ATOMIC ENERGY OF CANADA LIMITED

CHALK RIVER PROJECT

RESEARCH AND DEVELOPMENT

OXIDATION OF Pu(iV) TO Pu(VI) IN SOLUTIONS

OF NITRIC ACID, ALUMINIUM NITRATE
SODIUM NITRATE, AND URANYL NITRATE

CRDC-697

BY

I.H. CROCKER

CHALK RIVER, ONTARIO

MAY, 1957

AECL NO. 488

 DISCLAIMER

Portions of this document may be illegible in

electronic image products. Images are produced
from the best available original document.
OXIDATIOI OF Pti(I?) TO Pm(?I) IN SOLOTIOIS

OF IITPJC ACID, ALUMIIItJM IlfMTEs

SODIUM IITMTS, fflD UMIYL IITMTl

by

loHo Crocker

CRDG - 697

ChaUc River J Ontario

May, 1957
MCLASSTFIKD CRK-697

ABSTRACT

The effects of temperature, plutonium concentration, n i t r i c

acid concentration^ and n i t r a t e ion concentration on the oxidation

of Pti(I?) t o Pu(?I) have been studied. The r a t e of oxidatioa i n -

creases as temperature and Pu concentration increase, decreases as

the n i t r i c acid concentration increases, and, in general, decreases

as the n i t r a t e ion concentration increases^ p a r t i c u l a r l y when the

n i t r a t e ion i s supplied by a highly ionized n i t r a t e s a l t , such as

MaMOj or 11(103)3<. Uranyl n i t r a t e , which i s strongly complexed in

n i t r i c a d d s o l u t i o n , i n h i b i t s Pu(?I) formation when present i n

high concentration^ but enhances i t s forraation when present in low

concentrationo

Quantitative data have been obtained 0¥er a range of n i t r i c

acid - n i t r a t e s a l t concentrations5 t h a t should enable prediction

of t h e oxidation s t a t e of Pu in most process solutionso

TWCLASSIPIID Gfiaj-697

COMTEITS

Page

Introduction 1

Sxperiwental 1

lo Spectrophotometric Analysis 1

(a) Apparatus 1
(b) Technique 1

(c) Calibration of Spectrophotometers 2

II. Oxidation of Pu(I?) t o Pu(fl) 3

(a) Heagents 3
(b) Apparatus and Method 3
Results k
lo Effect of Temperature 6
2. Effect of Pu(If) Concentration 6
3« Effect of Mltric Acid Concentration 6
ito Effect of Foreign Mitrate Salt Concentration 6

Order of Reaction and t h e Rate Coefficient 7

Discussion 8

SuMinary 12

leferences 13

Appendix I Bibliography of the Spectrophotometiy of Plutonium 1^

II Calculation of Rate Coefficient 17

UlCtASSIPIlD CRm-^97

liTEODUCTIOl

Most aqueous plutonlum p u r i f i c a t i o n schemes are based upon t h e separa-

t i o n of Pu(I?) froM contawinating ions in n i t r i c acid solutlono Plutoniun
in other valence s t a t e s generally does not follow Pu(I?) through t h e p u r i f i -
cation process, but insteadj goes with the contaminating ions t o lower t h e
plutoniuK yields This i s t r u e i n the Dowex-1 anion exchange process, and
t o a l e s s e r extent, i n the trlbutylphosphate solirent extraction process,
both of which are used at Chalk M f e r ( l ) ( 2 ) , The conditions under which
Pu(l¥) i s stablSj and t h e effects on the s t a b i l i t y of acidity, plutonlum
concentration, temperature, and foreign s a l t concentration need t o be de-
fined as exactly as possible so t h a t losses of plutonlum, because of Pu(?I)
foraation, may be atoideds

Liadted information about t h e growth of Pu(fl) i n n i t r i c acid solutions

i s available i n the l i t e r a t u r e « the d e t a i l e d investigation of lasha and
She l i n e , Gonnick and Mc¥ey, and Sabideau were carried out i n hydrochloric and
p e r e h l o i l c acids (3) (k) (5) ( 6 ) . I'raus has published a l i t t l e information
about the oxidation of Pu(lf) i n n i t r i c acid and in n i t r i c acid-uranyl n i t r a t e
solution ( 7 ) . Q u a l i t a t i v e l y , Connick's paper conceitiing the redox reactions
of Pu i s of i n t e r e s t , but i t , t o o , contains only limited infoiTnation about
n i t r i c acid solutions (8)^

The puipose of t h i s report i s t o provide sufficient additional informa-

t i o n about the oxidation of Pu(IV) t o Pu(¥I) i n n i t r i c acid media t o enable
process conditions t o be regulated for most efficient plutonium recovery.

HPEPIMHTAI.

The laboratory work i s considered i n two parts s

I, SpectrophotoKetilc analysis«

IIo CMdatioE of Pu(If) t o Pu(¥l)o

lo Spectrophoto!ttetri.c Analysis
(a) Apparatus

Spectrophotometric analysis was c a r r i e d out with Beckisan Quartz spec-

trophotometers (Model DoIJo), numbers 2,137 and 92^8611, using calibrated
Corex c e l l s of 10,00 1 0«01 m.Mo l i g h t paths«

(b) Technique

The spectrophotometry of plutonium i s r e l a t i v e l y complicated^ Ifether

than e ^ a n d an already well-docuraented subject, only the more outstanding
requirements for successful analysis of various plutonium oxidation s t a t e s
w i l l be given here, along with a l i s t of references (Appendix I ) t o the
papers which were found t o be useful in developing the methods of a n a l y s i s .
IMCMSSIFIED , 2 - CErc-697

P u ( I I l ) and PU(I?) possess spectra whose iaportant absorption maxima

obey Beer's and Lambert's laws^ Hence^ a knowledge of t h e i r extinction co-
e f f i c i e n t s , such as Figures I , I I and I I I provide, enables analysis for
e i t h e r of these oxidation s t a t e s t o be performed. With a knowledge of the
interference of the other Pu species, analysis of mixtures of Pu oxidation
s t a t e s for P u ( I I l ) and PuCif) i s r e a d i l y carried out^

The analysis for Pu(fl) i s complicated by the f a c t t h a t i t s most d i s -

t i n c t i v e absorption maidmuia, near 83I m^u*^ apparently does not obey Beards
and Lambert's Laws, due t o instruiaental Hmitations (9)» Hence c a l i b r a t i o n
curves are necessary for each n i t r a t e concentration t o he studied. Figure
¥111 consists of t h e c a l i b r a t i o n curves constructed for a range of n i t r a t e
concentrations for one spectrophotometer. These curves are not n e c e s s a r i l y
applicable t o any other instrument, because of the extreme thinness of t h e
831 peak# To obtain reproducible r e s u l t s using t h i s peak, c e r t a i n d e f i n i t e
precautions i n the use of the spectrophotometer have t o be observeds

(1) S l i t width s e t t i n g s have t o be made exactly, and from t h e same d i -

rection each time, t o avoid e r r o r s due t o play i n the mechanical
linkage«

(2) Deflection of the galvanometer needle must be used t o obtain an exact

s e t t i n g of the wavelength d i a l ; no other method i s s u f f i c i e n t l y
accurates

(3) A knowledge of the s h i f t i n g or disappearance of t h e peak due t o

changes i n solvent concentration i s v i t a l * Figures ¥1 and ? I I i l l u s -
trate this.

Quantitative analysis for P u ( I I I ) , Pu(I?) and Ptt(¥l) in nixtures of

the t h r e e i s possible when the proper precautions, are taken*
Pu(¥}, whose spectnia i s shown i n Figure Y, can be determined s p e c t r o -
photometrically, but i t s small extinction coefficients reduce the s e n s i t i v i t y
of t h e analysis« Pu(?) was not of i n t e r e s t in t h i s study» Colloidal Pu(I?)
can be detersiined only roughly by the spectrophotoneter because no two polymer
uilxtures give the same absorption spectrum. The size of the polymer p a r t i c l e s
determines the amount of absorption at a ^ v e n wavelength, and t h e size varies
with time, concentration, and temperature* Figure I ? shows the type of
spectra t h a t are obtained for c o l l o i d a l plutonium,
(c) Calibration of Becksian Quartz Spectrophotometers
No. 2137 and Mo. 9 2 , ^ 5 ^ "
A stock solution of Pu(If) was prepared i n the following manners 1
Pm(M03)i| solution t h a t was knowi t o be 98®2^ pure was applied t o a SKiall
Dowex-1 ion exchange column i n 7*5 M MOj^ The i a p u i l t l e s were washed through
the coluBin with fresh 7,$ M HIO3, and then a one column volume of 1 M MO3
spacer wash was passed through* The Pu was eluted with 10^ iH20H«HM03« The
l a t t e r was decomposed i n b o i l i n g 8 M ffl03 and the Pu was concentrated by
evaporation t o 2li#0 mg/ml i n 15«2 M MO3, Final concentration of t h e solution
was determined by a-counting using a C«F»I^S,-2 gas-flow proportional counter
with an A«B J^-llili8 l i n e a r amplifier^ The absence of more than 1^ Pu(¥l)
was v e r i f i e d spectrophotmetrically^ P u ( I I l ) could not e i d s t a f t e r t h i s t r e a t -
went.
TOICLASSIFIID - 3 CfflB-697

Standard Pu(If) solutions for c a l i b r a t i o n of t h e spectrophotometers

were prepared by d i l u t i n g the stock solution with the appropriate volumes
and concentrations of IWO3 s o l u t i o n . Except i n two cases, t h e concentra-
t i o n of t h e d i l u t i n g HMO3 solution was maintained greater than 0®2 M t o
avoid l o c a l disproporbionation and hydrolysis effects^ In these two cases,
the d i l u t i o n s had t o be made with water,. To minimize the effects of t h i s ,
the c a l i b r a t i o n s were made with t h e utuost r a p i d i t y , and corrections for the
presence of P u ( r i l ) and Pu(?I) were applied, A stock P u ( I I l ) solution was
prepared by adding hydroxylaiaine n i t r a t e t o the diluted Pu(If) stock and
allo-Ming the solution t o stand s e v e r a l hours u n t i l complete reduction was
effected^ A stock Pu{?l) solution was prepared by adding eerie amioniua
n i t r a t e t o the diluted Pu(I?) stock and allowing i t t o stand oventight*^ Both
solutions were then re-standardizeds Appropriate dilutions of these solutions
were made with d i l u t e acid for t h e c a l i b r a t i o n of the speetrophotoaeterss
Figure f i l l i s an example of the c a l i b r a t i o n curves obtained for the 83I ».Uo
peA. of Pu(fl)^ Figure IX i l l u s t r a t e s the v a r i a t i o n of the o p t i c a l density
of t h i s peak at t h r e e concentrations of Pu, as the n i t r a t e ion concentratiai
i s changedo This figure shows t h a t the n i t r a t e radicals of alundnujE, sodium,
and uranyl s a l t s , and of n i t r i c acid, are equivalent i n t h e i r effects on
t h i s absorption «arf.iiumo Calibration curves for Pu(f) and Pu polymer were
not constructed, and l i t e r a t u r e values were used when necessary^

II, Oxidation of Pa(I7) t o Pu(fl)

The four controllable factors t h a t influence the r a t e of fonaation of

Pu(?I) i n Pu(lf) - n i t r i c acid solutions arei
(1) Temperature
(2) Pu(IY) concentration
(3) Nitric acid concentration
(h) Foreign n i t r a t e s a l t concentration

lach of these factors was examined i n t u r n ,

(a) Reagents

Plutonium ( I f ) l i t r a t e j The speetrophotoBietrically pure Pu(I¥) s o l u -

t i o n was prepared as discussed i n Section 1(c)o
11(103)3, ^ ^ ^ ^ J ^^^ ^ 2 ( 1 0 3 ) 2 solutions were prepared fron reagent
grade chefflicals, and standardized, (10) (11),

(b) Apparatus and Method

Oxidations were performed at room temperature, at 98®C, and at reflux

temperature (about 110*C) on aMquots of the standard solutions made up t o
5 ffilo i n v o l u a e t r i c flasks^

A Since Ce(I?) ion absorbs below 500 MOU., the values obtained for Pu(¥l)
interference with the Pu(I¥) peak near k7^ in«,u» were corrected for Ce(I?)
absorptions
OTCLASSIFIED - It - ClI»-^97

( i ) Room Temperaturei I t room t e n p e r a t u r e , the reactions were

carried out in the 5 rale volumetric flasks« The coapositlons of the s o l u -
t i o n s were detennlned each day for several days,
( i i ) 98ll°Si Steam provided t h i s r e l a t i v e l y constant temperature i n
a simple bath made from a 600 mlo beaker and a rubber stopper^ (Figure X),
Ihen the 5 »!• volumetric flasks containing t h e t e s t solutions were suspended
i n the steam bath, equilibriuffi temperature was attained i n two minutes» The
stoppers of the f l a s k s , ungreased t o avoid contamination of the s o l u t i o n s ,
were always checked t o i n s u r e t h a t they were f i r a l y seated** After a p r e -
detennined i n t e r v a l , t h e flasks were rapidly cooled t o room temperature by
shutting off t h e steam and allowing t a p water t o s w i r l past the flasks«
Cooling tiaie was one-and-one-half minutes« The solutions were placed in t h e
spectrophotometer c e l l s by t r a n s f e r p i p e t t e , and the o p t i c a l d e n s i t i e s were
observed» 1fter returning t h e solutions t o the $ a l , voluaetrlc f l a s k s ,
heating was resumed, A correction had t o be made for the heating and cool-
ing periods, and one-half of t h e time required for heating and cooling (i#e»,
on© and t h r e e - q u a r t e r s itAnutes) was added t o t h e t o t a l t i n e of reaction at
98'Go The time e r r o r then would be s i g n i f i c a n t only for extremely short
reaction periods« The r a t e s of dlsproporfcionation or oxidation were slow
enough at room tewperature except i n acid solutions below 0®3 M t h a t no s i g -
nificant changes would occur during the short i n t e r v a l s in which readings
were taken«

( i l l ) Beflux Temperaturei Reflux tenperature was used because i t

roughly corresponded t o evaporator or dissolver temperatures« The serious
disadvantage of using reflux temperature was the s i p i l f i c a n t vapour loss
which occurred, even when a s p e c i a l condenser was employed. (Figure XI). I n
addition, Srlenaeyer flasks had t o be used as reaction vessels instead of
volumetric f l a s k s , since the l a t t e r made poor influx vessels« Hence no ready
volume check on t h e t e s t solution could be maintained, and several t r a n s f e r s
back-and-forth for volume checks reduced the accuracy of the woik, ftily a
few t e s t s were carried out i n t h i s tenperature range^

The r e s u l t s of t h e oxidation experiments are presented graphically i n

Figures I I I t o XXXII« A t a b u l a t i o n of graph t i t l e s i s given belows

Fig^ XII Oxidation of Pu(IV) t o Pu(?l) i n HMO3 solution at room tempera-

t u r e . Pu concentrations 2e22 x IQ-S M t o ^„56 x 10"3 M<,
Fig« XIII Oxidation of Pu(IV) t o Pu(¥l) i n 11103 solution at reflux
temperature, Pu concentration 1«03 x 10"3 M^
Figo Xlf Cfeidation of Pu(If) t o Pu(?I) i n MO3 solution at 98®C, Pu
concentration 1«03 x 10~3 M.

4 I t was determined t h a t a well-seated stopper would prevent s i ^ i f i c a n t

evaporation i n 100 hours at 98*C,
UlCMSSIFIED - 5 - CEIX3-697

Pigo M Oxidation of P u ( I f ) t o P i i ( f l ) xn HIO3 s o l u t i o n at 98'G showing

r e t a r d i n g e f f e c t of c o l l o i d a l Fu» Pu c o n c e n t r a t i o n I0O3 x
10°3 Ko

Fig. i n Gxidatlon of P u ( I f ) t o pTi(fl) i n fftlOj s o l u t i o n a t 98'C Pu c o n -

c e n t r a t i o n liol3 X 10''3 Ko

Figo X H I Oxidation of P u ( I f ) t o P u ( ? I ) m HIO3 s o l u t i o n a t 98''C f o r

l o n g e r p e r i o d s , Pu c o n c e n t r a t i o n Ii*l3 x 10~3 Mo

Figo X f l l l Oxidation of P u ( I f ) t o P u ( f l ) i n Iffl03 s o l u t i o n a t 9B'C. Pu

c o n c e n t r a t i o n 6 « 8 l x lO^B M,

F i g . XIX n i d a t i o n of P u ( I ? ) t o Pu{?I) i n MO^ s o l u t i o n a t 98^Co Pu

c o n c e n t r a t i o n 9«73 x 10=3 ! „

F i g . XX Oxidation of P u ( I f } t o P u ( ? I ) i n 11(103)3 - HIO3 s o l u t i o n a t

98*Ce Pu c o n c e n t r a t i o n I9O3 x 10-°3 |f„ (A) - c o n s t a n t a c i d
c o n c e n t r a t i on«

P i g , IXI Oxidation of P u ( I f ) t o P u ( ¥ I ) i n #.1(103)3 " ^ ^ 3 s o l u t i o n a t 98"

Cs Pu c o n c e n t r a t i o n lo03 x 10'°3 Mo (B) - c o n s t a n t s a l t c o n -
c e n t r a t i on o

Figo n i l O x i d a t i o n of P u ( I f ) t o P u ( f l ) i n 11(103)3 -= Hi03 s o l u t i o n a t 98*

Ge f o r l o n g e r p e r i o d s I'd.th i n c r e a s e d s a l t c o n c e n t r a t i o n , Pu
c o n c e n t r a t i o n I0O3 x IC'S M*

Fig» XXIII O x i d a t i o n of P a ( I f ) t o P u ( ? I ) i n I a l 0 3 - HIO3 s o l u t i o n a t 9 8 '

Co Pu c o n c e n t r a t i o n l e 0 3 x 10-°3 Mo "^

Flgo XXIT O x i d a t i o a of P u ( I ¥ ) t o P u ( f l ) i n 1102(103)2 - W % s o l u t i o n a t

98*Co Pu c o n c e n t r a t i o n 1.03 x 10-3 U.

Pigo XX? I n i t i a l Reaction Rate and Order of Reaction by D i f f e r e n t i a l

Methodo

Figo I 1 ¥ I E f f e c t of T e n p e r a t u r e and l l i t r i c I c i d C o n c e n t r a t i o n on Eate

Coefficientc

Pigo XXfll E f f e c t of P a ( I ¥ ) C o n c e n t r a t i o n on Rate Goefficiento

F i g . I X f l l l E f f e c t of a Foreign S a l t on Eate C o e f f i c i e n t o

Pigo XXIX P e r c e n t a g e of Pu(1fl) Formed xn 500 Minutes i n l i t r i c Acid a t

98*'C*1*C w i t h loli9 M and 3..0 M M i t r a t e Added as 11(103)30

Figo XXI P e r c e n t a g e of P u ( f l ) Fortned m ^00 Minutes i n N i t r i c I c l d a t

98*Gil*'G w i t h IS K M i t r a t e Added as IaM03.

Pig. n i l P e r c e n t a g e of P u ( f l ) Foraed xn 500 Minutes i n M i t r i e Acid a t

98^ail*C w i t h IS md 3 . 0 ¥ l i t r s t e Added as 1102(103)20

Flgo XXXII Pereeiitage of Pu(1?T) Fcrmed i n $00 m n u t e s i n l i t i i c Acid a t

98*Cil^G w i t h Various Amounts of 11(103)3^ l a l O j , or 1102(103)2
Addedo
IWCMSSIFIED _ 6 - GR13G-697

1^ Effect of Temperature
A comparison of Figures
of Pu(rf) t o Pu(?l) i s highly
t i v e amounts of Pu(?I) formed
anil at reflux t e i ^ e r a t u r e , i n
2, Effect of Pu(I?) Concentration
XII, XIII and XI? shows t h a t t h e oxidation
temperature dependents For example, the r e l a -
i n JOO minutes at roon temperature, at 98°C,
1.7 M IMO3, were 0^, 631 and 79^, r e s p e c t i v e l y .

Figures XI?, X?I, X f l l l and XIX show t h a t as t h e i n i t i a l Pu(If) con-

centration i s increased, the r a t e of formation of Pu(?l) i n c r e a s e s . Mhen
t h i s r a t e of increase i s expressed as a percentage of the t o t a l Pu i n s o l u -
tioHj however, i t i s apparent t h a t i t i s not proportional t o the i n i t i a l
Pu(I?) concentration. In 5<.0 M HMO3J t h e percentage of Pu(¥I) formed i n gOO
ndnutes, at 98*C, increases from 0% t o IW as the i n i t i a l Pu(If) concentra-
t i o n i s increased fro» 1„03 x 10-31 t o 9«73 x 10"°3M. In 2^Ui I IW03s however^
the percentages of Pu(¥I) formed i n 500 sdnutes are 2$%, Ski, 50^ and 146^5
for t h e four i n i t i a l Pu(I¥) concentrations studied, I n ascending order^

3# Effect of H i t r i c Acid Concentration

Fi©ires XII t o XXXf, with the exception of XX, i l l u s t r a t e t h a t the

r a t e of formation of Pu(fl) decreases with increasing n i t r i c acid concen-
t r a t i o n , except when t h e n i t r i c acid concentration drops below 0e2 M at room
tenfierature or 0.5 M at 98"C. Figures XII, I f and XXI show t h a t the effect
of decreasing the n i t r i c acid concentration below these values i s t o decrease
the r a t e of formation of Pu(?l)s Hydrolysis products, including Pu(If) -
polymer, which r e s i s t oxidation, are believed t o be responsible for these
r e s u l t s i n low acid^

k» Effect of Foreign N i t r a t e S a l t Concentration

Three general c l a s s i f i c a t i o n s of n i t r a t e s a l t s have been exandned
for t h e i r effect on t h e oxidation of Pu(I?) t o Pu(fl) i n n i t i l c acid at 98*Ct
C l a s s i f i c a t i o n of Salt Actual Salt Studied

(a) highly ionized, with a non- 11(103)3 and l a i 0 3

oxidizing cation

(b) complexed by n i t r a t e , with a 1102(103)2

non-oxidizing cation
(c) with an oxidizing cation l i t r a t e s of the corrosion
products of s t a i n l e s s
steel
(a) Aluainfaiii Mitrate and Sodium Mitrate

The retarding influence of 11(103)3 and iaN03 on the oxidation of

Pu(rf) t o Pu(¥I) i s i l l u s t r a t e d i n Figures XX, XXI, XXII and XXIII. I n -
creasing the concentration of s a l t n i t r a t e ions at constant a c i d i t y r e -
duces t h e r a t e of formation of P u ( ? I ) , but t o a l e s s e r extent than when an
equivalent aroount of n i t r i c acid i s added* Salt n i t r a t e delays the appear-
ance of Pu(rf} hydrolysis products as the a c i d i t y i s dropped below 0,55 M«
For example, t h e oxidation curve for 0^35 M acid plus 1^9 I aluMnlum
UNCLASSIFIED - 7 - GRDC-697

n i t r a t e i s above t h a t for 0,55 M acid plus l.li9 K aluminiurn n i t r a t e . With-

out s a l t n i t r a t e these two curves would be reversed (Figure I f ) , In 0^21 M
HIO3 plus l6li9 N almainiuri n i t r a t e , hydrolysis product formation once more
reduces the r a t e of oxidation of PuCi?). The effects of equivalent concen-
t r a t i o n s of 'MaWj and 11(103)3 appear t o be siiallaro
(b) Prenyl Witrate

Uranyl n i t r a t e differs considerably from sodium n i t r a t e and aluininiuiii

n i t r a t e i n i t s effect (Figure XXI?)o When the n i t r a t e concentration of a
solution i s 1«,5 M due t o uranyl n i t r a t e , and the n i t r i c acid concentration
i s less than 1.5 M, uranyl n i t r a t e affects the r a t e of oxidation of Pu(I?)
s i m i l a r l y t o sodium n i t r a t e or aluminiun n i t r a t e , though t o a smaller ex-
t e n t . In n i t r i c acid above 1«5 M, however, t h i s amount of uranyl n i t r a t e
accelerates the r a t e of reaction above i t s value in unadulterated n i t r i c
acid of t h e sarae iiolari.tyo The mapiltude of t h i s acceleration decreases
with increasing a c i d i t y , but does not disappear, Mhen the uranyl n i t r a t e
concentration i s increased t o 3 M, with respect t o n i t r a t e , t h i s accelera-
t i o n i s reduced., U"ranyl n i t r a t e thus causes two apparently opposite e f f e c t s ,
depending upon i t s concentration r e l a t i v e t o the n i t r i c acid concentration^

Order of Reaction and t h e Rate Coefficient

A more s t r i k i n g p o r t r a y a l , t h o u # possibly a less valid one here, of

t h e effect of the variables on t h e r a t e of 03d.dation of Pu(I?) t o Pu(?l) can
be ^ v e n by comparison of the r a t e coefficients for t h e reactiono The
d i f f e r e n t i a l method of v a n ' t Hoff (12) for detennining the order of a r e -
action was applied t o the results» A plot of log (-dc/dt) against log c,
where c I s the concentration of P u ( r f ) , ^ v e s the r e s u l t s shown i n Figure
H f for 1.03 X 10-"3 M Pu at 98*0, A s t r a i g h t l i n e , the t e s t for non-
complexity, was obtained for the r e s u l t s i n 1.15 K HIO3, and the slope of
the l i n e indicated a t h i r d order r e a c t i o n . The i n i t i a l rate of reaction,
obtained by extrapolation t o zero time, i s li,6 x lO"'^ moles H t e r " ^ second'"-'-®
Other plutoniuiB and n i t r i c acid concentrations gave marked deviations from
linearityo

In s p i t e of the fact t h a t t h e reaction i s generally complex, and

appears t o obey t h i r d order k i n e t i c s only under l i a t t e d conditions, i t was
f e l t that calculation of the r a t e coefficient at various a c i d i t i e s , temper-
a t u r e s , plutonium concentrations, and s a l t concentrations, assuming t h i r d
order k i n e t i c s , would serve t o delineate the effect of t h e v a r i a b l e s . The
r a t e coefficient, k, t h e r e f o r e , was calculated by the method of i n t e g r a t i o n
(13), using the t h i r d order r a t e equations
k = _1 » 2 ^ _ ^ _ ^ l i t res 2 moles "2 a i m t e - l
2t 1^(7^)2
where a i s the I n i t i a l Pu(I?) concentration and x i s the Pu(?l) concentra-
t i o n at time t . This simple equation obviously i s inapplicable when p r o -
ducts other than Pu(?l) are formed, so t h a t t h i s treatment i s not valid
for oxidations at room temperature or i n low acid concentrations» The
values of k derived by use of the equation were found t o be reasonably
constant with time for many of the conditions imposed, as the tabulation
of k values in Appendix I I shows» Some of the values of k varied widely,
however, p a r t i c u l a r l y at high i n i t i a l concentrations of Pu(I¥)a The aver-
age valties of the k*s as determined for various conditions have been p l o t t e d
against n i t r i c acid concentration i n Figures XXfl, XX?H, and XXflllo
OTCMSSIFIID _ 8 - cire^97

(1) Effect of Temperature (Figure IX¥I)

The oxidation of Pu(I?) t o Pu(fl) exhibits a large temperature depend-
ence. In laO !' HIO3, k increases from Ool3 at room temperature t o 105 l i t e r s ^
sioles'"^ iiiiriiite"l Q% reflux temperature o

(2) Effect of Pu(I¥) Concentration (Figure X l f l l )

If t h e oxidation reaction were t h i r d order, the rate of Pu(¥I) f o m a t i o n

would be proportional t o the t h i r d power of the Pu(I?) concentration, and t h e
curves of k vSo a c i d i t y for the different Pu concentrations would be superim-
posed one on the othero Instead, k decreases with increasing Pu(I¥) concen-
t r a t i o n , p a r t i c u l a r l y at low a c i d i t i e s , showing t h a t the rate i s proportional
t o something l e s s than t h i r d power,,

(3) Effect of l l i t r i c Acid Concentration (Figures XXfl, X l f l l , Xlf I I I )

fhe r a t e constant decreases froit 9 x 10^ i n 0®55 1 HIO3 t o 3 x 10^

l i t e r s ^ Boles*°2 mnute""! i n 3<,0 M ffl03 for an i n i t i a l Pu(If) concentration
of 1.03 X 10*"3 M HMO3 at 98°Co For each 1 M increase i n IWO3 concentration
at 98*C, k decreases by a factor of about t e n . By extrapolating t h e curves
t o e s s e n t i a l l y zero r a t e , a value of the acid concentration above which no
Pu{fl) w i l l form can be obtained^ i t room temperature t h i s value i s about
1,5 M while at 98'C i t i s about 8.0 H, Below 0»5 M Hi03 at 98^C, k decreases
with decreasing a c i d i t y because of Pu(I¥) hydrolysis^ The point of maxiiium
k depends upon t e n p e r a t u r e , plutonium concentration, and foreign s a l t concen-
tration .

(h) Effect of a Foreign Salt (Figure XXflll)

The r e s u l t s for only one concentration of 11(103)3 ^^ various acid

concentrations at 98®G are p l o t t e d . The reduction i n r a t e of Pu(I?) oxid-
ation due t o t h e presence of l l ( I 0 j ) 3 i s evident. Mhy t h e effect seeiis t o
go through a maxlBuii at about 2oli M raOj i s not known.

DISGUSSIOH
The r a t e of oxidation of Pu(I?) t o Pu(fl) i n n i t i l c acid solutions
i s a function of several r e a c t i o n s .

(1) Msproportionation of Pu(I¥) t o give P u ( I I l ) and P«(fl)o

(2) l i t r a t e oxidation of Pu(III) t o PTi(If},

(3) Hydrolysis and polymerization of PuCif) i n low a c i d i t i e s .

ik) Complex n i t r a t e formation by Pu(If) and P u ( ¥ l ) .

(5) Complex n i t r a t e fomation by f o r e i p i c a t i o n s , such as 1102**®

(6) leduetlon of Pu(¥I) and oxidatioa of Pu(If) by a and h i g h - i n t e n s i t y

p-radiation, r e s p e c t i v e l y .

Most of the experiinental r e s u l t s nay be i n t e r p r e t e d i n at l e a s t a q u a l i -

t a t i v e fashion by reference t o these r e a c t i o n s .
OTCtASSIFIlB - 9 - Gire-^97

Oxidation of Pu(I?) t o P u ( ¥ l ) , i n solutions containing no oxidizing

agent other than n i t i l c acid, i s brought about by two reactions - dispropor-
t i o n a t i o n of Pu(If) I n t o Pu(?I) and P u ( n i ) , and n i t r i c acid oxidation of
Pu(III) t o P u ( l ¥ ) . The disproportionation reaction has been studied i n
hydrochloric and p e r e h l o i l c acids by l a s h a and Shellne (3) (h) and by Rabl-
deau ( 6 ) . Gonnick and Icfey analyzed the f o m e r experiments in d e t a i l ( 5 ) .
The r a t e - c o n t r o l l i n g step of the disproportionation reaction was found t o bei

(1) Pu*^ + Pu*^ + 6H2O ^ Pu*3 + pu02* + ^130*

This i s followed by t h e rapid reactionj

(2) fn*h + Pm02'' ===± Ptt*3 + pnOg**

Combining (1) and ( 2 ) , the o v e r a l l reaction becomes;
(3) 3Pu*^ * 6H2O :===: 2Pu+3 + PTI02** + ^O*
In n i t r i c acid mediufli, Pu*3 fomed i n the disproporbionation step i s oxidized
t o Pu*^ ( l i t ) . Conditions of a c i d i t y w i l l detenaine whether disproportionation
or n i t r a t e oxidation w i l l be the r a t e - d e t e m i n i n g step for the overall oxid-
ation reaction^ The present work Indicates that the following t a b l e i s applic-
able!

TABIE I
Dependence of Eate-determinlng Step on Conditions
of Concentration and Teaperature

Conditions
Pu(I¥) Coa- late-determining
cent r a t i on Acidity Temperature o Step

High (>>10-2M) Low (Z. 0.7M) loom litrate teidation

High High 0 0o7M) EOOM Disproportionation
Low i^z.^io-m) Almost any loom ttsproporfci onati on
High and low Almost any Elevated Disproportionation

Consideration of Table I and the disproportionation equations leads

t o the conclusion t h a t P u ( I I l ) and Pu(?) (i®e,, PUO2''*) cannot e r i s t i n n i t r i c
acid at 9B°C*.
The fundamental rate-determining equation, ( l ) , indicates t h a t the
reaction should be second order with respect t o Pu(I¥) concentration unless
I t i s modified by side r e a c t i o n s . Figure XX?, of course, shows t h a t t h e
order of the reaction i s approximately t h i r d , within a narrow range of con-
c e n t r a t i o n s . In a l l but d i l u t e n i t r i c acid, n i t r a t e complexing of Pu(I¥)
must be responsible for the gross deviation from second order. Pu(I?) foras
a series^of conplexes, ranging from Pu(I03)*3 in d i l u t e n i t r i c acid t o
Ptt(i03)6~ i n 10 M n i t r i c acid, (15) ( I 6 ) . These coiaplexes increasingly

A The siKplification of the spectrophotoitetric analysis t h a t r e s u l t s from

t h i s i s obvious.
OTCMSSIFIID - 10 - GEI3C-697

retard the r a t e of disproportionation of Pu(I¥) as t h e n i t r i c acid concen-

t r a t i o n i s r a i s e d . The effect of a c i d i t y cooperates in slowing the d i s p r o -
portionation reaction, as equation ( l ) shows. Gonnick and Mcfey found t h a t
the disproportionation reaction r a t e exhibited an inverse t h i r d power de-
pendence i n perchloric acid* at constant i o n i c strength (5)«

For eveiy condition of temperature and Pu(If) concentration, there i s

a n i t r i c acid concentration such t h a t the r a t e of disproportionation approach-
es zero. Figures XXfl and X l f l l show that t h i s i s about 1^5 M 1103 at room
tenperature and about 8 M at 98®C, for solutions t h a t are approriaately 10"3
F i n plutonium.

In concentrations of n i t r i c acid below about 0.5 M, hydrolysis of Pu(I¥)

w i l l occur, according t o the equation?
(k) Fo*^ + yffoO^ -^ Pu(0H)+3 + I30* or, more probably,

(5) Pu(H20)8*^ + H2O ^ ^ : z : ± P u ( H 2 0 ) 7 (0H)*3 + H3O*

As t h e a c i d i t y i s further reduced, additional hydrolysis occurs, p r o -
ducing Pu(H20)6(OH)2*2, Pu(H20)5(OH)3*, and f i n a l l y Pu(H20)l4(Oi)li, (18) (19).
The s o l u b i l i t y product of the l a t t e r i s reported t o be 7 x 10-56 (20), In
low a c i d i t y Pu(I?) polymer i s apt t o form, especially when t h e solution i s
heated. Ockenden and Welch report t h a t over 1^0^ of a Pu(I¥) "Bonoaer" poly-
merized i n 30 minutes In 0 . 1 M IWO3 at room temperature (21). Figures X?
and IXfl i l l u s t r a t e best how hydrolysis and polymer fomation lower the r a t e
of oxidation of Pu(If) t o P u ( f l ) . For a ^ v e n Pu(rf) concentration t h e r e
w i l l be a specific n i t r i c acid concentration which w i l l give a iiari.Hniii r a t e
of Pu(¥l) f o m a t i o n . For 10"3 M Pu(I?) at 98"C, t h i s w i l l be about 0^55 M
HIO30 At rooM temperature the inaxiini» r a t e would occur in l e s s than 0.55 M
HIO30 The maxiiniii for 10"2 1 Pti(rf) would occur i n a n i t r i c acid conoen-
t r a t i o n greater than 0.55 M.

1 c h a r a c t e r i s t i c of the oxidation reaction i s the non-proportional

increase i n the r a t e of reaction with increase of i n i t i a l Pu(I¥) concentra-
t i o n . This i s shown c l e a r l y in Figure X l f l l by the fact t h a t the average k
for a given acid concentration decreases i n value as the i n i t i a l Pm(I¥) con-
centration i n c r e a s e s , especially for lower a c i d i t i e s .

A possible explanation for t h i s phenomenon i s that t h e r a t e of the

disproportionation reaction i s slowed by Pu(¥l) i o n s , s i i p l e and complexed,
above a c e r t a i n concentration. Some weight i s given t o t h i s argument by
the shape of the % Pu(¥l) v s . time curves for each Pu concentration. They
show t h a t the r a t e of % Pu(¥I) increase I n i t i a l l y i s much greater for t h e
higher Ptt(I?) concentrations than f o r the lower, but t h a t i t f a l l s off
More rapidly f o r t h e higher plutonium concentrations than for t h e lower^
This would seem t o indicate t h a t the Pu(?I) product concentration, above
a c e r t a i n value, was influencing the r a t e of oxidation of P u ( I f ) .

Figures XIIX t o IIXII are presented t o show the relative effects on

Pa(I?) oxidation of 11(103)3, »aI03 and 102(103)2<» In Figure XHX t h e

t Pu(lV) i s believed t o be uncoaplexed i n perchloric acid below 9.I4 I! ( 1 ? ) .

UlCMSSIFIED - 11 ^ CRDC-697

percentages of Pu(¥l) foraied in 500 ninutes at 98®C in various solutions of

n i t r i c acid and aluiiiniuii n i t r a t e are p l o t t e d against t o t a l n i t r a t e concen-
t r a t i o n . The t h r e e s o l i d , steep curves represent the percentages of Pu(¥l)
formed in a range of n i t r i c acid concentrations with ( l ) no s a l t n i t r a t e i n
solution, (B) with 1^1|9 M n i t r a t e derived fron 11(103)3, and (C) with 3.0 M
n i t r a t e derived froa 11(10^)3, r e s p e c t i v e l y . The dashed curves of l e s s e r
slope represent the percentages of Pu(?l) formed at constant acid concentra-
t i o n s as the 11(103)3 coiicen"tration i s progressively r a i s e d .

lach point p l o t t e d i n Figure XXIX represents a value of Pu(¥l) which

i s not an equilibriuM value (which would require hundreds of hours t o achieve
In the higher acid concentrations), but i s r a t h e r one which could be achieved
i n a single day and yet allow the r e l a t i v e effects of a c i d i t y and s a l t con-
centrations t o be visualized® Figures XIX and XXXI are s i B i l a r p l o t s for
sodium n i t r a t e and uranyl n i t r a t e , respectively. Figure XXXII i s a composite
of Figures XXIX, XXX and XXXI. I t enables the effects of different s a l t s t o
be compared d i r e c t l y .
Sodium and aluniniua n i t r a t e s have p r a c t i c a l l y i d e n t i c a l i n h i b i t i n g
effects on Pu(If) oxidation. This i s t o be expected since neither are com-
plexed i n n i t r i c acid solution and both are highly ionized^ l e l t h e r s a l t i s
as effective as n i t r i c acid i n i n h i b i t i n g Pu(If) oxidation, but, as has been
pointed out previously, t h i s superior i n h i b i t i n g effect of n i t r i c acid i s
probably due t o the acid-dependence of the disproportionation reaction.

The uranyl ion, unlike sodium or alumnium ions, i s complexed by n i t r a t e

ion (22), and i t s effect on Pu(I¥) oxidation r e f l e c t s t h i s additional compli-
cation. With 1.5 M n i t r a t e , as uranyl n i t r a t e , in n i t r i c acid up t o 1.5 M,
t h e r e i s a small and gradually decreasing i n h i b i t o r y influence froa uranyl
n i t r a t e on the Pu(IV) oxidation reaction, and the effect i s s l i d l a r t o t h a t
of sodium or aluBiniuiu n i t r a t e s , though smaller. At 1,5 M n i t r i c acid, the
i n h i b i t o r y effect of 102(^03)2 i n ^his concentration i s neutralized, and
above 1^5 1 n i t r i c acid, 1,5 M n i t r a t e as 1102(103)2 accelerate the oxidation.
I f the uranyl ion i s assumed t o undergo a s e r i e s of complexing reactions
with n i t r a t e , t h i s behaviour can be eiqilained.

(6) UO2** * mf ^ ^ 1102(103)*

(7) U02(103)* + I 0 3 " ^ = = = ± 102(103)2

(8) 1102(103)2 * 103" ^ r r — ^ , TO2(M03)3~ *

The gradually decreasing i n h i b i t o r y effect of 1®5 M n i t r a t e , as uranyl
n i t r a t e , on Pu(lf) oxidation, as the acid concentration i s raised, could
be due t o a s h i f t i n g of the equilibrium of the above equations t o the r i g h t .
The amount of n i t r a t e available for Pu(If) complexing would become smaller
and smaller u n t i l , above 1^5 M 11103, ^'^^^^ would be l e s s n i t r a t e available
than in n i t r i c acid alone, and the uranyl n i t r a t e would thus appear t o
accelerate the Pu(I¥) oxidation r e a c t i o n . When the n i t r a t e concentration,
due t o uranyl n i t r a t e , i s increased t o 3 M, the r a t e of oxidation of Pu(If)
i s not further increased, but r a t h e r , i s somewhat decreased. This i s l i k e l y
due t o the increased 1102(103)2 concentration displacing the equlUbriuffl of

* These complexes have been reported in t h e l i t e r a t u r e (22) (23).

IMCMSSIFIED - 12 - CRDC-697

t h e reactions t o the l e f t , thus making more n i t r a t e available t o complex

Pu(I¥). Iven with t h i s reduction, the r a t e , in acid above 2 M, i s s t i l l
greater than i n n i t r i c acid alone.

Sufflmarizing, t h e effect on the r a t e of oxidation of Pu(I¥) t o Pu(fl)

of n i t r a t e s a l t s whose cations do not have oxidizing or reducing properties
w i l l be dependent on t h e i r contribution t o the free n i t r a t e ion concentra-
t i o n of t h e s o l u t i o n .

The oxidation of Pu(l¥) t o Pu(¥l) by the corrosion products of s t a i n -

l e s s s t e e l , C r ( ¥ l ) , C r ( I I l ) , F e ( l i r ) and l i ( I l ) , i n refluxing 10 M n i t r i c
acid, was investigated i n t h i s laboratory at an e a r U e r date (2lt). Of these
i o n s , only l i ( I l ) did not cause oxidation of Ptt(I¥) t o Pu(¥I) i n refluxing
10 M HMO3 by i t s e l f . However even l i ( I l ) exhibited a c a t a l y t i c effect i n
the presence of other corrosion product i o n s .

Radiation can have an effect on the ionic species present i n plutoniuai

s o l u t i o n s , a - p a r t l e l e s from plutonium produce free r a d i c a l s i n aqueous s o l u -
t i o n which slowly reduce P u ( ¥ l ) . The r a t e i s s t a t e d t o be 0.015 equivalents
per day i n 1 K perchloric acid, decreasing as the a c i d i t y i s increased (16),
Compared t o the r a t e of disproporbionation at 98®C, t h i s i s not s i ^ i f i c a n t ,
but at room temperature i t must be taken i n t o account 0 Gonnick and Mc¥ey
considered the a-reduction r a t e when they studied t h e disproportionation r e -
action i n perchloric and hydrochloric acids ( 5 ) . High-intensity p~ r a d i a -
t i o n i s reported t o be able t o produce active species in solution t h a t w i l l
oxidize Pu(I?) t o Pu(¥l} (25). The r a t e , i n general, would be too low t o be
significant.

STOMRY
The r a t e of oxidation of Pu(If) t o Pu(fl) i n n i t r i c acid has been
found t o increase as temperature and Pu(I¥) concentration Inci^ase, and, i n
general, t o decrease as n i t r i c acid concentration and n i t r a t e ion concentra-
t i o n i n c r e a s e , when t h e n i t r a t e i c a i s derived from a highly-ionized n i t r a t e
s a l t , such as sodium n i t r a t e or alumlniua n i t r a t e . Uranyl n i t r a t e , whose
cation i s complexed i n n i t r i c acid s o l u t i o n . May i n h i b i t or accelerate the
formation of Pu(¥l), depending upon the r e l a t i v e concentration of acid and
salt.

In solutions of low a c i d i t y , hydrolysis and polymerization of Pu(I¥)

are apt t o occur, e s p e c i a l l y at elevated temperatures. The products of
these reactions are r e s i s t a n t t o oxidation.

Quantitative data have been obtained over a wide range of tempera-

t u r e s and concentrations t o enable prediction of the oxidation s t a t e of
plutonium in process s o l u t i o n s . The rainiraura concentration of n i t r i c acid
required t o prevent Pu(¥l) fomation at rooM temperature i n a solutlcai I* x
X0"3 M i n Pu(l¥) i s 1»5 M| at 9S®C the required n i t r i c acid concentration
i s 8 M.
 IMCMSSIFIED = 13 - CEIC-^97

REFERMCIS

1. Allison, G.F. and l a r t , E.G.

'•The Separatioa of Pu by Irdon Exchange in 10 M l i t r i c Acid Solution".
P.D.B.-86.

2. l l k i n , AoMo, Russell, S.H., et a l .

T.B.P. Process developiaeBt r e p o r t s , O.E.I. s e r i e s .
3e fasha, 1. and Sheline, G.I.
"IOBIC E q u i l i b r i a and leaetion Kinetics of Pu Ions I B HGl Solutions",
l o l . l . S o f o l . If, H B , p.180.

li. Kasha, F.
«leactions between Pu Ions i n HGlOJiSolution; l a t e s , Mechanisms and
E q u i l i b r i a * . 1 . 1 . l . S . If, 1I|B, p.295o

5# Coniiick, S.S. and McVey, W.H.

"Disproportionation Equilibria and Rates i n HC10||_ and HCl Solutions
of Puj Influence of a - p a r t i e l e s » . J.Am.Chem.SoCo 75, hlk (1953).
6. labideau, S.W.
••Iquillbria and leactioB Hates i n the Disproportionation of Pu(IV)«».
J.lm.Chem.Soc. 75^ 798 (1953)o

7. Iraus, I.A.
«tteidation of Pu(If) t o Pu(iri) by l i t r i c Acid«», I . I . E . S . I ? , liiB,
p«26li,

8. Gonnick, '?=lo
•Oxidation S t a t e s , P o t e n t i a l s , Equilibria and Oxidation - Seduction
leactions of Plutoniua". Chapt. 8, I . I o l . S . If, l l | l , p . 2 2 1 .
9. Gonnick, I . E . , l a s h a , M., Mcfey, W.H. and Sheline, G.E.
"Spectrophotosetric Studies of Pu i n Aqueous Solution".
I.MoEoS. If, II4B, po559o

10. folthoff, I.M. and Sandell, l . B .

••Textbook of Quantitative Inorganic I n a l y s i s " . 3rd Ed, Macmillan
Coe (1952) p.320.
llffi lodden, C.J.
"Analytical Ghendstry of t h e Manhattan Project". 1st Ed. McGraw-
H i l l (1950), P»57, 67.
12a Laidler, E . J .
•Oteaical Kinetics»». 1st Ed. McGraw-Hill (1950), P.II4.

13. Ibid, p.12.

lit„ Gonnick, S.E., M o l . l . S . I ¥ , l l i l , p«271, Chapto 8.

15® lindfflan, J.C.
•'Ionic and Molecular Species of Pu in Solution*. Chapt, 9,
I.N.E.So If, lliA, p«339.
WCMSSIFIID -111 - GHaj-697

16. Hurst, lo
•The Msproportionation Heactions of t h e Heavy l l e n e n t s " , I B "Kinetics
and Mechanisns of Inorganic ReactiOHS in Solutions'*, leport of a
Symposiupi held at t h e Chea, Soe. London, Feb. k, 19^ks p»55.

17. Hindman, J.G.

Chapt. 9, l . l . S . S . r ? , l l | l , p,336,

18. I b i d , P.31I0

19. Ibid, p.317

20. ffurst, Ro, Hall, G.H., lerninan, P.D. and Walter, A.J.
"The Hydrolysis of Pure Aqueous Pu(I¥) Solutions and the Formation of
Colloidal Pu(I¥)». A.E.EoB. G / M - 8 5 .
21. Ockenden, D.¥., and Welch, S . l .
«*fhe PiBparation and Properties of Some Pu Compounds. Part f.
Colloidal Quadrivalent FnJ* J . Chem. Soc. (1956), 3358.

22. l a p l a n , L., Hildebrant, R . l , , and M e r , 1 .

"fhe T r i n i t r a t o u r a n y l Complex in l e t o n i c Solvents**. ASCD-=30l5 (1950).
23. B e t t s , RoHo and Mlchels, R . I .
•Ionic Association in Aqueous Solutions of Uranyl l i t r a t e and Uranyl
Sulphate*. J . Cheat. Soc. (19lt9) supplementary issue 2s286.

2I|. Crocker, I.H.

"The Oxidation of P-a(I?) in litric Acid by the Corrosion Products of
Stainless Steel*. KI--18 (1956).

25o lirey, L., ishworth, G.^ lyde, f.

"Some Effects of High Intensity pf Radiation OH a T.B.Po Primary
Separation Process". I.B.1C1.-C/R-1561O
UICLASSIFIID - 15 - CRIK-697

APPEMDIX I

Bibliography of the Spectrophotometry of Plutonium

(a) Plutonlua ( I I I )

1. Hindraan, J.G. and Imes, D.P,

"Plutonium ( I I I ) in Solutions of ¥arious Anions". M.D.DX.-1213 (19li7).
2. Hall, G.t. and Hemiaan, P.D.
*The Spectrophotometric Assay of Pu i n Aqueous Solutlcai".
1.E.H.E.-C/E-975 (1952).
(b) Plutonium (17)
3. Hindman, J.C.
leport for Month Ending Sept. 1, 19ljlt.
•CoBiplex Ions of Pu(If) and l i t r a t e " . GI-2088.

li. Ai^in, A.M., Moss, M, and Bruce, T.

•fhe Extraction of Pu with Triethylene Glycol Bichloride".
G.E.I.-13 (1952).

5. Hindman, J.G.
« l i t r a t e Complex Ions of Pu*. M.D,D.C.-1256.
(c) Plutonium Polymer

6. Hurst, R., Hall, G . l , , Hemiman, P.D. and Walter, A.J.

«The Hydrolysis of Pure Aqueous Pu(I¥) Solutions and t h e Formation
of Colloidal Pu(If)'«. A . l . R . l . C / M - 8 5 (1950).

7. fraus, f . i .
"Studies on Polymeric Pu(B'') - Depolymerizatlon of Polymeric Pu(If)
Solutions i n IWOj". G.I,-3399 (19li5}.
8. Ockenden, D„¥. and Welch, G.l.
•The Preparation and Properties of Soine Pu Compounds. Part ? .
Colloidal Quadrivalent Pu». J . Chem. Soc. (1956), 3358.

(d) Plutonium (?)

9. Gevantiaan, L.H. and Kraus, f . l .

••Chemistry of Pu(¥), S t a b i l i t y , Spectrophotomet^". M.D.B.C.-1251
(19ii5) o
UiCMSSIFIED - 16 - GEDC-697

(e) Plutonium ( ? l )

10. Hindman, J.G. GM-2088.

11. l l k i n , A.M., Moss, M. and Bruce, T. loc. c i t .

12. Healy, T.¥. and Gardner, A.M.

"Solirent Extraction of Pm(¥I) l i t r a t e from HMO3 and IHLIOJ". l.E.R.E.
- C / R - 8 0 0 (1952).

13® Foore, G.E. and f r a u s , K^A.

^Spectrophotometry of Pti(fl) in Perchlorat© Solutions•». lDIC-1105

(t) Comprehensive Papers

111. Gonnick, R.S., fasha, M., Mc¥ey, W.H., and Sheline, G.E.
"•SpectrophotoBietric Studies of Pu in Aqueous Soltitlon".
M.D.D.C.-892 (19li6)«
l5s Hall, G.R., Hemlman, P.D., and Walter 1.J.
wSpectrophotoiBetric Studies ©f Pu i n HIO3 Solution, Part I » .
A.B.I.I.-C/I-712 (1951).
 OTGLASSIFIED - 17 » CRK-697

APFEWDIX II

GalCTilation of r a t e coefficient

k ^ J : . I g ^ -•£„— ( l i t e r s 2 TOles=2 m±n.^^

T ^ 98»C

I n i t i a l Pn(I¥) P « ( ? I ) (x)
Concentration mOa t Concentration k Average k
(a) (l.xlO=3) (M)^ (minutes) (SxlO-Ji) (l2ii-2 « i n - l ) ( l 2 a-2 n i n - 1 )

1.03 0,55 20 5o67 9.31 X lOJ*

50 6.85 7J47 X lOf
100 7.89 8,III X 104
200 8086 ia8 X 10^ 9 ©18 X IcA
300 9o38 1^96 X loft
liOO 9.69 3o35 X 105*

1.03 0.95 20 kM 14.92 X idi

50 5«72 3o95 X 10^
100 6,70 3.39 X lOJ*
200 7»8i| 3.90 X 10^
300 8.35 li»30 X lOtt
loo 8.55 3o97 X 10^ h^QJ X 10^

I0O3 lal5 20 3.20 2o6l X 10^

50 lio95 2,55 X lOf
100 6.19 2.ii9 X 1#
200 7.32 2„58 X lojt
300 7 083 2o58 X im 1
iiOo 8.II1 2S6 X lolt 2.56 X 1 #

1.03 l„3l4 20 2.06 lo33 X IcA

50 3o92 1„52 X im
100 5«56 lo76 X 10^^
200 6.60 lo59 X loh
300 7«22 I06O X idi
liOO 7,57 la56 X 10^ 1.56 X IC^

± Onn-tted from Average.

 UICLASSIFIID - 18 - CHDC-697

^ n l t i a l PiiCr?) i Pii(fl) (x)

Concentration t Concentration Ai?erage k
(a) (M.xlO-3) (M)^ (ainmtes) • (l&10"«) :CI2M-^ mn-1) •(l2 ffi»2 jri.n-1)

1.03 1.51t 20 IM 8.29 X 103

50 2.99 9.29 X 103
100 kokJ 9.80 X 103
200 5.51 8.5? X 103
300 6.19 8o30 X 103
too 6.65 8.21 X 103 8.71 X 103

1.03 1.81 20 0.821 1.28 X 103

50 1^70 li©10 X 10|
100 2©68 3.90 X 103
200 3.92 3e79 X 103
300 lio8l* 1.02 X 103
liOO 5.57 loll X 103 |»08 X 103

1.03 2.0lt 20 0,536 2.66 X 103

50 I0I3 2.17 X 103
100 1«82 2«2| X 103
200 3.02 2<.36 X 103
300 3.86 2al5 X 103
llOO lioli7 2.50 X 103 2o|5 X 103

1.03 2.13 20 0.309 1©|8 X 103

50 0.619 1.25 X 103
100 0.92? 9.80 X 102
200 1.55 9olO X 102
300 lo96 8.26 X 102
itOO 2.30 7.76 X 102 1«0| X 103
1.03 3.02 20 0.155 7©27 X 102*
50 0.309 5.93 X 102
100 0,360 3 e | 8 X 102
200 0.515 2.55 X io2
300 0,721 2 o | 6 X 102
ItOO 0.927 2©2| X 102 3.33 X 102

1 la03 0<,ii5 20 5.82 1^01 X 10?

50 6.65 6o57 X lOf
100 7©31 5.13 X lOf
200 8^08 1.81 X lOl
300 S.35 1.23 X lOf
loo 8.12 3.12 X lOtt 5.72 X 10*t
U--_ _^
4 Omitted from Average.
 tWGMSSIFIED . 19 „ CRK-697

1 Initial P U ( 1 ¥ ) P«(fl) (x)

Concentration mo3 t Concentration n ^n Average k
1 (a) (K.xlO-3) (M)^ (minutes) (IxlO-it) (l2 11-2 Bdn-l) (l2 a-2 Bdn-lj

1.03 0.35 20 5©26 7.19 X 10^

50 6.21 5.13 X im
100 7.01 1.15 X lOJi
200 7.63 3.27 X im
300 8.01 3©11 X lOl
loo 8.30 3.01 X lOl 1.36 X IC*

1.03 0^21 20 3«I0 2©90 X 10^

50 3.97 1«55 X loli
100 1.18 1^01 X loli
200 5«o5 6.72 X 103
300 5©31 5©13 X 103
loo 5©|6 1.16 X 103 1©18 X 10^

l©13 2.15 20 1.13 3 ©13 X 102

50 9ol0 3.79 X 102
100 1|©1 3,83 X 102
200 18.8 3©17 X 102
300 21©9 3©61 X 102
100 2I0I 3.15 X 102 3©60 X 10^

1.13 3^02 20 1©65 1.25 X 102

50 3 ©92 1©29 X 102
100 7.03 lo33 X 102
200 11©3 1©31 X 102
300 13 ©7 1.21 X 102
loo 15©5 loll X 102 la3 X 102

1.13 5.01 100 0.113 5.95 X 10%

200 0©62 1.50 X loO
300 0.95 |©66 X 10°
loo 1.21 |©60 X lOO |©6 X loO

6.81 2 ©II 20 16.3 3.93 X 102

50 23 ©2 2©80 X 102
100 26©2 1©77 X 102
200 27©9 loOl X 102
300 29 o9 0©78 X 102
loo 32©0 0.69 X 102 1©83 X 102

6«81 3.02 20 6.13 1©12 X 102

50 13 ol I0I5 X 102
100 18.1 1.78 X 102
200 21.8 6.27 X lOl
300 2|©5 5©17 X lOl
loo 26.6 |©56 X lol 9.1 X lol

* f i t t e d from Average,
 TOICMSSIFIID - 20 - GHDG-697

I n i t i a l PtiCl¥) Pii(¥l) Cx)

Concentration HiOj t Concentration Average k
(a) (M.xlO-3) m (airmtes) (MxlO-^)
r^ ^o -^
( 1 ^ m-2 ^ i ^ - 1 ) (1*^ n"^ Kin"-*-)
6,81 5oOO 50 1,63 loO? X 10^
100 2«72 2o3l| X lOl
200 it, 22 7o35 X lOO
300 5.93 7.17 X loO
^00 7M9 7o08 X 10° 9.3 X 10°
6.81 Oo95 5 3li«5 6„70 X 103
15 55»0 2o32 X 103
30 35o5 l o 2 1 X 103
90 37oO lie55 X io2
210 39.0 2o30 X 10^
ii75 kk^$ IM X 1G2 1.85 X 103
6«8l 1.15 5 28,5 lie22 X 103
15 3ii.O 2a5 X io3
30 36o0 1«26 X 103
90 37.5 ii.73 X 10^
210 39.0 2o30 X 103
li75 ii3.0 IM X 103 i J i l X 103
6.81 i.5li 5 23.0 2,76 X 103
15 30,5 la6li X 103
30 33 »0 9a9li X 10^
9P 3lioO 3a58 X 102
SIO 35.5 1«73 X 102
it75 39,0 1.02 X 102 1.00 X l o 3

9.73 0.95 5 Ii2.0 2,21 X 103

15 Ii7o0 9o65 X 102
30 52.5 6.55 X 10?
90 52.5 2ol8 X 102
210 59.S l . y X 102
!i75 7ii.O 1«83 X 102 7.29 X 102

9o73 i.5t 5 33«5 l a 3 3 X 103

15 36.7 5«57 X io2
30 38,5 3«06 X 102
90 l*2«0 1.23 z 102
210 1*9 »0 7o69 X 10^
ii75 55oO iio77 X 10^ l|.07 X 10^

9.73 2.lit 20 26»8 2o39 X 102

50 31.6 lo26 X 102
100 33.6 7.0k X l O l
200 36.3 hoOB X 1 0 ^
300 38,9 3.13 X 10^
!
l|00 lil.5 2,69 X I Q I 8 , 9 1 X 10^
f
: • '«'• 1
UlCMSSIPIlB - 21 - ClIX-697

I n i t i a l Pti(IV) PTI(?I) (X)

Concentration t Concentration Average k
( a ) CM.xlO-3) (aliiiites) (ttclO-tt) ( l 2 m"2 n i n " l ) ( 1 ^ Bi°2 m n J-)

9,73 3.0? 20 18.5 1.39 X 102

50 2k.k 8o25 X lOl
100 26.8 k>7B X lOl
200 28,9 2o70 X 10-*-
300 ! 31.1 2oOlt X 10^
llOO 33.It lo7t X 10^ 5.6 X l O l

9o73 5.00 50 3.60 8,27 X lOO

100 6o30 7060 X loO
200 9o73 6»19 X IQO
300 llo7 5olli X IQO
llOO 13 a li.li3 X 10" 5.3 X 10°
T « llO^C
1.03 0.55 20 8,50 7.li9 X lof
50 8.96 5.li8 X ml
100 9.17 1.20 X 105
200 9o32 2,58 X 105
300 9.35 1.83 X 105 r^
koo 9«37 i.to X io5 3«,8ii X lOi^

1.03 l.7li 20 1.85 1.15 X loj*

50 3.35 I0I3 X lOf
100 k.S9 1«06 X lOf
200 5.98 1.11 X lOf
300 6.91 1.29 X lOf
llOO 7.60 1.60 X 10«* i a 2 X 10^

1.03 3^02 20 0.155 7.27 X 10^

50 0<,36l 6.98 X 102
100 0»619 6.23 X 102
200 1.03 5o53 X 102
300 l«3li 5.05 X 102
llOO lo65 k.93 X 102 60O X 10^

1.03 14.85 50 O0IO3 lo92 X loj

100 Oo258 2«li6 X lOl
200 0«1|12 2»01 X lOl
300 0„536 1«77 X 10^
itOO O0650 1.6li X lOl 2 . 0 X 10^

* Omitted from Averageo

 IJIGLASSIFIED - 22 - CRDC-697

1 I n i t i a l Pti(lf) Pu(¥l) (x)

Concentration t Concentration k Average k
( a ) (M®xl0-3) ;(M)^ (mn-tttes) (Mxl0"tt) ( l 2 11--2 jnin-1) ( l 2 K-2 Bdn-l)

T = Room Temperature
l4»13 0®7 20
50
100 0,21 2o95 X loj
200 O.lil 2^97 X 10°
300 0.62 2a98 X 10^ A
iiOO O083 3o02 X 10° 3 . 0 X 10°
30,1^20 8.26 0o55 X IO"A

I1.0I3 laOl 3,180 0,27 1„21 X 1 0 " !

8,725 0.60 1.00 X 10"J-
28,980 1.80 l e 6 l X 10"1 lo27 X 10"]
I03~(l) T = 98°C
1(11(103)3)
'
1.^9 1«03 0«21 20 6.60 1.59 X 10^
50 6.95 7o98 X lOtt
100 7«21 lto77 X im
200 7.52 3«00 X 1»
300 7.73 2e37 X lOf
iiOO 7o83 1.93 X 10** $.99 X 10^

l«li9 1.03 0o35 20 6o91 1.91* X 105

50 7.68 1.36 X 105
100 7.97 8o75 X lOf
200 8.35 6o35 X lOf
300 8.76 6.88 X lOf
IiOO 9.12 8,87 X 10^ 1.06 X 10^

lJi9 1.03 0.55 20 5.88 1^05 X io5

50 7ai 8089 X lOf
100 7.69 6.88 X lOf
200 8, Hi 5.13 X lOf
300 8.1i5 li,72 X lOf
I4OO 8o76 5.16 X im 6,88 X 10^

1..II9 1.03 0o95 20 2o92 2.2k X loj*

50 kohl lo96 X 10^
100 5.67 IM X lOf
200 6.70 1.69 X lOf
300 7»31 lo71 X lOf 1
itOO 7o9ii 2ol3 X 10^ 1.93 X 10^

i Omitted from Average,

 UICMSSIFIID - 23 -= CRDC-697

I n i t i a l PTI(I?) PTl(fl) ( x )
Concentration HIO3 t Concentration k Average k
(a) (M.xlO-3) (minmtes) (1x10"^) ( 1 ^ m°°2 rain"!) ( l 2 ^ - 2 n i n - 1 )

lo^'Cif)
1(11(103)3)
L__ —.,-_
I®li91 1.03 lo5li 20 O062 3.11 X 103
^ 50 1«29 2„89 X 103
100 2<,11 2a7li X 103
200 3.22 2.63 X 103
300 It, 02 2.66 X 103
liOO li«63 2®71 X 103 2«79 X 103

loli9 I0O3 2.0li 20 oa6 7o27 X 102

50 Oo33 6.35 X 102
100 0®62 6®23 X 102
200 ia6 6.37 X 102
300 60O6 X 102 ^
1|00
1.55 5®98 X 102 ; 6®38 X 10^
1®91

l«l»9 1.03 2M 20 0.052 2o37 X 102 \

50 0.10 1.92 X 102
100 Oo2li 2.25 X 102 i
200 O.I16 2®27 X 10^
300 0,69 2.3I4 X 10^ 1
I4OO 0®91 2o39 X 102 2®26 X 102

l.k9 1.03 3M 20 0»012 5®68 X lOl

50 O0O26 I1.75 X lol
100 0«052 l4®75 X lol
200 0.10 I1.79 X IQJ-
300 0.16 ii J i t X 10^
I4OO 0o21 lio87 X 10^ 1 I4.95 X 10^
90
FROM
M . 0 . 0 . 0 . 1213
80

70

SO

50
3
G)

40 H

30

20 t 11 I
10

f1 ^?s^tt^
: --
\ } JlZtt^lU
{ J \X^i J \^ i . jtk
£-
400 800 600 700 800 900 1000

WAVELENGTH {mil) o
o
— 0 . 2 0 M.HNO3 o
4^) SPECTRA .- 1.00 M. HNO3
I
m
w
-- 3.00 m. HNO3 -J
.. 5 . 0 0 M. HNOg
 (f/uJ) Hi9N313AVM
0001 006 008 00/ 009 OOS 00 fr
0>
<£>
i
O
O
O 01
OZ
VI v
M
%NH 'N 86*1
^ONH -N £0'l
8 I - ' I ' 3 ' 0 WOMJ
08
VMlD3dS (3r|nd
06
 (tfm) Hi9N313AWM
0001 006 008 001 009 OOS OOfr
OS
to
o
Q
cr
o
SQNH ' N 2-01
^ONH 'N B'l
^ONH "N 0 >
81 - - i - a - D WOMJ
06
 COLLOIDAL PyW SPECTRA

4. t N l i . lOe. ( i f M I 3898

a
•0
H
€

M€0 COLLOIOAL P i ^ )
« t i i mumoAL pMI
m O.IM.HiOa)

o
10 o
o
I

m
1
TOO 800 900 1000
WAVILIieiH ImM)
20

FROM M.D.D.C. - 1251

IS

l\n
10
H

f\ \ .
V ^
V

Ay
HN [\,y\ •V. ^
\
^

100 450 SOO 650 SOO 650 700 750 800 850 900 950 1000
WAVELENGTH (m/i

P u ^ ) (IN eg. 0 . 0 3 M. HCI04^ O

JO
O
SPECTRUM O
I
m
 {fm) Hi9N313AV«
0001 006 008 mi 009 OOS oo»
T
SQNH N £VP - — -
CQNH N frfr'l — —
I
01
81- l i D woaj
VMlOadS (^^ 08
06
90

>W SPECTRA
FROM C.E.I.-18
80

TO

60

50 5.9 N. HNO3
o
€ II N HNO3

5 N HNO3 n
40

30

20

o
aj
10 o
o
m

400 500 600 1000

WAVELENGTH
 CROC-697
0.50
COWCEMTRflTlOW

FIG. ^ 0 1

CALIBRATION CURVES : BECKMAN D.U-2137

0.45
OPTICAL DENSITY Vs. Pu (K) CONCENTRATION
WAVELENGTH = 831 mjd (PEAK)
SLIT WIDTH = 0.015 m w
0.40 TEMPERATURE - 2 3 i 3°C
NITRIC ACID SOLUTION

0.35

0.30

0.2!

0.20 —
>-
t
m
z
u
Q
0.15
O
h-
a.
O

0.10

0.05

3 4 5 ^ t J 10 12 13 14
CONCENTRATION OF Pi?X 10" ^ M
 CROC-697
0.50

3 4 5 6 7 8 9 10 II
CONCENTRATION OF NITRATE RADICAL (M)
 CROC - 697

FIG. T
OXIDATIONS AT 9 8 ° ! I^C

THERMOMETER SET IN
S ml VOLUMETRIC FLASK
CONTAINING HNO3

RUBBER STOPPER WITH

SEVEN HOLES

STOPPERED 5 ml.
VOLUMETRIC FLASK

STEAM INLET

6 0 0 m l . BEAKER

EFFLUENT-*—£

, WATER OUT

FiG.yr
OXIDATIONS AT REFLUX

CONDENSER

COLD WATER IM

2S ml. EHLENMEVER FLASK

HOT-SPOT" HEATER
^ '
 OXIDATION OF p J ^ ^ TO pi™^ IN HNO, SOLUTION
AT ROOM TEMPERATURE
30
LEGEND
cmcmnMion m COMCEMTBATIW
OF m m\
o.oii t.tt X 10"' D
0.22 S.5« X io-» A
0.30 a.m X 10-3 X
Q.m S.S« X 10-3 y
o.so S.S6 X lO-S •
I.OI 4.13 X lO-S « •
I.SO 4.13 I 10-5 O

O
O
O
I
0>
300 400 600
10 60 110 160 210
TIME IM MINUTES TIME IN HOURS
 OXIDATION OF p J ^ ^ TO Pu^^^ IN HNO3 SOLUTION
AT REFLUX TEMPERATURE
TOTAL Pu CONCENTRATION - 1.03 X lO'^M

100
HNO3 (M)

0.55

o
o
o
m
w
•4

300 4 00 500
TIME IN MINUTES
 OXIDATION OF Pu^™^ TO Pu^^^ IN NITRIC ACID SOLUTION
AT 98 i I <*C

TOTAL Pu CONCENTRATION = •03 X 1 0 " ' M

100 NITRIC ACID

NORRdALITY
0-55

o
3)
O
o
I

500
TIME MINUTES
 OXIDATION OF Pu^™^^ TO P u ^ ^ N NITRIC ACID AT 981IX
SHOWING RETARDING EFFECT OF COLLOIDAL Pu

TOTAL Pu CONCENTRATION = 1-03 X 1 0 ' ^ M.

100
NITRIC ACID

o
o
o
e

«®

200 250 300 350 400 450 500

TME IN MINUTES
,miMUflM_^E_gMyLTQ Pu^^ IN NITRIC ACID SOLUTION

TOTAL ^i emmmmTmn * 4-i3 * IO^^M.

NITRIC ACIO
MJMAyJX 2

o
»
o
o
I
m
m
-4

200 250 300 380 400 450 500

TIME IN MINUTES
 OXIDATION OF P u ^ ^ TO Pu^™^ IN HNO3 SOLUTION
AT 9 8 ° C FOR LONGER PERIODS

TOTAL Py CONCENTRATION = 4 - I 3 X I 0 ' ' M

•n

NITRIC ACID
5-00
NORMALITY

u 20|_
o

10 20
TIME IN HOURS
 OXIDATION OF Pu^°^4o P y ^ ^ N NITRIC ACID SOLUTION
AT 98 ^C

TOTAL Py CONCENTRATION - 6 • 81 x I 0 " ' M .

too

90
2

^•0
NITRIC ACID
FORMALITY
p 70

200 250 800 400 450 500

TIME IN MIMUTES
 OXIDATION OF P u ^ ^ TO P y ^ ^ IN NITRIC ACID SOLUTION
AT 98*^0

TOTAL Pu CONCENTRATION = 9-73x10-3^.

tool

901

NITRIC ACID

o
O
O

0>
«0
-J
2S0 300 500
TIME IM MIN0TE8
 OXIDATION OF Pu^™^ TO Pu™^ IN Al. (NO3} - HNO3 SOLUTION AT 9 8 " C

TOTAL Pu CONCENTRATION - i-03 x 10"'M.

100-

90

COWCEWTRATION m)
SO a
HNO SALT TOTAL
NITRATE NITRATE

250
TIME IN MINUTES
 OF Pucm)*
(II)
OXIDATION TO Pu ' IN AI.CNOH)^- H N O ^ SOLUTION AT 98° C

CONSTANT SALT CONCENTRATION

TOTAL Pu CONCENTRATION - 1-03 x 1 0 " ^ M.

100 i - CONCENTRATIONS CM).

HNOg SALT TOTAL
90 NITRATE NITRATE
1-84
-n
80 O

70

60

50

40 I t

30
o
20 o
o
I

10 -J

0
25© 300
9
500
TIME IN MINUTES
 t # f

OXIDATION OF P u ^ ' TO Py"^' IN At (NO^)^ ~ HNO^

SOLUTION AT 98 ^C. FOR LONGER PERIODS
WITH INCREASED SALT CONCENTRATION

10 20 30 40 50 60 70 80 90 100
TIME IN HOURS
 OXIDATION OF Pu-^^ TO P u ^ ^ N NoN, - HNO^ SOLUTIONS
AT 9 8 ° C.

TOTAL Pu CONCENTRATION = I- 0 3 X 1 0 ' ^ M.

100

90 CONCENTRATIONS (M.)
HNO3 SALT TOTAL m
NITRATE NITRATE

200 250 300 350 400 450 500

TIME IN MINUTES
 OXIDATION OF Py ' TO Pu ^ IN U02CN0^ Ig - HNO^ SOLUTION

TOTAL Pu CONCENTRATION = 1-03 K I 0 " 3 M .

CONCENTRATIflNS_iJiJ.
100
HN©3 SALT TOTAL
NITRATE NITRATE

250 300
TIME IN »«INUTES
 CROC - 6 9 7
10-6
9
FIG ^ m
8

7 INITIAL REACTION RATE 8 ORDER OF

REACTION BY DIFFERENTtAL METHOD
INITIAL Pi/*'COMCENTRATION • I . 0 3 X I 0 - ' M

A. Mm
.6X10-^ MOLES LITRE
SEC- I

•OBOEW OF WEACTIOM;
3 S.08

2.S
I
O

u
o
s ,-7

i
- 10"

T
U
6
IE

2.S

1.5 -

10-
10-4 2 2.S 3 S 10-*
Py^™* CONCEMTBATIOM IMl
 FI6. ^ m CROC-697

EFFECT OF TEMPERATURE AND NITRIC ACID

CONCENTRATION ON RATE COEFFICIENT

PU eOWCEMTWAXIOM SYMBOL
1.03 X 10"' M A
.03 X IO-'« o
4.13 X I0"3M

OJ
1.0 2.0 3.0 4.0 5.0 6.0
HNO3 CM)
 FIG. mm CROC - 6 9 7
10*

EFFECT OF Pu«3I) CONCENTRATION ON

RATE COEFFICIENT

TEMPERATURE PU CONCENTRATION SYMBOL

sa®c 1.03 X IO"§M O

91 4.13 X l O ' ^ M a
10'
19 6 . 8 1 X 10-3 M A
«t
9 . 7 3 X 10-3 M A

10*

u
h-
3

M
I 10^
UJ
_l
o
s

10

N
3

1.0

0.1
1.0 2.0 3.0 4.0 5.0 6.0

HNOg (M)
 FIG. ,XXVT!T CROC-697

10'

EFFECT OF FOREIGN SALT ON

RATE COEFFICIENT

10*
NOg- C0NC.CM) TEMPERATURE PU CONC. SYMBOL
Al ( N O g j g (®C1 (M)

NIL S8 1.03 X 1 0 ' ^ O

1.49 98 1.03 X I 0 - ' A
10

-r '0'
u
h-
3

UJ

O
s

- 10

1.0

0.1
1.0 2.0
1
3.0 4.0 5.0 6.0
HNO3 (M)
 PERCENTAGE OF Pi/™) FORMED IN 500 MINUTES IN NITRIC ACID
AT 9 8 0 i | ® C WITH 1.49 M AND 3.0 M NITRATE ADDED AS A! (NOjla

MOLARITY
100 I - HNO3 NOTE: HEAVY BLACK CURVES CONNECT POINTS OF
EQUAL SALT CONCENTRATION.
1.49 M NO
ADDED AS Al (^03)3 BROKEN CURVES CONNECT POINTS OF EQUAL
90 HNO3 CONCENTRATION.
SMALL NUMBERS ARE HNO3 CONCENTRATIONS
80 3
TOTAL Pu CONCENTRATION = 1.03 X I O " ' M X
70
3.0 M NO3-
AODED AS AKNOj),
60
3
a.
^ 50

40

30

©3

20 O
«
o
10
o
1

TOTAL NITRATE CONCENTRATION He, HNO3+• SALT) IN MOLES PER LITRE

 PERCENTAGE OF P i ^ ) FORMED IN 500 MINUTES IN NITRIC ACID
AT 98<'± l®C WITH 1.5 M NITRATE ADDED AS SODIUM NITRATE

TOTAL Po CONCENTRATIONS I.O3XI0"'M

ITRIC NITRATE
0
J so

_ONADULTERATE0
NITRIC ACI0
u NOTE: HEAVY BLACK CURVES SONNECT POINTS
o 40
u OF EQUAL SALT CONCENTRATION,
a. BROKEN CURVES CONNECT POINTS OF
EQUAL HNO3 CONCENTRATION,
SMALL NUMBERS ARE HNOG CONCENTRATIONS

O
O
O
1
TO
«0
3 4
TOTAL NITRATE CONCENTRATION «M)
 PERCENTAGE OF p J ^ ^ FORMED IN 500 MINUTES IN NITRIC ACID

AT 98° ± |0C WITH 1.5 M AND 3.0 M NITRATE ADDED AS UOg (NOalg

MOLARITY
OF TOTAL Pu CONCENTRATION 1.03 X 10"^ M
100 HNO3

CSSX" "~- —
90-

80
NITRIC ACID PLUS I.SM NITRATE

70

3
^ 60

o UNADULTERATED
»- 50 NITRIC ACID PLUS 3.0 M NITRATE
NITRIC ACID/A4-) 2,04

5 40
NOTE: HEAVY BLACK CURVES CONNECT POINTS
u OF EQUAL SALT CONCENTRATION
a.
«30 BROKEN CURVES CONNECT POINTS OF
EQUAL HNO3 CONCENTRATION.
SMALL NUMBERS ABE HNO3 CONCENTRATIONS
t 20

TOTAL CONCENTRATION IM)

 ( A COMPOSITE OF FIGS. ^ ^ , 2 2 X AND 3 X a j

PERCENTAGE OF P u ^ FORMED IN 500 MINUTES IN NITRIC ACID

AT 9 8 ° ± l°C WITH VARIOUS AMOUNTS OF Al (N03)3, Na NO3.
OR U02(N03)2 ADDED.

CONCENTRATION OF Pu = 1.03 X 1 0 " ' M

1.5 M. NITRATE ADDED AS No NO3

1.49 M. NITRATE ADDED AS AlCN03)3

I . S M . NITRATE ADDED AS UO2 CNGslg

X
X
TRATE AS A I ( N 0 3 ) 3 X

NITRATE ADDED AS UOgCNOsSs

NOTE: SOLID LINES CONNECT POINTS OF

EQUAL NITRATE (AS SALT) CONCENTRATION.
BROKEN LINES CONNECT POINTS OF EOUAL
NITRIC ACID CONCENTRATION. SMALL NUMBERS
ARE HNOg CONCENTRATION

@ HNO3 ONLY, NO SALT O

O HNO3 + A l (N03)3
O
/\ HNO5+ NONOg
a HNOg + UOaCNOjlg
o
1

->l
TOTAL NITRATE CONCENTRATION IN MOLES PER LITRE