^

AEC RESEARCH AND

HW-68003 REV
DEVELOPMENT REPORT

>7 MASTER
3 i ^
(

n
SELECTIVE REDUCTION OF PLUTONIUM(VI)
TO PLUTONIUM(IV) IN A PLUTONIUM(IV-VI)
NITRIC ACID SOLUTION

M . H. CAMPBELL

FEBRUARY, 1961

CHEMICAL PROCESSING

HANFORD ATOMIC PRODUCTS OPERATION

RICHLAND, WASHINGTON

GENERAL ELECTRIC
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 HW-68003 REV
U C - 1 0 , C h e m i c a l Separations P r o c e s s e s
F o r Plutonium and U r a n i u m
(TID-4500, 16th E d . )

SELECTIVE REDUCTION O F PLUTONIUM(VI)

TO PLUTONIUM(IV) IN A PLUTQNIUM(IV-VI)
NITRIC ACID SOLUTION

By
M. H, C a m p b e l l

Analytical Control
P u r e x Operation
Chem.ical P r o c e s s i n g Departm,ent

F e b r u a r y , 1961

HANFORD ATOMIC PRODUCTS OPERATION

RICHLAND, WASHINGTON

Work p e r f o r m e d u n d e r C o n t r a c t No. AT(45-^1)-1350 between the

Atom.ic E n e r g y Com.mission and G e n e r a l E l e c t r i c Company

P r i n t e d b y / f o r the U. S. Atomic E n e r g y C o m m i s s i o n

P r i n t e d in USA. P r i c e 50 c e n t s . Available f r o m the

Office of T e c h n i c a l S e r v i c e s
Departm.ent of Com.m.erce
Washington 25, D. C.
 -2- HW-68003 REV

SELECTIVE REDUCTION O F PLUTONIUMCyi)

T O PLUTONIUMCIVI IN A PLUTONIUM(IV-VI)
NITRIC ACID SOLUTION

INTRODUCTION
Plutonium s e p a r a t i o n by solvent e x t r a c t i o n o r ion exchange i s gen-
e r a l l y dependent upon a specific v a l e n c e s t a t e . F o r e x a m p l e , plutonium
naust be p r e s e n t in the f o u r - v a l e n c e s t a t e for e x t r a c t i o n by t h e n o y l t r i -
fluoracetone or n-tributylphosphate, (1) o r for absorption on an anion
(2)
exchange r e s i n .
When a plutonium(IV) n i t r a t e solution of 2 M n i t r i c acid o r l e s s
is concentrated by heating, a plutoniumdV-VI) s y s t e m is f o r m e d . T h e
concentration of each valence s t a t e i s a function of t i m e , t e m p e r a t u r e and
initial n i t r i c acid concentration.
T h i s r e p o r t d e s c r i b e s the development of a technique for adjusting
the valence of t h e plutonium in t h i s plutoniuni(IV-VI) s y s t e m to the f o u r -
valence s t a t e n e c e s s a r y for efficient solvent e x t r a c t i o n o r anion exchange.
BACKGROUND
In m o s t m i n e r a l a c i d s , plutonium(IV) will d i s p r o p o r t i o n a t e a s
follows:.(3,4)

3Pu"^^—-2Pu-^3 + Pu+^
In addition, plutonium will form c o m p l e x e s with a n u m b e r of a n i o n s , ^
N i t r i c acid solutions of 1 M and below exhibit t h i s d i s p r o p o r t i o n a t i o n and
(c)
a v e r y imdesirable formation of p o l y m e r . Between 1 :and 5 M n i t r i c ^
+3
acid, a plutonium n i t r a t e complex with the formula Pu(NOo) is pos—
(7)
ulated. The brown color of the plutonium solution can be a t t r i b u t e d t o <
this complex. At 7. 7 M n i t r i c acid and above, the brilliant g r e e n color is
attributed to formation of the Pu(NOg) complex. ^ '
If a plutonium(IV) solution 2 M o r l e s s in n i t r i c acid i s heated, some
of the plutonium(IV) i s oxidized t o plutonium(VI). T h e oxidation is rapid
at low n i t r i c acid concentrations and i s inhibited at higher c o n c e n t r a t i o n s .
At 7 M v i r t u a l l y no oxidation o c c u r s . T h e r a t e of oxidation i n c r e a s e s a s
the t e m p e r a t u r e i n c r e a s e s . The longer the t e m p e r a t u r e i s naaintained, the
g r e a t e r t h e oxidation. T h u s , when a l o w - a c i d plutonium(IV) n i t r a t e solution
 -3- HW-68003 REV

is concentrated by heatings a plutonium(IV-VI) system results^ with the

concentration of each valence state a function of time, temperature and
initial nitric acid molarity.
According to Seaborg and Katz, the ferrous ion will reduce
plutonium(VI) and (IV) to valence state three by the following reactions:

PuOg^^ + Fe+^ -PuOg^ + Fe"^^

PuOg"^ + Fe+^ + mi -Pu"^^ + 2H2O + Fe+3

Pu+^+Fe+2---Pu+3+Fe+3 .
The purpose of this investigation could thus be accomplished by reduciiii^
both valence states to three with the ferrous ion, and subsequently oxidizing
to the four-valence state with nitrite. This reaction was the basis of tiiis
investigation. F e r r o u s sulfamate was selected as the source of the reducin:;
ion because of its demonstrated stability in nitric acid solutions.
SUMMARY
The valence of the plutonium in a plutonium(IV-VI) nitric acid solu-
tion is adjusted to four by reduction with ferrous sulfamate. It was not
necessary to reduce the valence to three and then oxidize to four with nitrate.
Dilution, time elapsed, and nitrite formed due to radiation degradation of
nitric acid do not affect the reaction. Nitric acid concentration must be
between 2 and 6 M to avoid plutonium disproportionation on the one hand
or sulfamate precipitation on the other. Temperature during the reaction
has no im.portance between 23 C and 50 C. Ferrous sulfamate concentration
is kept below 1 M to prevent crystal formation after the reaction, Plutonium,
concentration may be as higli as 250 g/1.
APPARATUS AND REAGENTS
A Beckman DK-2 recording spectrophotometer, calibrated for
plutonium(III), (IV) and (VI), ^(9) was used for all measurements.
 -4- HW-68003 REV

A 4 M n i t r i c acid solution containing 250 g of plutonium p e r l i t e r was

p r e p a r e d and found to contain 200. 2 g/1 of plutonium(IV) and 40. 8 g/1 of
plutonium(VI). Dilutions w e r e m a d e using 4 M n i t r i c acid.
F e r r o u s sulfam.ate was obtained from G;erieral Chem.ical Company in
50 p e r cent solution.

E X P E R I M E N T A L WORK AND RESULTS

The possibility of changing the plutonium valence distribution by
dilution o r by n i t r i t e form.ed by r a d i a t i o n degradation of n i t r i c acid was
studied. The v a l e n c e change obtained in a plutonium(IV-VI) s y s t e m by
r e a c t i o n with f e r r o u s sulfamate was investigated. The v a r i a b l e s considered
w e r e : the effects on the r e a c t i o n of plutonium concentration, n i t r i c acid
c o n c e n t r a t i o n , and tem.perature, and t h e stability of the valence adjustment
with r e s p e c t to t i m e . T¥/o other s o u r c e s of f e r r o u s ion w e r e investigated.
All r e a c t i o n s w e r e perfornaed at 23 ± 2 C u n l e s s otherwise indicated.

Effect of Dilution
The stock solution was diluted witn 4 M n i t r i c acid and analyzed for
valence states. The r e s u l t s a r e m T a b l e I.

TABLE I

E F F E C T O F DILUTION
ON PLUTONIUM VALENCE STATE DISTRIBUTION

T o t a l Pu (fi/1) Pu(IV) ( g / D * Pu(VI) ( . J D *

250 200.3 4:,r.

25 200.0 50,8
12,5 200.2 4J. . 5
* T h e plutonium. ion c o n c e n t r a t i o n s w e r e n o r m a l i z e d to tne
stock solution c o n c e n t r a t i o n s for e a s e of com.parison.

E a c h dilution was analyzed at e i g h t - n o u r i n t e r v a l s o v e r a period of 25 h o u r s .

No change in v a l e n c e s t a t e d i s t r i b u t i o n was o b s e r v e d .
 -5- HW-68003 REV

Effect of N i t r i t e F o r m e d by Radiation Degradation

Sodium n i t r i t e was added to a o n e - t o - t e n dilution of the stock solu-

tion and the r e s u l t i n g solution analyzed for valence s t a t e s . The r e s u l t s a r e
shown in T a b l e II.

TABLE II
E F F E C T O F NO^" CONCENTRATION ON PLUTONIUM VALENCE
STATE DISTRIBUTION IN A 4 M HNOg SOLUTION
N i t r i t e Concentration (M) Pu(IV) (g/1) Pu(VI) (g/1)
0 200,1 49.7
1.5 X l O ' ^ 200. 3 49.6
1,5 X lO"^ 199.9 49.7
0.15 200,1 49.6
No change in valence s t a t e distribution in t h e s e solutions was o b s e r v e d
after a 16-hour standing p e r i o d .

Reaction with F e r r o u s Sulfam.ate

T h e r e a c t i o n of 0. 8 M f e r r o u s sulfamate with the stock solution was

studied in two different w a y s , F i r s t the f e r r o u s sulfamate was added in
0.016 millequivalent units to a dilution containing 25, 0 m g of plutonium from
the stock solution. The r e s u l t s of plutonium-ion concentration m e a s u r e -
m.ents taken d u r i n g t h i s t i t r a t i o n a r e l i s t e d in Table III.
TABLE III
SEQUENTIAL PLUTONIUM VALENCE CHANGES
DUE TO ADDITION O F FERROUS ION IN A 4 M HNO^ SOI:..UTION

Millequivalents of Fe(II) PuCiV) (mg) Pu(VI) (mg) Pu ,(III) (mg)

0.000 20.0 5.0 ___
0.016 21.8 3, 1
0,032 23.9 1,2
„«_
0.048 23. 6 1.5
0.064 20. 2 --- 4.8
0.080 16.4 8.4
 -6- HW-68003 REV

The r e a c t i o n was further verified by p r e c a l c u l a t e d s t o i c h i o m e t r i c additions

of f e r r o u s sulfam^ate to stock solutions containing v a r i o u s concentrations of
plutonium(VI). T h e r e s u l t s a r e in T a b l e IV.
TABLE IV

ADJUSTING A PLUTONIUM(IV-VI) SYSTEM

TO PLUTONIUM(IV) WITH FERROUS SULFAMATE IN A 4 M HNOg SOLUTION
Initial Pu C o n c e n t r a t i o n s Millequivalents of Final Pu Concentrations
Pu(IV) (mgr~Fu(VI) (mgj Fe(II) Added Pu(IV) (mg) .Pu(VI) (mg)

20.0 5.0 0.042 24,95 - —-

21.8 3.1 0.026 25.05
23.9 1.2 0.010 24.90 ----

Standard Deviation, a = 0.72%.

Effect of Blutoninm. Concentration

T h e possibility of side r e a c t i o n s o c c u r r i n g in m o r e concentrated

plutonium solutions was investigated by adjusting tiie valence of i n c r e a s i n g l y -
concentrated aliquots of the stock solution to the four s t a t e . The r e s u l t s a r e
listed in T a b l e V .

TABLE V

E F F E C T O F PLUTONIUM CONCENTRATION
ON VALENCE ADJUSTMENT IN A 4 M HNOg SOLUTION

Initial P u C o n c e n t r a t i o n s Millequivalents of F i n a l P u Concentrations

PuClvHrng) Pu(VI) ( m i ) Fe(II) Added Pu(IV) (mg) .Pu(VI) (mg)
2.0 0.50 0.0042 2.495
20,0 5,0 0.042 24.89
200.0 50.0 0.420 249,6
 -7- HW-68003 REV

Effect of N i t r i c Acid Concentration

The effect of n i t r i c acid concentration on the r e a c t i o n is shown in
Table VI.
TABLE VI
VALENCE STATES OBSERVED AS A FUNCTION
O F NITRIC ACID CONCENTRATION AT THE TIME OF ADJUSTMENT
M HNO„ Plutonium Concentration (g/1)
=—-^ pu(iv) —""^Pulvi)—"TOTir
1.0 22.5 L8 0.5
2 . 0 , 3.0, 4 . 0 , 5.0 24,95
A volum.inous p r e c i p i t a t e of sulfam.ate was obtained witn nitric acid c o n -
c e n t r a t i o n s above 6 M.

Effect of ' t e m p e r a t u r e

T e m p e r a t u r e s during all the p r e v i o u s experim.ents w e r e maintained

at 23± 2 C . In c o n s i d e r i n g the t e m . p e r a t u r e , the m.aximum was set at 50 C
(8)
due to the g r e a t e r p o s s i b i l i t y of oxidation by n i t r i c acid noted by K r a u s .
Stoichionaetric v a l e n c e adjustmient was successfully p e r f o r m e d at 50 C. The
solution was m a i n t a i n e d at 50 C for six h o u r s after adjustment but no valence
change was o b s e r v e d .

Stability With R e s p e c t to T i m e
The stability of the valence adjustm.ent with r e s p e c t to tim.e is shown
in T a b l e VII.

TABLE VII
VALENCE STATE STABILITY WITH RESPECT TO TIME
A F T E R ADJUSTMENT IN A 4 M HNO„ SOLUTION
T i m e Since V a l e n c e Adjustment Plutonium Concentration (g/1)
(Days) Pu(IV) Pu(VI)

0 24.90
1/4 24.91
1/2 24.89
1 24.90
3 24.91
5 24.90
 -8- HW-68003 REV

F e r r o u s Ion Chemistry
When ferrous sulfamate more concentrated tnan 1 M v/as added to
250 g/1 plutonium at 23 C, a few transparent, colorless crystals formed
after a four-hour standing period. These cryjtals did not appear when tiie
solution was maintained at 50 C. Crystal form.ation had no effect on the
valence adjustment.
In nitric acid solutions of ferrous sulfanaate, a nitric acid concen-
tration of over 6 M causes form.ation of a voluminous precipitate of
sulfamate.
F e r r o u s ammonium^ sulfate and ferrous sulfate were tried in place
of ferrous sulfam.ate. Both compounds were unsatisfactory because of taeir
instability in nitric acid,
DISCUSSION
These investigations show tnat plutonium(VI) could be reliably
reduced to plutonium(IV) with ferrous sulfamate. The original concept of
reduction to plutonium(III) with ferrous sulfamate followed by oxidation to
plutonium(IV) with nitrite was abandoned.
If a mistake is m.ade during the adjustment step and a plutonium(IV-III)
system is formed, the readjustment can be accomplished by adding the stoichi-
ometric quantity of plutonium(VI) to oxidize the plutonium(III) to plutonium(IV).
While this reaction was only perform.ed once, added evidence v^as observed
each time an adjustm.ent was miade. At tne instant of contact between the
stock solution and ferrous sulfamate, a bright blue band form.ed at tne inter-
face, visually indicating the presence of plutonium(III). After 30 seconds of
mixing, there was no plutonium(III) present^ as indicated in Table III.
An attempt was mtade to determine toe time dependence of the reaction;
however, the reaction was always com.plete within the mininaum analytical
time lag of three m.inutes after the reactants were mixed.
 -9- HW-68003 REV

During the entire series of experiments, plutonium. polymer was

observed only in the case of valence adjustment in a one norm.al nitric acid
solution. Detection was by the method of Brunstad.
Of the variables considered, time, nitrite conoentration and dilution
were found to have no effect. Nitric acid concentration had a two-fold limit.
The first was the minimum concentration of 2 M to prevent formation of
plutonium(III); the second was the maximum of 6 M to prevent sulfamate
precipitation. Temperature could be varied between 23 C and 50 C with no
undesirable consequences. The maximum of 50 C is reconanaended to avoid
secondary oxidation by nitric acid, Plutonium at any concentration up to
250 g/1 could be stoichiometrically adjusted by this method. The reaction
rate can be considered instantaneous,
RECOMMENDED PROCEDURE
The plutonium valence state concentrations of the solution to be
adjusted are determined spectrophotonaetrically. The ferrous ion addition
is calculated according to the equation;

4H'*' + Fu02"^^ + 2Fe"'°^—^Pu"^^ + 2H2O + 2Fe+^ .

The calculated quantity of ferrous ion is prepared in 1/2 M nitric acid of
such a volume to provide the final desired conditions in acidity and plutonium
concentration. The plutonium nitrate solution is added to the prepared
reducing solution. After a five-minute agitation period, the valence adjust-
ment is checked on the spectrophotometer. From this point on, any desired
acid adjustmient may be made. The brown colored solution turns enaerald
green after butting to 7 _M nitric acid or above as noted by Kraus.
The critical conditions of the technique are: preparation of the
ferrous sulfam.ate must fall within prescribed conditions; the nitric acid
concentration of the adjusted solution m„ust be between 2 and 6 M; the tem-
perature of the reducing solution should be no greater than 50 C.
 -10- HW-6800 3 REV

If the calculated millequivalents of ferrous sulfamate are in e r r o r ,

a second adjustment may be made by adding more ferrous ion to reduce any
remaining plutoniumCVI), or by adding more plutonium(IV-VI) to oxidize any
plutonium(III) that is present. Nitrite may be used for this oxidation, but
an excessive quantity is needed because it reacts with the sulfamate before
it oxidizes the plutonium(III). A significant amount of nitrogen dioxide is
evolved during the reaction.
ACKNOWLEDGEMENTS
The author wishes to express his gratitude to G. T. Furner for
special analytical work skillfully and expeditiously performed.
 -11- HW-68003 REV

REFERENCES

1. Schneider, R. A. and K. M. H a r m o n . Analytical Solvent E x t r a c t i o n .

HW-53368. N o v e m b e r 1, 1957.
2. Ryan, J. L, "Species Involved in the Anion-Exchange Absorption of
Quadrivalent Actinide N i t r a t e s , " J. P h y s . C h e m . , 64: 1375.
O c t o b e r , 1960.
3. Kasha, M. and G. E . Sheline, The T r a n s u r a n i u m E l e m e n t s . P a r t i : 198.
New York: M c G r a w - H i l l , 1949.
4. Seaborg, G. F . and J. J. Katz. The C h e m i s t r y of the Actinide E l e m e n t s ,
292-330. New York: Methuen & Company, Ltd. 1957.
5. McLane, C. K. , J . S. Dixon and J . C. Hindman. The T r a n s u r a n i u m
E l e m e n t s , P a r t i : 358-369. New York: McGraw-Hill, 1949.
6. B r u n s t a d , A. The P o l y m e r i z a t i o n and P r e c i p i t a t i o n of Plutonium.(IV) in
N i t r i c Acid, HW-54203. D e c e m b e r , 1957.
7. Hindmian, J , C. The T r a n s u r a n i u m E l e m e n t s . P a r t I: 388. New York:
M c G r a w - H i l l , 1949.
8. K r a u s , K. A. The T r a n s u r a n i u m E l e m e n t s , P a r t I: 264-267. New York:
M c G r a w - H i l l , 1949.
9. M y e r s , M. N. Absorption S p e c t r a of Plutonium and Impurity Ions in
N i t r i c Acid Solutions. HW-44744. July 31, 1956. DECLASSIFIED.
 -12- HW-68003REV

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