The radiochemistry of zirconium and hafnium

58 Pages·1960·2.218 MB·English

by  Ellis P Steinberg, National Research Council (U.S.)

v
‘~,11 National
—
Academy
T
I
of
Sciences
National Research Council
B
NUCLEAR SCIENCE SERIES
The Radiochemistry
of Zirconium and lHafnium
:$-:9: CNcmLHRARY
c,))
COMMITTEE ON NUCLEAR SCIENCE. :’-
. :.
‘..
L.F.CUR=, Chuitvnan ROBLE,YD.EVAN& ViceC~rman
NationaBlureauofSt.adards MassachusettIsnstituotfeTedmology
,,.,
J.A.bJUREN, Secretury
WestlnghoueEelectriCcorporation
H.J.CURTIS G.G.MANOV
BrookhavenNat.lonLaalboratory Tmmerlab,Inc.
SAMUEL EPSTEIN W<.WAYNE bfIiIkE “““
CaliforniIauetituotfeTechnol~ UniversitoyfMichigan
HERBERT GOLDSTEIN A.H.SNELL
NuclearDevelopmentCorpfitionof ‘“ oakRidgeN,ationaLl@ho~torY
knerlca
E. A.UEHLING
‘H.J.GOMBERG UnlversltoyfWashbgton
UnlversltoyfMichigan
D.M. VAN PATTER
E.D.KLEMA BartolResearchFoundation
NorthwesterUnniversity
ROBERT L.PLATZMAN
ArgonneNationaLlaboratory
LIAISON ,MEMBERS
PAUL C.AEBERSOLD W.D.URRY
AtomioEneqy Comdsston U.S.AirForoe
J.HOW~”?dd#fLLEN WIIiW”E: WFUGHT
NationaSlcienceFoundation OfficeofNavalReeearoh
SUBCOMMITTEE ON RADIOCHEMISTRY
W. WAYNE MEINKEC Ckirnwn EARL HYDE
UnlversiWof Mkhigan Unlversl&ofCdlforda(Berkeley)
NATHAN BALLOU HAROLDKIRBY
NavyRadologlcaDlsfenaeLshoratory Moud Lahmatory
GREGORY R.CHOPPIN GEORGE LEDDICOI”TE
Florida-bs Universally OakRidgeNationd Lahomtory
GEORGE A.COWAN ELLISP.STEINBERG
LoeAlamosSclentlfLlacboratory ArgonneNationaLlaboratory
ARTHUR W. FAIRHALL PETER C.~EVENEON
UnlvereltoyfWaehlngton UnlversltoyfCaliforni(aLivermore)
HARMoN FINSTON LEO YAFFE
BrookhavenNationaLl@oratory McGU1 University
The Radiochemistry of Zircomium and Hlafnium
By ELLIS P.STEINBERG.
Argonne National Laboratory
Lemont, IlliM”s
January1960
Subcommitteeon Radiochemistry
NationalAcademy ofSciences—National Research Council
PrinteidnUSA.Price$0.50A.vailabflreomtheOfficoefTechnical
ServiceDse,partmeonftCommerceW,ashingt2o5n,D.C.
FOREWORD
TM Subommd.tteoenRadiodmnistriysoneofa numberofsubcommittees
%KmlcinugndertheCommitteoenNuclearSciencewithintheNetio:naAlcademy
ofSoUmees-NationRaelsearchCouncil.Itsmembersrepresengtovernment
industriaalndtmivsrsitlyaboratorieisntheareasofnuclearchemistry
andanalyticaclhemis&y.
TheSubcommitteheasconcerneidtselfwiththoseareasof:nuclear
sciencewhichinvolvetheohemist$suchastheoolleetioannddistribution
ofradiochwtbxpirlocedurestheestablishmeonftspecti%ationfsorradio.
cthetioall-ypurereagamtsjtheproblemosfstockpilinugncontaminatmeadteri.-
.aMpthem?ailabi.lfo.ftcyyclotrotnimeforserviceirradiationtsheplace
ofradicmhetistirnytheundengradua%ceollegeprogmm9etc.
T’Msseriesofmonographhsas outof%heneedforq-to-date
gi”o~
eompiktionsof’radiocbtio~informatioanndprocedures,TheSubcommittee
haseadeavox’teodpresenta serieswhichwillbeofMs&.mumuse%0the
workingscientisatndwhichcontainsthelatestavailablienformation.
&ch mmgraph aol.1.amh%sonevmlumethepertinenitnformatiornequired
for~adicwhetitwiorkwithanindividuaellementora groupofclosely
relatedelements.
Anexpwtin the radioehemistry d thepartiemladremerithaswritten
themno~aph$ f’ol.lowalmsgtanderfdormatdevelopebdytheSubccxmd.ttm.
The.AtomicEnergyCommissiohnassponsoretdheprintingofthesexles.
TheSubconzki.titsxscwonf%ien~thesepubl.tcatfownisllbeusefulnat
onlytotheradiochemisbtutalsototheresearchworkerinotherfields
suchasphysios,biochemistroyrmedicinewhowishestouseradiochmicsl
techniquetsosolvea specifipcroblem.
W.WayneFMnke,Chairmen
SubcommitteoenRadiochemidry
iii
CONTENTS
1. GeneralReviews of the Inorganicand Analytical
Chemistryof Zrand Hf. . . . . . . . . . ...1
11. GeneralReviews of the Radiochemistryof’Zr and Hf. 2
111. Table of Isotopesof zirconiumand Hafnium . . . . 3
Iv. Review of those Features of Zirconiumand Hafnium
Chemistryof Chief’Interestto Radiochemlsts. . 4
v. Problemsof Sample Dissolutionand Interchange
with Carrier. . . . . . . . . . . . . . . . . . 19
VI* CountingTechniques. . . . . . . . . . . . . . . . 20
VII.. Collectionof DetailedRadiochemicalProcedures . . 22
iNTRODUCTION
This volume whichdealswiththeradiochemistorfy
zirconiuamndhafniumisoneofa seriesofnmnog=phson
radiochemistorfytheelements.Thereisincludead review
ofthenuclearandchemicalfeatureosfparticulairnterest
tothemdlochemista,discussioonfproblemsofdissolution
ofa sampleandcountingtechniquesa,ndfinally,a collec-
tionofradiochemicparlocedurefsortheelementasfound@
tieliterature.
Theseriesofmonog=phawiU coverallelementsfor
whichtiiochemlcaplrocedunsareperttient.Plansinclude
revisionofthemono~ph periodicallaysnewtechniqueasnd
procedurewsarremt.Thereaderisthereforeencouragetdo
calltotheattentioonftheauthoranypublisheodrunpub-
lishedmaterielontheradiochemistorfyzirconiuamndhaf-
niumwhichmightbeincludedIna revisedversionofthe
monograp.h
vi
I. GeneralReviews of the Inorganloand AnalytlaalChemistry
of Zimonlum and H4Mm.
~ Nostrand ~0., Irm. New York, 1958.
Pp. 628-653, “Chemioal Elements snd their Compounds,”N. V.
Sldgwlok, Word Unlverslty Press, 1950.
Pp. 564-575, ‘Applied InorganioAnalysls,mW. F. Hlllebrand
et al., John Wiley and Sons, Inc.,New York, 1953.
Chaps. 12 and 13, “Chapters In the Chemistry of the Less
FamiliarElements,”B. S. Hopldns, Stlpes PublishingCO.,
Ohmwaign, 111., 1939.
‘Hafnium,’ Chap. IV in “Modern Advames in morganio Chemlstry,8
E. B. Maxted, Oxford University press, 1947.
R. L. Barnard and R. E. Telford, Chap. 20 In “Analytloal
Chemistryof the Manhattan Projeot,nC. J. Rodden, eds.,
HoGraw-HillBook Co., New York, 1950.
E. B. Read, OhaP. 12 In “Metallurgy of Zirconium,” B.
Lumtman and F. Kerze, Jr., eds., Mo(Waw-HillBook Co.,
New York, 1955.
tielln~s Handbuoh der Anorganlsohem Ohemle, Systems NV. 43,
8th Edition (Ve% lag Ohemle, Gmb H. Ueinhelm - Bergstrasse,
1958.)
‘Ziroonlum,(”3.I.MUler, AcademioPress(1997).
‘ReoentAdvancesIn the Chemistry of Ziroonlum and Hafnlum,=
E. M. Iarsen, J. Chem. Ed. 28, 529 (1951)0
1
Msclvent-traction in AnalyticalChemistry” G. H. Morrison
and H. Freiser,Wiley (1957).
“Ion-Exchangersin AnalyticalChendst.ry,WO. Samuelson,Wiley
(1955)
l
‘Chemistryof the Metal ChelateCompounds,nA. E. Marten
and M. Calvin, Prenttce-Hall(1952).
11 GeneralReviews of the Radiochemistryof Zirconiumand
l
Hafnium.
No general reviewshave been published. D. N. Hume pre-
pared a pre13.minaryreview of the radiochemistryof some of
the major fissionproduct elementsin 1945, but it was not
published. Some materials from this review has been incor-
porated in the followingpresentation.
More completeinformationon the radiationsof these isotopes
and referencesto the originalliteraturemay be found in “Table
of Isotopes,nD. Strominger,J. M. Hollander,and G. T. Seaborg,
Revs. Mod. Phys.~, No. 2, Part II, April 1958.
111. Table of Isotopesof Zirconiumand Haf%xium.
Isotope Half-1ife Type of Decay Method of Preparation
!ZP86 17 hr EC Nt Ap,spall.);As75(N14,3n)
#7
94 fin Zr ‘(cx,n)
ZP88 85 day w Ni(p,spall.)
~r89m
4.4 min It(93$%),EC(5.6~),P+(l.8~) Zr(X-ray)
Z2?@ 79.3 hr EC(a75~),f3+(~25j%) Y(d,2n]
0.83 sec IT ‘Z@go(n,nl)
L1X106 yr B- Nuclearfission
65 day $- Nuolearfission
17.0 hr B“ Nuclearfission
.-dmin P- Nuclearfission
35 sec P- Nualearfission
~+
112 tin Lu(p,6n)
16.0 ‘hr EC Lu(p,5n),Yb(cz,3n)
..5yl? EC Lu(p,ytj(a,xn),Ta(d,2P9n)
23.6 hr EC Lu(p 3n);Yb(a,xn)
14
70 day EC Hf 7 (n,y)
4,8 S13C IT daughter‘2.1 hr T.’78
19 seo IT Hf178(n,y)
5.5 hr IT Hf179(n,y)
~- Hf180
44.6 day (njy)
64 min P- W(n,a)
.-.——..—
m. Review of those Features of zirconiumand Hafnium Chemlst~
l
of Chief Interestto Radiochemists.
1. The Metallic State
zirconium and haf%lum are diffloult to prepare as pure metals.
They are very infusible and react vigorously at high temperatures
with carborbo~gen, and nitrogen. When finely divided, the dry
metal powdersare Wophorlo and should be molatened for safe
handling. In oaspaot fom and at low temperatures the metals
are ve~ inert ohemloally, being attacked app??eoiablyonly by
RF, aqua regla, and fused KN03. The best method of preparation
of’the pure metals Is probably the van Arkel-deBoer method of
reduolng the Iodides on a hot filament. Thla producesthe so-
l
oalled oryatalbarn metal.
2. Soluble Salts
l%e solution ohemlstryof ziroonfumIs not veqy well under-
stood, and oonalderableoomfuslonexists in the literaturere-
garding the lonlo species present in aqueous solutions.
~18
results mainly frcm the fomnatlon of collolds and the fact that
ziroomlum ions undergo extensive hydrolysis and polymerization,
strongly dependent on PH and conoentratlon.(1) The only Important
cddation number Is #l. The nitrate, chloride, bromide, iodide,
perchlorate and sulfate of zlroonium are soluble In sold solu-
tlon.
3. llmolubleSalts
Among the more Insoluble oompounds Is the very Insoluble
-18 (~~
phosphate, ZFO(qP04)2 (K~p=2.28x10 ) which precipitates even
“Zlrconlumand hafnium show a remarkableslmllarltyIn mo6t
of their chemicalproperties,and unless otherwisenoted, any
statementsmade concerning one generally will apply equally well
to the other.
4
. .