【放射化学系列】钾的放射化学

5’%.5 K! 959f- C.5 I National Academy d Sciences National Research Louncil B NUCLEAR SCIENCE SERIES The Radiochemisty of Potassium —— ._—- COMMITTEE ON NUCLEAR SCIENCE L.F. CURTIM, Ckt~ ROBLEY D.EVANS,VJcaC~ NmtkmalBureanof sfaduda MaMuhuette hotituta of TeabrdosY J.A.DeJUREN,S@cfetory weetfq#mM EleutrlcComratinn C.J.BOHHOWSIU J.W. IRVINE,JR w Ridgemud IAhereterg M.MsEAusetilnmthtad TdmolosY ROBERT !3.COCHHAN E.D.KLE~ Teas &riouliunlad Meufumieel NorthwesternUnimreiw cellqJe W.WAYNX MEINKE SAMUEL EP81Zm UniversimefMlehfpp CellbrntnInetihI@ofTeuhmlew J. J. NfCKBON U. FANO Memorial Heapi(al, New York Natlouel Burmu II! Std8rda” ROBERT L.PLATSMAN BKRBERT QOLD6TlitN IAberatnfre& Chide Phyeique NIwlearDevdePMedCorPJratlehof D.M.VAN PA’f?l’ER &iielrIea Barb]BaeaamhFmdetion LIAISONMEMOERS PAUL C.AEBERSOLD CHABLES E.REED AtemloEmrw Commlaslen U.S.AirFeme J. HOWARD MeMCLLEN ~E, WRJGRT Natbmel&lenoeFeurdnfieo OfficeofNavalReneemh SUBCOMMITTEE ON RADtOCHEMISTRY W. WAYNE MDNKE, Chufnaaa EARL NYDE llmtvarni~ofhfi~en Unwernityof Cnlifornie (Berkeley) NATHAN 13M1.OU JUHAN NfEl&JZN NavalRadlologiedDefensektmrairq HanfordIahorateflea GREQORY 1%CHOPPD4 G.DAVIDO’KELLEY FlOride Etate Univmrd@ Oak Ridge Ne.fiordLaboratory GEORGE .L CCFWAN ELLIS P. 6TEINRERQ Los Ahnn3,9 SciertUO LAmrainry Arsvnne NationalIaheratmy ARTHUR W. FATRHALL PETF.RC.STNVE~N UeivereityofWe,eb@tm Univer6i*efCulibrnin(Ltvmmeere) JEROME HUDIS DUME N. SUNDERMAN Braokhaven Nntlord Laboratory Bntblle Mmneriel Institute CONSULTANTS HERBERT M. CLARK JOHN W. WINOHESTER Renneeleer Pelytsdmic Instltu* MesIIw!huAtsImtitutad Teehm~ (wt5% cHEMIsTaY (-+-+.~, The Radiochemistry of Potassium W. T. MULIJNS AND G. W. LEDDICOTTE Oak Ridge Nationul Laboratory Oak Ridge, Tennessee November 1961 Ef .- Subcommittee on Radicwhemistry National Academy cd Sciences —National Research Cuunci.1 PrintedinUSA, Prtce$0.60.AvailablefromtheOfficeofTeobnical Sarvioes,Depmmeot of Commerce,Weehtagtoo25, D.C. The Subcommittee 8ubcommitteea worklrm FOREWORD on Radl.ochem16try Is one of a number of under the CommLttee on Nuclear Science within the National ~oademy of Sciences - National Research council . Its members represent govevnt., industrial, and university laboratories in the areaa of nuclear chemlBtry and analytical chemistry. The Subcommittee has concerned Itself wl.tihthose areas of nuclear aclence whioh Lnvolve.the chemist, such as the collec- tion and distribution of radlochemical procedures, the eBtab- liehment of specifications for radiochemlcally Pure reagents, availability of cyclotron time for service Irradiations, the place of radlochemistry in the undergraduate college progrem, etc , “Thla series of monographs has growq out of the need for up-to-date compilations of radiochemlcal information and pro- cedures. TQe Suboommlttee has endeavored to present a Eeries which will be of maximum use to the working scientist and which contains the latest available Information. Each mono- graph collects in one volume”the perttient information required for radiochemlcal work with an individual element or a group of closely related elements. An expert in the radiochemistry of the particular element has written the monograph, followlng a standard format developed by the Subcommittee. The Atomic Energy Commission has sponsored the printing of the series. The Subcommittee Is confident these publication will be useftd not only to the radiochemis,t 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 MeLnke, Chairman Subcommittee on Rkdlochemlstry iii INTRODUCTION This volume which deals with the radlochemlstry of potassium is one of a series of monographs on radlochemistry of the elements. There is Included a review of the nuclear and chemical features of paxtlculax Tnterest to the radlo- chemlst, a dlscuaslon of problems of dissolution of a sample and counting techniques, and finally, a collection of radlochemical procedures for the element as found In the literature. The series of monographs will cover all elements for which radlochemlcal procedures axe pertinent. Plans Include revlslon of the monograph periodically as new techniques and procedures warrant. The reader is therefore encouraged to call to the attention of the author any publlshed or un- published material on the radiochemlstry of potassium which might be included In a revised version of the monograph. Iv CONTENTS I. II. III. Iv. v. VI, VII. VIII. General References on the Inorganic and AnalyHcal Qmn5.stryofPotassium .. . . . . . . . . ... . . . . . . . 1 Radioactive Nuclides of Potassium. . . . . . . . . . . . . . 2 The Chemistry of “Potaasiumand Its Application in Armlysis Methods for the Potassium Radionuclides . . . . . . 2 A. The 1. 2. B. The 1. 2. 3. 4. General Chemistry of Potassium . . . . . . . . . . . 2 Metallic Potassium . . . . . . . . . . . . . . . . . 3 The Chemical Compounds of Potassium. . . . . . . . . 3 a. Pete.esiumHydrLde, KE. . . . . . . . . . . . . . 3 b. The Oxides of Potassium. . . . . . . . . . . . . c. Potassium Evdroxide. KOH . . . . . . . . . . . . i d. The e. The f. The The ;: The i. The Nitrogek Compounds . . . . . . . . . . . . . i SuEide, Sulfate, and SuEite Compounds. . . : Ralogen Canpound.sof potassium . . . . . . . phosphate Compounds ml?Potaaslum . . . . . . 9 Carbonate Ccmpound.s. . . . . . . . . . . . . Cyanide and Cyanat&CompouniLe. . . . . . . . ; il. Other Potassium Ccqouuds. . . . . . . . . . . . 10 Analytical Cherd.stryof Potassium. . . . . . . . . . 10 Se~t@nsb yPrecipitation ~ . . . .. . . . . . . . “11 Separationsby Electrolysis. . . . . . . . . . . . . Solvent Extraction Separations . . . . . . . . . . . ;. chrcmatoFm3PhYSJ=Pal=tions. . . . . . . . . . . . . a. With–In&-&nl; Absorbents. “.. . . . . . . . . b. With Organic Absorbents. . . . . . . . . . . . With Ion Exchange Resins.. . . . . . . . . . :: By Paper Chromatm~pby. ..”.... . . . . . Difisolutionof Samples Containing PotaBsium. . . . . . . . Safety -ctices . . . . . . . . . . . . . . . . . . . . . Couating Techniques for the Radioactive Po~sium Isotopes Radlochemical &ocedures for the Potassium Padionuclides . Refemnoea. .o . . . . . . . . . . . . . . . . . . . . . . lli H . l!” . 16 . 17 . 17 18 37 The w. Radiochemistry of Potassium T. MULLLNS AND (3. W. LEDDICOTTE Oak Ridge National Labwatwry* Oak Ridge, Tennessee I. GENEHAL REWERINCES ON TKE INORGANZC AND ANALYTICAL CHEMISTRY OF FmAsauM 1. 2. 3. 4. 5. 6. ‘i’. 8. 9. 10. XL. m, H., Treatise on Inorganic Cheudstry, Volume I, Eleevier, Amsterdam 71956). Kleinberg, J., Argersinger,W. J., Jr., and Griswold, E., korganl c chemistry, Heath, Boston (1960). Hillebrand, W. F., Lundell, G. E.”F., Bright, H. A., ad Hoffman, J. L., Applied Inorganic AnalyaiB, Johu Wiley and Sons, New York, 199. Wilson, C. L., and Wilson, D. W., ComprehensiveAnalytical.chemistry, Elsevier, Ameteniam, 1959. Sienko, M. J., 4 Plane, R. A., ch&Btryj hk&8w-Hi~, NW York, 1957. Chariot, G., and Bezier, D., QuantitativeInorganic Analysis, John Wiley and tine, New York, 1957. Sidgwlck, N. V., The Chendcal Elements and Their ~E I university Prees, ~ord, 1951. Hutchineon, E., Chemistry - The Elamente and Their Reactions, Saunders, Philadelphia, 1959. Sneed, M. C., and Maynard, J. C., General College Cinemiatry,Van Nostnand, New York, 194.4. Sneed, M. C., md Braeted, R. C., CmugrehensiveImrti c Chemistq, Vol. 6, ‘The AIJsaliMe~s, ” Van Nostti, New York, 1957. lather, W. M., .sndHildebnmd, J. H., Reference Bcmk of Inor@c chast~ MacMilJan, New York, 1*. *Operatedfor U. S. Atcmdc”Energy Conmlsslonby Union Wbide Corporation. 1 n. RAImmmE~ cwmlA8sm4 The ‘e&active mlclldes of ljobulaiumthat * of “W&t h the rEiio- chedntry of..potuJsiunm @van in TbbleI. This .tablchaa been c~hd frm IMm”iion appaming in mp9Mm by ~, et ~m)(l) and, by Hughes 9!ABLEI Haaf-Ldfe 1.3 E 7.7 m .l.32xlo9y 6.7 x 10-g o 12.b h 22.4 h 17 m. TOERmmAmmE lmImE2aFmlMarQ4 .# 4.6. P+ 2.8 7?.16, . p- 1.33 71.46 ~~ 1.55 7 -1.3 5-3.73 7 1.2, 13-0.81 0.24 7 -0. 4 mducea”~ ti-7-2n Cl--n, K-n-2n,,K-p-pm K-T-n, Cm-d-a I!7atumlsource ~~ A4’ +GP, K-d-p, K-n-y Ca-n-p, Sc-wa A-&p Ca-n-p In. ~~OF~AB’DITS~OE MAEUX81S w51!EOMmmPm!MSIwa~ Rldloclledcal anal.7Bio ~ Ueuaw foU.m7 the * ti techniques emtabliehed by mre ~ ==m~ ~tode~anonmdio- active alemmt in au imctivu ample m&rial. Sbce thet3emthode - preci- pitdiq Oolvant extmctic& chmautcgmphy, ad electrolysis --~t q *c=l *I- b bmng * to completion,the general infomtion @vwl Mlou m the f-tire of pot9Seiwl Ccqmude and their behavior in sqemation meti la titmdd to mtabliah the uaefulmna of such idaaE and *dmiuuea in analyzing a mdloactive (or ncmm?lioactive) md..er5alfor the potaloiumIuaiomlclideo. A. me Oeneml Chenddry of Fbkmium mm earkhfa cruet Contdme at ht 2.5gjpteeeium. ~sium cm&uhde am found in eoila, sea wati”r,ndneml water, &woue mcke and “dmml.e: The 2 chief *ml sources of potassium ma carnallite,KClmMgC12“~O; K#4- W4 -2-4” 2E$O; BYlfite~ KC1; Eilvlnlte, a xdxture of KC1 .9Ch6tite, Mg904-K2S04-~o; .=d kahite, M3S04+Q3C12‘K2m4” 6~0 . P- haute, and NaCl; Potassium metal is usually prcduced by an electrolyticprocess In which an aqueous aohrtlon Of the ~e??d iB eleChO~Zed @ the haoltile lZIpUritie8, such as Mg(OH)2sra filtered off. The solution of KCl remdning -r this filtration Is further electrolyzed to produce a aolutlon of KOH. The KOH solu- tion is then evaporated to dryness W elementary potassium obtained by an electrolysis of the fused KOH. 1. Metalllc Potssslum Potaz13iwnm@al is a soft, silver-whitemetal having Potassium is composed of three isotopes: K 4039 (93.@), K a density of O.%. (0.1~), and K41 (6.%). Km is a naturally occunlng radioactive Isotope having a haM-llfe of 109 yeare. Potassium till melt at 62° and it has a boiling @-nt of 7600. Potassium metal =pfdly develops an Oxide coating If it is exEOsed to air. It till react with water to form hydrogen and solutions of the correspondingbases. It will ccmblne with hydrogen to form a hydride. Most of Its salts axe very soluble in water. It will dissolve In smmmils to form a blue solution and when it is volatlllzed, a blue vapor co~sed of mnatomic molecules is given off. 2. The Chemical CompXMs of Potasslum I?otassiumhas only a +1 oxidation state. It is mme active t~ the non-metals than ,ls,,sodium; however, its chenzkal properties are similar to Scdluul. It will react with carbon,clloxide,hydrogen, oxygen, nitrogen, sul- fur; and the halogens. The reactions of Fotasslum with these and other ele- ments is presented In some detiil below. Table II shows the solubili~ of many of the pota8fiium compounds in w3ter and other reagents. a. Pot3ssLum Hydride, KH. PotneBium will coniolnadirectly with hydrogen on heating b form KH. The colorless crystals of NH deccsqpaserapidly on heating and uI1l react with inter to proihlcehydrogen gas. b. The oxides of Potassium. Potaesium oxide, heating potassium nlttite or titrate with potaeslum ‘2°’ c= be ‘-UC* by In the absence of air. If ,, 3 potassium metal 1s burned b a calculated emount of air, pot.easlumperoxide, ‘2°2’ till be formed. Potassium metal will react at room temperature with oxygen to form potassium tetroxide, K20b. Potassium tetroxide, an ore.nge-red ,golid,WI.11decompome on heating to fozm oxygen and the Peroxide, K#2. All of the potassium oxide compounds react vigorously with water to yield KOH, oxygen, and hydrogen peroxide. c. potassium Hydroxide, KOH. Potassium hydroxide can be pre~d either ,by the electmlyeis of potae8ium chloride, KC1, or by reacting calcium hydrmdde with potassium c=honate, K2m3” KOH ia highly dellquescent and very soluble in water. Iti chemical behatior Is similar to that of flcdiumhydroxide, NaOH. Its solutio= are strongly basic. - d. The Nltmgen Cmpunda . potassium, like qcdium, can react with nitro- gen in an electzlc &Lecharge tube to form @ essium nitride, K N. 3 K3N iS d it is rapidly atticked by water to fozm KOH and NH3.green-black in color, an Putassium azide, ~ , can also be formed by the action of nitrogen upon .3 potasaium. KN3 will decompose upon heating h a vacuum to form K3N and nitro- gengaa. Potassium nitrate, KNO is tie by reacting NaN03 with KC1. ICN03is Y more soluble in hot water than in cold. It ulll melt at 334° and be decomposed. When heated at temperatures above k30°, KN03 till lose oxygen to form ~otassium nitrite, KN02. Potassium titfite WI1l decompcme at 850° to produce potassium peroxide, K202. It is soluble in water, and when the solution is boiled it will hydrolyze to produce nltmue acid, EN02. e. The SuMide, Sulfate, and Sulfite Compounds. Po&ssium will react with sulfur to form p tassium monosulfide, %s’ ‘= tasaium polyeulfide, %2s2” The monosulfide compouud,K2S, is a colorless crystalline compourd that is hydroscopic and till react mpidly ulth water. Potassium stiate, K#04J like sodium sulfate, occurs freely $n nature. It is prepared by extracting the mineral demsit, schcmi~, M@4.~s04.6~0, and treating the concentratedaqueous solution with ~tassium cblozide. K260k is very soluble in water. If K2S04 is treated with the proper quantity of sulfuric acid and the ndrture heated, ptaa slum hydrogen sulfate, or potassium bisulfate, KHSOk, is produced. KHSOk dissolves in water to give 4 ccunpouna Formula BromideB KBro 3 m’ KAUB’4 KIBq ~r6 Chlorides KC1O3 Kclok Km Kclo “K#u(H20)C15 K@u(OH)C~ KAwlk Kcro 1 ,F Iaclh FhorideE KF Table II. Volubility Of pO&BiUM Watkr”Solubllity Cold Hot 3.1°13.340 53.480 slightly BOIUble Decomposes Very soluble 7.120 0.750 34.7m Very eoluble Soluble Soluble; decomposes 61.8= Soluble; decomposes Decomposes 92.318 49.75100 102100 ve~ Bobble 571* 21.8100 56.71W Very Boluble Soluble Soluble &.260 Very eoluble cmpouuaE otherSolventm Slightly soluble in alcohol; Insoluble In acetone 0.5 alcohol; soluble In glycerin; slightly soluble in ether Soluble in alcohol 0.6~ alcohol; soluble in alkali Insoluble in alcohol and ether Blightly soluble inalcohol; solu- ble in alkali, ether and glycerin Slightly soluble in alcohol Insoluble in alcohol Soluble in acid; 25 alcohol Soluble in acid DecompoBea in ether ~~= and~3; ‘mO1uble ‘n (Table continues on follotingp~e. ) Ccaupoud Formula KF-+0 =2 Table 11. Solukdlity of PotisiumC~~s ( k@F6 IOdides Iao3 IU04 m 1(13 KAU14 Water Volubility Cold Hot 349.3U Very soluble 4121 Very soluble 0.1217.5 0 .9541@3 Slightly soluble; decomposes 2.15 6.6 .536° 1 .2’72~ 1.320 .7812 251m 4.740 ~m5100 0.6613 Soluble w .5° 2081m Very soluble Soluble; decomposes continued) Other Solvents Soluble in HI?;insolublein alcohol Boluble in lK@$2; insoluble in alcohol Soluble in HC1; insoluble in HH. and alcohol Slightly Eoluble in HF Decomposes in acid; insoluble alcohol Min. acid; insoluble in”NH3 2 In Insoluble in NH3 Soluble In KI; insoluble In alcohol and NH3 Very slightly soluble inKOH 14.3 alcohol; soluble in NH3; slightly soluble In ether Soluble in alcohol andKI Soluble in dilute solutionKI 4 ‘3h16 %3 K2PtI 6 Nitrideo KN 3 Imo 3 Oxides K#’m2)~ Iaio2 K20 ‘2°2 K204 sulfide~ %2s KHs Very ooluble Decwnpoaea Soluble Decomposefl Soluble soluble Soluble Very soluble ve~ BOIUble Vexy soluble; decompose Sohitde ‘2s2 SuM’ate K2S04 KHS04 Soluble Soluble Soluble %luble: decomposes Soluble Soluble Soluble Very soluble Very soluble Ve~ soluble Very soluble Decoqpoaes Lkcomposefl FOhible Soluble Ibsoluble in alcohol Soluble in alcohol, ether, KI and acetic acid. Ineoluble in @cohol Very soluble in NE and alcohol; soluble in alcohol? insoluble in gk~ alcohol Soluble in alcohol Sbluble in almhol and ether Decompses in alcohol Soluble in glycerin;”insoluble in ether Soluble in alcohol Soluble h alcohol an acidic solution, and it can be used to convert oxides and si~icates intg sulfatee. When It is heated at a temperature of ~“, It la converted tito p tasslum pyrosulfate, K#1207. W’henK#207is stmnglyignited, S03 is releaaed and norms.lpotisium 9ulfate, ~so~, Is produced. The electro- lyals of a concentratedqolutlon of KEE04wlll prduce F aeelum Pem- sulfate, K#208. pOtZSBiUIU@?O& n eulfite, or @easlum dieuli?lte,KHSO3’ can be pro- duced by eat~th.g’a solution of potaesium carbonate or pokeium hydroxide with sulfur dioxide. Nonw31 potaaelum mdfite, K#03, Iefonuedbytreathg the Bolution with an additional amount of potassium tibonate. The euJfitea are eZSI~ dec~sed by heating to form stable sUlfate, K#34. The etiitee can also be eaBlly cmidized to produce the correspondingsulfates. f. The Halogen Compunds of fitaseiwll. Potassium fluorlde, ICE’,is obtained by neutralizinghydrofluorlc acid with KOH or K SO2 3“ If the solu- tionie evapomted, a white de~quescent eolid Is obtitied. If the Bolution is treated ulth an equiuolecularamount of hydrofluorlc acid, potassium hydro*n fluofide, KHF2J is produced. ~KCl, can be obtained in the natural date; however, It iB frequently prcduced by the action of HC1 upmpotaesium hydroxide. If a hot solution is treated with bromine, or Iodtie, respectively,@aeeium bromlde~ KBr, and ~Bium Iodide, ICE,are produced. All of the potaeeiumhalide salts are completely lon12.edand are readily soluble In water at room temperature. Potassium”chlorate, KC103, @=mslumpe rcblorate, KCIOk, potassium ~chlorlte, KC1O, ~SiUIZ bromate, KBrO , and ~3 tassiuviIodate, KIO , are3 all salts of the oxygen aclde of the halogens. KC103 is prepared by passing chlorlne gas into hot, concentratedpotaesium hydroxide. It is a colorlees salt that is nmch more Boluble in hot water than In cold, KC~03 cem also be prepar4 by adding hot KC1 to hot NaCIO solution. KC103 is a strong3 oxidizing agent, and it will decompose with a violent explosion to produce free chlorine and oxygen. ~r03 and K103 can be prmiuced in the same ~er as KC1Oj, and they exhibit the same chemical reactions ea KC103 doee. PtissiwI perc~orate, KC104, is prcduced by an’anodic aidation of KC103. It Is produced as a colorleee cmpnmd that is used as a strong oxidizing 8 agent. potassiumhypochlorite, KCI.O.~0, is prduced either by the reaction of chlotie gas upn a cold eolution of KOH or by au electrolyeie of KC1 solutions in the preeence of potseeitzzhydrmzide and chlofine. Potassium hypochlorlte cenbe easily reduced to chlofide ions and oxygen. g. The Phoephate Compounda of potassium. Putsseium hydroxide, lSke SOUUm ~de, can also enter into reaction with H3~4 ti form yat-saeium d14ydro ‘=pw~~~’%~k’- slum ZKmohydrogen phos*tej K.#f34, ~ tfi@azeium phos *te’ ‘3m4” Aqueous solutions of KE2K)4 m acidic, while eolutione of K#F04 and K3P04 wmy in their dkalinlty. If KH#)k ie heated, a aeriee of @23eeiuz metaphoephates,ICFO 3’ are fonzed. When~~ ie treated, it will decompose to fomn KhP207 and water. K3P04 ie etable towud heat. h. The Carbonate Cazpunde. Potaseium carbonate,K CO~ s, ie p~ by a sefies of chemical reactions tivolting magneeium carbonate and potassium chloride. Potaseium hydrogen caxbonate, KHCO~, is ptiuced either by Psin$ carbon dioxide gas into a “eat-ted solution of ~C03 or by We= cafbon dioxide over a mixture of K#3 @ c~c~. ~~3 W ~co3 eolutions are alkaline becauee of the basic action of the CO 3 lone and the slight hydrolysis of the HC03- ions. i. The Cyanideand cyanate CozgOmde . Poteesium forzlecomplex c~&s with iron: i.e., ~taselum ferrocyanlde, KkFe(C’N)6,and @.aeE.ium ferricyanide, K3Fe(CN)6. potassium femocyanide ie p~rad ea a by-prmiuct of the coal gas industry. In the procese, hydrogen @de, HC’N,iS released from the C@ gas to react with FeO to form fe~c acid, HkFe(~)6, which re~ti ~th Fe2