50

Current D i s t r i b u t i o n a n d blass T r a n s f e r i n E l e c t r o c h e m i c a l Systems

John Newman
i n o r g a n i c M a t e r i a l s Research Division, Lawrence R a d i a t i o n Laboratory, and
Department of 'hemical Engineering, U n i v e r s i t y of C a l i f o r n i a , Berkeley

i
1

Fundamental e q u a t i o n s d e s c r i b i n g t r a n s p o r t i n d i l u t e e l e c t r o l y t i c s o l u t i o n s
have been know! s i n c e t h e t u r n of t h e c e n t u r y . In a n e.Lect,rochemical system, many
p r o c e s s e s occur simultaneously, and t h e treatment. of such systems i n v o l v e s cons-id e r a t i o n o f t h e ohmic p o t e n t i a l drop, c o n c e n t r a t i o n changes n e a r e l e c t r o d e s , a n d
t h e k i n e t i c s of t h e heterogeneous e l e c t r o d e r e a c t i o n .
A p p l i c a t i o n of t h e s e p r i n c i p l e s has followed two main courses.

t r a n s p o r t problems.

There a r e sys-

"

A t c u r r e n t s much below t h e l i m i t i n g c u r r e n t it i s p o s s i b l e t o n e g l e c t concent r a t i o n v a r i a t i o n s n e a r t h e e l e c t r o d e s . The c u r r e n t d i s t r i b u t i o n i s t h e n d e t e r mined b y t h e ohmic p o t e n t i a l drop i n t h e s o l u t i o n and by e l e c t r o d e o v e r p o t e n t i a l s .

Mathematically, t h i s means t h a t t h e p o t e n t i a l s a t i s f i e s L a p l a c e ' s equation, and
many r e s u l t s of p o t e n t i a l t h e o r y , developed i n e l e c t r o s t a t i c s , t h e flow of i n v i s c i d
f l u i d s and s t e a d y h e a t conduction i n s o l i d s , a r e d i r e c t l y a p p l i c a b l e . Let u s c a l l
Zl
t h e s e p o t e n t i a l - t h e o r y problems. " The e l e c t r o d e k i n e t i c s provide boundary condit i o n s -4hich a r e 1:sually d i f f e r e n t from t h o s e encountered i n o t h e r a p p l i c a t i o n s of
p o t e n t i a l theory.
Problems have been t r e a t e d which do not f a l l w i t h i n e i t h e r of t h e s e two
c l a s s e s . F i r s t , t h e r e are " i n t e r m e d i a t e problems," where convective t m n s p o r t i s
e s s e n t i a l but n e i t h e r c o n c e n t r a t i o n v a r i a t i o n s n e a r t h e e l e c t r o d e nor t h e ohmic
p o t e n t i a l drop i n t h e s o l u t i o n can b e n e g l e c t e d . These i n v o l v e c u r r e n t s below,
b u t at a n a p p r e c i a b l e f r a c t i o n of, t h e l i m i t i n g c u r r e n t .
Some problems a r e n o t so g e n e r a l , b u t c a n h e regarded as a n e x t e n s i o n of t h e
c o n v e c t i v e - t r a n s p o r t problems. A t t h e l i m i t i n g c u r r e n t t h e ohmic p o t e n t i a l drop
i n t h e b u l k o f t h e s o l u t i o n may s t i l l be n e g l i g i b l e , b u t t h e e l e c t r i c f i e l d i n t h e
d i f f u s i o n l a y e r near e l e c t r o d e s may l e a d t o a n enhancement of t h e l i m i t i n g c u r r e n t .
The c u r r e n t may t h e n b e d i s t r i b u t e d i n a similar fashion, b u t t h e magnitude i s
changed.
In porous e l e c t r o d e s convection may not b e p r e s e n t , b u t it i s u s u a l l y necess a r y t o c o n s i d e r t h e ohmic p o t e n t i a l drop, c o n c e n t r a t i o n v a r i a t i o n s , and e l e c t r o d e
k i n e t i c s . Most t r e a t m e n t s a d o p t a macroscopic model which does not t a k e account
o f t h e d e t a i l e d , random geometry o f t h e porous s t r u c t u r e . R e s u l t s o f p o t e n t i a l
t h e o r y a r e then not a p p l i c a b l e s i n c e l a p l a c e ' s e q u a t i o n does n o t hold.
T r a n s p o r t 2 e l e c t r o l y t i c s o l u t i o n s . The c o n c e n t r a t i o n and p o t e n t i a l d i s t r i b u t i o n s
a r e t o b e d e t e m i n e d from t h e e q u a t i o n s
N . = -Z.U.F'c.VO

-1

1 1

D.Vc
1

-+

IC

i '

(1)

The f i r s t s t a t e s t h a t s p e c i e s i n t h e s o l u t i o n can move by m i g r a t i o n , d i f f u s i o n ,

and convection. The second i s a m a t e r i a l b a l a n c e f o r a s p e c i e s . The t h i r d s t a t e s

51
t h a t t h e c u r r e n t a r i s e s from t h e motion o f charged p a r t i c l e s . The f o u r t h i s t h e cond i t i o n of e l e c t r o n e u t r a l i t y . These laws provide t h e b a s i s f 3 r t h e a n a l y s i s of e l e c t r o c h e m i c a l systems. The f l u i d v e l o c i t y i s t o be determined from t h e laws of f l u i d
mechanics

E l e c t r o d e k i n e t i c s . The d i f f e r e n t i a l e q u a t i o n s d e s c r i b i n g t h e e l e c t r o l y t i c s o l u t i o n
r e q u i r e boundary c o n d i t i o n s i n o r d e r f o r t h e b e h a v i o r o f a n e l e c t r o c h e m i c a l system
t o be p r e d i c t e d . The most complex o f t h e s e concerns t h e k i n e t i c s o f e l e c t r o d e react i o n s and r e l a t e s t h e normal component o f t h e c u r r e n t d e n s i t y a t a n e l e c t r o d e t o t h e
s u r f a c e o v e r p o t e n t i a l . The s u r f a c e o v e r p o t e n t i a l qs can be defined a s t h e p o t e n t i a l
of t h e working e l e c t r o d e r e l a t i v e t o a r e f e r e n c e e l e c t r o d e of t h e same kind l o c a t e d
j u s t o u t s i d e t h e double l a y e r .
There i s no completely g e n e r a l e x p r e s s i o n d e s c r i b i n g e l e c t r o d e k i n e t i c s . However, it i s adequate f o r our p r e s e n t purpose t o assume that t h e c u r r e n t d e n s i t y depends e x p o n e n t i a l l y on t h e s u r f a c e o v e r p o t e n t i a l i n t h e f o l l o w i n g form:
i = io [exp

{g

qs}

exp

i-+ 11 .
1

I.

(5)

Convective-transport problems. For t h e r e a c t i o n o f minor i o n i c s p e c i e s i n a solut i o n c o n t a i n i n g excess s u p p o r t i n g e l e c t r o l y t e , it should be p e r m i s s i b l e t o n e g l e c t

t h e c o n t r i b u t i o n of i o n i c m i g r a t i o n t o t h e flux of t h e r e a c t i n g i o n s , so that equat i o n ( 1 ) becomes
N. = -D.Vc.
1
1

(6)

and s u b s t i t u t i o n i n t o e q u a t i o n (2) y i e l d s

(7)
T h i s may b e c a l l e d t h e e q u a t i o n of convective d i f f u s i o n . A similar e q u a t i o n a p p l i e s
t o convective h e a t t r a n s f e r and convective mass t r a n s f e r i n n o n - e l e c t r o l y t i c solut i o n s . Since t h e s e f i e l d s have been s t u d i e d i n d e t a i l , it i s p o s s i b l e t o a p p l y many
r e s u l t s t o e l e c t r o c h e m i c a l systems which obey e q u a t i o n (7).
The systems t y p i c a l l y s t u d i e d i n h e a t and mass t r a n s f e r involve l a m i n a r and
t u r b u l e n t flow with v a r i o u s geometric arrangements. The flow may b e due t o some more
o r l e s s w e l l c h a r a c t e r i z e d s t i r r i n g ( f o r c e d c o n v e c t i o n ) o r may b e t h e r e s u l t o f dens i t y d i f f e r e n c e s c r e a t e d i n t h e s o l u t i o n a s part o f t h e t r a n s f e r p r o c e s s ( f r e e convec t i on ).
E s s e n t i a l t o t h e understanding o f c o n v e c t i v e - t r a n s p o r t problems i s t h e concept
o f t h e d i f f u s i o n layer. Frequently, due t o t h e small valuo of t h e d i f f u s i o n c o e f f i c i e n t , t h e c o n c e n t r a t i o n s d i f f e r s i g n i f i c a n t l y from t h e i r b u l k v a l u e s o n l y i n a t h i n
r e g i o n n e a r t h e s u r f a c e o f a n e l e c t r o d e . I n t h i s r e g i o n t h e v e l o c i t y i s small, and
d i f f u s i o n i s important t o t h e t r a n s p o r t p r o c e s s . The t h i n n e s s o f t h i s r e g i o n permits
a s i m p l i f i c a t i o n i n t h e a n a l y s i s , b u t it i s erroneous t o t r e a t t h e d i f f u s i o n layer
as a s t a g n a n t region. Figure 1 shows t h e c o n c e n t r a t i o n p r o f i l e i n t h e d i f f u s i o n
layer, w i t h t h e e l e c t r o d e s u r f a c e a t t h e l e f t . F a r from t h e s u r f a c e c o n v e c t i v e
t r a n s p o r t dominates, w h i l e a t t h e s u r f a c e i t s e l f t h e r e i s o n l y d i f f i s i o n .

To i l l u s t r a t e t h e c u r r e n t d i s t r i b u t i o n obtained i n t h i s t y p e of problem, cons i d e r two plane e l e c t r o d e s o f l e n g t h L and s e p a r a t e d by a d i s t a n c e h and which form

parts o f t h e walls of a flow channel with o t h e r w i s e i n s u l a t i n g w a l l s . For laminar
flow fran l e f t t o r i g h t , w i t h a n average v e l o c i t y <v>, t h e l i m i t i n g c u r r e n t d e n s i t y
has t h e d i s t r i b u t i o n , as i l l u s t r a t e d i n f i g u r e 2,

52

where x i s t h e d i g t a n c e a l o n g t h e e l e c t r o d e . The m a s s - t r a n s f e r r a t e i s i n f i n i t e a t
the upstream edge o f t h e e l e c t r o d e where f r e s h s o l u t i o n i s brought i n c o n t a c t with
t h e e l e c t r o d e . The c u r r e n t d e c r e a s e s w i t h i n c r e a s i n g x s i n c e t h e s o l u t i o n i n t h e
d i f f u s i o n layer has a l r e a d y been d e p l e t e d by t h e e l e c t r o d e r e a c t i o n ifurther upstream.
I a t e r it w i l l be i n s t r u c t i v e t o compare t h i s c u r r e n t d i s t r i b u t i o n w i t h that which
would be obtained when t h e ohmic p o t e n t i a l d r o p i n t h e s o l u t i o n i s c o n t r o l l i n g .
Other c o n v e c t i v e - t r a n s p o r t problems which have been t r e a t e d include f l o w i n a
p i p e and i n a n n u l a r c o n d u i t s , a f l a t p l a t e i n a f r e e stream, r o t a t i n g c y l i n d e r s ,
growing mercury drops, r o t a t i n g d i s k s , and free convection a t v e r t i c a l and horizont a l p l a t e s and o u t s i d e spheres and c y l i n d e r s .

When c o n c e n t r a t i o n g r a d i e n t s i n t h e s o l u t i o n can
A p p l i c a t i o n s of o t e n t i a l t h e o r
be ignored, e q u a p m , d a n d (4) y i e l d

-i

(9)

= -1670

where

(10)

i s t h e c o n d u c t i v i t y o f the s o l u t i o n .

Equation ( 2 ) when m u l t i p l i e d by zi and summed

over i y i e l d s

(11)

v2(0=0,

'

that i s , the p o t e n t i a l s a t i s f i e s I a p l a c e ' s equation.

The boundary c o n d i t i o n s are determined with e q u a t i o n
&/aY

= 0

(9).

On i n s u l a t o r s

(121

where y i s t h e n o m 1 d i s t a n c e from t h e s u r f a c e . On e l e c t r o d e s , e q u a t i o n (9) relates t h i s p o t e n t i a l d e r i v a t i v e t o t h e s u r f a c e o v e r p o t e n t i a l through e q u a t i o n ( 5 ) .

If the p o t e n t i a l (0 i n t h e s o l u t i o n i s measured w i t h a r e f e r e n c e e l e c t r o d e of the
same kind as t h e working e l e c t r o d e , t h e n the s u r f a c e o v e r p o t e n t i a l can be eliminated
with t h e relation
(13)
1
', = v
(0,

where V i s t h e p o t e n t i a l of t h e metal e l e c t r o d e . The r e s u l t i n g boundary c o n d i t i o n

i s a n o n l i n e a r r e l a t i o n s h i p between t h e p o t e n t i a l and t h e p o t e n t i a l d e r i v a t i v e and
i s n o t commonly encountered i n o t h e r a p p l i c a t i o n s o f p o t e n t i a l t h e o r y .

In so-called primery-current-distribution p r o b l e ~ st h e s u r f a c e o v e r p o t e n t i a l is
n e g l e c t e d a l t o g e t h e r , and t h e s o l u t i o n a d j a c e n t t o t h e electrode i s t a k e n t o be an
e q u i p o t e n t i a l s u r f a c e . The r e s u l t i n g c u r r e n t d i s t r i b u t i o n f o r t h e p l a n e e l e c t r o d e s
i n t h e flow channel c o n s i d e r e d earlier i s shown i n figure 2 f o r L = 2h. The d i s t r i b u t i o n i s symmetric s i n c e convection is n o t important. The c u r r e n t d e n s i t y is
i n f i n i t e a t t h e ends of t h e e l e c t r o d e s s i n c e t h e c u r r e n t can flow through t h e solut i o n beyond t h e ends of t h e e l e c t r o d e s . T h i s is a g e n e r a l c h a r a c t e r i s t i c o f primary
c u r r e n t d i s t r i b u t i o n s . The c u r r e n t d e n s i t y where a n e l e c t r o d e meets a n i n s u l a t o r
i s e i t h e r i n f i n i t e o r z e r o unless t h e y form a r i g h t angle.
The s o - c a l l e d secondary c u r r e n t d i s t r i b u t i o n t a k e s i n t o account the s u r f a c e
overpotent'lal, a l t h o u g h t h e boundary c o n d i t i o n i s f r e q u e n t l y replaced b y a l i n e a r O r
a l o g a r i t h m i c ( T a f e l ) r e l a t i o n between t h e potential and t h e p o t e n t i a l d e r i v a t i v e The general e f f e c t of e l e c t r o d e p o l a r i z a t i o n i s t o make t h e secondary c u r r e n t d i s t r i b u t i o n more n e a r l y uniform t h a n the primary c u r r e n t d i e t r i b u t i o n , and a n i n f i n i t e Curr e n t d e n s i t y a t t h e edge of e l e c t r o d e s i s e l i m i n a t e d .

been t r e a t e d with account t a k e n o f c o n c e n t r a t i o n v a r i a t i o n s , ohmic p o t e n t i a l drop,

and s u r f a c e o v e r p o t e n t i a l . The r e s u l t s a r e , as one might expect, i n t e r m e d i a t e between t h e two extreme c a s e s . The f o r m u l a t i o n of t h e problem so a s t o t a k e advantage
Of the t h i n n e s s o f t h e d i f f u s i o n l a y e r h a s a l s o been d i s c u s s e d e 3
7

\
)

s i t y i s d i s t r i b u t e d a l o n g t h e e l e c t r o d e i n t h e same manner as when m i g r a t i o n i s negl e c t e d , b u t t h e magnitude o f t h e c u r r e n t d e n s i t y a t a l l p o i n t s i s i n c r e a s e d o r dimi n i s h e d b y a c o n s t a n t f a c t o r v h i c h depends upon the b u l k composition of t h e s o l u t i o n .
This e f f e c t has been t r e a t e d 3 j 4 for t h e r o t a t i n g d i s k , t h e growing mercury drop,
p e n e t r a t i o n i n t o a s e m i - i n f i n i t e medium, t h e s t a g n a n t Nernst d i f f u s i o n layer, and

Current D i s t r i b u t i o n under F r e e Convection Conditions." . J o.u r n a l o f the Electro107, 242-246 (1960).

. chemical S o c i e t y ,
h

John Newman. The Effect of Migration i n Laminar Boundary Isyers.

December, 1$6--John Newman. " E f f e c t of I o n i c Migration on Limiting Currents."
Engineering Chemistry Fundamentals, 3, 525-529 (1966).

'\

Ucm-16665-Rev.
Industrial &
g

,54

0,

3
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