National Academy of Sciences National s

NUCLEAR SCIENCE SERIES

Research council

The Radiochemistry of Molybdenum

COMMITTEE
L. F. CURTISS, Chairman National Bureau of Standards

ON NUCLEAR

SCIENCE

ROBLEY D. EVANS, Vice Ckainna?I Massachusetts Institute Technology of

J.A. DeJUREN, Secretary WestinghouseElectric Corporation H. J. CURTIS Laboratory BrookhavenNational SAMUEL EPSTEIN Californianstitute Technology I of HERBERT GOLDSTEIN NuclearDevelopmentCorporation of America H. J. GOMBERG University ofMichigan E. D. KLEMA NorthwesternUniversity ROBERT L. PLATZMAN Argonne National Laboratory G. G. MANOV Tracerlah, Inc. W. WAYNE MEINKE University Michigan of A. H. SNELL Oak Ridge National Laboratory E. A. UEHLING University ofWashington D. M. VAN PATTER BartolResearch Foundation

LIA SON MEMBERS

PAUL C. AEBERSOLD Atomic EnerW Commission J. HOWARD McMILLEN National ScienceFoundation W. D. URRY U. S.Air Force WILLIAM E. WRIGHT Office ofNaval Research

SUBCOMMITTEE
W. WAYNE MEINICE, Chai?man University Mlchlgan of NATHAN BALLOU Navy Radiological DefenseLaboratory GREGORY R. CHOPPIN Florida StateUniver~ity GEORGE A. COWAN Los Alsmos Scientific Lshoratory ARTHUR W. FAIRHALL University ofWashington HARMON FINSTON Brookhaven, National Laboratory . .

ON RADIOCHEMISTRY
EARL HYDE University fCalifornia Berkeley) o ( HAROLD KIRBY Mound Laboratory GEORGE LEDDICOTTE Oak Ridge National Laboratory ELLIS P. STEINBERG Argonne National Laboratory PETER C. STEVENSON University CaliforniaLlvermore) of ( LEO YAFFE McGill University

The Radiochernistry
By E. hf.SCADDEN and N. E. BALLOU

Molybdenum

U. S. Naval Radiological Defense San Francisco, California January 1960

Laboratory

Subcommittee on Radiochemistry National Academy of Sciences National Research Council

Printed inUSA. Price$ 0.S0 Availeblerom theOffice f ofTechnical Servicee, LMparhnent ofCommerce, Waehingtcm 26,D. C.

FOREWORD
IheSubcommittee on Rsdiochemistry 1s one of a number of .vubcommitteeamrkhg uoder the Committee on Nuclear Science within the National Academy of Sciences-National Sesesrch Cmmcil. Its memberE represent government, industrial, and univer,eity laboratories in the areas of nwlear chemistry and analytical chemistry. The Subcommittee has concerned iteelf with those areas of nuclear science which involve the chemist, such aa the collection and distribution of radiochendcal procedures, the establishment of Specificatiu for radiochemically pure reagents, the problems of stockpiling uncontaminated materials, the availability of cyclotron time for service irradiations, the place of rsdhchem.istry in the undergraduate college program, etc. Ibis series of monographs has grown out of aPilatioM of radiochsmical Info-tion the need for

and procedures. The Subcommitteehas endeavored to present a series which will be of maximum use to the working scientist and which contains the latest
uP_ti-*te available information. Each umograph collects in one volume the ~rtinent information required for radiochemical work with an individual element or a group of closely related el~nts. An e~rt in the radiochsmistry of the particular element has written the nnnmgraph, following a standard format develo~d by the Subcommittee. The Atomic Energy Commission has sponsored the prtiting of the series. The Subcommittee is confident these publications will be useful not only to the rsdiochemist but also to the research worker in other fields such as physics, biochemistry or medicine who wishes to use radiochemlcal technique to solve a specific problem. W. Wayne Meinke, Chairman Subcommittee on Sadiochemistry

ill

CONTENTS hKt2
I. General Reviena of the korgauic and Analytical. Qnx&itry of Mol.ybiemrn Table of Isotopesof M.ybdenum
1

IL

III. Review of Those Featu.ms of Molybdenum Qu9mistryof QrLef bbrest to Radiochemists 1. 2. 3. 49 59 6. 7. e. Iv. v. VI.
k=C

2 2 3 4 8 9 II 16 20 21 21 22

mo~bdenum and ud-ybdenum Woxbde

Soluble Carlpounds f molybdenum o Insoluble caqmnde &mpla of mol@denum

ions of mol@denlml

Chelate campoundaof molybdenum Solvent Extraction of molybdenum Chrcuuatographic behavior of molybdenum Electrochemicalbehavior of molybdenum
saraplas

Dissolutionof

for RadioactiveMolykdemm Deterniinatione

kunting Techniques for RadioactiveMolybdenum Collectionof Dait.ailad RadiochemicalProcedures for k?mlybdenum

DNTRODLICTK$N
~is volume which deals with the radiochemistry of molybdenum ia one of a series of monographs on radiochemiatry of the elementm. lhere s included a review of the nuclear i and chemical featuree of pertucuhr in-rest ta the radiochemist, a discussion of problem of dieaolution of a sample and counting techniques, and finally, a collection of radiochemical Proced-s for the elemnta as found in the literature. all elements for 17mseries of monograph will cover which radiochemical procedures are pertinent. Plane include revision of the monograph periodically a6 new techniques and procedures warrant. !lheeader is therefore encouraged to call to r the attention of the author any published or unpublished material on the radlochemimtry of molybdenum which might be included in a revised version of the monograph.

T-i

I.

GENEFbU RXVIEW ~

THE INCEGANICAND ANAUTICAL m?JmTRY

mLYmENuM

WA (huprehensive Treatise on tigani c and TheoretAcsl ~t&, J. W Mella, Vol. XI, Chapter ~ Lqgnane, Green and b., New York (1931) Ansl@cal &amistIT of the Manhatlxin Projeot, G J. Redden and J. C. W@?, pp. 4x-455, M&rawHill Book b., k York (1950) ~Applied Inorgauic AIIS&SiSn, IHllebrand, MdeKl, -t and HofJohn Wihy and SODS, hce, New York 2nd e&, MolyMero.Y@, pp. 302-316, (1953) wFtits QM@= Epbrdm Iuorgadc &mist&, P. C. ~ Thorne and E. R. ltdsrts~ k York (1954) m, 6th d, rev., Nor&man Publishing b., Ino.., No. 53~ W e&~

%fnelints Handbucb der AnorganiscbenChemi#, Sys* Verlag Qusmle,G.M.B.H. Berlin (1935)

IIMOI.@&~ QYMPOWW, D. H. Kllleffer and A. ldns, hte.rsdenosPuliMshers O New yOrk (1952)LurdeH. ad J.I. Hoffmsrq Wutlbes of Methods of Qmmical kalysis~ Go.EoFo John Wiley and Sons, hlC., New york (1938) WiusldtativsAnalysis for the F&e Elements, A.A. Noyes and W.c. Bray, The h~ b., New York (1948) PreferenceBook of Inorganic -sW, W.lL Lather and JX. HildebraQ 3rd cd., The Mami.llan b., New York (1951) Scdtts Standard Nst.lmds C&micsl Ansl@sn, N.H. Fumau~ Editor, of 5th ed., Vol. I, KNoI@denuu?,pp. 585-613, D. Van Nosixami k., hlC., New York (1939 ) lf~atim ~., New on Imrgauic -SWs (1956) H. -, Vol. llP Elsevier Puld&hing

York

Isotope

Ealf lffe

Type Of Wcav

Method d

FTeptim

lip
Mo91m M091

5.7 br 66 aec 15.5 min 6.95 br IT

19-i%(p,-)Mow
M& Mow Mo* (7,n)B&h 91 (7,n)MO (n,2n)ktc#l

lTb93(d,2n)Mo93m ITb93(p~n) M093n am a k@*

>2 ~ 66.0 hr

14.6 ndn 11.5 mln a2min

P-, 7 PP-

fiaaIm

fiesion

See lhble Ieotopesby D. S~ of

Reviewe of Modem

r, J. Hollader

and G. -berg,

PhyeicB x$

Ho. 2S Part 112 April 1958 for mre

infmto

tion concerningdecay echems, daughter productej etc. and for mfemnces tbe Ortginal litemtllm .

III. REVIEWS OF mm

FEATURE m MoImDElm! CHEMISTRY OF CHIEF IN-T ~ RADICCEWIS!tS

1.

Metillic idol.y%iem.aw Molybdenum Tricdde and

liolyWlenum a hanl mtal; -y IB ance h conqact fm

In

powder

fomn

and

silvery in appar-

It has a denelty of 10.2 ani its mlting point la

about 2620%.

he potential (E@ for the Meblo(VI) couple ie + 1.05 volte. 1 of the metal include reduction of mol.ykdenun rioxlde t
molykdate with hydrogen.

Metials of p~p~tion

with hydrcgen or carbon or reduction of ammnium Saface

oxidation of the m3til prcceeds slarly at room tempexwatm. diluta nitric acid, ~ aq= regia or hot ccmthe metil passive.

!lhenKItal ia soluble h cent~~ euMurlc ac Id.

Ccmcentm3tad nitric acid mnde=

It 16 Insoluble in Concentratedh@~OriC

f3Cid, @drOfhmiC

8Cid (thOU@l

soluble in a ndxtwm of nitric and hydrofluoric or raulfuricacids), cold concenbted sulfuric acid, dilute euliuricacid, or for all pmctical or scdim hydroxide. Fusion with potaesim purpc9es

aqueoue ytaaeiuu

nl*ite,

-nit=te, -chlorate, Eodiua pe=ide, nitmte,

or soditm carbonate plue po-siwn

azidisee the nmtal to a soluble mlybdate.

matar,

Molybdenum trioxide,M003, 18 a white powder, slightly soluble in

readily soluble in cauatic alkalis, anminniumhydraxide or in alkaline solutiane gene7eJly. cent~tad

Ignited nml.ykdenum oxide IS solublm in h@mfluoric

Molylnlic oxide melti at 791%.

or mn-

eul.fwic acid.

Accom5ing to !Clmae

T. Dupuis ami C. Duval,2 the ox~e does not aublim helm 780%. authore report magenta, weighing form and te~mtum ignition of varioua cqmds of mlytdemnn.

ltmita for W K. H. C-3

S. C. Limg u

reccziwnd ignition of molybdic oxide at 500-550% for analyticalpurpoees. Methods of prepxratimnof molybdenum trioxide ticltie axidationof tbe metil or molylulenite (14&2)by i&@tion h air or by decwqxxition of molyb dataa with acida such aa nitric or hydrochloric.

2. Soluble Ccmpounds of Mo4bdenum Mol@denum hae SIX oxidationatitis: 0, +2, +3, +4, +5$ +6 oxidation st.ataia the one met +6. Die

conmmnly found in aqueoua solution.

Molybdenum la genemlly conaidemd to exist in aolutlcm aa an oxygemted anim in * +6 atita. It la eaaily reduced by the usual reducing agenti

such aa ztnc, atannoue chloride, suJfm dimide, hydmzine, etc. Her controlledcmditions, i.e., neutml or slightly acid solution,mild min ductim of mlybdenun(VI) will prduce mlybdenum blue, otheruiae ml@denm(III) la the usual end ~cduct. It is not yet known what the exact na~ of the

blue intermediatereduction prduct 1s, whether it la a nrlxture the +6 Of and +5 or * +6 and +4 cmidation statis. must lx3Protecw

Mol.@denm(III) IS very aenaitive to oxidation

fmm air (oxygen) and other oxidizhg substances.

mO~eId~)

is md-

With ImxcUry9 -lybdmm IS

Z8d.@d-UdV)WbiCh

blue is not P
is 81S0

duoed but the -UCt

of the *UCtiOn

susceptible

tO air Oxidaticm. lbs +5 state *

be psrtially stabilizedby the ~S=Ce

of a ccmplexbg ion such as thiocyanata. Water soluble compoumle of molybdenum pobmsim and =WB ticltie the ~=~ EICdlUW

iun salta of norml mlybdataa.

3.

InsolubleCompounds of Molybdenum
The

Jhble lieti the oidlnary insolubleccmpounde of molybdenum. I molybdatieazw genemlly all raadi~ eoluble in acid~.

nm-

Silver arcllead molyliiate mlybdenum cupfermste,&hyhaxyquirdate ~ a-benaoinoxhcatekve all been used in the gmsv-tric bdenum in msdiochemietry.

determination of moly-

The preclpikting prqm-tiee of these magente for molybdenum~ ths fissim Producti and *r elemnti which my be pmeent In k solutim will h

briefly Iwviewed. Detailed diecuasioneconcerningtheir use in analysiswill be found in the references in Part 1. Iaaa mlybaate : The ~vimstric molybdate ie a ccmmnly en@qed det+s~tim of mly~enum as bad

procedura in tiiochemietry.

!l!k ml.ybdate

ie pmcipitatad fmm hot, weakly acid eolutionby the addition of lead nitmbe. The precipitatemy be dried at 110 or ignited to md heat. Iaad molyMate Is prefemble to eilver mdybdate because cmditiona for precipitation(absence of chloride aMolybdmum sulfate iau) am
cuufermte:

not ae critical.

Molybdenum

ie precipibstgd from a fairly strong

Hm3ever, cupfermn 69knyof

acid solution by cupferron (nitroeophenylhydraxyl.amine . ) ia not a selectiv8 ~nt for umlybdenm

ae it will also precipi~ti

the fiseion prcducta~ e.g., Zr, Nbj RI, etc.B U(IV) (but not U(VI)) -

other

eI.mmnte. Themfure it Is useful ae a pmcipl=t @eld of nd.ybdenuu

for the determinationof the not present or

only in eolutionswhara these elemmts am

can be

are preferentiallyconiplexed.The cupfermte dekrmhed ae mlybdenm trioxide.

ignited and mlyldenwm

TABIE

I.

momm

cwPolmm

OF MomBDIQm

llKRGMIC Remgent & &+2 ~i+3

+2 Ca @.2

Pm3cipltata

Solubllitg in Water .0044 ~/100 .~/loO m(25)

Volubility in Other Reagenta e. BIIOYKCH,Earn, Fm40H eolne.

A@~ E9Mc04 Bi2(M~)3

caMoo4

mla(23) el. sol. in acid v. sol. b acida

e. aclde, i. alcohol and ether

.02 glne/loo ~
Insoluble

cdMq -4 k2(q
FM4d4

el. soluble Ineolubls )3 el. soluble

heoluble

s. aclde, BE40E, KCR

42 =+3
+2 Pb

13.acida
d. cone. H#~, i. alcohol s. acide, K03,

9=+2

S** T@4cc4)2 M& 3

.0104 gm3/100 mle(17) e. acids Ineoluble Insoluble 0. acida s. EK4~, alkline eulfldee

~+4 s=

ORGAnc Reagent Soluble in

Precipitatedm l-~ Kcl or H2S04 buffered acid solution, e.g., acetic acid-acetata ~ acid eolutiana

cupferrms 8-hydmxyquinoline a-benzotiainw

@ Fmo:, @ RH40S mhieml acid

mo3, ~403 + %02

* nitroeopheny@droxylamhe. t O~iC mt,erlal partti~ midl~~.

Molybd has tie

entm oxinate: 8-hydroxyqufnoline(oxine) ae a e~, property aa cupf

reagent

for molylx3enum

mime

i.e., It pmclpltatee a large nunbfm of to Ribll amd

elemmte fmm

a slightly acid or alkaline eolution. Acc@ing

Malat4 , molykilenum cm be ee~mted

from Fe (III),Al, Be, Zn, Iii,Co, Mn, Fb,

Cd, Bl, Cu and Hg(II) by precipitatim uf molybdenumoxtite frm an ~im acetate-aceticacid buffered solution contatilngWe (ethylenadtieti-cetic dl-soditm salt of RDIM

acid). Tungsten (VI),V(V) and u(~) aleo prebefOrS ~cipi-tim. Maltiek5 states

cipitate. Titanium must be m~

that V can be held in soMxticM by mduc~ with EmYl at pE 1-2. MolyMenua oxlnate my 2 aa Mo02[C9 H6 ~] z.
Molybd emm
trbsnzoinoximta :

it to V(II) and then C~lSXillg it be dried at bO-270 w weighed

Alpha-benzolncixime practical- a specific is and Cr(VI) interfere h

~~t

f-

nmlybdenm. 6

Only W, N, V(V), Hb, W fmm

the pmcipitatlm

of mlyMenm

1 ~ acid solution by tb addition of an u b reduced to

alcoholic Solutiml of the reagent. Chromium and vamdim I.cnrer valence s~tes in which they do not pmclpitite.
must

Eiobium, w~ M and H

be removed. b

fiemian prduct chemtatry,nlobtm la removed ae the mlladlum Iadlcactlvitye 80 insigi

hydmti

oxide with imn as cmier.

to the

nificant in ccmpriaon

mlybdenum activity in lcw energy fission that

no special procedure is requi=d to remove it. Molybdenum oximte may be ignited SJM weighed as molyMic oxide. Molybdeman sulfide: Molybdenum sulfide is ganemlly not ueed in the ~vimetrfc detemdnaticm of nmlyMenwn In mdlochemistry, for there are far
awsilable. It has been employed as a ~ of sepsmating rely%

bettar mthods

denum fmm

tbs fission

7,8 productswhich do not form sulfides in acid solution.

H2S through the acid solu-

liolyMenua uulfide is precipitated by paeshg

tion contatiing molytdenwn or by acidifying a thiomolybdati eolutbn.

Molyb-

denum sulfide ehould not be weighed ae ~uch because its compoaitlon IS genemsdly indefinite .

(H2S reduces some of the molybdenum to lower tidation states. ) te lhrva19, there is no plateau in the thsrmogradmetric curve convatid to mmlybdic oxide. The sulfide should be

Also, accorQ

until the .wJfids has hen

ignited carefullyand weighed as molybdic aide.

Comec

iwitationof nlolvbde~ : Several methods are mentioned here which,

wh&

not deallng specificallynith tracar amounts of molybdanma,were used ta 6

separate,preswmalily qusntitativ81y, microgram quantitiesof mlykdemnn, and thereforemight be applicableto the carryingof tracer molylxleruzn. Picket and Hmidrs10 made a study of the co-precipitation mol.ytdanum, of cobalt and copper, h Hum tracer and ~. amounts, as the 8-h@wq@nolate9 with

or alumhnxn as carriera.Precipitationwas ti

an aummniu acetati

buffered solution at pH 5.2. Aluminum or i.ndhmn oxinata alom carried 85 par cent or more of the ld.@denum present. In the presenrx of oxina plus tgnnic acid snd thioanXbMe, al~ molylxienun. Niobium, tallur%xn and mol.ybdenm are SpSCifi~ of the fission products which is more than 10 ~ h = tion on mangam3se dioxide. removed fran a solution or hdiun carried better than 95 pm cent of the

nitric acid by co-precipita-

Pm-k12 reprted the practicallyquantitatims~ frcm orn

iog of O ii-2 mgs. molybdenum, autimo~ and bismuth on maugamse di~de

Eter of tmil@g solution by the sddition of ptassium bromide snd potassium pennangsnate. The procedunswas used for separatingtraca impuritiesfmm Poh113 employed the amnoniun salt of Pyrolidim-thiocarbamati, thslMum( I) as carrier, for precipita~ includingmolybdenum, away from aluminum 14 Schamer and Eberhardt precipitated100 mge. of biemuth as the suHide to carry molybdenumas a preliminaryse~mtion amounts of molybdenum in soils, plants md in the deterdnation of tmce copper.

with

a large mznkm of tram impurities,

animal products. Molybdenum uay be

collected on other acid-insolublesulfidea such as antimony or copper.

ultramicm

quantitiesof molybdenum

are 9=ntita*i~Q

CO-CrYStSlliZ* solution

from slightly acid aq~oue eolutionswith u-benzohmxim.

An ace-

of the reagent 1s added to the aqueous eolution containingmolybdenumat such concentmtion that the solution remains homogeneous. The solution is hiled to drive off the acetone whereupon, the oxlme, due to Its lW
water, crys-bllizes

volubilityIn

out camyln.g molybdenum with it.

be sepamtad

15

Molylx5enum my

from these matrices by dissolution or destruc-

tion of the precipitate,by solvent extractim, ion exchemge techniques,Precipitation f.the carrier or a combinationof these rathode. o

4.
BfolyMenml

Cmplax Ions of MOlybdemm is very Compl- and, as yet, not thoroughlyumieP States (Incllslinghe t
ch the c&ley8tem

Chemlsa

o Stood or inveatigatd. The poaaelaai(m f six cddatim O stata) does not aiqlfiy matim.
tims, i.e., tewmat-j A~ntly .semll

pE, ccmcent=ticma,

etc. s of a pm%iculsu

under inveetigatim

can scsmstlmesmrkedly

affect this system. in the litimatmw

Thi8 kas led concerning

to a good daal of confusIau and cantmMictlcm mol@denum

species, oxidation atatea involved and equilibria.

It ia genemslly believed that the principal mdy?iienum species existing h alkaline aoluticm la the siqle the @ nmlybdate ion M~=. & acidifying much a

aolutiou, I.e., lmering

past 7, mlybdati i-

ccdanae to f-

Phhmti

16 ions. Limiqvist, cm the baais of apsctrophotomtric atudlea sequence:

has propc9ed the follmhg

~lgbdanun hag a strong capacityfor forming ccmplax anions. Besides tlm ieopolpdybdatea, molyManum forma (a) heteropo~ aci&, cauplaxaaof
mol@dic

acid with phosphoric~sflcic~ tillurio acids~ etc., (b) peroq percdde, (c)

molybdatia~ ccmpoundaor csmplaxesof molybdateawith &dmgan coqil-s in the (VI) and l-r

oxidation states with hslidea, cyanide, thioo~anic substancea~

cyanati~etc.j and (d) complexesor compoundswith q

such as oxalic aci~ citric aci~ tbioglycollicacid, phaql hydrasim~ catachol,EDTA, l~lo-phenanthrolim, etc. While q cauplaxasor ccqounda, both organic and inorganic, are _

there is very kittla definite quantitativeinfonuationavailable mncernhg theti atreogthaor even theti fomnilae. ~euh ~ ~.fi17 atudi.ed the kehavior of molybdenum in various sol-

vent erkraction ~atems.

They propsed the fommila k02X2(H20)y(Ether)n, where inti die*l or Us* ~asitile

X represents a hsMda io~ for the spcies aXbract@ propyl ether frm ~

~ HOl or 6 ~ HE-, and also dlacussed at length w

factors involved in the mechanism of this solvent extraction aystan. Mamond, I-8 8

in a series of papers, has axtanded tbie stu& b aqnssion

the detiopsnt

of a ge~ral

for the &atribution ccefficiemtof a metal haEda lmtween an aqueous of

i@rohalio acid phase and an organic solvent and has testid ti vtidi@

this expressionfor the extractionof ndybdsnum(VI) and indium( III). Scme information~ meric fome
obtained concerning the aqueous mol@demnu(VI) swcies; poly-

can exist at hydmhalic aoid ooncenkatione tdow 6 ~ (and <0.1 ~ of a~& sti~r WSII HQo

molytim.nn);the md.n spcies are apparently the dou

investigatedtba nature of the nmlybdsaum tblocyanatecomplex. Perrln$ Through apactrophotomtric studies in @# acetone-uatersolutlona,he concltied that in ~ hydrochloricacid, molybdenum
in f onus thloqanate complexes

which the mtio Mo:~

is 1:3, 1:2 and 1:1 for high, mdiemte ard la !!!he complex is amber, fairly 1:3 iE the CO1c~lex used

cciicent~tlonaof thlocyanate~spctivsly. etable,uncharged and probably lbO(CHS)s; WS

in chemical analysis. The 1:2 coqlex is yellcw and unstable. The 1:1 complex is colorless. !be logs of the aaaociatlon constantsfor the coqlexes In @ acetonemter at 20-3 and icdc etrength 1.W-1. 10, m 1.85, 3.01

and 3.2 for the 1:3, 1:2 and 1:1 complexes>rw~ctivel.ym

5.

Chelate Ccmpomds of Molybdenum

Molybdenum form many chelata complexes or Compolmda Som have been . used in udybdenum tiiochemistry, but the~r use has not been extensive. Many molybdenum chelate complexes or compoundshave been employed in analytical chemistryfor the sepa=tion and/or determinationof mol@denum in a wide variety of mterlala tilochemiEI@
and som of these chelates

should be useful in the

of ma~bdenum.

A brief discussion of a few molybdenum chelate cozrplexeeill show their w

broad application.

~cipitation

with cupfemon, 8-hydr~uinoltie

and C%-benzoinoxime has

already been mentioned (III, Part 3). Acetylacetonela a 1,3-dlketonewhich posseee@o the fairly unique chmacteristic of being both chelatingagent and solvent and cerb3in extm3ctiona

may

be C.eJThd out from high acid concentitiona with It. Holykdanm, as can M qwantitatiwly ext~cted fimm 6 ~ aulturic cid by a a

W32(C*02)2, l:lmixtum

of acetylacetone and chlozmform. 20

lWyMeum(VI),

tungd.en(VI)snd rhmimn(VII) in acid mlution react with soluble in bu~l or amgl

tduane-3,4-dithiol to form chelate oanpounda that am acetate and aartmn titiacbloride.= dithiol nmlemiles to each ndylxlenum ak

Gilbert23 found that tire are three in the caqbx and also~ that wlwn

molybdenum(V)is treatedwith dithiol, the (V) ca@lax dlsproportionataa kelamen the mol@danum(VI) aauplex and a mlykdemnu( IV) ccmqibc;the ratio of h can@exIwsdepemia on the acidi~. MolybdanunI( III) doee not nact. (VI)/(IV)

Mlylxlenmq

may lM separatedfrmn tungstan by inhlbi.ting the formationof the tungsten cunplas through control of the acid can~ntration or tlm addition of citric acid.24-26

aruianhal tissuesss. Ethylemwiiamimtatraawtic acid (EI?TA) foma tion with molybdenum chekta cunpl~s in acid solueach

and (V) in which there are -

abna of mlybdernm b

mle cule of EETA. The EDT.Amrqlax holds molybdenumin the (V) oxidation state h solution at pH <7. The fomnulas for the (VI) and (V) ccm@sxes are

solution by the di-sodium salt of EDTA while uranium( IV) is precipitatedby cupferron denum at pH 4-6. 35
However, EDTA does mt

affect the artxactionof molybAlso, as

by t%ydm~quinolirm

fib

36 clihrofoxmat pH 1.6-5.6.

pointed out in Section 111,3, precipitationof molybdenum oxinate from an aummnium acetate-aceticacid buffered solution contai~ of EDTA serves to separaia No frcan bxge a the di-sodium sslt

4 number of other elements. (separationfrcan rhenium)~

i% The canpoundeof molykdenunwith cupferron end a-benzo ~~

are soluble in chlorof omn. The extractionof molybdenum

tith a-benzoinoxim is the first stap in a rapid sp ctrophotometric dater4J. mlnation of the element in tkmrimn oxide, uranyl sulfata and steel.

10

Mclytdenummy fluoride or IIITAb l-butanol 42 .

be separatedfrctm most metals in the presence

of sodium

0.1-0.53 hydrochloricacid by extractionwith Mcrin into

Molybdenwnforma cnmplexeswith sodium diethyldithiocarbsmata (soluble 43 h U chloroform),xanthate 2 n (separatlo from rhenim) 45 and di-sodium-1, -di-

hYdroxY-3, 5-bennem3isulfonate (Ttin) .ti The Tiron cunplex is the basis of a VeKY sensitive colmimetric (aqueous)procedure for mol.ywnum.

6.

Solvent Extraction

The extractionof molybdenum from an aqueous eolution inta an organic solvent has been studied by maIW investLgatcrsfor maqy different systems. A few of these haw been briefly mmtioned h Molybdenum. Relative- little lnf~t ion is available In the litemstconcernin8 Part 5: Chelats lbmpoundaof

the extinctionof madlasctivsnmlybdenmu. Hwewsr, them am ences for the deta-tlon of mic~

nmsrous refep

quantities of molybdenum in soils,

as

ptits, staele~ alloys, pure smtsla, et-c.which employ solvent extmctiom

a ~ of dete-ing h * elmmnt colortitricalJy or spsctrcgmsphically.

Again, ~ference

these ~thods

may prove helpful to 12usmadiochemist.

Colorimetrlc Methds

of Analysis by Snell -

Sne1147 and Colorbtric

Detaxminaticmof l%sces of Metal# by Sandellm prod.de excellent covurage of this subject. TWO classicalnmt.hds which have been fissIm prcduct molybdenumam complexes of molyMenm
employed In the

separatiacof, or chloride

the extmctlon of the thim~ts

into diethyl ether.

Thiocyana te: ldolykdenm in dilute acid in the pnsence of a -ucing agent, such as stwmoua chlcrride, omm a red-coloredcomplex with thiof cyanata. TME =action has been used for nany yaara as a nnans of determining molybdenum colorlnmtrically. Hiskey ad
Btited that it was fto molybdenum was 3:1.
Meloche,

49

in a at-

of

the

complex,

with mclybdenum(V ] and that the mtlo

of thiocyanate

R. Bock50 ~EI tie a detailed investigationof the 11

exlzactim of W.rioua metal thlocyanatesat 0.1 g Calcentlmtimle e~r frcm 0.5 ~ hydrochloricacid solutionewhich wem ~lum Wllocpte 1 b 7 ~

Wocyanste e By~*

ccmcentraticm9

etc.s molybden~ can be cep4mt0d i?rom number of fissicm a producte~ umniu(VT) aml other dmenta. The mcQbdenwn(V) complex ie Holtile in much solvents ac amyl alcoholj bu~l acetzati, ieo-propylather~ ethyl acetita M lhia51 etmliti ths ecrtmctionof mlybdenum cyclohexanol. Gotc and by wario= organic

t.hhcyanate

eolventi for apectmphotcmetric purpcme; ethyl acetits or iec-bu~l alcohol and lb ndxfnme with chloroformor carbcm te-chlorida Vwntao Wilkhacn and Grum#
incorpcQlSt9d the

ware suitable eol-

LalRmLction f md.ykdemuu(v) o

thiocyanateaa a etip h a procedure for eepamting mlybdenum frcm umanium and other fiseion pmducti. Molybdenum sulfide was pracipiixatedj dieeolved

h aqua z-egia md

the molybdenumextmacted from h ~ hydrochloricacid eolu-

tian into ethyl ether ae the thiocyauatecomplex (~ wee the reducingagent). B!olylRIenn as back extmcte% with 8 g hydrochloric w tion of the aqmoua ext=ct and trea-nt wae pmcipititad twice Mol@demwn

KICidj WJII, after

evapom-

of the reeidue with nitric acidj

lad amlylxlati.
from

can be eepmted agent

rhenimj vandium -

chromiumby USthen axtmacthg

mmcury ae the mducm

(rheniunie not reduced) -

the mol@denum(V) thiocyanaticomplexwith butyl acetate (tlM colored vanadium w chromiuc reductionproducts arc not eoluble h butyl acetati ).52 from

In the preeemce of EIcdiu fluoride and ED!M, mlybdanum ie ee~mted

titaniwm and other metals by extraction of the thiocyanate complex by a

1:1 tit-

of carbon tetmachloride-

-l

alcohol. 53

will efimct into ethyl ether frcm klcgen E@y 1 Ether: liol@kh3num acid eolutione. tiflt~ reported 80-~ extinctionfmma 6 ~ BCI. ~em

Snvestigatirsreport 54, 9.7 and 6.5 per cent extractionfrom 6 ~ HBr55, 3.5 N I-F56 and 6.9 ~ H157 solutionsrespectively.

12

Stit and Maagher58 prepared carria-freen H093S99, whiob had been ~ duced in sn (a, reaction with sirconium,by ether extractio~ n) The zticonitrn

target WaS dissolved in L? ~ H2SOk, the solution evaporated to fumes, then diluted with watir and the chloride and hydrogen ion ooncantrationaadjustud to 6 & M.ylxiernmIas then extracted quantitatively w with &et&l used ether extractionsto sepamh ether.

Wiles and k@.159

molybdenm from

frm 6 ~ Ha, back axbracted fission product mixtures. Molybdenm was ert.ractid fran the ether phase with watir, the aqueous phase wag scavsngedwith a ferric ~& Ptipitati and molybdenum precipitatedaa the M@wxyquimlate

for mounting and counting. See Prooedure C in Section VI in this report. A rapid separationof molybdenum and techmtiun fran fission products and each other wss effected by extractingMlybdenma(VI) with ether frcm a 6 ~ Ha solution of irradiateduranium, precipitatingthe molybdenm with and separatingor milldng the tacbmtium frm molybcbnm by,

W@roxyquinoLate precipita~

60 nitron pert4schMtat0with rhenium as the carrier. NeMdm and DiamOI#7 conductedan e.xknaive in-

vestigation of the etiaction khatior of mol@denun(VI)~ using ti99 and

M09* tracers, from aqueous halogen acid solutionsinto Yarioua ketomm, esters,
ethers, an alcohol and SCSESm~genated be consulted for detailed information. solvant.a. The originsl paper should

A very brief resmk of some of the

results of their ImvsAigation follows. The non-cixygenatedolvents, carbm te-chlorlde, s

extrOwmly poor extractaita for molybdenum. tbe ketcmes, eate= and the alcohol we= chlorofwm, etc. were solvents, than the cor> ether. h The

Of tbe oxygena~

all better ex-ctanti

responding ether; the czder being: esters and alcohol > ketmes nature of tbe halogen acid tifecti extncticma the extmctlon

of molybdenum.

geneml,

fmm hydrobrcmicacid solutionswere better and from hydmf luoric extmcticme from hydrochloricacid aolutions.

acid molutlane wem worse ~ The effect of tempemtum

was also notad: bettar extractionswere obtainedat

5 than at 45 with tbe exception of extzsictioney the alcohol (2-etbylb

hIS-01)

which seemd to be independentof the teqamture 13

in the mnge examined.

Var@ng the Initial Cmcamltratim of mlybdmun

BqUaouc Elk@e m
two

10-9 M to 10-2 M did not amect tbe Iaicta-ibution coefficients for m

~ Solvente tesi?ad (hexccleand P#138-ai iethyl Table II is a ma~e@nhtiwc e~r).

~itatOf tlw solvcmteWith which dtitribu-

tion coef?ficiemtes DB at romn telaparam .

[(MO) m3./(m)

6W0-J kmaa-r tm.n lo WOl?aOlxmrwed

Mc$byl ieob~tylkra$ma (komne) n m m

6~Ec1 7~Ecl 5gHBr

20 29 17

Yananod s~ied acid by ether~ ~1 mi.xtlmcO. m

@rtracti= of molybdame fmm

2-7 ~ @&Oc~C -N bimary

alcohol$ anyl awtits~ butyl acetate of etbr

with

1:1 ~

bu@l C.cetiteO amyl alcohol or bu@l When the aolwentswere teeted 82.5% of the nwlykdenum exfor * ext~cticm

alcohol eatmcted ower ~

mpe.mtely

of tlM mlyMenum. e-ctant:

buel acetate waa the lmt

acid.

tmcted from 5.4 g hydmxhloric was dropped to 10j over ~

When the tucpamtum

of tk mlybdenum wee extmactedby butyl acetata

fmm 7.5 g hydrochloricacid. ~: Methy1 ieobutylketone (hOXOl10 Waterb~ 62 and Bricker detised & pro-

cedure for the determinationof .011.@ molybdenum h plutonium and plutonim alloye. An allquot of the dissolved eampl@ containing100y or I.eea mQb&mua of is tie tia 6 ~ in hydrochloricacid and 0.4 ~ in I@rofluoric acti. ~ solu-

ie ccmtacted three times with quili~ted

kxone and the mlylx3enum h

the combined or@snic pheees back-extmcctadwith three portione of water. ie Molybdenum is then determimml iR the aqueoue phee calorimetrically with chlozm.niliccid after fmeehg the combined extracts from hydroi%aoricacid a

14

by evapolaticmtith Cmicentratadacid U
h@mxide fdilute alkaline solution. PhaDkta D~17 (Il@ : mpcrt

tfcm by Preclp%tatttmof the

hibutyl Helidcm ad

!l!BP 0 an excellent artmctit 1 [

for molybdan~. /(MO)

aq.

distributicm coefficient

(MO)~.

fmm

1 ~ and 2 ~ hytbchloric acid solutions of b.O d

65 respectivelywith ~~ distribut-

D tic~ing ion

tith Incmaehg

acid ccacent~tion.

~ut63 ti

c- fficienta of 8.5 and 21.6 from neu-1

dim

2 ~ mlfuric acid

1301utimla ?lapctimly. m !53P and bxme am ueed for the solwwnt recovery of uzunia
both alao ext=ct and plutonium.

Umier varioua cmniiti-,

thoriun, neptunium md

fissicm

producti such ae ruthenim, zirccmium,and cerim; TBP can alao extinct tbs ear-&a.&65 Other Solvents: Other claaaes of solventswhich my eolvent extmsctim of molybdernau m a di- d tkm mmpzwve useful in the

and di-al?@phoephatea, tha secondary and tertiary

tri-alkylphoephine oxides, and the eimple pr-~~ no =femnces

ambles. While there am

to the uee of these 1301venta the in

mdiochemical -1.ya IS of molybdenum,some of them should be quite helpful. A fev exnmpleawill give aonm idea of their poesibilitiea. More than ~ of the molylMenum(VI)was ertmacted fmm ~lu leach 66 keroeene.

liquors by 0.4 ~ DOW Wmction

(mono ester of dcdecylphcephoric acid) h

ccefficientaof zICOO we=

obeermd for molylxlenum(VI) when lJo/ml we= c~tacwiti a

sulfuric acid soluti-

(P.E containing3 ~ 2)

approximatelyequal volwne of 0.1 ~ solutims of the amhes~ e.g., l-(3-ethylpentyl) -&ethyloctylamtne, dikurylamine~
~rbon diluent. mthyl dilaurylamine, in an aronBtic

HcWeverj these amine ertx73ctionaha8a the cbam5cteris-

tic that ae the concentmtim eo does lb

of molybdenum in the aqueoua phase decraaeee~

67 dhtributicm coefficient.
the extraction behavior of over forty elements with the Molybdenum(m) was completely ~cted from

white69 stdied
txialkylphoaph~ 1 ~ ~drochloric

~ides.

or sulfwic

acid solutions by 0.1 ~ t.ri--octy~phosx

15

cddeinqmlohexmeand~ 0.1 M tris-2-etJlylk@phos-

c=tmmtsd ads.

same aqmoua media by

Several papers concerningthe ~aotdon solventswere ~sented at ths Se-

of otbr elaments with these

Unitid Nations Internatdond Wnferenoa

on the Pea@ful uses or A-C of the -aotion

69 Energy. Morrison amd Freia.er provide a sincludblgmolytde~ amims . by tri-

of various ~.

of Mol@xi3mm

Molybdenum

is adsorbed very strongti onti strong base anion resius (Dowsx-1 =ntiati(Kd =2000 a minhum at --0.1g (lo-m) at

and 2, Ambsrlits IRA-400] at low HQ HOl). As the Ha 1.5 ~ HQ9

=nmntra tion inmwaees~ Kd drops h at 5 J! Ha

rises to a max5mum (MO-250)

and tbm very sl.mdy ds-

oml.ses.70-73 The dip in the IIdcurve Hcates species of molybcbmm ~sent at low HQ

that there are pesiblg *

concentrations. which are ma adsorbed

Thus molybdema can be separatedfrom ~nts strongti at high Ha tlm adsorptionfrm all the ehnts

concentiationa. Kraue and Nelson74 havs amnfled data for hydrochloricacid solutions oh Dowe.x-l for sasentially

in the periodic table. The alkeld mAals, slkalina earths, rare thorims nidml and almimmi are

earths, yktriun9 addd~ HQ

sOhtiOIleO

not adsorbed *

Uranhu,

mptunim~

plutonium zirconim fmn HQ

amd (IV)~ niobim and tungsten am >8 E HQ and pmtactinim b

adsorbed >I_O~

strongly from >6

E HQS

HC1. Americium is mt h the other ~

adaorbed f-

solutions.

raolybdemnu should km separable frcm elauenta that are HufX Oswalt and Wi31ime72 separated ml@form. lblybdemzm

adaorbed strongly frcm 1-2 ~ HQ.

denun frcm te0hm3tiumon a Ikwex-1 ~llsul (3 ms x 21 mm), chlori$e

was removed qus,ntitativslgy elution with 1 ~ HCl and techmtium was then reb moved with 4 ~ ~03.

16

Distributionmf

ficienta have hen onto *-2

detennbed for w

adsorptionof

rncl.@denus and other ~ts *OAC75

frcm nitric73~ mlfuric 73 ami phoeS-3Y fmm all three acids

acid solutions. Hclybdenumis adsorbed ww the adso~on

at O.1 M acid concentrationand ~n acid conoentiation.

drops rapidly with increasing

At 0.1 ~ HN03~ Kd is 500 and then tips with increasing acid ccnosntration h 0.4 at 11 ~ HN03. Yttriuu, Sr, G, Am and Nb am not adeorbedbekl~
adsorbed; T&

U~VI) and For-

Zrarenot

HN03and allthmaepeakamund

8~HN03.

tactinim, Kd at 0.1 # HN03 is 3, st~s fsirly constant to 11 rises @apeekatg~HNO 3 . Rut.heniwn &haW3S h mo~bde~

HH03 ami then but its dsO~

tion dropa much lsss rapidly. In sulfuric acid, the Kd for molybknsa is 10,CKXl 0.1 ~ H2SOL and drops at ti u at 5 X 2s04 Niobi~ U(VI), Zr and Pa behava simiLrly though mm Y2 @ and AISdid

have aa high a Kd in dilute H2SOk as mcl.@dernsa.Stinti~ ~t shcw ~

significantadsorption. !lhriuis and Ru have retitive~ low Kd?s in a mimbmm at 1-2 # H SO 2L at ~ 11 ~ H2S04. ti 0.1 ~ H3POL; the Kd dacxeaees rapidly and then rises sgdn.

dilute acid; adsorptiontips b fhoriu adsorptionchows a Yak

IWybdenum has a Kd of ~&,000 ~ 4 at al-2.5 Y H~04.

ZirCOniU% Nb, U(VI) and NFJbehave .simjlarly. &sim lees than 1 and & and Sr &stribution

and Te(~)

distributioncoeffi~ents -

coefficientsare kss

~ H PO . 34 Buchanan,et al., studied the adsorptionof sixby elements onto lbwax-1 is not adsorbed f-

than 10 frcm 0.1 ~ to D

frcm nitric acid nmiia. They found that mdybti(JI) 1 g to IA ~

HN03Y

The adsorptionbehavior of molybdemnn in HQ-HF-anion exchange systems has been studied by several investigators. The presence of fluorick ion has made possilik several separationswhi~ we= solutions e 17 not fessibk in hydrochloricacid

for tlm separationof othsr on Dwkmx-1 (*M

per

tungsten and urani~

from

eaoh ohber on a k-l thrae -mba wen

cdtmn (10 pm

aant mss

linkages 200-a

sash).

put cm tha ODlmn in 0.5 M HC1-1 ~ HF, uranlu?a was eluted ~StJSn waa ~d~tith9~HC1-l~HF
and

with 0.5 ~ HQ-1 ~ ~~

molybdemm WM

eltrbd &t

with 1 ~ HQ. elutiona with HQ-HF, H3POL and HN03 tQ provide a

~1sh78

baa c=abhd

method for the rapi~

oarrie~~e

separation of Np~ ~

US ZrS NbO Te and M

flesion pmduat

frm eaoh otlmr and tJmfi quantititivaremvsry from -d

solutions on ~2 (see Proosdum

Do Ssction VI in this nport). BS Secticm VI in this report) ad ~or W EOhltim mdioc~mi=l USM imdetar-

BamesardhM79( Stcmmsalj Hicks @ ~ti~

see Prooadure

80 Lavy bavs developsd procedures

fmm mixd

Of mlyMenum(VI)

i?iSSi~ ~UCt

exchange techniqms o !llbilprocediuras m from 6 ~ =1

Stripph8

briefly: admrptim waahims w 6 ~ mm reaim with

of molybdenum variou ehmnte$

mto

an hi
off

axchange
w resin

rastiJ
with

mlylx%anum

or 6 ~ amaalilm acetitip aca-

en8iz@ the mol.ykdenum-contati~ effluent with ferric h@rQxide ard thm precipitation of ~lytdenum Other Media The behatior of rhenim ad moQbdenu on IRA-400, chlonsta ffor meld determinations and comt.ing.

(IRA-WC)

is a st~
a -~~

lxme anion resin) with p*ssi= f~ ~ se~tia of~cm f-

oxalate has been imcorpomst43dinto fkm rhanlm.

quantities of molyElenm

The elemanta ara lded remvwd

onto the mmti

an alkaline soluticm, nmlylxlenum is

with 1 ~ po~sius

oxal.atiand rlwniwa is etripped off with 1 ~ =104.70 frcm TCW oia~-~j cbl-te

Molykdenm

target matertil was se~ted

fore, by stripping off the nmlybdenm with K2C2~-KOE with k~ 81 Witi 0.5 ~ m4SClJ.
mtber

mixture and then elutins

82 Blasiue, Pitt&c and Hegwer report a se~ticm of mg. amnm~

unique procedure

for w
of

of tungeti frum molybdenum by Ming

advantage

18

a Snell-pomd Pa-tit-m

mssin, chloride f-

tlIr16stoti* km _~C at PE 5.8.

ie f-

in tha pmaence of mlybdata by additicm & . me aqueoue

laolutialof the Crystalline Slq
*wh the COII-

~B03 ~

is adjueted to 5 g Eel.

This

solution Is tlum mased

of %-it-~ to

~e~.

MoIYti~~

ie adaorbed, but the tun8atobomti ~~j d~ the pome of tbs msln W

elutexlwith lia~c.

its larm size, cannot penetmte

W COIULU. MolyMenun
ie

thus paesee thmUh

Cation Exchange

The queetia of the exletance of a caticmic speclea of mol#bdenm(VT),

euch ae Mc02 +2 , he not been eettled. a D~83 ~(catlcm -sin) that there mae little from 1-12 ~ El

or no adsorption of mlybdenum

Douex-m

or

1-6 ~ ~r, W,

E#~

or H803 solutionsbut t.bat * the cation reein.

1-6 ~ =104 the= was

elight adsorption a

l%wr Chromt@mar@ The tichnique of psper c_to8msphy has not been extemelvelyemployed a large mnber of ta~tams hSVS made.

for msdiochsmlicalqamstilma . ~qar S studied for other

pmpoeee and a great variety of sepsmatima can h 84 and Welle.85 by Weil by paper c=t-~

Revleva of the subject kve been prepmd b exaqle cd?molybdenm se~tlon

IS -t

of

Mo(III) in diluti El

by use of the devmlopsr n-bubsnol aatmtad ie sep,~ti

with 2 ~

HH03 and 2 ~ HCl~6 Mo~~~ Cu by thle mthcd.

from U, V, Cr, Mn, Fe, co, HI and

Molybdenum(V)can be sepa~tad from molybdenwI(VI)by fIltir psper cbxmmtoMaphy with a mixtum of cm. ECl:~O:ether:lle~ in the mtio 87 4:15:50:30 or by ascandlM papsr chrwmt@m@Y 88 acid - KSQJ. Almassy and Straub@ deve@ed cationa by aecen~ (4:1:5). ~Miu ~ papr vlti W sol~nt %~acet~c

a spcific separationfor molybdenm frcm

chromat.ogra~ with tlm solvent EtOH-con. HC1-H O 2 separatedmolgbdenm from tungsten (as their

~kw90

oxslati ~s)

by paper duvmatography uith EtCt-I-CHQ3- o per oent aqueous l

19

oxalic acid (7:281) aa tlM -bile phase. kkmr M04 d Tcwo:

91

I.86-h separatsdRe 04

frau McC$ tith a mixture of ba~l almhcl with ~ Ha, eluant. of ~ mbss for over fif& ions, with fiwe diffamnt is de-d as *

1.5 ~ HlK13 1.5 & aqmaous .smmiia as * or ~erbs ~d in~ ~nr92 publdslmd a Hat

molybdati~ for asosmiingpaper ~tigraphy Om -ban k. 10 lhe ~ wdm

mhtures Of BROHWMH20

dlstan~ travelledby the some divi%d by the distance travailedby tlm IQId

front.
Thorough Cowemge tion
CIBl

of tb

subject
chaiis~

of papr chmmatogra@w ad its SPPUW

is provided by bderer ad Le&er93

in the field of imrganic

mock, Durmm and zweig.gk

e.

EleCtrcchemicalBehatior of Molybdsrnml pclamgraptg, controlledpotential electrolycathode electrol@s is of scam interest in

The bshaticr of mol.ybknum h sis and ccmetant ~nt

nmr~

radiochemicslseparative. Mmitsd with mdybdamm etudias of this elamnt.

H~ver

the use of these tedmi.queshas been ratkr in radiochachal

and they have had no significantu A =-t

review of the subject of mnitrolled~ cmnpmhaneiwe bock on ele~

tial elewkrolystiis inoludad by Lingsme in MS analytical chamis@.95

A useful tabulationof elenmnts which can be ele~

depositedby the constant currentmercury cathode techniqueis given by Iundell and Hoffmaue96 An ex~ent review of this subject has also been given by

Max.wll and Grduune97 A nmre recent detailed examinationof the dspoeitiou

in a mercury cathode of a~ tel.ytwnty elenenti is nporbd by BcxSfand

Hocketein.98 They found 0.35 per cent of the mol.ybdernm ramhing phase aftar electrolysisof a 0.1 ~ H2904 solution fcm 1.5 hours. D. 1.0ve99 destibss a ~omdum while not diractlyinol~ m~ & @ ds~,

in the aqueous

for dstemining fiesicm product M099, whi.~

molybdenum~is of interest. TcWm the daughter through selective @barographic reactiti~ ds-

is amalgaatid with M

duction at a dropphg Hg electrode. The amalgam is counted and MOW tamrinsd by making tie appro@ati ~ctions.

20

N. @e

DBSOLUl!ICWW

sAMPLEsF~

FULDIOACIXVE X.YBDENUM IWEMINATIQNS M

of the problms the radiockui~t must deal with in the dissolution is S8aursn- that aX0haW3 bO-

of a ssa@la for a radiochsmiti &tsminati=

twen the added inaotive carrier and the radioisotope of the element t.a be d dst&umuk3 is can@ets. If the radioaatim isotape can be present in several tidatim thesmetime, tends b cmsormcmoftich mmfhlllttad species, dizecmmsdme~ statea at ifit

fomn ordloida or polymric

or M e@kLbrium

ratis between

diffemsnt SP oies are slow, etc., exdmnge may h

cUf hult to obtaim

oxidizingfluxes will gemrally achieve exchange and oxidize molybdemnn ta the +6 oxidation
StJ3ti.

Howsvsr9 a word of caution about the us

of psrchloric ad&

Mol@denum

apparenw
@b

axisti

to a cartain

axhent in a

speciesi prchloria acid that is t

i@rodiloric S-

tiferent frun tk species axistm behaves differ=n~

in nitric, sulfmi%

acids, etc., and wM*

frcm these other species m

of the &molcal reactions involved in molybdsnm radiodmmical separations. Thus if psrc.hloric acid has been used in the dissolutionof the sample it has been found advantageousto remove it by fuming with concentratedsulJ7uric acid before prforming any subsequent tiadstry.~ For diascCiuticmroceduresfor a tide varie~ of sam@es fw p mimatiau of molgbds~ mnsult SnelL and -Ills the dete~

Cblorb3tric Methods of

AnalysisA7 and SandellrsColorimtric Deteminatiom of fraoes Mstals.@ of

~eb_99

ie generally tlm only radioactiveisotow of mo~bdenum

isolatad fra mimd ffision product solutions;the other molybdenum fission -d iSotiFJe9 _ VS~ Short live% Of the order of minutes or less.
21

Mol@denulll 99 has a 66.C-hour half-~e (83 Par writ) to tedmsthm9m. dew

years.

and detxya via a 1.18+ev Phas a

6.0+-

Teohmtium*

half-life @

99 via y arldssion technetium whioh h= ta

a lamg haU-lifeB -72 x 105

The activi~ d

molybdemnn- my

be nwasured by eitbsr a lm~

or garom& daughter

Oountero In the latter case it is ne~mszy

to allow the teobnetium m

acttvity to rea& equilibriumwith the parent activity bef-

oount5ng. How+ absorber of

everm if the aotivi~ la measured in a bst-countar~ an dudnum approdmtely ~-tim9* 13 mg/a2 mqy be used to remove * and ths sauple ~ omwnaion

aleetaona frcm

be ouuntad hmdiately

instead af waiting

for equiMbrium to be reachsd.

VI.

COIUCIIm CF IET-

RADIOCWEMICALPROCZDLEESFCR MOLYBRENU MamDENuM EmG3DWE A

awcl!ml 2hie prmedum ~ct for the radio-cd dstemination of Mo in fission

mixburm is based on precipitationreactions and is dsrivad fran the steps are pradpitatione

101 procwiures of Ballou and Scadden.au2 The udn of M

with u-benzoinoxime~pracipitatidissoluticmand removal of cope cipifollowed by pm cipitationof PbY@ 4

tabed tipuritieson ferric ~-de~

for chemicalyield determinationand munting.

Precision of tidividual

deteminationa is about 1 per cent (standarddeviation) aud purities are ~ greater than 99 per cent. Chemicalyields are about 75 per cent and four det.etitiOIla can h made in about 4 hours. If tungetan is preeent~ it wUl ~t htarfemnce be separatedfrm M.oby this procedure. ~ I=&Q them with

by V or Cr, if presentP can be elimina ~d

H#03 prior to pre@itation PROCEDURE 1.

of Mo with a-ben50hmximeOm3

Ten mg.of molybdenum

are added to the sau@

a L@-ml.

22

A (Centd)

centrifugetubes and the volume ie adjusted to 30 ml. and the aoidi~ to ~tely cent a=benso~ lx (Note l). Five ml. of 2 per

inetbanol areadded, and the mixture

etlrread9 thenmmtrlfhged at high speed. The precipitateis washed with 30 ml. of water. 2. The preoi@tat.eis dissolvedin 3 ml. fuming HN03; the solution iS diluted to 25 DIL with water, wtislly 1-2 ml. of cone. amonium l@rd&$ 3. The ndybdenum neutralisedtiti

and oooled in an ioe bath.

is repreclxtatid by adding 5 ml. of the mime

reagent. The mixture is stirred and centrifuged. The prec@itate is washed with 30 ml. of water. 4. 5. Steps 2 and 3 are repeatede dissolved in 3 & of fwdng mitic

The precipitateof Step 4 is add.

Three ml. psrohloric acid am

added. The solution is

boiled to prchloric acid fume b 6. drymss (Nob 2).

Then the

(cautiod ) and then fumed slmst

mixhre

is

cook&

Ten ml. of watir and 1 mg. of ferric ion are added; ammonium ~k
l@rcdde

iS SMed untilthe mdybdic oxide diasol~s

has wecipitatad.

and ferric

The mixture is filtered through

ang fast filter papr

such aa Whahan 4 or U.

7.

The filtrate is neutralizedwith 6 ~ HN03 (litmus paper) and 1.5 ml. more of 6 M HN03 is added. & (100 ~ Pb+2/~ ml. of Pb(N03)2 solution

is added and the solution heatid to boiling. fomn one drop cone. NH40H is added, @is&

If a precipitate starts b

while if no predpitate appears two drops conG. NHLOH -e

The solution is then boiled for sevmral eeconda only (Note 3). The solution is ffitered hot through a weighed disc of Whatman 42 filter paper and the precipitateis washed with three 5 nil. porkLona of hot water and one >3 ml. -on of -* ~tJTYl

23

PRCCEMIRX A (Centd) ~cipitati is dried at 105-110C for 15 mins,

for 20 min.~ weighed, ami munted for oounkhg

1.

If the pevioue histary of tbs mqil.e is eu~ UChange bdaeen osrrier and radioactdw digestion with con~ HN03 is neoessary. a-

(e.g., reduced) that may be inOaspleteB the ~senoa

In addition,

of fluoride fiterfereewith subseqwmt stem and slmil.d rmoved be by fmhg 20 with about 1 ml. cone. H2SOL. ad.ula-fumbg

Much frothing ocours on boiling dorm the mlyb&mm

nitric adt+psrcbloric acid solutions and cam must be exeroised to pent 30 Tk loss of Solution fmml the tube. fommd in this way yields a repzwdudldy munMng. This is desirable since

PbW004 precipitate

uuifom

Eanple for bekray

beta-r~ cvnnting characteristics a sam@e are sensitive to of suti fach 4. If beta-r= 13 @an2) ~c$% hto as ~ci~tate
counting of ?#

dumping and -ding. ie ta be done, an Al absorber (about

electxmna of 6.o-hIr

can be used to remove the comvmwion e~ta

and thus eq@Jibriuub

the neoessi* of uaiting for it to gruM

ION AND STANDARIUZA TION OF CARRIER ze tywitlk Dissolve I-&k g. (NH&) M070a Q-120in 1 liter H20. Standsrd 6 drawing quadru@icata aldquots of 5.00 ml. H20 and 2.5 ml. glacial HC2~02. ti4~-tm(c2%22 Wam and b each aliquot add 80 ml. add 5.3

dnmat t.athe boiJlng @nt,

0 ) soluticm drqadse and let stand for several

minutes. Filter through a tared fine stite?.wd glass crucible,wash pwcipltate with three 15 ml. portions hot H20 and tith 5 ml. _OUS %OH. w

at M5-110C for 15 ndlb~ CmOl in air 20 mir.b~ weigh. Repeat dry5ng procees to -neat weight.

24

~N T&is ~ocedure for the radiochmioal detemina tion of Mo in fissiau product mixtures is based largely on auion SXdange resin reparationsas deSabed 79 by Barnes and I.@lg. And&r anion -Change ~oedurs Uhich also ise m and Levy the follow5ng

latse Ho very effectivelyhas been ~ven by Stevenson, Mob, and Ufere in saw of tbe el.uante used. The main sta~ b

pocedure are adsorptionof MO on a oolmn of Ikmo3x-1 anion exchange resin fra 5-9~ Ha, removal of impurities by elutionawith 6 ~ HQ, 0.1 ~ HQ-O.05 ~ m, ~ 3 l!NH40HS eluti~ of MO with 6 M NH4C2~02s Predpitation of ferric of MO with wbena~ yield dete~

l@ro2chie for additionaldecontamination,~@itation h, ti~ ~r

and ignition of this mecipitate to M003 for &emi* and Oouna.

tione is bettar thsn 1 Precision of biividual detenmina gremter than 99 per cent.

cent (standarddsmiatdon),and purities am

Ohemicalyields ars about 75 ~ in abut 4 hours. H

cent and eight determinationsoan be perfonwd

tungsten is present, it will not be ~d~tiepo~(nor~

that of Stmm-leon, EMS,

and Iavy)4

m~
1. Add the sample to 3.0 ml. of MO @rrier in a @-ml. shor&tipm conid b cenkifuge tube. Add 1 ml. of Br2-H20 (Note 1) and bring over a burner. (If tie volume is greater than I-Oml.,

a bti

the solution should be evqmrated ta 5 to lo ml. in a 125-ml. Erlenmeyer fkelc.) Add suffident cone. Ha 5t09~in 2. thisacid(Note 2). b make the solution

Heat the solution to boilbg~ transfer to the Douex-1 snion resti colmn (Note 3 and 4), and pemit to run through under Rravi*. Addltm2niL. of6~HCl to the colmm, and when add 10 ml. of

the level of acid readme the tap of the res~

PHWEUUHEB

(Centd) Wkn * bvd of the HF-HCl

ml. of

hot HF-HCl SOhltiOXl @Ote 5)0

solution -aches the top of the res5ns add 5 30 AS .mon as the lmd

3 M M140H0

of the NH&OH reaohes W

top of tie reein~ the appmtithe

all efflwnta collectedta this point are @aoed h @ate waeta bottle. Addloml. ofhot6~NHC O 42!32

resin aml permit to pass through~ catclean 4GmL osntrifugetube (NOti 6).

the k

eluata in a

To the eluats add 2 nl. of cmn~ _

NHhCXiO sti.r~and then add lo

of Fe carrier. BuL1 fcm 1 mim with stdmzlng. &ntrifuge. to an ioe-cold mixhre of 6 ml. of conHN03~

Add the suzte mdl JLOf

Br2-H20~and OOOlti anicebath

forakmut5ndm

Add 10 ti. of a-lmnsaUmxLms solution SlldSw.r d@row&. Filter cmta No. 41 H Wbatman filter paper, cmqile~ the transfer

6.

Place tlM filter ~ (tire O) ~ Wite b

and mntenta in a prcaldn

mucible

Mo03 at 550 for about 3/4 hr. (Nota 7).

7 ,e

Aftar igrdtion SUOW the crucible to ooo1 and grind tie M003
toaf~conaistanq wikh the endofast3rringrocL

Add2

drew of ethanol and slurry; then add an additional5 mL of ethanol, sW, and filter onto a previoue4 msheds dried and weighed No. 42

Whatmsn filter cdrcle, using a groun&off Hirs& fund. and sless steel. filter chimney. Wash with ethanol and dry at 11o for abut lo A Cools wBigh~ and mount (Nob 8).

1.

Hthesauqi

kwntain alargeamountsof Uor P,atthispoht ~

Fmecipitata the MO with 10 ml. of a-tmnzmlnoxim solutiorh Stir wells mklfuge~ aud filtar onto No. Q H h%alauan fil~ paper.

26

PROCEDURE B (Centd) Wash the prec@tata washes are @aced h mll with 1 B HN03. (The filtrata and all the appropriatewaeti bottle.) at 550. Rlsmlm Ignits the

precipltatafor about 15 mim 3 *FS

the Mo03 uith

of COMC. H2S04 by heating te boiling. Dilute ta 5 L add 1 ml. of Br2-H20, lmdl~ and ~ceed that axchange be-en -am b StiP 2.

with 6 ~ HQ~ 2. If it ~ars nd.ght k

and radiawl@xienm of sane

ticmplete, pxrha~ because of the ~senoe add 0.5 to 1.0 ML of =c.

orgaml. oqaund, c

H~htOBE@S SO

and MO carrier snd evaparate the solution to demee white fumes= Coolant add4t05niL. W-ed 3. ti StiP 3. at U M (g of6~ HGlandl ml. of Br2-H20. Then H2S04 should *O ~~ be

with -G

swnpls cent.dna a~chbl.e k-l, b

iom )

The amlm ree~

prepared for use fi the folkdng

of the dry resin in alarget*

manner. Place alargequ3ntiLty (3 b 4 diameter

and 1 to l-lj2s bmg) tith a mediun or coarse SIURY with ~thauol or ethanol wMJJs

fritted disk at the bet-.

the bottun of the tube is stoppered and tien suck tie resin dry. Slurry the resti with mnc. HQ NsM33 pm min. cmmtdnhqg about 1 BL aF 0.5 M

lMI ml.of HOl and lat the slurzy stand for at laast 30 have reducing ~

(Anion resins, aa obtsined cmmrckl&,

ties. The NaEM3 presumablyoxhiiaes any reducing spcies present in the resin.) ULowthereetiti drain, and then m~at the *a*

ment. Wash the reeh with a large volume of distilled H20. The tube should be filled tith H+ slvrried~ .!@ su~ed dm at le=t fi~

times. Slurry the resti with a 1:1 mixture of H20 and cmc. NH&OH and let stand for a while. Su&themein dryandrhae with four

to five filXngs of distilled H200 TheQ slurry the rssin with 6 ~ HCl, ~m to stand, and SU& dry. flwry again with the acid and

transfer the slurry to a stirage bottle.

27

~ 4. TO prepare the da gkes wool h

B (Centd) mlmn for use: (a)@maa@ug

Qf
5an. heightof

the tip of the mlunm; (b)add4ta

resin;(c) sll.cw the acid to drain off.

5. 6. The HF-HQ wash removes moderate quantitiesof U and Pu. If the sample step should b
contains macro quantities

of Pu, an additioml mlwn HN03 to the MO eluate

performed. Add 3 nL

of mm%

and precipitati$ignite, and dissolve the Mo a9 ti Note 1. Rcqmat Stap 29 with the exceptiom of the addition of 3 M NH401L Eluti *h 7. 4c2%02 = h tip 3-d ti muffle cm@ex tip 4 MO

As*aofti_~tie version of the Mo(vI)bemoinoxhe

hrnaceddsintb~ to Mo03.

8.

l?hesample scsnbemowrte and covereduLth ~bm

don Al @ates

with twu-sidedScstch tap

SOltiOn (1 w cant

filmo Four drqm of Zap

Zapon in ethanol) are used to keep the M003 under the ~lar filnb

~ssdve anddiluhs

18.4

&of

(M4)6~0#d20 HQ.

ti

H20, *

1 ~.

of O*5 M NM3,

tollitarwith6Y

Pipet 5.0 ml. of the solution into a 50-ml.

Add 1 ml. of Br2-H20, 3 ml.

beaker and dilute b

stout 20 ml.

of

-c.

EN039

anda)ol hanicebathfcmlo

t.015mina

Add15ml. Filter

ofa-bens~

soltltion~ filter the filter

stil.r vigorowlyj and let stand for 5 min. PaPers rbe *

onto No. 42 Whabm b

Waker titb 1 X HN03, and transfer the rinsings

paper. Transfer precipitateand pa~r ta a weighed prceldn and igniti to tie oxide at 550 for 1 hr. (2001 and w *

crud.ble (bore 1) m3.

28

C (Centd)

with 15 nil.H20, tiansf to a weighed fflter disc, wash with 5 er ti. e~l ~cohol 8nd tith 5
d. dktbl etirD ~ at Moc m

min.,W13ighand mount for counting. 11. Addition of mro3 is ta ensure the previous hisof the sam@e is

hexavalent state. I-hwver, M

such that a13changd belareen carrier and radioactive atxma may be incalpletiby this procedure, digestionwith mnc. destructionof the HNO= with -co > Ha is necess~.
HNO~

followed by

2. Fission product elements in addition to MO vrhitiare exhractid ta mry5mg depees under these condltioneare G% Sb~ Is &. 3. he Fe(CH)3 p-eci@tatd.onservee ta removw most of the oontamina~ Tcs As, Ges Teo 9n,

elaaenti exkact.ad by tie ether.

4.

The precL@tation

of molybdenum f3-~c@noL9te

provides additional

decontandnationfran sane of the eknents extxactedwith MO by diethyl ethers in addition to fhrniehing a stitable gravimetricand counting precipitatefor Moo

ION AND S!l!ANDARDIZAT~OF CARRm Dissolve l&4 & (NH4)6M07044H20 in 1 liter H20. Standar& ze the sol-

tion by withdrawing quadruplicatealiquots of 2.00 ml. and to eati eJiquot add 20 ml. H20. Make the solutions $ust add b methyl orsnge~ add 5 ml. 5 per

cent N.G+1302, hat nearly to balling and add 2 ml. 5 per cent E-l@mxyquinolhe in 1 J HCL Let etand several ** and filter through a tared with 15 ml. H20, 5 ml. ethyl

fine sintered glass cruciblepwash pwdpitate

alcohol, and 5 ml. diethgl ether. Dry preclpitataat 1.200C for 15 min., cool in air 2Y min., weigh. Repeat drying process to mnstant might.

30

mTxmENuM
P30W)URE

~ This procedure for the radiochmical deterdnation of MO 3n fission product mbr!ames is baaed on ion exchange techniqueswbi& ~mties of sep=atid el~ts~8 give quantitative

In additions seversl other elements removed with quantitativerecoveries.

(h, Nb, Np, U, !l%, Pu) are sequent&JQ

Dire ct garana-ray countingof isolated solutions can be done in a well-type NaI(11) sCinution counter. Principal stew in the proceduzw are separ~

tion of Ru by volatAllzationwith HCIO&, adsorptionof Mo (and other Mcated eiemnts ) on an ania exchange resti column frcuncane. HCl~ elution of Zr with 12 ~ HQ-o.06 X HF, elution Np, Nb and Fu with 6.0 ~ HO&O.06 u 14? of (Note 4), elution of U and Te with 0.1 ~ HQ-0.06 ~ HP (Note 6), and elution of l% and Tc with 12 ~ HNO . %edsion 3 2 per cent (standard of individual detemminationais about cent.

deviation) and purities are greatir than 99 pm ~

Chemical@elds a *O

are 100 per cmt, and about 12 detemhations

can be made in

JTtomw
a 1. To a 1-5 ml. sample ir.? centrifugetube (Note 1) add 1 ml. mnc. HO10 , 1 ml. cone. HNOs, and 2 drops @nc. H2S04, heat 4 b fumes of H2S04 (Note 2), let cool and carefullyadd about

2 ml. cone. Ha. 2. Quantitativelytransfer the solution ta a 0.2 =2 by 6 on. high column of Dowex-2 anion exchange resin in tb us= washes of cone. HQ chloride fomn

as required. Remove Zr quantitatiw~

~rom the mlumn by elutionwith 12 ml. 12 ~ HQ-O.06 ~ H!? containing2-3 drope of Br2 water (Note 3). A flow rate of 1 drop per lo seconds ie used here ~d in subsequentelution .ste~. Ehlt#3 Np, Nb snd ~ quantitativelywith 12 nil.6.0

31

and 4). 3. Dry the ahmn Walling it with by allowing air to pass through it and then 34 ml. ethyl almhol (Note 5). After the

alcohol haa drdned tbraagh,remove U and Te quantitatively by elution tith 12 ml. 0.1 ~ HQ-0.06 4. Elute Mo and Tc ~titatively HNo 3 Oount the eluata tictly
~ HF (Nota 6).

from the mlumn In H

rd. L? ~

in a well-Qpe NaI (Tl)

sd.ntillationwunter (Note 7).

M?zEs
1.
Sjnoe recoveries are

quantitativey b

this

~oedure9

addition

of carriersis not necaesary. 20 DistJJlationuith HQ04 serves to reutove Ru which

ie

otherwiee

M.kely to contaminateZr and other fractione in an Weducible way. If recovery of Ru is dedred the distill.ation

can be ~rformed in a distilktion apparatuemade from a 30-40

ml.

test tube uith an -

5nlet tube reachhg nearly to the

both

of the tast tube. A aide arm dellveq tube is exhausted solution of >3 ~ NaOH. The distil.htion through the system. and U in

inta a Ru cane ~

is performedwith an air stream wsing 39

The eluant oontahe an oxbiizing agent to keep ~ thefi higheet @dation statee.

4.

If either Np or NbPu fractione free of the other are desired, a t-step elution can 1= performed at thie paint. Following quantitativelyeluted with 1.2ml.

removal of Zr, the Np can k

6.5 ~ HO1-O.004~ HF. Then the Nb and Pu can be quantitatively eluted together with U? ml. 6.o ~ HC1-O.06~ HF.

32

PROCEDURE D (Centd) 5. The resfi must be dried before elution of U and Te or some Mo will be lost in that fraction due to the dnimum in the Mo Kd curve at about 2 ~ HQ. 6. If isolation of separati Te and U fractiona is desired, a twostep elution can be performed at this @nt. 4 Following re-

moval of the Nb fraction the calumu is vaeh~ with 35 ml. of abssluti almhol made 1 I in phosphoric acid. Te ia quantlt* tively eluted with 25 ml. 1 1!F$P04. The resin is converted back ta the chlorldeform with 35 ml. of absolti al~hol saturatedwLth HOl g=. Then U is quantitativ~ eluted with

12 ml. 0.1 a HQ-O.06 # HF. 7. G~ray countingis done in a 7 diawter ~ 3 high NaI(Tl) with

crystaltiti a w811 about l-1./W dimtir such a crystal, count@ dHferences of >3 ml.

by >3./4 ~ep.

efficienciesare fienaitive to volume

33

REFERENCES
WxidationPotentiA.sll,. M. Latimer, 2nd Edition, p. 252, Prenticew fiu, llE., New York (1952) 2. Anal. Chim. Acts ~ 17>9 (1950) T. DllpUiS and C. DUVd, 3. S. C. Hang and K. N. Chang, Science Record~ 366=72 (19b9) R. Pribil and M. Malat, CoUection Czech. Chem. Cozen. ~, 120 (1%0) :. M. Malinek, Chem. LLsty LL8 38 (195h) 61 H. Knowles,Bur. Stds. Jfiesearch ~, 1 (1932) Studies: The Fission Products,C. D. J. B. Dial, ll~~och~cd 70 Cnryell and N. Sugaman, eds.5 National Nuclear Ene~ Series, Div. IV, Vol. 9, Book 3, 1536, bkGrawWJl Book Co., New York (1951) 8. G. Wil!dnson and W. Grummitt, Nucleonics 9 No. 3, 52 (1951) c 9. InorganicTherraografietri Analysis, Cf . Duval, Chapter 39, Elsewier PublishingCo., New York (1953) E. Picket and B. Hankina, Anal. Chin. 30 47 (1958) H. Gest and L. Glendenin,National Nucd ear Energy Series, Div. IV, Vol. 9, Book 1, 170 (195) 12. B. Park, Ind. Eng. Chsm., Anal. Ed. 6 189 (1934) 13. F. Potd, Z. And. Chan. ~ 19 (1951i5 K. Scharrer and W. Eberhsr t, Z. Pflanzenernahr.Dung. Bdenk. @ * 4. US (1956);Chem. Abstrs. 51, 2461 (1957) 15. H. Weiss, private communic~ion, data to be published. 160 I. Lindqvist,Acts Chem. ScancMa ~ 568 (1%1) (ti English) I. Nelidow and R. Diamond, J. Phys. Chem. 59, 710 (195.5) 17. 18. R. Diamond, ibid. 61 69, 75 and 1522 (19~ D. Pen5n, J. AIU. da. SOC. ~, 3540 (1953) 19. 20. J. McKaveney and H. Freiser, Anal. Chem. ~, 290-2 (1957) 21. J. Hamence, Analyst 65, 1s2-4 (19ho) 22. C. C. Miller, J. (lhem. SOC. 151, 792 (1941) 23. T. Gilbert, Jr., Theeis, (Um~ of ?thn., Minneapolis). Univ. Microfilms (firm Arbor, Mich.) Publ. No. 22489Z 156 pp.; Dissert. Abstrs. ~ 1894 (1957) 24. J. Wells and R. Pemberton,Analyst 72 185 (1947) 25. B . Ba@awe and R. Truman, Analyst ~ 169 (1947) 26. C. Bicldord, W. Jones and J. Keene, J. Am. Pharm. Assoc., Sci. Ed., 37_s2% (19L8) 27. H. Short, Analyst 76 710 (1951) 28. C. Piper and R. Be~rth, J. So.. Chem. Ind. 67 374-9 (1948) 29= L. Clark and J. Axley, Anal. Chem. ~ 2-20~ (1955) 30. P. Jeffrey, Anal@ ~ 104 (1%6) 31. A. North, Analyst 81 660-68 (1956) 32. A. Ashbrook, Chem#AnaJyst u No. 1,5 (1959) S. Allen and u. Hamilton,Ana#Chim. Acts ~ 483 (1953) 5~96-500 (1956) ;;: R. ?ecsok and D. Sawyer, J. Am. Chem. Sot. ~ and J. Ray Chowdhury~Anal. Chim. Act-a@ 57&7 (1958) 35. A. llajumdar 1.

35

36- R. Taylor, Ph.D. Thesis, Princeton Univ.> Disserto Abstrs. ~g

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