Electrochemical and Spectroscopic Studies of Some Less Stable Oxidation States of Selected

170 Pages·2017·2.43 MB·English

by  David Edward Hobart

UUnniivveerrssiittyy ooff TTeennnneesssseeee,, KKnnooxxvviillllee
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Doctoral Dissertations Graduate School
6-1981
EElleeccttrroocchheemmiiccaall aanndd SSppeeccttrroossccooppiicc SSttuuddiieess ooff SSoommee LLeessss SSttaabbllee
OOxxiiddaattiioonn SSttaatteess ooff SSeelleecctteedd LLaanntthhaanniiddee aanndd AAccttiinniiddee EElleemmeennttss
David Edward Hobart
University of Tennessee - Knoxville
Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss
Part of the Chemistry Commons
RReeccoommmmeennddeedd CCiittaattiioonn
Hobart, David Edward, "Electrochemical and Spectroscopic Studies of Some Less Stable Oxidation States
of Selected Lanthanide and Actinide Elements. " PhD diss., University of Tennessee, 1981.
https://trace.tennessee.edu/utk_graddiss/1600
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To the Graduate Council:
I am submitting herewith a dissertation written by David Edward Hobart entitled
"Electrochemical and Spectroscopic Studies of Some Less Stable Oxidation States of Selected
Lanthanide and Actinide Elements." I have examined the final electronic copy of this dissertation
for form and content and recommend that it be accepted in partial fulfillment of the
requirements for the degree of Doctor of Philosophy, with a major in Chemistry.
Joseph R. Peterson, Major Professor
We have read this dissertation and recommend its acceptance:
Gleb Mamantov, M. H. Lietzke, Paul G. Huray
Accepted for the Council:
Carolyn R. Hodges
Vice Provost and Dean of the Graduate School
(Original signatures are on file with official student records.)
Tot heG radutaeC ouinlc:
I am sumbititngh erweiht dai ssertiaontw rittebny D aivdE dward
Hobaernttti lde "Elcetrocmhiecaaln dS petcroscc oSputidieso fS ome
LessS atblOexi daitno StatoefsS eletcedL anthaannidd et Aicdnei
Eelmnets."I recmmeondt hati tb ea ccepedti np atrailfu lfilmlenotf
ther equiemerntsf ort hed egroefeD ocot ofP hiolspoh,yw itha maojri n
Chemitsyr.
J
Weh avree atdhi sd issertiaotn
andr emcmoenidst accetpnace:
Acceptfeodrt he Conuci:l
ViceC hanecllor
GradtueaS utdies andR esearch
ELETCROCHCEAMLAI NDS PCETORSOCPCI STUDSI EOSFO MLEES SS TABLE
OXIDIAOTNS TAST OEFS ELECLTANETDH ANAINDDE
ACTINIEDLEE MENTS
A Dissaetroitn
Prensteefdo rt he
Dotcro ofP hiolsophy
Degree
The Universiyt ofT ennessee,K novxille
DaivdE dwaHrobda rt
June
1981
3051973
DEDCIATION
Thea uthwoisrh etso d ediactet hisw ortko h is loviwnigf ,e
Barrba,a alnodvl eyd autgeh,rM ichelel,f ort heri patiencaen du nder­
satndidnurgni gt he coursoef t hise nedvao.r
ii
ACKNLOEWDGMENTS
Thea uthowris hse toe xpershsi sg rtatiudaen da pprieaicton to
Dr. Josehp R.P etesro,n taecehr,c ollegau,ea ndf rien,df orhe lpful
advicaen ds upoprtt hrougthhoecu otru seo ft hisr eesar.c hThea uthor
isi ndteebdt oD r.K amalS mahoufno rv albulea lcolbaoriaotna nd
freindsihp. kHniolswde gea nd ntieccahalss itsnacea re greatly
appercaietd.
Sniceraepr peciiaotni se xtentdoeD dr. G lbe Mamantfoorv h elpful
guidaen,cs ugegsiton,s and oeunrcagte.mDe rn.M amantvo andD r.sM .H .
Litezk,eP .G .H uray,a ndJ .P .Y ounga rea ckwnloedgfeodhr e lpful
discuisosnasn d rfeoadrni ga nd itcirqinugt hism ancurisp.t Sepcial
thantkosM issC arol Proafposrt ypitnhigs d isrsatetoin.
The authoirs g rateuflt ot he Deaprmtenotf C hmeitsr,yU nviersyi t
ofT ennsesee (Knolxelv)if orf inainaclsu ppto frisrti nt hef orm of a
teaicgnh assisntthasip andt heans a reesarcahss sitanhtisps,p onsdo re
byt heU .SDe.pa rtmenotf E nerugnyd ecro nttr DaEcA-S0-75E6R04474.
Apperciatoini sa lseox tnedetdo t he ROiakd get oiNnaaLlab orayt or
(RONL),o peradt efor U.St.hDe e partmoefnE tne rguyn decrot narct
W-740e5n--g26w itthh eU nionC aribdeC oropraito,na ndt ot he
TransuranRiesumer achL aobraotry( RTL)f ort heu se oft heirf aicilty.
Thes uprptoa ndc oorpaeitono ft heO RNCLh meitsryDv iiiso,nu nder
thed iretciono fD r. 0.L .K elelr,J r.,i sr ecnoigzeadn d
ackwnlodeged. The tahuoirs i nedbtd etot hee ntries tafoff tThReL
fort hierp atiencaen dt echincaslu popr.t Inp articlura,t hea uthor
iii
iv
isg rtaeuflt oD rs.R . HLah.n ,R .G .H air,e G.M .B egnu,D .D .
Ens,o Sr.E .N avea,n dG .D .O 'eKlelyf orh elpufla sssitnacea nd
discuisosn;sM r. E.L .E alre,yC aptna iT. MCi.tn o,nM r. K. So,w der
Mr.A .M assye,M r. J.H . iOvle,rM r.J .B urhkaletr,a ndM r. J.R .
Tarranftor tecihcnaalss iasncte;M s. JH.am bya ndM rs.B .M ercefror
thoutgufhlenssan dp ateince; atnodM r. CE..H aysn,eM r. WD..
Card,eM nr.T .C ollnis,M r. J.S miht,a ndM r. B.A .P owresf orh ealht
physicssup pto.r
Apperciaitoni se xtdeendt ot hea uth'oscr olleaegs,u cowoerr,ks
andf rien,d Dsr.L ieeuntanDt. HMe.bm re,eM r. MK..P asotricc,h
Mr.V .E .N orevl,lD rs.F .D avi,d BG.ui lalum,eJ .B oursg,Ge .B eal,l
B.A llrad,M .H ara,M s. I.S hcau,eM rs. K.l lKyMe,r. J.M otetr,nM r.s
S.A .M orirsa,n dm anoyt hefrosr ssiatsnace ands upoprt.
Speicamle tnoini sm adoef p ersontsh ea uthhoasr a dmiraendd
emulateadn d Who phrvaovied elde aedrhsipa nde ncoaugreemn,t
Mr.D .B .H obatr,M r. AE..D empsye, S.F rom,eD r. G.C oTc.ah nr,
Dr.
ande spceaill,y H.E .H elwlege.
Dr.
ABSRTACT
Thet echnioqfu mesu tilnaeouosbs evratoino fe lcertocmhiecaaln d
sepctrocsopicp rorpteeis( psetcreolercotcmhietsrya)t o ptcially
trapnasreeneltct rod(eOsET 's)h asb eeanpp iledt ot he genreaitona nd
chartaecriizoanot fs omlees ss atbleo xidaitons tatoefss eledc te
lnahtanidaen da ctniidee lemetns( eC,P r, Sm, Eu,Y b, U,N p,
Tb, Am,
andC m)i nc moplienxga ndn onmcpolxeing aqsuoleuotuniss.o Optcially
tarnspareelcnettr oduesesd i nt hiss utdy inculderdet ciulaetd
viteroucsa bron( VRC)a ndm etalsrc eeOnTE 'asn d neaw OT E mafdreo m
poromuetsa lfoa m( MPF.)
Cylcivco ltammetyr atm icrloeecotdrse wasu sedi nc onujntcoin
witshp cetroleetcorchmeitsyr fort hes utdy ofo xidation-rteoidnu c
(erdo)x copule.s Ins omcea seadsid itonala nlatyicateclh niqwuerees
appleidf ori dneticfaitonio f eectlorchiecmlayl genreateodxd iaiton
statsep eiecs;t hesienl cudesdo liuotnab sroptino,s oldi-satte
refclteacne,a nd lRaasmearsn p etcroscso,pX i-erapyo wddeifrf raicont
andt hergmroaimvetr-miascss epctarla nalyss,er adiomcihceal
measuernetmsa,n ds petcorhpotmeotirca ndp otenitomterirce dox
titmretiry.
Thef orlm raedtuoicnp otentia(l0E' )va leuso ft heM (III)M/(II)
rdeoxc oulpesin 1 KMC la tp H6 w erfeo unbdyv otlammteryt ob e
-0.34
� 0.10 V fro Eu,- 11.8+ 0.0V1 forY b, and-1 .5+0 0 .10 V for Sm.
Spectrpootentisotact dietmeinratoino fE 0' fort heE u(IIIE)u(/II)
redocxuo plyeie dleda valueo f V.
-0.319� 0.005
Spetcorptoenitsotact mieasumreenotf t he (VCI)ee/C(IIIr)e docxo ulpe
inc onecntreadct arbonsaotleun t giaovEe01 e qula to V,
0.051 0�. 005
v
vi
whihc isa bou1t. V7 l ess poistviet hatnhe E01va leu inn onomcpelxing
solunt.iT ohiss maed ifefrencien p otentiwaasl o bservefdo r Et10h e
valuoefst heP r(VI)/Pr(IIIa)n dT b(VI)/bT(IIIr)e docxo ulpesin
cabronastoleu ito,na ndt huPsr I(V)a ndT b(VI)w erset albziiedi nt his
meduim. Thes oluitona bsoripotn ectsrpaa ndr edopxr oeprtesio ft hese
aqueso supceies arer eoprte.d sAol di Tb(VI)c-ontianincgo mpowuasn d
alspore paraetda nR VCe lcetordei nc arnbaotseol ution.
The UV(I)U/V()/UI(V)a ndU (VI)/U(II)Ir edox cowuerpesl utedise d
in1 MK Cl atO TE'.s 237Np, 24A3m,a nd24 8cmw eres tduiedi n
contanmeint glvoedb ox cifatleiis. Spcetrpootnetitoasct miesaumreetn
of tNhpe( )VN/IpV()r edocxo ulpei n1 MHC l40 gavaen E 0'v aleu of
1.410+ 00.05V . Np(IVIw)as geenratbeyde letcrloysoifsN p(VIi)n
2M Na2C30 atp H1 3, and stolheu otnia bsoprtoina ndl aseRamra ns petcar
werer ecor,d aendda nE 0v1a leu o0f.6 4 0.0V1 ftohre Np(IVI)N/p(VI)
+
couep wlas founbdyv olatmmetyr.
Oxiadtiono fAm (III)w ass utdiedi nc ocnentratedt ec arbona
soltuio,na nda revresbile cylcci volatmmorgma for theAm (IV/A)m(III)
copule yileeddE 01= 0.29� 0.0V1 i nt hism eidumt;h ivsal eu was used
toe stmiatteh es atndarredd tuicopno teinalt (E0)o ft he coulpea s
2.26 + 0.0V1. T hes oluitona bsoprtions petcurma ndr edobxe hiarov of
Am(IVw)e rec ompatroet dho seo fAm (V)an dAm (VI)i nt hiss ammeed ium.
Attempst too xidie zCm(IIIi)nc onecnttreadc arnbaotseol utni o
weren ot scucefsuslwh ichs ugegsttsha tt hep reidcteEd0v aleu for the
Cm(VI)/mC(IIIr)e docxo ulpem ayb ei ne rr.o r
TABLOEF CONTENTS
CAHPTER PAGE
I.I NTROTDIUOCN 1
•
A. Backrgoun.d 1
B.P rospdeo Resaerch 3
Spetcroetlreohcecmsirty. 4
c. •
1.D esrcipiton 4
2. Theo.r y 6
.
3. LiteruarteR eivew 9
D. TheL anthaannidAd ceti nideE lmeetns. • 11
1.E lcetronSirtcu tcur.e . • • 11
2. OxidaitonS tat.e s 12
3. Oxidatn-iRouectdionP otenitals 23
4.S oliuotnAb soripotnS petcar. 27
II.E XPERTIAMLED NETAILS • • 29
A. Inrtodtuoicn• • • 29
1.S petcrpohotmoeter• s• 29
2. Voltmmaeter 29
•
3. GloveBdo xe. s• • 29
4.A ccesorsyE quimpent 31
B.E lcertodeasn dC ells• • • 33
1.C onvteoinnla WorkinEglc ertodes 33
2. Optciayl Tlranpsarte Enlcetroeds. • 34
3. Refenrcee Eelctrosd •e • • 36
4.C ounteErle ctordes. 36
s. Teflno CellH oldre • . • 36
c. Reagtesn • • • 37
D. Procureeds 40
• • •
1.G enearlP roecduers. • • 40
2. Lanhtainde Eleemnts • • • 41
3. ActniidEeel metns
• 44
4.D ataT reatmetn . 48
vii