212 J. Electrochem. Soc.

: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y
10. Joseph J o r d a n and H. L. Finston, "Identification of
Active Electrode Sites by Radioactive Tracers,"
Brookhaven National L a b o r a t o r y Report BNL-
6110 ( F e b r u a r y 1962).
11. S t a n l e y B r u c k e n s t e i n and B a r r y Miller, This
Journal, l l ' L 1044 (1970).
12. W i l l i a m H. S m y r l and J o h n Newman, This Journal,
119, 212 (1972).
13. D. H. Angell, T. Dickinson, and R. Greef, Elec-
trochim. Acta, 13, 120 (1968).
February 1972
14. J. D. E. McIntyre and W. F. Peck, Jr., This Journal,
117, 747 (1970).
15. John Newman, ibid., 117, 507 (1970).
16. W. J. A l b e r y and S. Bruckenstein, Trans. Faraday
Soc., 62, 1920 (1966).
17. Leonard Nanis, P a p e r 150 presented at Electro-
chem Soc. Meeting, Dallas, May 7-12, 1967.
18. T. Dickinson, R. Greef, and Lord W y n n e - J o n e s ,
EIectrochim. Acta, 14, 467 (1969).

Ring-Disk and Sectioned Disk Electrodes

William H. Smyrl*
Boeing Scientific Research Laboratories, Seattle, Washington 98124

and John Newman*

Inorganic Materials Research Division, Lawrence Radiation Laboratory, and
Department ol Chemical Engineering, University ol California, Berkeley, California 94720

ABSTRACT
Integrals relating surface concentration to surface flux for the diffusion
layer on a rotating disk are used to evaluate collection efficiencies for a
r i n g - d i s k system and to assess the error involved in using this system as a
sectioned electrode to measure the c u r r e n t distribution. E x p e r i m e n t a l results
are reported which confirm these predictions at the limiting current. Below the
limiting current, a n o n u n i f o r m c u r r e n t distribution is obtained.

The Diffusion Layer on a Rotating Disk
Equations relating to the diffusion layer on a rotating
disk are used to rederive in a new way A l b e r y and
Bruckenstein's f o r m u l a (1) for the collection efficiency
of a r o t a t i n g r i n g - d i s k system. The same method is
then used to assess the accuracy of using a r i n g - d i s k
electrode as a sectioned electrode for the direct m e a -
s u r e m e n t of the c u r r e n t distribution on a disk electrode.
Steady transfer of a solute species obeys the equation
of convective diffusion
where it is assumed that the m a s s - t r a n s f e r process does
not influence the fluid motion.
Equation [2] forms, in essence, the basis of the deri-
vation of the l i m i t i n g c u r r e n t at a disk electrode (3, 4).
It is also the starting point for N e w m a n ' s analysis of
the c u r r e n t distribution on a disk electrode below the
limiting c u r r e n t (9) and for Albery and Bruckenstein's
analysis of the collection efficiency of a r i n g - d i s k sys=
tern (1). It is c o n v e n i e n t to introduce the dimensionless
distance from the disk

v-Vc~ : Di~72c~ [1] : y(a~/3D~) 1/3 (12/v) 1/2 [3]

if, for one reason or another, electric migration of this so that Eq. [2] becomes
species can be ignored. This condition applies to a
n e u t r a l solute and to a m i n o r ionic solute in a solution ( 0ci0__~_ 0cl ~ O2ci~0--- [4]
with an excess of inert, supporting electrolyte. The
equation also applies to a solution of a single electro- The boundary conditions for Eq. [4] will normally
lyte where the m i g r a t i o n terms can be e l i m i n a t e d b y
include
means of the e l e c t r o n e u t r a l i t y condition (2-4). I n this
case, Di is replaced by the diffusion coefficient of the ci:c| at ~ = ~ a n d OcJOr:O at r - - 0 [5]
electrolyte.
The appropriate form of this equation for the diffu- as well as a specification of the concentration co or the
sion layer on a rotating disk is concentration derivative Oci/O~ or a combination of
these on the surface of the disk at ~ = 0. The problem
can be solved formally to yield either the derivative at
a y a ( a l v ) ~ ( r Ocior -- y ~y
Oc, ~
/ = Di 02Cio2y [2] the surface in terms of the surface c o n c e n t r a t i o n (10)

The radial diffusion terms are neglected on the basis {~Ci I __ --r yo' dCo I dr"
0~ ~=o r(4/3) r=r' ( r S - - r'3)1/3 [6]
of the thinness of the diffusion layer, compared to the
radius of the electrode. We treat the neglect of these or vice versa (11)
terms in a separate paper (5). For large values of the
Schmidt n u m b e r Sc = v/Di, as encountered in elec- - 1 1"r Oci r' dr'
trolytic solutions, the diffusion layer is also much t h i n - co(r) - c| : r(2/3----~ ,~o n ~=0 ( r z - - r,3)2/3 [7]
n e r t h a n the h y d r o d y n a m i c b o u n d a r y layer, a n d it is 0~
appropriate to approximate the n o r m a l a n d radial com- These equations are analogous to those integral e q u a -
ponents vy and Vr of the velocity b y the first terms of tions c o m m o n l y used to relate the surface concentration
their power-series expansions in the n o r m a l distance y a n d the n o r m a l derivative of concentration for p r o b -
from the disk. This introduces the rotation speed 12, the lems involving unsteady, linear diffusion in a s t a g n a n t
kinematic viscosity v, and the dimensionless constant a medium. E q u a t i o n [6] should be regarded as a Stieltjes
from the solution of the h y d r o d y n a m i c problem (6-8), integral.
* Electrochemical Society Active M e m b e r . Rosner (10, 12) has discussed the application of these
K e y w o r d s : c u r r e n t distribution, collection efficiency. equations to certain aspects of the r i n g - d i s k system

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 Vol. 119, No. 2 RING-DISK AND SECTIONED DISK ELECTRODES 213
and to other geometries [see also Chambr~ (13) and Table I. Values of c~ and ca for the various cases
Chambr~ and Acrivos (14)]. Analogous expressions
have been derived for h e a t - t r a n s f e r problem by Tribus Case cd c
and K l e i n (15). A p p e n d i x II treats other geometries
at high Schmidt n u m b e r s .
At the limiting current, the concentration of the L Collectionefficiencies cd 0
IL Sectioneddisk 0 c~
reactant is zero over the entire surface of the disk IIL Ringonly c= c~
electrode. I n Eq. [6], Co is regarded in this case to
change discontinuously from c~ to 0 at r = 0, and concentration, the surface flux on the disk being given
dco/dr is zero over the r e m a i n d e r of the electrode. by Eq. [12].
This equation then yields C~ -- ca ~ro r' ~r'

c~Ci ] C| Co = e| -- r ( 2 ) - 3 ~ ' / 3 ) )o (r 3 _ r'3) 2/3 ( a n n u l u s )

0~ ~=0 -- r ( 4 / 3 ) [8]
[13]

the result of Levich (3).

In Appendix I it is shown how to evaluate this inte-
gral. With that result, Eq. [13] can be expressed as
Ring and Disk Electrodes C| -- Cd [
The integrals i n Eq. [6] and [7] can be applied to
co : cd + r ( 2 / 3 ) r ( 4 / 3 ) [ "6x/~
evaluate the collection efficiency of a r i n g - d i s k system
and to treat the limiting c u r r e n t on a sectioned disk
1 (20--1) I In (1-t-#) 3 ]
electrode. We wish to treat three cases. It should be + ta -' + T 1+ [14]
emphasized that the application of the m a t h e m a t i c a l
expressions [6] and [7] represents a n e w t r e a t m e n t
of these three cases and completely confirms the older where
w o r k referenced. On the other hand, Eq. [6] and [7] o~ : rS/ro3 -- 1 [15]
and their extensions in A p p e n d i x II are more widely On the ring electrode, the surface concentration is
useful t h a n just for the three cases described here, zero, and the surface flux can be obtained from Eq.
which illustrate their use for disk and sectioned-disk [6], the surface concentration on the disk being given
electrodes. by cd and the surface concentration on the a n n u l u s
I. I n most applications of rotating r i n g - d i s k elec- being given by Eq. [13] or [14].
trodes, an u n s t a b l e i n t e r m e d i a t e is g e n e r a t e d on the
disk and detected on the ring. The appropriate b o u n d -
ary conditions on the surface are ~ci I : --r f Cd-- C|
-~- ~=o r (4/3i- r
0 "~ r ~- re (on the disk) co : ca
ro < r < rl (on the i n s u l a t i n g Oci/0f = 0 t [9] -l- o ~ r=r' (r3 -- r'3) I/~ (r~ r1"--3)t/3 [16]
annulus)
From Eq. [14]
rl'~r~-~r~ (on the ring) Co: 0
dCo c| -- Cd to2
Here Ca is the concentration of this species on the disk, -- (annulus)
where it is produced. N o r m a l l y the b u l k value is c, dr r(2/3) r(4/3) r ( r 3 -- roS) 2/8
= 0. It should be pointed out that the condition of [17]
u n i f o r m concentration on the disk surface is, strictly and Eq. [16] becomes
speaking, an assumption, problems of c u r r e n t distribu-
tion on the disk h a v i n g been ignored. F u r t h e r m o r e , = C| -- Cd
Eq. [1] and [2] do not account for a n y homogeneous P -~ ~ ~=0 (T3--T13) 1/3
decomposition of the species produced on the disk.
II. W h e n both the disk and the ring are at limiting C| -- Cd frl rro2dr '
c u r r e n t for the same reaction, the b o u n d a r y conditions r(2/3)r(4/3) Jro r ' ( r 's -- %3)2/3 (rz _ r'3)1/3
on the surface are [18]
0 ~ r ~-~to, Co=O } Let us evaluate a q u a n t i t y jr, proportional to the
ro<r<r,, 0ci/~=O [10] total flow of the species to the r i n g

T1 ~ r ~ T2, C o = 0
III. W h e n no c u r r e n t is passed t h r o u g h the disk and
Jr :
~r r20ci t
I W [=0
rdr [19]

the ring is at limiting current, the b o u n d a r y conditions I n t e g r a t i o n of Eq. [18] i n this way over r gives
are
O ~ r < rl, 8ci/8f -- O 1 f (c| -- Cd) (r~~ -- rl ~)
[11] Jr = 2r(4/3-------~
rt --~ r ~-~r2, Co:O f (c| -- ca)to s ~n
This case, of course, also applies w h e n there is no disk + Co(rl) (r2z -- rlS) 2/3 -- r ('273Tr-(47~ J'ro
electrode. Obviously, Co = c| for 0 ~ r < r~, as shown
b y Eq. [7]. (r23 _ r'8)2/3 - (rl s -- r'3) s/s dr' "~
These three cases will be discussed in detail, and the
concentration a n d c u r r e n t distribution will be derived (r'3 __ To3) 2/3 ~ ~ [20]
for each region on the rotating surface. These cases can
be treated s i m u l t a n e o u s l y with the appropriate values I n A p p e n d i x I it is shown how to evaluate integrals
of c| and Cd given in Table I. of the type involved here. Similarly, let
On the disk, the surface flux is given by Eq. [6]. 0ei c~ -- ca
~ o r ~ [21]
c3Ci C| -- ca Jd : "~ ~=0 2F(4/3)
= ~ (disk) (12)
af [=0 r (4/3)
I n order to avoid w r i t i n g complicated expressions
On the i n s u l a t i n g annulus, the surface flux is zero. more t h a n once, let us define N as the following f u n c -
Hence, Eq. [7] can be used to d e t e r m i n e the surface tion of the geometric ratios r2/ro and rl/ro

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 214 J. EIectrochem. Soc.. E L E C T R O C H E M I C A L SCIENCE AND TECHNOLOGY February 1972

N ---- (r23 -- r13) 2/3 r ' dr' k i n e t i c s b e c a u s e of u n c e r t a i n t y in t h e r e l a t i v e i m -

f O rO
p o r t a n c e of o h m i c p o t e n t i a l d r o p and c o n c e n t r a t i o n
ro2r(2/3)r(4/3) (rl a -- r'a)2/3
a n d s u r f a c e o v e r p o t e n t i a l s . O n t h e ring, t h e i n f l u e n c e
722 - - r l 2 1 (rl of s u r f a c e o v e r p o t e n t i a l a n d o h m i c p o t e n t i a l d r o p is
n e g l i g i b l e w h e n it is o p e r a t e d at t h e l i m i t i n g c u r r e n t .
ro 2 ~- r ( 2 / 3 ) r ( 4 / 3 ) J~o T h e k i n e t i c s of g e n e r a t i o n of t h e a c t i v e i n t e r m e d i a t e
(r2 a -- r'3) 2/3 -- (rl 3 -- r'3) 2/3 dr' on t h e disk is less w e l l k n o w n , h o w e v e r , b e c a u s e of
t h e n o n u n i f o r m i t y of t h e c u r r e n t d i s t r i b u t i o n on t h e
(r'3 __ ro 3) 2/3 r' disk. T h e a s s u m p t i o n of a u n i f o r m s u r f a c e c o n c e n t r a -
tion on the d i s k s u r f a c e is q u e s t i o n a b l e for case I of
1 + 03 T a b l e I.
_-- (A s _ B 3) 2/3 r ~/~-, i n
L 4~ (1 + 0) a W h e n t h e r i n g - d i s k s y s t e m is u s e d for p l a t i n g - t y p e
applications, t h e s a m e r e a c t i o n w o u l d o c c u r on b o t h
electrodes, and t h e y w o u l d n o r m a l l y be o p e r a t e d at t h e
_ ~ tan-1 q- s a m e p o t e n t i a l . If b o t h a r e o p e r a t e d b e l o w t h e l i m i t i n g
W 7 c u r r e n t , t h e n o n u n i f o r m c u r r e n t d i s t r i b u t i o n on t h e
N/3 1 + A3~3 3 ( 2A~ -- 1 ~ 1 disk a g a i n m a k e s it difficult to a n a l y z e t h e e l e c t r o -
c h e m i c a l kinetics. H o w e v e r , it is j u s t b e c a u s e of t h e
+ 4= In (1 + A~) a + 2= t a n - 1 "\ ~ ) + "4"
n o n u n i f o r m c u r r e n t d i s t r i b u t i o n t h a t a r i n g w o u l d be
used w i t h t h e disk. T h e r i n g - d i s k s y s t e m m i g h t be
_A 2 [~/3.1n lq-@ 3 used to d e t e r m i n e t h e c u r r e n t d i s t r i b u t i o n , o r t h e r i n g
4~ (1 + ~ ) 3 m i g h t be i n c l u d e d to m a k e t h e c u r r e n t d i s t r i b u t i o n
m o r e n e a r l y u n i f o r m on t h e disk. S i n c e t h e n o n u n i -
fortuities a r e g r e a t e s t on t h e o u t e r e d g e of a disk, t h e
3 tan-1 [22] r i n g m i g h t be v i e w e d as " s o a k i n g u p " t h e n o n u n i f o r m i -
ties. T h e j u s t i f i c a t i o n for use of t h e r i n g for e i t h e r
where
p u r p o s e m u s t c o m e f r o m an a n a l y s i s of t h e c u r r e n t on
A = r2/ro, B = rl/ro, ] [23] a r i n g as c o m p a r e d to t h e c u r r e n t o v e r an e q u i v a l e n t
a r e a of a d i s k e l e c t r o d e .
1 (Aa--B3) '/3 S i n c e s e c t i o n e d e l e c t r o d e s a r e c o m m o n l y used to
o---- ( B a - - 1)1/3, ~--.~ Ba'-- m e a s u r e t h e c u r r e n t d i s t r i b u t i o n on an e l e c t r o d e , f r e -
q u e n t l y at t h e l i m i t i n g c u r r e n t , it w o u l d be v a l u a b l e
Then we can write to assess t h e e r r o r i n t r o d u c e d b y t h e n o n z e r o t h i c k n e s s
of t h e insulator. One s t a n d a r d of c o m p a r i s o n w o u l d
C| - - Ca C| ( r 2 3 - - r l 3 ) 2/3 be t h e r i n g c u r r e n t d i v i d e d b y t h e c u r r e n t d e n s i t y on
Jr -- - - ro2N -Jr" -~ the d i s k a n d t h e a r e a of the r i n g e l e c t r o d e . F r o m Eq.
2 r (4/3) 2 r (4/3) [24], this r a t i o is g i v e n b y
C| ( r 2 3 r l 3 ) 2/3
- - jctN d-
- -

[24] (r23 __ r13)2/a __ ro2N

2 r (4/3) ]1 = [28]
r22 -- rl 2
If no o t h e r r e a c t i o n s occur, t h e r a t i o of t h e t o t a l r i n g and is t a b u l a t e d in T a b l e II. D e p a r t u r e s of this r a t i o
c u r r e n t to t h e t o t a l d i s k c u r r e n t for t h e first case in f r o m u n i t y s h o w by h o w m u c h t h e a v e r a g e c u r r e n t
T a b l e I is f o u n d to be d e n s i t y on t h e r i n g e x c e e d s t h e c u r r e n t d e n s i t y on t h e
-- Jr/in = N [25] disk. S i n c e l i m i t i n g c u r r e n t s a r e b e i n g c o n s i d e r e d , t h i s
c u r r e n t d e n s i t y o n t h e d i s k is t h e a p p r o p r i a t e s t a n d a r d
since in t h i s case c , ---- 0 a n d atl t h e a c t i v e i n t e r m e d i a t e since it w o u l d p r e v a i l e v e r y w h e r e if t h e i n s u l a t i n g
w h i c h r e a c t s on t h e r i n g is p r o d u c e d at t h e disk. Then, a n n u l u s w e r e of z e r o thickness.
N is c a l l e d t h e c o l l e c t i o n efficiency, a n d Eq. [22] a g r e e s As a second s t a n d a r d of c o m p a r i s o n , w e t a k e t h e
exactly with the expression derived by Albery and r i n g c u r r e n t d i v i d e d b y t h e c u r r e n t d e n s i t y on t h e disk
B r u c k e n s t e i n (1) b y a n o t h e r m e t h o d . T h e s e a u t h o r s and t h e a r e a of b o t h t h e r i n g e l e c t r o d e a n d t h e i n s u l a t -
h a v e t a b u l a t e d v a l u e s of N for g i v e n v a l u e s of rl/ro ing annulus. This r a t i o is g i v e n b y
a n d r2/rl. T h e a n a l y t i c f o r m of t h e r e s u l t m a k e s it
easy to e v a l u a t e N n u m e r i c a l l y for v a l u e s of rl/ro a n d (r2 s _ rl 3) 2/3 _ ro2N
r2/rl o u t s i d e t h o s e t a b u l a t e d . f2 = [29]
r 2 2 - - 7"o2
F o r case III, w h e n t h e r e is no d i s k e l e c t r o d e , Cd = C.,
a n d t h e t o t a l flow to t h e r i n g r e d u c e s to and is t a b u l a t e d in T a b l e III. Again, d e p a r t u r e s of this
ratio f r o m u n i t y s h o w b y h o w m u c h t h e a v e r a g e c u r -
(r23 -- r13)2/3 r e n t d e n s i t y on t h e r i n g a n d a n n u l u s is less t h a n t h e
3r = c| [26] c u r r e n t d e n s i t y on t h e disk.
2 r (4/3)
F o r t h i n i n s u l a t o r s or w i d e rings, b o t h of t h e s e
a r e s u l t first o b t a i n e d b y L e v i c h (16) and l a t e r b y ratios a p p r o a c h unity. F o r a r i n g e l e c t r o d e w h o s e a r e a
I b l (17) and R o s n e r (10).
T h e g e o m e t r i c q u a n t i t y N can also b e m e a s u r e d w i t h
Table II. Total ring current divided by the current density on
a ring-disk system where both electrodes are operated
the disk and the area of the ring (from Eq. [28]) for the case
at t h e l i m i t i n g c u r r e n t for t h e s a m e reaction. E q u a -
where both the ring and the disk are at limiting current
tions [21] a n d [24] t h e n y i e l d for t h e r a t i o of t h e t o t a l
for the same reaction
r i n g c u r r e n t to t h e t o t a l disk c u r r e n t , since Cd = 0
(case II in T a b l e I)
r~/ro 1.1 1.2 1.5 2 3
j~ (r2 3 _ r13) 2/3
.-:- = N [27]
3d ro2
~22 -- ~12
in a g r e e m e n t w i t h t h e r e s u l t of B r u c k e n s t e i n (18). 0.05 1.0366 1.0390 1.0395 1.0401 1,9409
0.1 1.0720 1.0724 1.0735 1.0749 1.6767
T h e r o t a t i n g r i n g - d i s k e l e c t r o d e s y s t e m is u s u a l l y 0.2 1.1304 1.1313 1.1336 1.1366 1.1400
u s e d as a p o l a r o g r a p h i c i n s t r u m e n t ; species w h i c h are 0.5 1.2713 1.2736 1.2795 1.2860 1.2928
1 1.4497 1.4540 1.4641 1.4746 1.4846
g e n e r a t e d at t h e d i s k a r e d e t e c t e d on t h e ring. T h e 2 1.7112 1.7181 1.7337 1.7491 1.7628
p r e s e n c e of u n s t a b l e i n t e r m e d i a t e s can be d e t e c t e d in 5 2.2156 2.2269 2.2514 2.2744 2.2940
10 2.7431 2.7584 2.7910 2.8209 2.8459
this way, b u t it is difficult to t r e a t q u a n t i t a t i v e l y t h e 20 3.4247 3.4446 3.4869 3.5252 3.5569

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 Vol. 119, No. 2 RING-DISK AND SECTIONED DISK ELECTRODES 215

Table Ill. Total ring current divided by the current density on Table IV. Sectioned-electrode measurements at limiting current
the disk and the area o~ both the ring and the annulus All solutions were IM in KN03. Solutions I, II, and III
(from Eq. [29]) far the case where both the ring and the disk were 0.005, 0.01, and O.05M respectively, in both
are at limiting current for the same reaction K4Fe(CN)e and K3Fe(CN)6

r2/ro 1.1 1.2 1.5 2 3

Rotation Ir Ir ro 2
Ring-disk speed -- )cs
rt2 - - re2 assembly Solution (rpm) la Ia r ~ -- to2 theory

r ~ - r~2
0.05 0.9894 0.9895 0.9900 0.9906 0.9914 RD1 I 1550 0.858 4- 0 . 1 % 0.879 0.871
0.1 0.9746 0.9749 0.9759 0.9772 0.9788 II 1550 0.852 ----0 . 9 % 0.872
0.2 0.9420 0.9427 0.9447 0.9471 0.9500 III 1550 0.852 -4- 0 . 1 % 0.872
0.5 0.S475 0.8491 0.8530 0.8574 0.8619 III 2500 0.847 -----0 . 1 % 0.867
1 0.7248 0.7270 0.7320 0.7373 0.7423 III 750 0.855 0.1% 0.876
2 0.5704 0.5727 0.5779 0.5830 0.5876 RD2 I 1550 2.300 -- 0.1% 0.801 0.798
5 0.3693 0.3712 0.3752 0.3791 0.3823 II 1550 2.308 0.2% 0.804
10 0.2494 0.2508 0.2537 0.2564 0.2587 III 1550 2.312 -- 0.2% 0.805
20 0.1631 0.1640 0.1660 0.1679 0.1694 III 2500 2.305 0.1% 0.803
III 750 2.295 -4- 0 . 5 % 0.800
RD3 III 750 0.832 0.02% 0.875 0.879
III 1550 0.833 0.3% 0.876
is t e n t i m e s t h e a r e a of t h e i n s u l a t o r , t h e e r r o r r e p r e - III 2500 0.831 "*- 0 . 0 3 % 0.874
s e n t e d b y t h e r a t i o f2 c a n b e e x p e c t e d to b e less t h a n
3 % w h i l e t h a t r e p r e s e n t e d b y I1 c a n b e g r e a t e r t h a n T h e r e f e r e n c e e l e c t r o d e w a s a s t r i p of p l a t i n u m
7%. T h e s e r a t i o s t h u s p r o v i d e a b a s i s f o r t h e d e s i g n p a r t i a l l y i m m e r s e d i n a side a r m c o m p a r t m e n t filled
of r i n g - d i s k s y s t e m s f o r c u r r e n t - d i s t r i b u t i o n s t u d i e s . w i t h t h e s o l u t i o n b e i n g i n v e s t i g a t e d . T h e side c o m -
S i m i l a r c o n s i d e r a t i o n s a p p l y to t h e d e s i g n of s e c t i o n e d partment was connected through a Luggin capillary
electrodes for other geometries when mass-transfer to t h e m a i n s o l u t i o n . T h e c a p i l l a r y t i p w a s p o s i t i o n e d
l i m i t a t i o n s d e t e r m i n e t h e c u r r e n t d i s t r i b u t i o n (see i n t h e p l a n e of t h e d i s k s u r f a c e a t 2.27 c m f r o m t h e
Appendix II). c e n t e r of t h e r i n g - d i s k a s s e m b l y .
T h e r a t i o f2 d e p e n d s m o s t s t r o n g l y o n t h e r a t i o of The anodic limiting current was attained with over-
t h e a r e a of t h e i n s u l a t o r to t h e a r e a of t h e r i n g e l e c - p o t e n t i a l s b e t w e e n + 4 0 0 m V a n d W800 m V . I n t h e
t r o d e . C o n s e q u e n t l y , w e h a v e u s e d t h i s f o r o n e of t h e limiting current region, both the ring current and disk
g e o m e t r i c p a r a m e t e r s i n T a b l e s II a n d III. W i t h a c u r r e n t w e r e c o n s t a n t w i t h p o t e n t i a l . I n T a b l e I V is
s t r o n g d e p e n d e n c e o n t h i s p a r a m e t e r , t h e c h o i c e of l i s t e d t h e r a t i o of r i n g c u r r e n t to d i s k c u r r e n t , i n t h e
t h e o t h e r p a r a m e t e r b e c o m e s less i m p o r t a n t ; w e c h o s e limiting current region, for each solution used and at
r2/ro, t h e r a t i o of t h e o u t e r r a d i u s of t h e r i n g to t h e s e v e r a l r o t a t i o n speeds. T h e r e s u l t s a r e t h e a v e r a g e
r a d i u s of t h e d i s k e l e c t r o d e . T h e s e g e o m e t r i c p a r a m e - of s e v e r a l r u n s , a n d t h e p e r c e n t of a v e r a g e d e v i a -
t e r s r e p l a c e t h e r a t i o s r l / r o a n d r2/rs. t i o n is a l s o g i v e n . A l s o g i v e n is t h i s r a t i o m u l t i p l i e d
b y t h e r a t i o of d i s k a r e a t o t h e a r e a of i n s u l a t i n g
Experimental D e t e r m i n a t i o n of C u r r e n t Distributions a n n u l u s p l u s r i n g e l e c t r o d e . T h i s m a y b e c o m p a r e d to
T h e e x p e r i m e n t a l i n v e s t i g a t i o n of t h e s e p r e d i c t i o n s t h e v a l u e of f2, also listed, c a l c u l a t e d f r o m Eq. [29].
w a s d i v i d e d i n t o t w o p a r t s . T h e first o b j e c t i v e w a s The experimental results agree with the predictions
to i n v e s t i g a t e w h e t h e r or n o t Eq. [29] w a s o b e y e d a t of Eq. [29] to b e t t e r t h a n 1%. Also, t h e r e is n o d e -
limiting current for the solutions used here. The sec- p e n d e n c e o n c o n c e n t r a t i o n or r o t a t i o n s p e e d , w h i c h is
o n d p a r t w a s to i n v e s t i g a t e t h e d e p a r t u r e f r o m t h i s also c o n s i s t e n t w i t h Eq. [29]. T h e d e v i a t i o n f r o m f2
e q u a t i o n b e l o w t h e l i m i t i n g c u r r e n t , i.e., to d e t e r - ( t h e o r y ) is c o n s i d e r e d to b e w i t h i n e x p e r i m e n t a l e r r o r .
mine whether or not a nonuniform current distribution T h e l a r g e s t e r r o r w a s p r o b a b l y t h e m e a s u r e m e n t of
could be observed. the electrode dimensions.
T h e e l e c t r o l y t i c s o l u t i o n s u s e d w e r e c o m p o s e d of T h e s e c o n d p a r t of t h e i n v e s t i g a t i o n , i.e., s e c t i o n e d
KNO3, K 4 F e ( C N ) 6, a n d K3Fe ( C N ) 6. T h e c o n c e n t r a t i o n electrode measurements below the limiting current,
of KNO3 w a s a l w a y s 1 m o l a r , a n d t h e c o n c e n t r a t i o n s w o u l d b e e x p e c t e d to r e v e a l a h i g h e r v a l u e of f2
of t h e o t h e r t w o c o m p o n e n t s w e r e v a r i e d b u t t h e i r ( m e a s . ) t h a n p r e d i c t e d b y Eq. [29]. T h i s is t h e r e s u l t
r a t i o w a s a l w a y s 1. F r e s h , f i l t e r e d s o l u t i o n s w e r e u s e d o b t a i n e d , as s h o w n i n Fig. 1 a n d 2. ,~ is t h e d e v i a t i o n
f o r t h e d e t e r m i n a t i o n s b e c a u s e it w a s f o u n d t h a t t h e of t h e m e a s u r e d r e s u l t s f r o m p r e d i c t i o n s of Eq. [29],
s o l u t i o n s d e c o m p o s e s l o w l y u p o n e x p o s u r e to l i g h t a n d p l o t t e d i n Fig. 1 as a f u n c t i o n of t h e f r a c t i o n of l i m i t -
air. T h e m e a s u r e m e n t s w e r e m a d e a t a b o u t 23~ i n g c u r r e n t o n t h e d i s k p l u s r i n g . ~ is z e r o a t l i m i t i n g
T h e r o t a t i n g r i n g - d i s k s w e r e c o n s t r u c t e d of p l a t i n u m c u r r e n t , a n d i n c r e a s e s w i t h d e c r e a s i n g i m p o r t a n c e of
w i t h e p o x y i n s u l a t i o n . T h e r e l e v a n t d i m e n s i o n s of t h e the concentration overpotential and the increasing im-
a s s e m b l i e s w e r e : r i n g - d i s k 1 ( R D 1 ) , ro = 0.441 cm, r~ p o r t a n c e of o h m i c p o t e n t i a l d r o p as t h e c u r r e n t is d e -
---- 0.502 cm, r2 = 0.620 cm, a n d o v e r - a l l r a d i u s 1.27 c m ; creased below the limiting current. The ferro-ferri-
r i n g - d i s k 2 ( R D 2 ) , ro -= 0.322 cm, rs --~ 0.478 cm, r2 ---- cyanide system was not under kinetic control in the
0.633 cm, a n d o v e r - a l l r a d i u s 1.27 c m ; r i n g - d i s k 3 concentration and potential ranges used here.
( R D 3 ) , ro = 0.441 cm, r l =- 0.498 cm, r2 ---- 0.616 cm, C u r v e s A a n d B of Fig. 1 w e r e o b t a i n e d f o r R D 2
a n d o v e r - a l l r a d i u s 1.27 c m . T h e r i n g - d i s k s w e r e p o l - a n d RD3 a t t h e s a m e r o t a t i o n s p e e d i n s o l u t i o n s of
ished before each run on a metallographic wheel with the same composition. The difference between the two
0.05~ a l u m i n a . c u r v e s is d u e to t h e d i f f e r e n t g a p w i d t h s of t h e t w o
The ring-disks were operated potentiostatically with assemblies.
a Wenking potentiostat. Both were operated anodically. S i n c e t h e o u t e r r a d i i of R D 2 a n d RD3 a r e a p p r o x i -
O n e o u t p u t f r o m t h e p o t e n t i o s t a t w a s t a k e n to a p a r a l - mately equal, curves A and B were obtained with
lel c i r c u i t i n o n e leg of w h i c h w a s a p r e c i s i o n r e s i s t o r t h e s a m e v a l u e o f t h e d i m e n s i o n l e s s r o t a t i o n s p e e d , N,
a n d t h e c o n n e c t i o n to t h e disk, a n d i n t h e o t h e r leg of N e w m a n ' s t h e o r y (9) ( n o t to b e c o n f u s e d w i t h t h e
w a s a v a r i a b l e r e s i s t o r a n d t h e c o n n e c t i o n to t h e r i n g . c o l l e c t i o n efficiency N ) . T h i s p a r a m e t e r is d e f i n e d as
F o r m e a s u r e m e n t s at t h e l i m i t i n g c u r r e n t , t h e p o t e n t i a l
drop across each resistor was measured, and the cur- ZFr2ilim
N ---- - - r ( 4 / 3 ) - ~
rent was calculated from this and the measured re- R T K~
s i s t a n c e of e a c h r e s i s t o r . F o r m e a s u r e m e n t s b e l o w t h e
limiting current, the potential across the resistors was T h e v a l u e s of N f o r c u r v e s A a n d B a r e I 5.84 a n d 5.89,
m a t c h e d to w i t h i n 0.05 m V . F r o m t h i s a n d t h e m e a - r e s p e c t i v e l y . T h e p a r a m e t e r is a m e a s u r e of t h e r e l a -
sured resistance, the current through each resistor was t i v e i m p o r t a n c e of t h e o h m i c p o t e n t i a l d r o p as c o r n -
calculated. These potential drops were measured with 1 T h e v a l u e s o f hr w e r e c a l c u l a t e d f r o m 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
a Honeywell potentiometric strip chart recorder. a n d t h e c o n d u c t i v i t y o f 1M K N O 3 , i . e . , ~ = 0.1 o h m - 1 c m - L

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 216 J. E l e c t r o c h e m . Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y F e b r u a r y 1972

B r u c k e n s t e i n and Miller (21) recently reported m e a -

I i
o.4
A c u r r e n t d i s t r i b u t i o n more uniform. They do not report
O.5~-
/k o.z B -
0.1
0 ,
0 0.2 0.4 0.6
Froct{on of l i m i t i n g current to t h e ring plus disk
Fig. I. A as a function of the fraction of limiting current. Curve
A-RD3, 1550 rpm, 1M KNO3, 0.05M K3Fe(CN)6, 0.05M K4F3(CN)6.
Curve B-RD2, 1550 rpm, 1M KNO3, 0.05M K3Fe(CN)6, 0.05M
K4Fe(CN)6. Curve C-RD3, 1550 rpm, 1M KNO~, 0.005M K3Fe(CN)6,
0.005M K4Fe(CN)6. I--indicates standard deviation.
i i i i
0.4
A ~ o . 6 ~
0.2
0.85
I
,I I I
8 I0 12 14
~--~I/2 (sec_l/2)
Fig. 2...4 as a function of rotation speed. Numbers on the curves
indicate the fraction of limiting current on ring plus disk. RD3--
1M KNO3, 0.05M K3Fe(CN)6, 0.05M K4Fe(CN)6. I--indicates
standard deviation.
pared to the concentration overpotential at a particu-
lar fraction of limiting current.
The effect of changing N was measured in two ways.
First, the composition of the solution was changed
from 0.05M in both ferrocyanide and ferricyanide to
0.005M in both ferrocyanide and ferricyanide. With
this solution, the value of N is 1 0.595 for RD3, and
curve C of Fig. 1 was obtained. These results m a y be
compared to curve A. Thus, by reducing the concen-
t r a t i o n of ferro-ferricyanide, one reduces the impor-
tance of the ohmic potential drop, at a particular
fraction of l i m i t i n g current, and the c u r r e n t becomes
more uniform.
N was also changed b y v a r y i n g the rotation speed,
with the results shown in Fig. 2. The increase of ro-
tation speed increases N and thus the importance of
the ohmic drop, producing a less u n i f o r m c u r r e n t dis-
tribution.
Conclusions
It has been possible to d e t e r m i n e the error involved
in using the r i n g - d i s k system as a sectioned electrode.
The predictions for operation at l i m i t i n g c u r r e n t were
verified by e x p e r i m e n t w i t h i n 1%. W h e n operated
below the limiting current, a n o n u n i f o r m c u r r e n t
d i s t r i b u t i o n is observed. The average c u r r e n t density
on the r i n g is higher t h a n the average c u r r e n t d e n s i t y
on the d i s k - - a n observation which is consistent with
N e w m a n ' s theory (9).
I I surements similar to those here but with a NaBr-
HC104 system. Their m e a s u r e m e n t s also revealed a
n o n u n i f o r m c u r r e n t distribution. They found that an
increase in conductivity (thus reducing N) made the
values of the i m p o r t a n t parameters for their system,
nor even the location of the reference electrode, so a
more direct comparison with the present results is not
possible. It is surprising, however, that the ratio of
ring c u r r e n t density to disk c u r r e n t density, which
they measure, is constant for various fractions of
limiting c u r r e n t (which fractions they do not specify).
This should be contrasted with the data reported here,
in Fig. 1. The e x p l a n a t i o n for this behavior is not
clear, but it m a y be related to the kinetic complica-
tions of the NaBr-HC104 system (22).
The diffusion coefficient for the ferrocyanide ion in
the systems used here has been calculated from the
,,
measured anodic limiting currents, a n d the equation
0.8 1.0 (3, 9)
nEe= a y/s
iur, = r (4"13) ( "3"/ 12~/2D~/Zv-1/~
In making the calculations, the viscosity of water and
the density of 1M KNO3 were used. The viscosity of
1M KNOz, 0.05M ferrocyanide, 0.05M ferricyanide was
found to be the same as that for w a t e r ( w i t h i n 5%)
at the same temperature. The results are:
(i) 1M KNOz, 0.05M KzFe(CN)6, 0.05M K4Fe(CN)6
rotation speeds of 750, 1550, and 2500 r p m
Di -- 0.567 X 10 -5 cm2/sec with a s t a n d a r d de-
viation of 0.0166 X 10 -5 cruZ/see.
(ii) 1M KNOz, 0.01M KzFe(CN)6, 0.01M K4Fe(CN)~
rotation speed of i550 r p m
Di --- 0.599 10 -5 cm2/sec with a standard de-
viation of 0.007 10 -5 cm2/sec.
(iii) 1M KNOB, 0.05M K3Fe(CN)6, 0.005M K4Fe(CN)6
I rotation speed of 1550 r p m
16 8 Di = 0.577 10 -5 cm2/sec with a s t a n d a r d de-
viation of 0.013 10-z cm2/sec.
The value of Di = 0.606 X 10-5 cm2/sec is predicted
from the correlation of Gordon, Newman, and Tobias
(23). This compares favorably with that reported here.
The theoretical results for sectioned electrodes can
be extended to a v a r i e t y of geometries i n v o l v i n g
forced, l a m i n a r convection, as shown in A p p e n d i x II.
Acknowledgment
This work was supported by the U n i t e d States
Atomic E n e r g y Commission and b y Boeing Scientific
Research Laboratories.
We wish to acknowledge the help of Robert L. Lee
of BSRL in m a k i n g the e x p e r i m e n t a l measurements.
Manuscript submitted March 8, 1971; revised m a n u -
script received ca. Sept. 29, 1971.
A n y discussion of this paper will appear in a Dis-
cussion Section to be published in the December 1972
JOURNAL.
APPENDIX I
First let us evaluate the integral
(1 - - ~)2/s (1 - - xZ) 2/3 (1 - - x3) 2Is
[30]
I n the first integral, make the substitution y = xZ; in
the second, m a k e the substitution
e3 = 1/x ~ - 1 [31]
Then we have

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 Vol. 119~ No. 2 R I N G - D I S K AND SECTIONED DISK ELECTRODES 217

ff xdm 15o~ dy ff d~
(1 Z ~)2/3 -- "-3 ~jl/3(1 __ y)2/3 -- 1 ~ 03 y
1 2 ~ 1 do
l(x 1 __
1
3
o 2--~
02--0+ 1
do=r (:-) r

1 1
~ln (1+o) +--ln(o 2-o+ 1)
3 6

1 t a n -1 2 0 - - 1 ]0 (2) (4) Fig. 3. An electrode on an axisymmetric body with axisymmetric

flow.
1 1 + 03 1 20 -- 1
-{- - - In --, tan- ~ - - tion (19, 20) is useful for treating such diffusion layers.
6 ( I + 0)a V~ - ~/~- 6~/3
[32] The diffusion-layer form of Eq [1] then is
Next we w a n t to evaluate the integral Oci 1 (~[3)' Oc~ 02ci
~':; ( A ~ - - x~) ~/3 dx y~ y2 _ _ -- Di [42]
I [33] 0x 2 ~ ay ~y2
J1 (X 3 - - 1) 2/3 X
where the coordinate system is indicated in Fig. 3, fl (x)
where A :~ x > 1. Let is the velocity derivative Ovx/Oy at y = 0, and for an
axisymmetric body ~ ( x ) is the distance of the surface
= x3/(x 3 - - 1) [34] from the axis of symmetry. For t w o - d i m e n s i o n a l dif-
Then fusion layers, ~ = 1. Outside the diffusion layer, at
y = ~ , the concentration is ci = c|
do) We solve the p r o b l e m first for the b o u n d a r y condi-
3 ~ .,(~,- 1) 3 w(fl~ - - 1) 1/3 tions on the surface

d~ c~:c| at y : 0 , X<Xo

where
- - (1 - - fl) f (~ - - 1) (fl~ - - 1) 1/3 ] [35] ci:0 at y : O , x ~ - - X o Y [43]

[3 1 -- 1/A 3 [36] In terms of the similarity v a r i a b l e

I n the first i n t e g r a l let y3 = /~ -- 1; in the second i n

t e g r a l let y3 = ( ~ _ 1 ) / ( 1 -- t~) T h e n we have = [44]

i = A2 ~,~ ydy ~ ydy the solution is (for x > Xo)

1+y3 * 1-t-y3 [37]
where c~ = o ( 0 - - - - 1 f: e-~ dx [45]
r (~o~ 1) z/3 1 ( A3-- x3 ) 1/3 c~ r (4/3)
= -- [38]
A ~---1 which gives for the concentration derivative at the
wall
The integrals here can now be evaluated in a m a n n e r
used above for the first integral
Oci c| [9D~ ]1/3
f ~ ydy f ~r ydy
I= (A2--1) o l+y 3 F l_}_y 3
The above solution can be used to treat the case of a
$ ydy v a r y i n g surface concentration by superposition of re-
-- A2 f9"o - -
l+y3
_ (,4.2 -- 1)r(4/3)r(2/3) sults for appropriate changes in the surface concen-
tration at m a n y points xo along the surface
1 1 FA3~ 3 1 [ 2A~--I \
+--ln ~ ~tan 1 L ) +
6 (1 + A ~ ) 3 __ ~ 6~3 -~ ~=0 r(4/3) ~ ~=~o
1 1+~ 3 dxo
- - A2 --ln [47]
6 ( i + ~)~
1 2~-- 1

By means of the coordinate t r a n s f o r m a t i o n

Note that
r (2/3) r (4/3) = 2~/3~v~ [40]
and that r3 = ~ X / ~ dx and f = YX/I~r

tan
( 2~--1 ) = ~ tan ~ (1) [41] [9D, f ~ x / -~ dx J11/a [48]
Eq. [47] becomes
A P P E N D I X II
Oci --r i'r dco ] dr'
Diffusion Layers in L a m i n a r Forced Convection O~ ~=o = r ( 4 / 3 ) ] r=r' (r3--r'Z) 113 [49]
at High Schmidt N u m b e r s
Because the diffusion coefficient is so small in elec- which is the same as Eq. [6]. The coordinate t r a n s -
trolytic solutions, the diffusion layer generally lies formation [48] also reduces Eq. [42] to Eq. [4].
v e r y close to the electrode surface and it is appropriate Equation [49] should have the same inverse [7] as
to approximate the velocity components by the first Eq. [6]. We can derive this in a more straightforward
terms in their power-series expansions in the n o r m a l m a n n e r than that used in Ref. (11) b y following
distance from the surface. The Lighthill t r a n s f o r m a - Tribus and K l e i n (15), p. 215. Write Eq. [49] as

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 218 J. Electrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y F e b r u a r y 1972

OCi --r' ~r" dco I dx (but not stated explicitly). ]1 is the c u r r e n t to the
! [50] second electrode divided by the c u r r e n t which w oul d
0~ ~=0 r(4/3) "o [ ~=~ (r'~ _ x s) ,/8 flow to the area of t h e second electrode if the in-
r=r" sulator w e r e an electrode, f2 is the c u r r e n t to the sec-
Multiply by (r 3 -- r '3) -2/3 3r'dr' and integrate from 0 ond electrode divided by the c u r r e n t w h i ch w o u l d flow
to r. to the combined area of the second electrode and the
insulator if the insulator w e r e an electrode.
;roc, t r'dr' ~r 3r'2 Consider the special case of sectioned electrodes in
3 ~ o-~ ~=0 (ra _ r'3)2/3 -- r(4/3----~ the wall of a flow channel (or a tube or an annulus).
f~ =f~o, a constant, and ~ is a constant. Then, according
f o r" rico dx dr' to Eq. [48]
[51] r3 = x ~ / ~ o [57]
T r=x (?,'3__ X3)1/3 ( r 3 _ r,3)2/3
Tables II and III still apply, but A = r2/ro = (x2/xo) 1/8
I n t e r c h a n g e the order of i n t e g r a t io n on the right. and B = rl/ro = (xl/xo) 1/3, and the p a r a m e t e r s on
~or 0c, I r'dr' --1 fr dco those tables are
3 ~ ~=0 ( r3 - - r'3) 2/3 - - r(4/3) "o - - ~ r ~=x r2 /X2~ 1/3 r12--ro 2 x12/3--Xo 2/3
ro )\'~o/
~ and r22 _ r l 2 x22/3 _ Xl 2/3 [58]
3r'2dr'
S~ dx [52]
(r,3 _ x 3) ,/s (r3 __ r'3) 2/3 NOMENCLATURE
a = 0.51023
In the i n n e r integral, let A = r2/ro
y = (r'~ -- x S ) / ( r 3 -- x 3) B = rl/ro
so t h a t c~ concentration of the species of interest ( m o l e /
cm 3)
~r 3r'2dr ' = ~' dy co surface concentration of the species of interest
( m o l e / c m 3)
x (r'3 -- X3) 1/3(T3 - - r'3)2/3 yl/3(1--_ y)2/3 c. concentration of the species of interest outside
the diffusion l ay er ( m o l e / c m s).
1 2 2:~ ca u n i f o r m concentration of the species of interest
near the surface of the disk electrode ( m o l e / c m 3)
Then w e h a v e D~ diffusion coefficient of the species of interest
(cme/sec)
f~ see Eq. [28]
~= dx = co(r) -- c~ f2 see Eq. [29]
into limiting c u r r e n t density on disk electrode ( A /
--1 t "r Oci r'dr' cm 2)
I see Eq. [33]
-- r(2/3-------) "~'o 0~ ~=0 (r 3 -- r'3) 2/3 [54] Jd proportional to the total m a s s - t r a n s f e r rate to
disk electrode ( m o l e / c m ) .
in a g r e e m e n t w i t h Eq. [7]. The inverse of Eq. [47] can jr proportional to total m a s s - t r a n s f e r rate to ring
thus be written, expressing the surface concentration electrode ( m o l e / c m ) .
as an i n t e g r a l o v e r the flux N dimensionless limiting c u r r e n t density for disk
(Di/3) 1/3 electrode [see Ref. (9) ]
co(x) -- c| -- N collection efficiency for r i n g - d i s k system
r(2/3) r radial distance f r o m the axis of the disk
ro radius of disk el ect r o d e (cm)
fo x Oc~ ~(xo)dxo rl inner radius of ring el ect r o d e (cm)
[55]
r2 outer radius of ring electrode (cm)
~=~o ~V~ dx distance of a x i s y m m e t r i c surface f r o m axis of
xo s y m m e t r y (cm)
Sc ----~/D~, the S c h m i d t n u m b e r
With these results w e can n o w work, for various v fluid velocity ( c m / s e c )
geometries, the same problems as outlined in Table I. x distance along electrode (cm)
The collection efficiency p r o b l e m m a y then not be y n o r m a l distance f r o m the electrode surface (cm)
realistic since we h a v e no justification for assuming t~ velocity d e r i v a t i v e at the wall ( s e c - D
that the surface concentration is u n i f o r m on the first r g a m m a functiort
electrode (unless the first electrode is at limiting cur- dimensionless n o r m a l distance for the diffusion
rent for the reaction w h i c h produces the active in- layer (see also Eq. [48])
t e r m e d i a t e ) . The third p r o b le m is t r iv ia l since we o = (r3/ro a 1) 1/3
- -

w o r k e d it out before the superposition (see Eq. [46]). : (B 3 -- 1)'/~

Let us h a v e two electrodes g i v e n by ~ solution c o n d u c t i v i t y outside the diffusion layer
O~--r~--ro and r l ~ r - - ~ r 2 (mho/cm)
v kinematic viscosity (cm2/sec)
with an insulator b e t w e e n (ro < r < rD. On the first see Eq. [44]
electrode, co = Cd, and Eq. [12] gives the flux. On see Eq. [23]
the insulator, ~c~/tg~ = 0 at i" = 0, and the surface i~ rotation speed ( r a d i a n / s e c )
concentration is given by Eq. [13] or [14]. On t h e
second electrode, Co = 0, and the flux is given by REFERENCES
Eq. [18]. 1. W. J. A l b e r y and S. Bruckenstein, Trans. Faraday
Note that Soc., 62, 1920 (1966).
2. W. Nernst, Z. Physik. Chem., 2, 613 (1888).
Jr= f~ 2 0cl ~=0
rdr
3. V. Levich, Acta Physicochim. U. R. S. S., 17, 257
(1942).
4. J. Newman, Advan. Electrochem. Electrochem.
( Di )1/3 ~x2 0Ci Eng., 5, 87 (1967).
= ~- ~, ~ .=0~dz [56] 5. W. H. S m y r l and J. Newman, This Journal, 118,
1079 (1971).
6. Th. v. K~rm~n Z. Angew. Math. Mechan., 1, 233
and is proportional to the total flow to the second (1921).
electrode. Similarly, Jd is proportional to the total 7. W. G. Cochran, Proc. Cambridge Phil. Soc., 30,
flow to the first electrode, and Eq. [21] and [24] 365 (1934).
apply. 8. E. M. S p a r r o w and J. L. Gregg, J. Heat Transfer,
F u r t h e r m o r e , for sectioned electrodes at the limiting 81C, 249 (1959).
current, fl and f2 have the m e a n i n g originally intended 9. J. Newman, This Journal, 113, 1235 (1966).

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 Vol. 119, No. 2 RING-DISK AND SECTIONED DISK ELECTRODES 219

10. D. E. Rosner, ibid., 113, 624 (1966). 18a. S. Bruckenstein, Elektrokhimiya, 2, 1085 (1966).
11. J. Newman, ibid., 114, 239 (1967). 18b. D. T. Napp, D. C. Johnson, and S. Bruckenstein,
12. D. E. Rosner, Symp. (International) Combust. Anal. Chem., 39, 481 (1967).
11th, pp. 181-194 (1967). 19. M. J. Lighthill, Proc. Roy. Soc., Ser. A, 902, 359
13. P. L. Chambr~, Appl. Sci. Res., 6A, 97 (1956). (1950).
14. P. L. Chambr~ a n d A. Acrivos, J. Appl. Phys., 27, 20. J. Newman, Ind. Eng. Chem., 60, 12 (1968).
1322 (1956). 21. S. B r u c k e n s t e i n and B. Miller, This Journal, 117,
15. M. Tribus and J. Klein, Heat Transfer Symp. Univ. 1044 (1970).
Mich. 1952, 211 (1953).
16. V. G. Levich, "Physicochemical Hydrodynamics," 22. W. H. S m y r l and J. Newman, This Journal, 119,
Sect. 18, Prentice-Hall, Inc., Englewood Cliffs, 208 (1972).
N . J . (1962). 23. S. L. Gordon, J. S. Newman, and C. W. Tobias,
17. N. Ibl, This Journal, 108, 610 (1961). Ber. Bunsen. Physik. Chemic, 70, 414 (1966).

Electrochemical and Chemical Corrosion of

Tungsten Carbide (WC)
John D. Voorhies *,1
Chemical Engineering Department, Stanford University, Stanford, California 94305

T u n g s t e n carbide (WC) has attracted interest in Sample II was obtained from Norton Company,
recent years because of its electrocatalytic properties Worcester, Mass., and also shows a clean diffraction
in anodic reactions of S2, CO, and other fuels (1-6). p a t t e r n with exact WC stoichiometry. The surface area
Bianchi et al. (7) have studied the general electro- is 2 m2/g.
chemical properties of a low area WC surface and All electrochemical m e a s u r e m e n t s were obtained
Mazza and Trasatti (8) have used WC as an "inert" with the W e n k i n g 61-TR S t a n d a r d Potentiostat used
electrode m a t e r i a l for solution redox measurements. only in its simple static mode with m a n u a l a d j u s t m e n t
In the work of Binder et al. (4, 5) and Pohl and of the controlled electrode potential in discrete poten-
BShm (1-3), there is evidence for chemical and electro- tial steps. The w o r k i n g electrode c o m p a r t m e n t was a
chemical reactivity of the WC surface in aqueous elec- P y r e x glass tube 10 cm long with a n I.D. of 11 m m
trolytes. B i n d e r cites anodic passivation of WC with and a fine fritted glass closure at one end, the bottom
evolution of CO2 and speculates that the passivated of the electrode c o m p a r t m e n t i n its n o r m a l vertical
surface consists of WO3 which is reducible to a hydro- orientation. I n the first experiments, the w o r k i n g
gen t u n g s t e n bronze. BShm (6) finds that preanodiza- electrode was contained in this compartment, and the
tion is necessary to achieve moderate levels of hydro- reference electrode was positioned in the electrolyte
gen adsorption on WC. There is also a consensus that outside of the frit. As the frit resistance was 15 ohms
oxidation of the WC surface is necessary for electro- saturated with 2N H2SO, electrolyte, the "controlled
catalytic activity in the anodic oxidation of fuels. potential" was actually the sum of a variable IR com-
The present work is a potentiostatic-coulometric ponent and the electrode potential. Nevertheless, use-
study of the anodic corrosion of WC powder and the ful coulometric i n f o r m a t i o n was obtained in 200-300
cathodic reduction of the surface anode product. Oxi- mV intervals with this setup, and the first two entries
dation of WC b y the one-electron oxidants, ceric sul- in Table I are from m e a s u r e m e n t s of this kind.
fate, and ferricyanide is also described. I n order to obtain more m e a n i n g f u l current-electrode
potential values, a glass sidearm was attached to the
Experimental working electrode c o m p a r t m e n t and the reference elec-
The sample of WC powder (I) used almost exclusively trode placed therein, t h e r e b y contacting the electrolyte
in this work was g r a t e f u l l y received from Prof. Dr.- within the w o r k i n g electrode c o m p a r t m e n t a n d elimi-
Ing. F. A. Pohl and Dr. H. B6hm of A E G - T e l e f u n k e n , n a t i n g the variable IR component.
Forschungsinstitut F r a n k f u r t , 6 F r a n k f u r t ( M a i n ) -
Niederrad, Goldsteinstrasse 235. The BET surface area Table I. Coulombicratio---anodic corrosion:
of this material is 5 m2/g. X - r a y diffraction shows a cathodic reduction of corrosionproduct
clean WC p a t t e r n with lattice constants for the simple
hexagonal structure, a = 2.9004A, c = 2.8444A and a n Sample Anodic Cathodic
average a p p a r e n t particle size from x - r a y line broad- I A E G WC) corrosionS") reductionCb* Ratio
~g) (coulombs) (coulombs) (A:C)
e n i n g of about 300A. Deviation of the lattice constants
from the accepted values, a = 2.906A, c = 2.837A (9)
0.49 15.2 0,S06 18,8
m a y be i n t e r p r e t e d as a slight deficiency of carbon, a 0,224 7.61 0.377 20.2
condition which is claimed (5) to favor electrocatalytic 0.125 5.32 0.246 21.6
0.50 32.9 1.65 19.9
activity of WC. Spectral analysis by uv emission 0.50 17.6 (c~ 0,437 40.2r
indicates about 10 p p m Cu, 2 p p m Mg, and 20 ppm Si.
(at C o r r o s i o n a t o n e or m o r e p o t e n t i a l s i n t h e r a n g e + 0 . 4 5 t o
* Electrochemical Society Active Member. + 0.75V v s . HE.
1 1970-71 S e n i o r E d u c a t i o n a l L e a v e f r o m A m e r i c a n C y a n a m i d Cbl N e t c a t h o d i c r e d u c t i o n of a n o d i c c o r r o s i o n p r o d u c t o n s u r f a c e
C o m p a n y , S t a m f o r d , C o n n e c t i c u t 06904. of WC.
K e y w o r d s : t u n g s t e n c a r b i d e (WC), c o r r o s i o n , s u r f a c e oxide. r E x p e r i m e n t i n 2M H3PO~, a l l o t h e r s i n 2 N H2SOt.

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