and Beamish,(24) the dis- tillate can be treated with H2S04 and boiled to rem?ve osmium. Ruthenium can then be obtained by a dlstilhtion from a bromate mixture.(13, 24) 3. l%=.=tion ~ Solvent Extraction (28)Osmium can not be extracted fmnn a 6.9 M K( solution with ethyl ether. This system canbe used to eeparate osmium (and Ir, Pt, Pd, and Ru) from AU+3, +2sb+3, Hg+2,cd+29and Sn . All of these elements are easily extracted from” an icdide qolution by ethyl ether. ml acetate extmctiom of HC1-NH4Cl-snC12, solutions have been ueed to etiract Ir,”Pt, Rh, Au, and Te and se~rate them from oemium and ruthenium.(29) only small SJnountsof plladium will extinct in this system. Osmium can be isolated from ruthenium, follcmi.nga collective distillation of the volatile tetroxidea,by forming ite diphenylthioureacomplex in 5-7 ~ EC1 and extracting the hniBcible product from the acid solution ulth CHC1 (w) 3. The complex, tetraphenyl-amonium hexachloros~te, formed in a 0.1-0.3 N HC1 solution can also be extmcted with CEIC1 (w) 3. Neither ethyl nor amyl acetate will extract the phenylthiourea cmnplex of 0s+4 from a dilute HC1 solution;(31) +2however, the Pd ad ~+2 c~lexes extract completely, The Ptb complex is +4, ~+3, fi+3, Au ,only partially ext~cted, while the Ir ‘3 Fe+3, Co‘2, Ni+2, +6 .and”Cr complexeB do not extract. 8 ~B+aforms a colored compldx with ephedrine hydrochloride and can be sepuated from platinum and rhodium by tiracting it from a slightly acid (*)solution into carbon tetrac~oride. The palladlumj iridium, and gold mmlexes dso etimct into carbontetrachlor5de. 4. Chl’cmatograpMC separations Beedsh(g) =Ptis that no successful anion-exchange resin separations of osmium < since the ease with which osmium salts can would preclude such separations. The only of osmium from other elements involves the applications of either cation- or (and ruthenium) have been recorded be reduced by organic reagents known cbromato~aphic se~tion use of cellulose columns. Burstall, et al(33) have wed such columns and meth