The radiochemistry of potassium

47 Pages·1961·1.508 MB·English

by  William T Mullins, G W Leddicotte, U.S. Atomic Energy Commission., National Research Council (U.S.). Committee on Nuclear Science. Subcommittee on Radiochemistry

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NUCLEAR SCIENCE SERIES
The Radiochemisty
of Potassium
—— ._—-
COMMITTEE ON NUCLEAR SCIENCE
L.F. CURTIM, Ckt~ ROBLEYD.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&riouliunald Meufumieel NorthwesteUrnnimreiw
cellqJe
W.WAYNX MEINKE
SAMUEL EP81Zm UniversiemfMlehfpp
CellbrntInnetihIo@fTeuhmlew
J.J. NfCKBON
U. FANO Memorial Heapi(al, New York
Natlouel Burmu II!Std8rda” ROBERT L.PLATSMAN
IAberatnf&reChidePhyeique
BKRBERT QOLD6TlitN
NIwleaDrevdePMedCorPJratloefh D.M.VANPA’f?l’ER
&iielrIea Barb]BaeaamhFmdetion
LIAISONMEMOERS
PAULC.AEBERSOLD CHABLESE.REED
AtemloEmrw Commlaslen U.S.AirFeme
J. HOWARD MeMCLLEN ~E, WRJGRT
Natbmel&lenoeFeurdnfieo OfficoefNavalReneemh
SUBCOMMITTEE ON RADtOCHEMISTRY
W.WAYNE MDNKE, Chufnaaa EARLNYDE
llmtvarnoif~hfi~en Unwernitoyf Cnlifornie (Berkeley)
NATHAN 13M1.OU JUHAN NfEl&JZN
NavalRadlologiDeedfensketmrairq HanfordIahorateflea
GREQORY1%CHOPPD4 G.DAVIDO’KELLEY
FlOride Etate Univmrd@ Oak Ridge Ne.fiorLdaboratory
GEORGE .L CCFWAN ELLIS P. 6TEINRERQ
Los Ahnn3,9 SciertUO LAmrainry Arsvnne NationaIlaheratmy
ARTHURW.FATRHALL PETF.RC.STNVE~N
UeivereiotfyWe,eb@tm Univer6ie*fCulibrni(nLtvmmeere)
JEROME HUDIS DUME N. SUNDERMAN
Braokhaven Nntlord Laboratory Bntblle Mmneriel Institute
CONSULTANTS
HERBERT M. CLARK JOHN W. WINOHESTER
Renneeleer Pelytsdmic Instltu* MesIIw!huAtIsmtitutdaTeehm~
(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
PrinteidnUSA,Prtce$0.60.AvailablferomtheOfficoefTeobnical
SarvioesD,epmmeot of Commerce,Weehtagto2o5,D.C.
FOREWORD
The Subcommittee on Radl.ochem16try Is one of a number of
8ubcommitteea worklrm 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. GeneralReferenceson the Inorganicand AnalyHcal
Qmn5.stryooftPassium.. . . . . . . . . ... . . . . . . . 1
II. RadioactiveNuclidesof Potassium. . . . . . . . . . . . . . 2
III. The Chemistryof “Potaasiumand Its Applicationin
ArmlysisMethods for the PotassiumRadionuclides . . . . . . 2
A. The General Chemistryof Potassium . . . . . . . . . . . 2
1. MetallicPotassium . . . . . . . . . . . . . . . . . 3
2. The ChemicalCompoundsof Potassium. . . . . . . . . 3
a. Pete.esiumHydrLde,KE. . . . . . . . . . . . . . 3
b. The Oxides of Potassium. . . . . . . . . . . . .
c. PotassiumEvdroxide.KOH . . . . . . . . . . . . i
d. The Nitrogek Compounds . . . . . . . . . . . . . i
e. The SuEide, Sulfate,and SuEite Compounds. . . :
f. The Ralogen Canpound.sof potassium . . . . . . .
The phosphateCompoundsml?Potaaslum . . . . . . 9
;: The CarbonateCcmpound..s . . . . . . . . . . . .
i. The Cyanideand Cyanat&CompouniLe. . . . . . . . ;
il. Other PotassiumCcqouuds. . . . . . . . . . . . 10
B. The AnalyticalCherd.stryof Potassium. . . . . . . . . . 10
1. Se~t@nsb yPrecipitation ~ . . . ... . . . . . . “11
2. Separationsby Electrolysis. . . . . . . . . . . . .
3. SolventExtractionSeparations. . . . . . . . . . . ;.
4. chrcmatoFm3PhYSJ=Pal=tions. . . . . . . . . . . . .
a. With–In&-&nl; Absorbents.“.. . . . . . . . . . lli
b. With OrganicAbsorbents. . . . . . . . . . . . H
With Ion ExchangeResins.. . . . . . . . . . .
:: By Paper Chromatm~pby. ..”.... . . . . . l!”
Iv. Difisolutionof Samples ContainingPotaBsium. . . . . . . . . 16
v. Safety-ctices . . . . . . . . . . . . . . . . . . . . . . 17
VI, CouatingTechniquesfor the RadioactivePo~sium Isotopes . 17
VII. Radlochemical&ocedures for the PotassiumPadionuclides. 18
VIII. Refemnoea. .o . . . . . . . . . . . . . . . . . . . . . 37
The Radiochemistry of Potassium
w. T. MULLLNS AND (3. W. LEDDICOTTE
Oak Ridge National Labwatwry*
Oak Ridge, Tennessee
I. GENEHALREWERINCESON TKE INORGANZCAND ANALYTICALCHEMISTRY
OF FmAsauM
1. m, H., Treatiseon Inorganic Cheudstry,Volume I, Eleevier,
Amsterdam71956).
2. Kleinberg,J., Argersinger,W. J., Jr., and Griswold,E.,
korganlc chemistry, Heath,Boston (1960).
3. Hillebrand,W. F., Lundell,G. E.”F., Bright,H. A., ad Hoffman,
J. L., Applied InorganicAnalyaiB,Johu Wiley and Sons, New York,
199.
4. Wilson, C. L., and Wilson, D. W., ComprehensiveAnalytical.chemistry,
Elsevier,Ameteniam,1959.
5. Sienko,M. J., 4 Plane,R. A., ch&Btryj hk&8w-Hi~, NW York,
1957.
6. Chariot,G., and Bezier, D., QuantitativeInorganicAnalysis,
John Wiley and tine, New York, 1957.
‘i’.Sidgwlck,N. V., The ChendcalElementsand Their ~E I
universityPrees, ~ord, 1951.
8. Hutchineon,E., Chemistry- The Elamenteand Their Reactions,
Saunders,Philadelphia,1959.
9. Sneed,M. C., and Maynard,J. C., GeneralCollegeCinemiatry,Van
Nostnand,New York, 194.4.
10. Sneed,M. C., md Braeted,R. C., CmugrehensiveImrti c Chemistq,
Vol. 6, ‘The AIJsaliMe~s, ” Van Nostti, New York, 1957.
XL. lather, W. M., .sndHildebnmd, J. H., ReferenceBcmk of Inor@c
chast~ MacMilJan,New York, 1*.
*Operatedfor U. S. Atcmdc”EnergyConmlsslonby Union Wbide Corporation.
1
n. RAImmmE~ cwmlA8sm4
The ‘e&active mlclldesofljobulaiumthat* of“W&t h therEiio-
chedntry of..potuJsiunm @van inTbbleI. This.tablchaa been c~hd
frm IMm”iion appaming in mp9Mm by ~, et ~m)(l) and, by Hughes
9!ABLEI
TOERmmAmmE lmImE2aFmlMarQ4
Haaf-Ldfe mducea”~
1.3E .# 4.6. ti-7-2n
7.7m P+ 2.8 Cl--n, K-n-2n,,K-p-pm
7?.16, . K-T-n, Cm-d-a
.l.32xlo9y p-1.33 I!7atumlsource
71.46 ~~
1.55
6.7 x 10-g o 7 -1.3 ~~ A4’
12.b h 5-3.73 +GP, K-d-p,K-n-y
7 1.2, Ca-n-p,Sc-wa
22.4 h 13-0.81 0.24 A-&p
7 -0. 4
17 m. Ca-n-p
In. ~~OF~AB’DITS~OE MAEUX81S
w51!EOMmmPm!MSIwa~
Rldloclledcal anal.7Bio ~ Ueuaw foU.m7 the * ti techniques
emtabliehedby mre ~ ==m~ ~tode~anonmdio-
active alemmt in au imctivu ample m&rial. Sbce thet3emthode - preci-
pitdiq Oolvantextmctic& chmautcgmphy, ad electrolysis--~t
q *c=l *I- b bmng * to completion,the general infomtion
@vwl Mlou m the f-tire of pot9SeiwlCcqmude and their behavior in
sqemation meti la titmdd to mtabliah the uaefulmna of such idaaE and
*dmiuuea in analyzinga mdloactive (orncmm?lioactive) md..er5alfor the
potaloiumIuaiomlclide.o
A. me Oeneml Chenddry ofFbkmium
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 sourcesof potassiumma carnallite,KClmMgC12“~O; P- haute,
K#4- W4 -2-4” 2E$O; BYlfite~KC1; Eilvlnlte,a xdxture of KC1 and NaCl;
.9Ch6tite,Mg904-K2S04-~o; .=d kahite, M3S04+Q3C12‘K2m4”6~0 .
Potassiummetal is usually prcducedby an electrolyticprocess In which
an aqueous aohrtlonOf the ~e??d iB eleChO~Zed @ the haoltile lZIpUritie8,
such as Mg(OH)2srafilteredoff. The solutionof KCl remdning -r this
filtrationIs furtherelectrolyzedto produce a aolutlonof KOH. The KOH solu-
tion is then evaporatedto drynessW elementarypotassiumobtainedby an
electrolysisof the fusedKOH.
1. Metalllc Potssslum
Potaz13iwnm@al is a soft, silver-whitemetal having a densityof O.%.
40
Potassiumis composedof three isotopes:K39 (93.@), K (0.1~), andK41 (6.%).
Km
isa naturallyoccunlng radioactiveIsotopehaving a haM-llfe of
109 yeare. Potassiumtill melt at 62° and it has a boiling @-nt of 7600.
Potassiummetal =pfdly developsan Oxide coatingIf it is exEOsedto
air. It till reactwith water to form hydrogenand solutionsof the
correspondingbases. It will ccmblnewith hydrogento form a hydride.
Most of Its saltsaxe very solublein water. It will dissolveIn smmmils
to form a blue solutionand when it is volatlllzed,a blue vapor co~sed
of mnatomic molecules is given off.
2. The ChemicalCompXMs of Potasslum
I?otassiumhas only a +1 oxidationstate. It is mme active t~
the non-metalsthan,ls,,sodium;however,its chenzkalpropertiesare similar
to Scdluul.It will reactwith carbon,clloxideh,ydrogen,oxygen,nitrogen,sul-
fur; and the halogens. The reactionsof Fotasslumwith these and other ele-
ments is presentedIn some detiilbelow. Table II showsthe solubili~ of many
of the pota8fiium compoundsin w3ter and other reagents.
a. Pot3ssLumHydride,KH. PotneBiumwill coniolnadirectlywith hydrogen
on heating b formKH. The colorlesscrystalsof NH deccsqpaserapidlyon
heating and uI1l reactwith inter to proihlcehydrogen gas.
b. The oxides of Potassium. Potaesiumoxide,
‘2°’ c= be ‘-UC* by
heatingpotassiumnlttite or titratewith potaeslumIn the absenceof air. If
,,
3
potassiummetal 1s burned b a calculatedemountof air,pot.easlumperoxide,
till be formed. Potassiummetal will react at room temperaturewith
‘2°2’
oxygento form potassiumtetroxide,K20b. Potassiumtetroxide,an ore.nge-red
,golid,WI.11decompomeon heating to fozm oxygenand the Peroxide,K#2. All
of the potassiumoxide compoundsreactvigorouslywith water to yield KOH,
oxygen,and hydrogenperoxide.
c. potassiumHydroxide, KOH. Potassiumhydroxidecanbe pre~d either
,bythe electmlyeis of potae8ium chloride,KC1, or by reactingcalciumhydrmdde
with potassiumc=honate, KOH ia highly dellquescentand very soluble
K2m3”
in water. Iti chemicalbehatior Is similarto that of flcdiumhydroxide,NaOH.
Its solutio= are stronglybasic. -
d. The Nltmgen Cmpunda . potassium,like q cdium, can reactwith nitro-
gen in an electzlc&Lechargetube to form@ essiumnitride,K N. K3N iS
3
green-blackin color,and it is rapidlyattickedby water to fozm KOH and NH3.
Putassiumazide,~ , can alsobe formedby the action of nitrogenupon
.3
potasaium. KN3 will decomposeupon heating h a vacuum to formK3N and nitro-
gengaa.
Potassiumnitrate,KNO is tie by reactingNaN03with KC1. ICN03is
Y
more solublein hot water than in cold. It ulll melt at 334° andbe decomposed.
When heated at temperaturesabove k30°,KN03 till lose oxygen to form~otassium
nitrite,KN02. PotassiumtitfiteWI1l decompcmeat 850° to producepotassium
peroxide,K202. It is solublein water, and when the solutionis boiled it
will hydrolyzeto producenltmue acid,EN02.
e. The SuMide, Sulfate,and Sulfite Compounds. Po&ssium will react
with sulfurto formp tassiummonosulfide, tasaiumpolyeulfide,
%s’ ‘=
The monosulfidecompouud,K2S, is a colorlesscrystallinecompourdthat
%2s2”
is hydroscopicand till react mpidly ulth water.
Potassiumstiate, K#04J like sodium sulfate,occurs freely$n nature.
It is preparedby extractingthe mineral demsit, schcmi~, M@4.~s04.6~0,
and treatingthe concentratedaqueous solutionwith ~tassium cblozide.
K260k is very solublein water. If K2S04 is treatedwith the proper quantity
of sulfuricacid and the ndrtureheated,ptaa slumhydrogen sulfate,or
potassiumbisulfate,KHSOk, is produced. KHSOk dissolvesin water to give
4