7.

2 THE ROLE OF OXIDATION POTENTIAL, Eh, I N THE DISSOLUTION OF NUCLEAR WASTE

WASTE MATERIALS -- W. B. White and W. P. Freeborn, Pennsylvania S t a t e
University

INTRODUCTION

Many elements occur i n h i g h l e v e l r a d i o a c t i v e waste i n more t h a n one v a l -

ence s t a t e . The valence s t a t e i n t h e f i n a l waste form i s an i m p o r t a n t f a c t o r
i n d e t e r m i n i n g b o t h e q u i l i b r i u m s o l u b i l i t y and r a t e o f d i s s o l u t i o n o f t h e waste
form. T a b l e 1 l i s t s some o f t h e s e redox couples. T a b l e 1 c o n t a i n s two k i n d s
o f redox r e a c t i o n s : t h o s e i n which an i o n i c species i s reduced t o a metal and
t h o s e i n which t h e r e a r e o x i d a t i o n o r r e d u c t i o n o f one i o n i c species t o
another. Some elements e x h i b i t both.

Reactions c o n n e c t i n g d i f f e r e n t valence s t a t e s r e q u i r e an exchange o f elec-

t r o n s such as an acid-base r e a c t i o n r e q u i r e s an exchange o f protons. Since
most waste forms a r e oxides, t h e s e r e a c t i o n s can be d e s c r i b e d b y o x i d a t i o n
potentials. I n a complex system such as a n u c l e a r waste, t h e r e a r e many reac-
t i o n s underway simultaneously. I f t h e system i s t o be a t e q u i l i b r i u m , a l l o f
t h e s e must be a d j u s t e d t o a s i n g l e o x i d a t i o n p o t e n t i a l which may be regarded
as a system v a r i a b l e .

The q u e s t i o n i s : how does one measure t h e o x i d a t i o n p o t e n t i a l i n a com-

p l e x system and how does one c o n t r o l i t ?

TABLE 1. Some Redox Couples Relevant t o Nuclear Waste

I o n - Metal P a i r s Ion - Ion Pairs Mixed I o n - Ion - M e t a l Couples

DEFINITION OF Eh

Redox p o t e n t i a l i s u s u a l l y d e s c r i bed by Eh, a macroscopic parameter

related t o the electron a c t i v i t y . Consider t h e analogy t o pH.

An e q u i v a l e n t parameter can be d e f i n e d f o r e l e c t r o n s .

Ift h e redox r e a c t i o n i s w r i t t e n as an o x i d a t i o n r e a c t i o n , t h e n

which connects t h e e l e c t r o c h e m i c a l q u a n t i t i e s o f pe and Eh t o t h e thermochemi-

c a l q u a n t i t y o f Gibbs f r e e energy o f r e a c t i o n . Since

The e q u a t i o n f o r Eh can be r e l a t e d t o t h e e q u i l i b r i u m c o n s t a n t

The standard f r e e energy o f r e a c t i o n can be r e l a t e d t o a standard e l e c t r o c h e m i -

cal potential

T h i s leads t o t h e usual expression f o r t h e Nernst Equation

 RT [oxidation products]
Eh = E O
-T - L
which serves as t h e u s u a l working d e f i n i t i o n f o r Eh.

I n t h e above equations, n = number o f e l e c t r o n s exchanged, F = Faraday

c o n s t a n t (96.487 k J V-' mole-' o r 23.062 k c a l V-' mole-') and R = gas
constant.

Redox r e a c t i o n s p e r t i n e n t t o n u c l e a r waste m a t e r i a l s and n u c l e a r waste

r e p o s i t o r i e s a r e l i k e l y t o t a k e p l a c e i n aqueous s o l u t i o n o r i n an aqueous
environment. I n t h i s case t h e r e i s a d i r e c t c o n n e c t i o n between Eh and pH. The
redox p o t e n t i a l s and hydrogen i o n a c t i v i t i e s must a l s o be i n e q u i l i b r i u m w i t h
t h e r e d u c t i o n and i o n i z a t i o n o f water.

+
H20 $ H + OH-

[H'] [OH-] = 10- 14.00 (z5o) (9)

Both e q u a t i o n s a r e w r i t t e n a t u n i t a c t i v i t y of H 2 0 When these equations a r e

combined through t h e Nernst Equation, we o b t a i n

which connects t h e oxygen f u g a c i t y ( o f t e n c a l l e d t h e "oxygen p a r t i a l p r e s s u r e " )

.r)
w i t h Eh and pH. Thus t h e system parameters f o r aqueous environments a r e l i n k e d
. by e q u a t i o n (10) and s p e c i f i c a t i o n o f any two o f them p e r m i t s c a l c u l a t i o n o f
the t h i r d .
 The r e a c t i o n s d e s c r i b e d by equations ( 8 - 10) a l s o p u t l i m i t s on t h e
s t a b i l i t y o f l i q u i d water. If Eh - pH c o n d i t i o n s a r e such t h a t e i t h e r f o p > 1
o f f~~ > 1 a t atmospheric c o n d i t i o n s , oxygen o r hydrogen gas w i l l be released.
Many m e t a l s cannot be i n e q u i l i b r i u m w i t h l i q u i d water. I r o n , f o r example,
w i 11 reduce water, become o x i d i zed, and r e l e a s e hydrogen gas. I n c r e a s i ng t h e
system p r e s s u r e t o t h e s e v e r a l hundred b a r values expected f o r a sealed r e p o s i -
t o r y w i l l s h i f t these e q u i l i b r i a b u t n o t by much.

DISPLAY OF Eh - pH RELATIONS

Q u i c k and easy i n t e r p r e t a t i o n o f t h e c h e m i s t r y o f complex redox systems

4
i s d i f f i c u l t because o f t h e l a r g e number o f v a r i a b l e s . These i n c l u d e P, T, pH,
Eh, and t h e a c t i v i t y o f any species deemed t o be mobi l e . The most w i d e l y used
d i s p l a y devices a r e Eh-pH diagrams (as t h e y a r e c a l l e d by geochemists) o r
Pourbaix diagrams ( a s t h e y a r e c a l l e d by m e t a l l u r g i s t s ) .

F i g u r e 1 i s a well-known example. Eh ( i n v o l t s ) and pH f o r m t h e y and x

axes. T = constant, u s u a l l y 2 5 ' ~ . P = 1 (atmosphere o r bar; t h e 1 i t e r a t u r e
i s o f t e n ambiguous). The two p a r a l l e l l i n e s a t t h e t o p and bottom o f t h e d i a -
gram mark t h e upper and l o w e r s t a b i l i t y l i m i t s f o r water. The p o l y g o n a l
" f i e l d s " denote r e g i o n s where t h e l a b e l e d species a r e dominent.

Various techniques can be used t o add c o n c e n t r a t i o n d a t a t o t h e diagram.

One way i s t o c o n t o u r t h e dominent species ( F i g u r e 2). Here we see t h a t t h e
c o n c e n t r a t i o n o f Fez+ i s v e r y s e n s i t i v e t o pH and Eh, r i s i n g r a p i d l y as pH
and Eh a r e lowered. I n c o n t r a s t , t h e c o n c e n t r a t i o n o f t h e n e u t r a l species
Fe(0H)O i s extremely l o w and e s s e n t i a l l y independent o f pH and Eh. Thus,
3
over a wide range o f pH and Eh, i r o n would be immobile, p r e c i p i t a t i n g o u t as
Fe(0H) 3 .

Other i n f o r m a t i o n can be d i s p l a y e d by c o n s t r u c t i n g v a r i o u s k i n d s o f spec-

i a t i o n diagrams. F i g u r e 3 shows t h e s p e c i a t i o n of Fe
2+
.
2+
S i n c e a l l concen-
t r a t i o n s are normalized t o (Fe ) , t h e diagram i s Eh-independent and d i s p l a y s
t h e changing c o n c e n t r a t i o n s o f d i v a l e n t i r o n species as a f u n c t i o n o f pH. Fig-
u r e 4 shows t h e same k i n d o f diagram f o r Fe 3+ species.

Many o t h e r d i s p l a y s have been used. A c t i v i t i e s ( o r f ugacities) o f other ..

'pecies ( e * g * , '2) can be used as v a r i a b l e s . Oxygen f u g a c i t y can be
 Eh,pH I n d e p e n d e n t

I
FIGURE 1. pH - Eh D i agram f o r t h e System Fe-0-H FIGURE 2. pH - Eh Diagram f o r t h e System
S howi ng Domi nant Di ssol ved Spec ies. Fe-0-H Showing Concentrat i o n
Contours f o r Domi nant Species.
FIGURE 3. S p e c i a t i o n Diagram f o r Ferrous I r o n FIGURE 4. S p e c i a t i o n Diagram f o r F e r r i c I r o n
Species Species
 used i n s t e a d o f Eh. The l a t t e r i s p a r t i c u l a r l y u s e f u l i n d e s c r i b i n g s o l i d -
s o l i d redox e q u i l i b r i a as a f u n c t i o n o f temperature.

MEASUREMENT OF Eh

It seems t o be g e n e r a l l y conceded t h a t Eh measurements i n aqueous solu-

t i o n s a r e simple i n p r i n c i p l e and d i f f i c u l t i n p r a c t i c e . The reference elec-
t r o d e f o r Eh i s t h e hydrogen e l e c t r o d e which can be replaced w i t h a p l a t i n u m
electrode. With a reference e l e c t r o d e o f calomel o r AgIAgC1, Eh can be read
d i r e c t l y from t h e c e l l voltage. The d i f f i c u l t y i s t h a t many s o l u t i o n s have
l i t t l e oxygen b u f f e r c a p a c i t y and t h e k i n e t i c s o f t h e redox r e a c t i o n s may be
sluggish. The e l e c t r o d e p o t e n t i a l i s t h e n n o t w e l l defined. Voltages d r i f t
and i t i s d i f f i c u l t t o r e l a t e observed Eh t o c a l c u l a t e d Eh. Eh measurements
i n aqueous s o l u t i o n s r e q u i r e a t l e a s t one r e a c t i o n w i t h mobile electrons. The
s i t u a t i o n w i t h nuclear waste leach s o l u t i o n s seems t o be p o o r l y known perhaps
because n o t t o o many people have t r i e d .

A b e t t e r approach i s t o c a l c u l a t e Eh from thermochemical d a t a i f such are

a v a i l a b l e u s i n g equations (5-7). This i s t h e approach used t o c a l c u l a t e t h e
Eh-pH diagrams f o r u r a n i um, p l u t o n i urn, and t e c h n e t i urn-beari ng species t h a t have
appeared. The problem w i t h en1 a r g i ng these in d i v i d u a l metal-oxygen-
water systems t o a complete s u i t e o f elements r e p r e s e n t a t i v e o f nuclear waste
m a t e r i a l s i s t h a t thermochemical data may be r e q u i r e d t h a t a r e n o t a v a i l a b l e .
The comprehensive computer codes f o r s p e c i a t i o n c a l c u l a t i o n s w i 11 be h e l p f u l
here.

A t h i g h tenperatures, oxygen f u g a c i t y , r a t h e r t h a n Eh, can be measured

d i r e c t l y u s i n g sensors t h a t make use o f t h e anion c o n d u c t i v i t y o f z i r c o n i a c e r -
amics. These g i v e good r e s u l t s a t h i g h temperatures b u t do n o t work w e l l below
500°C and are thus o u t o f t h e range o f most d i s s o l u t i o n experiments.

Perhaps t h e most promising technique f o r t h e 90 t o 300°C temperature range

1
o f i n t e r e s t i s t h e use o f s i l v e r o r palladium membranes which are permeable t o
hydrogen. One then measures hydrogen f u g a c i t y and pH and from t h i s c a l c u l a t e s
back t o Eh. Experimental chambers w i t h t h i n hydrogen permeable membranes seem
1 i k e a promising approach. These measurements w i l l work best a t t h e h i g h e r
.
I.

i
temperatures and w i 11 become d i f f i c u l t a t temperatures where t h e hydrogen
r e a c t i o n s become sluggish. One should f i r s t determine whether hydrogen f ug-
a c i t y measurements can be made t o o v e r l a p t h e r e g i o n where d i r e c t electrochemi-
c a l measurements are possi ble.

HOW TO BUFFER Eh

If measurement o f Eh i s d i f f i c u l t , c o n t r o l o f E h ' i s even more d i f f i c u l t .

Two approaches have been t r i e d , m o s t l y a t h i g h e r temperatures.

Any metallmetal oxide p a i r w i l l have an e q u i l i b r i u m oxygen pressure a t any

temperature and so long as n e i t h e r s o l i d i s completely consumed, t h e p a i r w i 11
serve t o b u f f e r oxygen f ugac i t y . Metal lmetal oxide (and ox i d e l o x i d e ) b u f f e r s C

work we1 1 above 500*~,where k i n e t i c s are rapid, b u t become s l u g g i s h a t reposi-

t o r y temperatures.

Control o f hydrogen pressure over a system remains a possi b l e approach t o

Eh b u f f e r i n g j u s t as i t i s an approach t o Eh measurement. The questions which
must be answered experimentally deal w i t h t h e e f f e c t i v e n e s s o f hydrogen-
permeable membranes a t experimental temperatures and w i t h t h e r a t e o f r e a c t i o n
o f gaseous hydrogen w i t h t h e v a r i o u s redox p a i r s i n t h e n u c l e a r waste system.
 I

I ACKNOWLEDGMENTS

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The p a r t i c i p a n t s i n t h e leaching mechani sms program wish t o thank a1 1 o f
1 t h e attendees a t t h e workshop f o r t h e i r many p e r c e p t i v e questions and comments.
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We much appreciate c o n t r i b u t i o n s o f t h e speakers from o u t s i d e t h e program, par-
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1 t i c u l a r l y these from t h e NWTS p r o j e c t s . They gave t h e workshop a f u l l y -
d
rounded p e r s p e c t i v e t h a t was valuable t o a l l .

1 Special thanks go t o C h a r l i e Faust and S i d P h i l l i p s , who stepped i n as

1 s u b s t i t u t e speakers a t v i r t u a l l y t h e l a s t minute and d i d e x c e l l e n t jobs.
1 B i l l i e Neth, as always, was very h e l p f u l t o a l l . Judy Hooper's e d i t i n g o f t h e
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r e p o r t i s much appreci ated as we1 1 as t h e p r e p a r a t i o n o f t h e camera-ready copy
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I by S c o t t Dudley.