The Mechanism of Oxygen Reduction on Iron in Neutral

Solutions
V. Jovancicevic* and J. O'M. Bockris*
Department of Chemistry, Texas A&M University, College Station, Texas 77843

ABSTRACT
The pathways and r a t e - d e t e r m i n i n g steps of o x y g e n r ed u ct i o n on iron in neutral pH range have been investigated.
The various mechanistic criteria are obtained as a function of the nature of the electrode surface: bare iron and passive
iron. The oxygen reduction on bare iron proceeds through 4e pathways with little hydrogen peroxide as an intermediate
and formation of superoxide radical in the rds. On passive iron, oxygen reduction proceeds through a 2e- pathway with
the formation of hydrogen peroxide as a reaction product. An rds involving chemisorption of oxygen is suggested.

A l t h o u g h the anodic reactions for metal and alloy (1-5)
dissolution have been e x t e n s i v e l y studied in solutions of
v a r i o u s pH's, t h e p e r t i n e n t c a t h o d i c p r o c e s s e s h a v e re-
c e i v e d little attention in the i n t e r m e d i a t e pH range (6, 7).
Generally, u n d e r practical conditions, the cathodic reac-
tion of h y d r o g e n ev o l u t io n is the depolarization reaction
in acidic solutions, w h e r e a s t h e o x y g e n r e d u c t i o n reac-
tion acts as a depolarizer in neutral and alkaline solution.
Th e p r i n c i p a l difficulty g e n e r a l l y c o n s i d e r e d to con-
fr ont e x p e r i m e n t a l w o r k in n e u t r a l s o l u t i o n s r e lat es to
alleged c o n t r i b u t i o n s to the p o t e n ti a l c h a n g e caused by
c h a n g e s in pH in t h e v i c i n i t y of t h e d o u b l e la y e r w h e n
the reaction occurs.
Only a few papers have been d e v o t e d to the study of 02
r e d u c t i o n on F e in n e u t r a l solution. F o r o u l i s (6) e x a m -
ined the effect of rotating disk velocity and the dissolved
o x y g e n c o n c e n t r a t i o n on th e initial c o r r o s i o n b e h a v i o r
of a rotating iron el e c tr o d e in " p u r e " water.
F o r 02 r e d u c t i o n at iron e l e c t r o d e s in n e a r - n e u t r a l so-
lutions (7), Delahay c o n c l u d e d that the O2 reaction was a
4 - e l e c t r o n p r o c e s s at p o t e n t i a l s m o r e n e g a t i v e t h a n
- 0 . 6 V (NHE), since little h y d r o g e n p e r o x i d e was de-
tected in solution.
Thus, t h e basic e l e m e n t s of th e m e c h a n i s m of th e re-
duc ti o n of oxygen, i n c l u d i n g the p a t h w a y and rate-deter-
m i n i n g steps, h a v e not b e e n e x a m i n e d in n e u t r a l
solutions.
T h e p r e s e n t study was u n d e r t a k e n to gain in f o r m at i o n
a bou t m e c h a n i s m s of 02 r e d u c t i o n on bare iron and pas-
sive iron in a borate buffer.
Experimental
The e x p e r i m e n t s were carried out in a cylindrical glass
cell u s i n g a r o t a t i n g Fe d i s k - P t ring e l e c t r o d e w i t h re-
m o v a b l e disk (Pine I n s t r u m e n t s ) . T h e iron of p u r i t y of
99.99% was o b t a i n e d f r o m Alfa V e n t r o n C o m p a n y . Th e
F e disk (0.5 cm diam) and Pt ring (0.75 cm id, 1.00 cm od)
e l e c t r o d e s was m e c h a n i c a l l y p o l i s h e d with silicon car-
bide paper, 600 grit (Buehler Limited) and ~ a lu m in a 0.3~
( B u e h l e r L i m i t e d ) and w a s h e d with: t r i p l y distilled
water. T h e s e t r e a t m e n t s of th e s u r f a c e w e r e a p p l i e d to
t he Fe disk e v e r y t i m e b e f o r e i n t r o d u c i n g it in t h e elec-
t r o c h e m i c a l cell.
T h e m e a s u r e m e n t s w e r e m a d e u n d e r c o n d i t i o n s of
c o n t r o l l e d o x y g e n partial p r e s s u r e r a n g i n g f r o m 0 to 1
a t m by u s i n g flow m e t e r s (with N2). T h e c o r r e s p o n d i n g
e l e c t r o d e s eal i n g was c a r r i e d out u s i n g t w o Teflon
O-rings p l a c e d in the cell c o v e r m a c h i n e d from Teflon
with 0.2 m m gap b e t w e e n the rotating e le c t r o d e and the
O-rings. The latter was lubricated with water (Fig. 1)~
Th e r o t a t i n g ri n g - d i s k e l e c t r o d e a s s e m b l y was cali-
b r a t e d u s i n g a f e r r o u s / f e r r i c c o u p l e of 10 -2 and 10 .3
Fe(CN)63- in 0.05M H2SO4. T h e v a l u e of th e c o l l e c t i o n
efficiency, N, d e t e r m i n e d in this w a y was 0.37, w h i c h is
in e x c e l l e n t a g r e e m e n t with the calculated value of 0.38
o b t a i n e d from the given g e o m e t r y using the t r e a t m e n t of
A l b e r y and B r u c k e n s t e i n (9). T h e cell had a s e p a r a t e
c o m p a r t m e n t for the r e f e r e n c e e l e c t r o d e (saturated sul-
fate, SSE) and c o u n t e r e l e c t r o d e (Pt-wire spiral). A
*Electrochemical Society Active Member.
1797
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L u g g i n capillary at a b o u t 2 m m b el o w the r o t a t i n g disk
e l e c t r o d e was used to m i n i m i z e the IR drop. All poten-
tials are r e f e r r e d to t h e n o r m a l h y d r o g e n e l e c t r o d e
(NHE).
T h e p o l a r i z a t i o n V-log i c u r v e s w e r e o b t a i n e d by
m e a n s of t h e p o t e n t i a l step t e c h n i q u e f o l l o w i n g a hold-
ing of the electrode at -0.74 (NHE) for 30 rain in N2 satu-
r at ed s o l u t i o n w h e r e t h e a i r - f o r m e d o x i d e is r e d u c e d .
A f t e r i n t r o d u c i n g t h e 02 for 15 rain at a g i v e n partial
pressure, the cu r r en t was m e a s u r e d at each potential un-
til the steady state value was established (about 1-2 min).
A series of potentiostated, steady-state currents were ob-
served at different potentials going from the cathodic to
the anodic directions. The m e a s u r e m e n t s were repeated
by t a k i n g s t e a d y - s t a t e c u r r e n t s w i t h t h e p o t e n t i a l se-
q u e n c e r ev er sed . Th e v a l u e s o b t a i n e d in t h e s e two pro-
cedures were essentially the same. In s o m e e x p e r i m e n t s ,
t h e p o t e n t i a l was s c a n n e d from the b e g i n n i n g of the
passive range to the h y d r o g e n evolution range at a rate of
0.5 mV/s.
Basic b o r a t e buffer so l u t i o n s w e r e p r e p a r e d f r o m
t r i p l y d i st i l l ed w a t e r of r e s i s t i v i t y m o r e t h a n 10612 cm -1
and 0.0375M analytical-grade s o d i u m t e t r a b o r a t e m i x e d
w i t h 0.15M a n a l y t i c a l - g r a d e boric acid. Th e s o l u t i o n p H
was 8.4. Other solutions of various pH were m a d e by ad-
j u s t i n g the pH w i t h boric acid (pH = 7) and s o d i u m hy-
d r o x i d e (pH = 9.8). S u p p o r t i n g electrolyte of s o d i u m sul-
fate was used at a co n cen t r at i o n of 0.5M in some experi-
ments.
Results
Tafet plots.--Potentiostatic Tafel plots for 02 r ed u c t i on
(Po2 = 1 atm) at different pH's are shown in the potential
r a n g e g o i n g f r o m 0.05V (passive layer) to t h e h y d r o g e n
e v o l u t i o n section (-0.7 V/NHE) in Fig. 2. The activation
peak at about -0.4 V/NHE c o r r e s p o n d i n g to the dissolu-
t i o n of iron is not o b s e r v e d e v e n at pH = 7, a l t h o u g h
RL~t,tL il]~ ]~hlc, I)i!~c I{h'ctrL~d~,
I c r l t m i)-I~iu25s
/ ]'t'l 1,1~1 (:t*l I C~,t'cr
Fig. 1. Rotating electrode sealing with Teflon o-rings
 1798 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 SCIENCE AND TECHNOLOGY S e p t e m b e r 1986

i i
OE ~ 0.15M HaBO3
0 5M H~B03
O0375MNa2B4O~-10H20 20 0 0375M Na2B4OT" 10H20 -043V
~c// PO~ 1 arm
~0
J
ODH7 B=O 14 mA/cm2rpm V2 _~_o._-~--~ - ~ o - - - ~
opHS.4
-0 ~ Z~pH94 P~ss,ve,,o,~

UT -O~
Z

-05 <
E

-0( -0.48V

10 ~ lOs 10~ 10a

i(A/cm ~)
Fig. 2. Tafel plots for 03 reduction on iron in borate buffer solution -0.58V
0,5
"~ -0.68V
s o m e d i s s o l v e d i r o n e q u i v a l e n t to (50 txA/cm -2) c o u l d be
d e t e c t e d u s i n g 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 in t h e in-
termediate potential range. In the polarization curves,
t h e c a t h o d i c c u r r e n t in t h e p o t e n t i a l r a n g e f r o m - 0 . 2 5 to
- 0 . 4 0 V / N H E was n o t c o r r e c t e d for t h e a n o d i c c u r r e n t
0 0101 012 0!03
s i n c e this was n e g l i g i b l e (ring m e a s u r e m e n t s ) c o m p a r e d - V 2 (rpm)-V2
w i t h t h e c a t h o d i c current. T w o Tafel slopes are o b t a i n e d ,
o n e of - 1 1 0 m V / d e c a d e at l o w c u r r e n t d e n s i t i e s (on t h e Fig. 3. ]/i v s . (o - t / 2 plots for O= reduction on bare iron as a function of
p a s s i v e layer) and t h e s e c o n d of - 120 m V / d e c a d e at h i g h potential.
c u r r e n t d e n s i t i e s (on b a r e Fe). T h e T a f e l s l o p e c o r r e -
s p o n d i n g to t h e first r e g i o n e x t e n d s o v e r t w o d e c a d e s of
c u r r e n t d e n s i t y at p H = 9.4, b u t o n l y h a l f a d e c a d e at p H t h e B value, a n d c o n s e q u e n t l y t h e d i f f u s i o n c u r r e n t , by a
= 7. T h e T a f e l s l o p e at h i g h c u r r e n t d e n s i t i e s w a s ob- f a c t o r o f t h r e e . T h i s l a r g e c h a n g e of iL w i t h e l e c t r o l y t e
t a i n e d u s i n g r o t a t i n g d i s k e x p e r i m e n t s in o r d e r to cor- c o n c e n t r a t i o n is d u e to t h e d e c r e a s e in t h e s o l u b i l i t y and
r e c t for t h e d i f f u s i v e c o m p o n e n t of t h e c u r r e n t . d i f f u s i v i t y of 02 by 50 and 25%, r e s p e c t i v e l y (11).'
F o r t h e f i r s t - o r d e r r e a c t i o n w i t h r e s p e c t to d i s s o l v e d 1The anomalous decrease of the solubility of 02 in the presence
02, t h e d i s k c u r r e n t is r e l a t e d to t h e r o t a t i o n rate b y t h e of the supporting electrolyte must be emphasized.
e x p r e s s i o n (10)
1 1 1
- + - - [t]
i ik B ~ '/=
0 48V~
w h e r e ik is t h e k i n e t i c c u r r e n t d e n s i t y for O2 r e d u c t i o n
a n d B is r e l a t e d to t h e d i f f u s i o n l i m i t i n g c u r r e n t (i0 by
t h e e x p r e s s i o n iL = Bo~'/2. B is g i v e n by
B = 0.2 (Do2)2/3v-'/6n 9 F . Co2 [2]
1.00 opH8.4 ~
F i g u r e 3 s h o w s a p l o t of 1/i vs. ~ - , n o b t a i n e d f r o m t h e
e x p e r i m e n t a l d a t a for d i f f e r e n t p o t e n t i a l s f r o m - 0 . 4 3 to
-0.68V NHE. The experimental value of B obtained from
t h e s l o p e in t h e s e plots is 0.14 m A / c m = r p m '/=. T h e theo-
retical v a l u e of B c a l c u l a t e d f r o m Eq. [2] for n = 4, u s i n g
d a t a for t h e s o l u b i l i t y ( 4 . 1 0 -~ m o l / c m 3) and d i f f u s i o n co-
e f f i c i e n t (5 9 10 -6 cm2/sec) of O2 in b o r a t e b u f f e r s o l u t i o n 0,75
E
(11), is 0.13 m A / c m 2 r p m '/2. T h e a g r e e m e n t b e t w e e n t h e s
T
experimental and this calculated value indicates the < /7 / /I/ ~00 0.46V
p r o b a b l e p r e s e n c e of t h e f o u r - e l e c t r o n reaction. E
T h e i n t e r c e p t o f t h e p a r a l l e l s t r a i g h t l i n e s for v a r i o u s
p o t e n t i a l s w i t h 1/i a x i s y i e l d s c o r r e s p o n d i n g l y t h e ik 0 ^
values. T h e s e v a l u e s are u s e d to p l o t t h e V-log i c u r v e at 0.50
h i g h c u r r e n t density. It s h o u l d b e n o t e d t h a t t h e s l o p e of
- 1 2 0 m V / d e c a d e was also f o u n d for t h e d i s k c u r r e n t d i -
////
r e c t l y m e a s u r e d at a r o t a t i o n s p e e d o f 5000 r p m .
/ 9
E f f e c t o f s u p p o r t i n g e l e c t r o l y t e . - - T h e T a f e l p l o t ob-
t a i n e d at h i g h c u r r e n t d e n s i t y (Fig. 2) is n o t c o r r e c t e d for
ohmic drop. This was minimized by using the borate 0.25

b u f f e r s o l u t i o n w i t h 0.5M Na~SO4 as a s u p p o r t i n g electro-

lyte. T h e s l o p e of - 1 2 0 m V / d e c a d e t h e n e x t e n d e d to 10 -2 Without SE B 0 14 mA cm.fpm ~2
A c m -2. With SE B 0.04 mA cm.rprn' 2
T h e e f f e c t o f t h e s u p p o r t i n g e l e c t r o l y t e at d i f f e r e n t
p H ' s on t h e d i f f u s i o n l i m i t i n g c u r r e n t , iL, a n d t h e k i n e t i c
r e d u c t i o n c u r r e n t , ik, is s h o w n in Fig. 4. A s i g n i f i c a n t ef- I
0.101 0.02 0.03
f e c t o f t h e s u p p o r t i n g e l e c t r o l y t e w a s o b s e r v e d on t h e ~)-12(rpm)-i 2
d i f f u s i o n l i m i t i n g c u r r e n t , w h e r e a s its e f f e c t on t h e ki-
n e t i c c u r r e n t w a s n e g l i g i b l e . T h e i n c r e a s e in t h e i o n i c Fig. 4, Effect of the supporting electrolyte on the limiting diffusion
c o n c e n t r a t i o n of t h e s o l u t i o n ( d u e to Na2SO4) d e c r e a s e s current of 03 reduction.
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 Vol. 133, No. 9 MECHANISM OF OXYGEN REDUCTION 1799

Reaction order w i t h respect to O H - . - - A series of Tafel

plots was m a d e in borate buffer solution at different pH's
r a n g i n g f r o m 7 to 9.4. A c h a r a c t e r i s t i c of the iron elec- 10-4
t r o d e in t h e s e s o l u t i o n s is a c h a n g e in th e n a t u r e of its
s u r f a c e in t h e p o t e n t i a l r a n g i n g from - 0 . 5 to - 0 . 3 9 ~0,25V,pH9.4 P~ssiveiron
m-048V,pH9.4
V/NHE. This was established by the presence of an acti- 10-2
v a t i o n p e a k in p o t e n t i a l - s w e e p e x p e r i m e n t s on th e ring
electrode (Fig. 5). Three different surfaces can be distin-
g u i s h e d d e p e n d i n g on th e e l e c t r o d e potential. At m o r e
p o s i t i v e p o t en t i al s , t h e p a s s i v e film is f o r m e d ; at inter-
m e d i a t e p o t en t i al s , iron d i s s o l v e s t h r o u g h the p a s s i v e 10 s
film; and at h i g h (cathodic) p o t e n t i a l s , t h e iron is bare. g-- g--
T h e p o l a r i z a t i o n data for o x y g e n r e d u c t i o n in the Tafel E E
range from Fig. 2 indicate that the a p p a r e n t reaction or- 10-3 o
< <
der with res p ect to pH is -0.4 for passive iron and 0 for
the bare iron.
Reaction order w i t h respect to O~.--Figure 6 shows the
r e a c t i o n o r d e r for o x y g e n o b t a i n e d on p a s s i v e iron 10 6
(-0.08V and -0.25 V/NHE) and bare iron (-0.48 V/NHE).
The r e a c t i o n o r d e r on b o t h surfaces is 1. The g r a d u a l
c h a n g e of the gradient of a log i/a log Po2 at low 02 partial 10-4
p r e s s u r e s (<0.2 atm) is d u e to the significant c o n t r i b u -
tion to total cu r r en t from the anodic current for iron oxi-
dation t h r o u g h the passive film. On iron, the l o g / - l o g Po2
plot gives two regions, both showing a reaction order of
unity. No hysteresis is o b s e r v e d b e t w e e n increasing and 10 ~!-z iI0-~ 1100
d e c r e a s i n g o x y g e n partial pressures.
Po2(atm)
Hydrogen peroxide.--A rotating ring-disk electrode
was u s e d to d e t e r m i n e w h e t h e r h y d r o g e n p e r o x i d e is Fig. 6. Reaction order with respect to O2 on passive iron ( - 0 . 0 8 V
p r o d u c e d either as a p r o d u c t in the c o n s e c u t i v e mecha- and -0.25 V/NHE) and bare iron (-0.48 V/NHE).
n i s m or as an i n t e r m e d i a t e in the parallel m e c h a n i s m for
O5 r e d u c t i o n on iron in b o r a t e b u f f e r (see Discussion). w h i l e no effect is o b s e r v e d on bare iron. This depen-
F i g u r e 7 shows the disk and ring c u r r e n t as a f u n c t i o n of d e n c e o f the ring cu r r en t on pH reflects the change of the
t he disk p o t e n t i a l at 5000 rpm. T h e p o t e n t i a l of t h e ring disk current with pH.
was held at + 1.0 V/NHE, w h e r e the H202 oxidation is dif-
Effect o f pH on the anodic t r a n s i e n t on the p a s s i v e
f u s i o n co n t r o l l ed . T w o a n o d i c p e a k s for H202 o x i d a t i o n
f i l m . - - T h e pH effect on t h e a n o d i c b e h a v i o r of t he
on the ring c o r r e s p o n d i n g to different disk potentials are
associated with the different nature of the surface of the
e l e c t r o d e . Th e c h a n g e from p a s s i v e iron to bare iron is
a c c o m p a n i e d by a decrease in the ring current. The com- 10 2
petition with t h e H2 e v o lu ti o n reaction at m o r e n e g a t i v e
potentials has a similar effect on the ring current. pH 8.4
iDIS}<
The influence of the pH of the borate buffer solution on
t h e f o r m a t i o n of H~O~ is s h o w n in Fig. 8. When pH de-
creases, t h e ring c u r r e n t i n c r e a s e s in th e disk p o t e n t i a l
VR 1.0 V/NHE /
range c o r r e s p o n d i n g to the p r e s e n c e of the passive film, v lm V/sec
10-3 OJ 500

V~=1.0 V/NHE
v=lm V/sec
w=5000 rpm 10-4
g--
- - p H 8,4 E
. . . . pH 7.0
<

E
10-5
< iR,~G
i I

I ..../H20#
J ; "
1

/ ~ .- 10 6
j

'
...'Y'-.. / ,~i,,;\~ :
..' / ~2q%.",~,

10-7
-0!08 -0128 -0.'48 -0168 -0.'88
I
+0~2 -0',08 -0128 -0!48 -0'68 -088 VD/NHE
VD VS N H E Fig. 7. Disk and ring currents as a function of the disk potential for
Fig. 5. i R VS. V D for iron oxidation and H202 reduction 02 reduction and H202 oxidation. Rotation rate is 5000 rpm.
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 1800 J. Electrochem. Soc.: ELECTROCHEMICAL SCIENCE A N D TECHNOLOGY September 1986

-0.08 V/NHE
7.5 VR 1.0 V/NHE
v l m V/sec

/
OJ 5000 rpm Bare ~ron

5.0
E
o

f
2.5 Passive iron

pH

0.( i i r
-r-
s

+0.12 -0.08 -0.128 -0148 -0~68 -0.'88

VD VS NHE
I J
Fig. 8. pH dependence of the formation of H202 0 2r0 4'0 6'0 8'0 100
t(sec)

p a s s i v e film was r e c e n t l y r e p o r t e d by Reies Iola et al. Fig. 9. Current transients at -0.08 V/NHE upon the stepwisechange
(12). To gain further insight into this effect, the change in of the pH.
t he a n o d i c c u r r e n t in th e p a s s i v e r a n g e as a f u n c t i o n of
b u l k solution pH in the absence of o x y g e n was studied. H202(a~ (k2). Th e adsorbed H202 can be r e d u c e d further to
C u r r e n t t r a n s i e n t at -0.08 V /N H E c o r r e s p o n d i n g to O H - (k3), o x i d i z e d b a c k to O2 (k-2), c a t a l y t i c a l l y d e c o m -
changes in the bulk pH (7-9.4) made by addition of acid p o s e d (k4), or d e s o r b e d and d i f f u s e d into t h e solution.
or alkali are shown in Fig. 9. The time d e p e n d e n c e of pH T h e c o n s t a n t s ks, k-5 and k6, k-G are for a d s o r p t i o n and
at t h e iron e l e c t r o d e was e s t a b l i s h e d by e x a m i n i n g t h e d e s o r p t i o n of 02 and H202, respectively.
c h a n g e of rate of H2 evolution on platinum. The time con- The r e a c t i o n s c h e m e [I] p r e d i c t s t h e r e l a t i o n s h i p be-
stant for t h e c h a n g e of c u r r e n t at t h e p o t e n t i o s t a t e d H2 t w e e n the ratio of current at the disk (ID) and the ring (IR)
e l e c t r o d e after the addition of acid or alkali was less than and t h e electrode rotation rate ~ as
ls. In c o m p a r i s o n , the r e l a x a t i o n t i m e for t h e o x i d a t i o n
of the passive film (from Fig. 9) is m o r e than 1 min. Dur- k6
ing the first 10s following the pH change, the current de- IR k2 -
creases rapidly (cf. Fig. 9) then approaches a steady-state
w h e r e A = (1 + 2kl/k2)(k-2 + k3 + k4) + (k3 - k_2) and Z =
value. 0.62 D2/~v-u6.
T h e s t e a d y - s t a t e c u r r e n t for the o x i d a t i o n of t h e pas-
In t h e s i m p l e r r e a c t i o n s c h e m e c o n s i d e r e d by Wrob-
sive layer o b t a i n e d for d i f f e r e n t p H ' s are p l o t t e d in Fig.
iowa et at. (15), w i t h o u t an a d s o r b e d O2(a) state and sup-
10. In t h e pH range from 7-8.5, a slope of -0.38 for the log
posing the adsorbed H202 to be in e q u i l i b r i u m with 02 in
i - p H relation was observed, w h i c h gradually decreases to
solution, the value of ID/IR is given by
0 with the higher pH.
Discussion + k6
D i s k - r i n g a n a l y s i s . - - R o t a t i n g ring-disk electrode data IR k2
were analyzed by Bagotskii et al. (13) considering a gen-
eral series-parallel reaction pathway for 02 reduction- 2 In 2k3 + k4 + ~ (k_2 + k3 + k4) [4]
n e u t r a l solution, t h e r e a c t i o n s c h e m e s can be repre-
sented as
k~(+4e-)
k~ O I k2(2e-) H202(a~ k3(+2e-)
O2(s) d i f f 1 2 * ~--s 2(.) \ OH- [I]
_ k_2(-2e ) /
k4 k6 1"~ k6
H~O2 *
H202(,)
(-2e-)
02

In this reaction scheme, the symbols (s), *, and (a) respec- E q u a t i o n [4] provides essentially the same diagnostic cri-
tively refer to the species in the bulk solution, in the so- terion for the O2 r ed u ct i o n pathway as a criterion first de-
l u t i o n a d j a c e n t to th e e l e c t r o d e surface, and in t h e v e l o p e d by D a m j a n o v i c et al. (16). F r o m Eq. [3] and [4],
a d s o r b e d state. The O2 can be r e d u c e d either directly to we see that a plot ID/IR VS. ~O-In yields straight lines w h o s e
O H - (kl) w i t h o u t the i n t e r m e d i a t e formation of H202 or to slopes and intercepts d e p e n d on potential.
2The more complete analysis has been given by Appleby and The e x p e r i m e n t a l disk-ring data for iron in borate solu-
Savy (14). tion are r e p r e s e n t e d graphically by plotting ID/Ia vs. r -~/~
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 VoL 133, No. 9 MECHANISM OF OXYGEN REDUCTION 1801

-0,08 V / N H E

10-s

9 -053V
[] -0.58V
9 0.63V
I000 i 0 "068V
E" o
E
<

Anodlc currenf

I P I 500
10 7 8 9 10

pH .// /
Fig, 10. Steady-state anodic current on the passive layer as a func- / f//~
tion of pH.

in Fig. 11 and 12. Figure 11 s h o w s the ID/IRplot obtained

at less n e g a t i v e p o t e n t i a l s for O~ r e d u c t i o n on p a s s i v e
iron at p H 8.4. The linear plots are i n d e p e n d e n t o f the
e l e c t r o d e r o t a t i o n r a t e ~. C o n v e r s e l y , the intercepts o f
the straight lines d e p e n d on the potential o f the elec-
trode. The more cathodic the potential, the higher are the I 0.102 I
values of IJIR. At about - 0 . 0 8 V/NHE, where the Fe is be- 0.0 0.01 0.03
c o m i n g increasingly covered w i t h the passive layer, the
i n t e r c e p t b e c o m e s 1/N, i.e., there is n o w no longer any Fig, 12, Io/IR vs. ~ - t / 2 on bare iron at different potentials
c o n t r i b u t i o n from a direct four-electron r e d u c t i o n of
oxygen. Figure 12 s h o w s ID/IRplots at different potentials
for a bare iron electrode. The slope of the plots decreases Thus, in s u m m a r y , two types of behavior for the ID/IR -
w i t h increasing potential~ w h i l e the intercept remains al- r -w2 plots are o b s e r v e d , d e p e n d i n g on the nature o f the
m o s t constant at about 300. electrode surface. A large intercept w i t h ID/IRd e p e n d e n t
The pH d e p e n d e n c e of the I,/IR vs. o~-1/z plots is s h o w n on co is o b t a i n e d on the bare iron surface, and an inter-
in Fig. 13. In the potential range corresponding to passiv- c e p t o f 1/N w i t h ID/IR i n d e p e n d e n t of co is o b s e r v e d on
ity, ID/Iffd e p e n d s sharply on pH. At more negative poten- passive iron.
tials, the ID/Ia plots are i n d e p e n d e n t o f the pH. Referring n o w to s c h e m e [I], and a s s u m i n g a parallel
m e c h a n i s m , k~ # 0, and s u p p o s i n g k~ and k~ have the

pH 8.4 o pH 70
100(
9 pH 8.4
[] p H 9.4

0.63V

300
-0 38~

0
200 50O

//
/"
/1 /
J

100t -028V 0 0 0 -0.18V

0 0

I
9 9 9 -O.~SV
Z=:-=Z--~===, ~ 9 | ?, ,~ -Q.~8~"
l 9 O.08V
00 0.01 0'02 0.'03 0.0 0.01 0[02 0.03 --
w-1 2(rprn) 1 2 ~-1 2 ( r p m ) - i 2

Fig. 1 1. ! J I R vs. r -1/2 on passive layer at different potentials Fig. 13. Io/IR vs. eo-1/2 on passive layer and bare iron at diffent pH's
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 1802 J. Electrochem. Soc.: E L E C T R O C H E M I C A L SCIENCE AND TECHNOLOGY September 1986

s a m e p o t e n t i a l d e p e n d e n c e , Eq. [3] p r e d i c t s t h a t t h e 400

slopes and intercepts obtained at various potentials from

t h e ID/IR VS, r ~/2 p l o t a r e r e l a t e d b y t h e e q u a t i o n

( 2k~ SZ6 I N
J= 1+~- z + [5]

w h e r e J a n d S a r e i n t e r c e p t s a n d s l o p e s at v a r i o u s p o t e n - J
tials, respectively. However, in an alternative assump-
t i o n i n v o l v i n g t h e a b s e n c e o f t h e d i r e c t 4e- f o r m a t i o n o f
O H - , s c h e m e [I] s h o w s t h a t

J = 1+ N [6]

E q u a t i o n [5] p r e d i c t s a l i n e a r r e l a t i o n s h i p b e t w e e n J o n S
w i t h t h e i n t e r c e p t g r e a t e r t h a n 1. E q u a t i o n [6] s h o u l d
y i e l d a l i n e a r r e l a t i o n s h i p w i t h a n i n t e r c e p t o f 1.
F i g u r e 14 s h o w s t h e p l o t o f t h e v a l u e o f J vs. S o b t a i n e d
for different potentials on the bare iron region from the
d a t a p l o t t e d i n Fig. 12. A s t r a i g h t l i n e is o b t a i n e d w i t h a n
i n t e r c e p t m u c h g r e a t e r t h a n 1, i n d i c a t i n g t h a t 02 r e d u c -
tion on reduced iron proceeds by the direct four-electron
r e a c t i o n p a t h w a y . F o r m a t i o n o f HzO2 as a n i n t e r m e d i a t e
i n t h e c o n s e c u t i v e r e a c t i o n p a t h w a y is less t h a n 1% o f t h e
t o t a l r e d u c t i o n c u r r e n t . C o n v e r s e l y , i n t h e p o t e n t i a l re- I I
g i o n c o r r e s p o n d i n g to p a s s i v e i r o n , t h e s l o p e , S, o f t h e 1 2

ID/IR p l o t is zero, a n d t h e i n t e r c e p t J = (l/N) i n d i c a t e s t h a t S x 104 ( r p m ) 1/2

02 r e d u c t i o n o n p a s s i v e F e is a t w o - e l e c t r o n p r o c e s s i n
w h i c h HzO2 is t h e p r o d u c t , a n d n o t a n i n t e r m e d i a t e , o f
the reaction.
M e c h a n i s m of 0 2 Reduction on Passive Iron
T h e k i n e t i c d a t a for 02 r e d u c t i o n o n p a s s i v e i r o n a n d
b a r e i r o n i n b o r a t e b u f f e r s o l u t i o n a r e s u m m a r i z e d in Ta-
b l e I. T h e c r i t e r i a s h o w n a r e u s e d f o r t h e d i s c u s s i o n o f
the mechanism of the reaction.
General.--It h a s b e e n s h o w n i n t h e p r e c e d i n g s e c t i o n
t h a t t h e p a t h o f t h e 02 r e d u c t i o n r e a c t i o n o n a p a s s i v e
i r o n film l e a d s to t h e t w o - e l e c t r o n t r a n s f e r r e a c t i o n , i.e.,
t h e f o r m a t i o n o f HzO~.
T h e r e v e r s i b l e s t a n d a r d e l e c t r o d e p o t e n t i a l for t h e for-
m a t i o n o f H202 i n t h e b o r a t e b u f f e r s o l u t i o n ( p H 8.4) is
0.11 V / N H E (17). T h e T a f e l p l o t , e x t r a p o l a t e d t o t h e re-
versible potential, gives an exchange current density of
a b o u t 1.2 x 10 -7 A / c m 2. A t t h e c o r r o s i o n p o t e n t i a l (0.05
V/NHE), the depolarization reaction of the formation of
H~O2 l e a d s to a c o r r o s i o n c u r r e n t o f 1.8 x 10 -6 A / c m 2.
Other parameters in Table I are directly measured quan-
tities.
Pathway and rate-determining step.--In T a b l e II, t h e
most probable pathways and rate-determining steps for
t h e f o r m a t i o n o f H202 a r e s u m m a r i z e d . I n c o m p a r i s o n
with these pathways, both for Langmuir and Temkin
conditions, we have three criteria with which we may
m a k e s o m e p r o g r e s s t o w a r d s m e c h a n i s m e v a l u a t i o n , i.e.,
t h e T a f e l s l o p e o f 2RT/F, t h e r e a c t i o n o r d e r w i t h r e s p e c t
t o o x y g e n o f 1, a n d t h e r e a c t i o n o r d e r w i t h r e s p e c t to
[OH ] o f - 0 . 4 o n p a s s i v e iron.
In the medium pH range, both the pH in the reaction
z o n e a t t h e e l e c t r o d e s u r f a c e a n d t h e T a f e l s l o p e m a y dif-
Fig. 14. J vs. S plot on bare iron
fer significantly from the values experimentally ob-
s e r v e d . H o w e v e r , i n t h e p r e s e n c e of b u f f e r , t h e s e e f f e c t s
c a n b e s h o w n to b e n e g l i g i b l e ( A p p e n d i x ) .
It c a n b e s e e n b y c o m p a r i s o n w i t h t h e a b o v e t a b l e t h a t
t h e o n l y p a t h w a y s w h i c h fit t h e s e c r i t e r i a a r e t h e A a n d C
( w i t h t h e c o r r e c t i o n for p.d. i n t h e d i f f u s e d o u b l e l a y e r i n
T a b l e II). T h e p a t h w a y C i n v o l v i n g t h e f o r m a t i o n o f O2H +
on a passive layer seems improbable because, although
the determination of the potential of zero charge on the
p a s s i v e l a y e r h a s n o t b e e n m a d e , it s e e m s l i k e l y t h a t it
m a y b e n e g a t i v e o n t h e h y d r o g e n s c a l e (cf., t h e p z c o n
b a r e i r o n , w h i c h is a p p r o x i m a t e l y - 0 . 6 4 V / N H E i n n e u -
t r a l s o l u t i o n s ) (20). T h e p o t e n t i a l r e g i o n i n w h i c h t h e
o x y g e n r e d u c t i o n o n t h e p a s s i v e l a y e r t a k e s p l a c e is
a b o u t +0.05 to - 0 . 2 V / N H E , i.e., p o s i t i v e b y a t l e a s t 0.2V
to the probable region for the potential of zero charge.
C o n s e q u e n t l y , t h e e x i s t e n c e o f a n HO2 + i o n u n d e r t h e s e
conditions seems unlikely.
Under these circumstances, only mechanism A can be
c o n s i d e r e d . I t g i v e s 2RT/F f o r t h e T a f e l s l o p e w i t h ~he
c h e m i s o r p t i o n o f 02 as r a t e - d e t e r m i n i n g s t e p a n d a r e a c -
t i o n o r d e r w i t h r e s p e c t to [ O H - ] o f - 0 . 5 , u n d e r T e m k i n
c o n d i t i o n s . T h e r e a c t i o n o r d e r w i t h r e s p e c t to 02 is 1.
T h e o b s e r v e d T a f e l s l o p e o f a b o u t 110 m V / d e c a d e i n d i -
c a t e s t h a t t h e p o t e n t i a l d r o p a c r o s s t h e film is n e g l i g i b l e
in comparison with that in the Helmholtz double layer in
the corresponding potential region. The small increase
i n t h e t h i c k n e s s o f t h e film w i t h t h e p o t e n t i a l d o e s n o t af-
f e c t t h e T a f e l line.
I n r e s p e c t to t h e r e a c t i o n o r d e r f o r [OH-], a v a r i e t y o f
pH dependencies, including those involving fractional

Table I. Kinetic parameters for 02 reduction on passive film and bare iron

Disc data Ring disk data

OV 0 log i 0 log i 0 IDJIR
Electrode i,,.o, i(corr) Sj/S I
surface 0 log i 0 log Po, 0 pH (A/c~ 2) A/cm 2 Oto(rpm) 'j2 JJ/s' (rpm) -1/~

Passive iron
pH 7 -110 mV 1 -0.4 1.2 910 -7 1.8 9 10-r 1/N
pH 9 -110 mV 1 -0.4 1.5 9 10-~ 2.2 - 10-6 1/N
Bare iron
pH 7 -120 mV 1 Po, < 0.2 0 8" 10 -'a 1 . 2 ' 10 3 -300 1.5-3.0.104 -250 7 - 10-4
1 Po, > & 3

pH 9 -120 mV 1 Po, < 0.2 0 1.5 9 10 -t3 1.3 9 10 -3 -300 1.5-3.0 9 104 -250 7 9 104
1 Po2 > 0.3

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 Vol. 133, No. 9 MECHANISM OF OXYGEN REDUCTION 1803

Table II. Proposed mechanisms for oxygen reduction on passive layer

RDS Langmuir Temkin

oE/o In i 0 log i/O log Po~ 0 log i/OpH
0 --~ 0 0 --~ 1 0 ----)0 0 ----) 1 0 -~ 0 0 --> 1 oEIO in i 0 log ilO log Po~ 0 log il~pH

0 2 ---) O 2 a d co -- 1 -- 0 -- 2RT/F 1 -0.5

A' O2~d + H~O + e- --) O2H~d + OH- 2RT/F 2RT/F 1 0 0 0 RT/F 1 -0.5
O2H~d + e --> O2H- 2RT/3F 2RT/3F 1 0 -1 0 2RT/F 0 0
O2H + H20 --~ H20~ + OH- RT/2F -- 1 0 -1 0 co -0.25 0
O~ + e- --) O~d 2RT/F -- 1 -- 0 -- oo 1 0
B2 O~d + H20 --* O~H~d + OH- RT/F -- 1 0 0 0 2RT/F 0 0
O2H~d + e- ~ O2H~d 2RT/3F -- 1 0 -1 0 2RT/F 0 0
O2H~ + H~O --~ H202 + OH RT/2F -- 1 0 -1 0 ~ -0.25 0
02 + H 2 0 - ~ O 2 H + + OH ~ -- 1 -- 0 -- co 1 0
C'~ O2H+ + e- --* O~H~, 2RT/F 2RT/F 1 0 -0.5 0 2RT/F 0 0
O2H~d + e- --~ O2H~d 2RT/3F 2RT/F 1 0 -1 0 2RT/F 0 0
O2Ha~ + H20 -~ H20~ + OH- RT/F -- 1 0 -1 0 ~ -0.25 0
O2 + H20 + e- --* O2H~ + OH- 2RT/F 0 1 0 0 0 2RT/F 1 0
D~ O~H,~+ e- ~ O,~ + OH- 2RT/3F 2RT/F 1 0 - 1 0 2RT/F 0 0
Oa~ + H20 --* H~O~ RT/2F -- 1 0 -1 0 ~ -0.25 0
O~ + e- ~ 0 ~ 2RT/F 1 0 0 -- 2RT/F 1 0
E~ O~a + H~O + e- --~ O~H,~ + OH- 2RT/3F -- 1 -1 -1 -- 2RT/3F 1 -1
O~H~ + H20 --) H~O~ + OH RT/2F -- 1 0 -1 0 ~ -0.25 0

Oxygen chemisorption path.

2 Bagotskii's path (18).
3 O2H§ adsorption path (19).
4 Oxygen-water discharge path.
Superoxide adsorption path.

o r d e r s , h a v e b e e n o b s e r v e d in t h e l i t e r a t u r e (21-25). 02 re- 02 -~ O2ads (rds) [II]

d u c t i o n on oxide-free P t in alkaline solution gives a reac-
t i o n o r d e r - 0 . 5 at l o w c u r r e n t d e n s i t i e s (22). T h i s w a s
a s s o c i a t e d w i t h a T a f e l s l o p e o f - 6 0 m V / d e c a d e a n d in-
termediate coverage with adsorbed oxygen species un-
der Temkin conditions.
O n o t h e r o x i d e - c o v e r e d m e t a l e l e c t r o d e s (Pt, Ni) (24,
26), t h e r a t e o f o x y g e n r e d u c t i o n is d e c r e a s e d f o r r e a c -
tion on the oxide compared with that on the free metal
s u r f a c e ; w h i l e t h e p a s s i v e o x i d e film o n i r o n s h o w s a
s t r o n g c a t a l y t i c e f f e c t for t h e 02 r e d u c t i o n r e a c t i o n . F o r
e x a m p l e , at p H = 7, t h e 02 r e d u c t i o n c u r r e n t is a b o u t 100
t i m e s h i g h e r t h a n t h a t o n b a r e iron.
I n r e s p e c t to t h e m o d e l w h e r e t h e a d s o r p t i o n Of i n t e r -
m e d i a t e i n t h e s t e p a f t e r t h e r d s f o l l o w s a T e m k i n iso-
t h e r m , (23), o n e c a n w r i t e
r O / R T = log [OH ] + F V / R T + const.
w h e r e r is a n i n t e r a c t i o n p a r a m e t e r for t h e a d s o r b a t e .
T h e r a t e o f t h e o x y g e n r e d u c t i o n c a n b e w r i t t e n in t h e
form
i = kPo2 e x p (-~FV/RT) exp (-~AGads/RT)
The chemisorption of oxygen has been recently consid-
ered (27) as an important step in the oxygen reduction on
catalytic surfaces.
Although the steps after the first rds [II] cannot be as-
certained, two possible sequences involving O-~ads and
(O2H)ads (Table II) as the adsorbed intermediate may be
considered. The pathway which involves, respectively,
the more strongly adsorbed intermediate is the more
likely one in view of the relatively high coverage ex-
pected from the implied applicability of the Temkin iso-
therm (0 > 0.2). 3
T h u s , t h e p o s s i b i l i t y o f c h e m i b o n d i n g o f 02 a n d O2H
may be essentially the same from the viewpoint of the
m o l e c u l a r o r b i t a l t h e o r y . H o w e v e r , in a q u e o u s m e d i a O~-
has an added hydration energy of about -100 kcal/mol,
[7] w h i c h w o u l d m a k e it m u c h l e s s a d s o r b e d t h a n t h e O2H,
a n d t h e r e f o r e l e s s l i k e l y t o b e p r e s e n t in t h e p a t h w a y .
A l i k e l y m e c h a n i s m for o x y g e n r e d u c t i o n o n t h e p a s -
sive layer could be d e s c r i b e d with r a t e - d e t e r m i n i n g step
[II] f o l l o w e d b y first e l e c t r o n t r a n s f e r s t e p s , p r o b a b l y o f
[8] the following kind

w h e r e k is a r a t e c o n s t a n t a n d AGadsis t h e s t a n d a r d f r e e 02ads ~- H20 + e- ~-- OzHaas + O H - [III]

energy of adsorption of intermediate following the rds,
w h o s e f r e e e n e r g y o f a d s o r p t i o n is a f f e c t e d as a f u n c t i o n O2Had, + e ~ O2H- [IV]
o f c o v e r a g e , 0. A s s u m i n g t h a t t h e r0 t e r m a f f e c t i n g hGad~
is t h e s a m e as t h a t in t h e i s o t h e r m [7], i.e. O 2 H - + H20 ~ H202 + OH [V]

AGads = AG~ + r0 [9] via p a t h A (Table II), w h e r e O2Hads f o l l o w s a T e m k i n iso-

w h e r e AG~ is t h e z e r o - c o v e r a g e v a l u e , t h e n
i = kPo2 e x p (-r exp (-~AG~
e x p (log [OH ] ~ - [ t F V / R T ) [10]
R e a r r a n g i n g Eq. [10] g i v e s
i = k ' P % [OH-] -1/2 e x p [ - ( ~ + V2) V F / R T ] [11]
w h e r e k' is a n o t h e r c o n s t a n t a n d ~ = V2. T h i s g i v e s a n or-
d e r o f r e a c i i o n w i t h r e s p e c t to O H - o f - 0 . 5 ( c o m p a r e ex-
p e r i m e n t a l v a l u e o f - 0 . 4 i n T a b l e I) a n d t h e c o r r e c t 02
r e a c t i o n o r d e r . T h e Tafel s l o p e u n d e r T e m k i n c o n d i t i o n s
for ~ = 0 ( c h e m i c a l r a t e - d e t e r m i n i n g step p r e c e d i n g an
e q u i l i b r i u m electron transfer) gives the correct value of
2RT/F. The most plausible chemical rate controlling step
will b e t h e c h e m i s o r p t i o n o f d i o x y g e n o n t h e s u r f a c e ac-
t i v e s i t e s , i.e.
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therm.
Interpretation of variation o f F e 2 + / F e 3+ w i t h p H i n t h e
passive layer.--The t o t a l c h a r g e Qt (at - 0 . 0 8 V / N H E ) ob-
t a i n e d in the a n o d i c c u r r e n t t r a n s i e n t s r e s u l t i n g f r o m a
s t e p w i s e c h a n g e i n p H c a n b e r e g a r d e d as a s u m o f t w o
c o m p o n e n t s o f c h a r g e , Qu a n d Q1 (Fig. 15), a s s o c i a t e d
with two different processes taking place simultane-
o u s l y . T h e f i r s t p r o c e s s (Qu) is t h e o x i d a t i o n o f t h e
p a s s i v e film a n d t h e s e c o n d o n e (Q~) t h e p r o c e s s o f t h e
g r o w t h o f t h e p a s s i v e film d u e to t h e d i s s o l u t i o n o f i r o n
i o n s i n t o t h e film ( c o r r o s i o n c u r r e n t ) (28, 29).
I n Fig. 15 ( c u r r e n t - t i m e t r a n s i e n t i n p H s t e p ) a n e x t r a
( h y p o t h e t i c a l ) c u r r e n t line has b e e n c o n s t r u c t e d to j o i n
the steady-state current existing before the given pH
s t e p to t h e n e w s t e a d y - s t a t e current. The q u a n t i t y of
e l e c t r i c i t y p a s s i n g b e l o w t h i s l i n e is c o n s i d e r e d to r e p r e -
3For the applicability of Eq. [7], the adsorbate on the right in
[III] must be much more strongly adsorbed than that on the left.
 1804 J. E l e c t r o c h e m . Sac.: E L E C T R O C H E M I C A L SCIENCE AND TECHNOLOGY S e p t e m b e r 1986

L - F e 2+ (OH)ad~ + OH---~ L - F e 3+ O O H + H 2 0 + e-
(OH)a~,
[VII]
w h e r e L is t h e o x i d e l a t t i c e (30).
T h u s , a n i n c r e a s e of t h e p H g i v e s r i s e to a d e c r e a s e i n
t h e s u r f a c e c o n c e n t r a t i o n o f F e 2+. F r o m t h e v a r i a t i o n o f
t h e c h a r g e Q, c o r r e s p o n d i n g to t h e c h a n g e F e 2+ --. F e 3+ i n
t h e film w i t h pH (Fig. 16) o n e c a n s e e t h a t t h e l i m i t i n g
v a l u e o f Q, a t t a i n e d a t h i g h e r p H v a l u e s c o r r e s p o n d s to a
s i t u a t i o n i n w h i c h m o s t o f t h e F e 2+ h a s b e e n o x i d i z e d to
QT = Q . + QL F e 3+. To c a l c u l a t e t h e c o n c e n t r a t i o n o f F e 2+ a t t h e s u r f a c e
a t a p a r t i c u l a r p H , o n e m a y a s s u m e t h a t t h e c h a r g e Q'u
-0.08V/NHE
r e l a t e d to t h e c o n c e n t r a t i o n o f F e 2+ is a d i f f e r e n c e b e -
t w e e n t h e c h a r g e a t t h e l i m i t i n g v a l u e , Q,.pH 10 ( a s s u m e d
zero) (see Fig. 16) a n d t h e c h a r g e a t a n y p a r t i c u l a r pH, Q,.
E T h u s , t h e c o n c e n t r a t i o n o f F e 2+ w a s o b t a i n e d f r o m t h e
< equation
\\\ [Fe 2+] = Q'u" 10 -5 ( m o l / c m 2) [12]
w h e r e Q ' . = f ( p H ) . T h e v a l u e s r a n g e d f r o m 2 9 10 10
m o l / c m ~ a t pH 9.4 to 1.7 9 10 -9 m o l / c m 2 a t p H = 7.0.
I n o r d e r to d e t e r m i n e t h e r a t i o Fe2+/Fe 3+ i n t h e film, t h e
c-- . . . . c o n c e n t r a t i o n of F e 3+ w a s c a l c u l a t e d f r o m t h e c o u l o m b s
r e q u i r e d for g r o w t h o f a p a s s i v e film at - 0 . 0 8 V / N H E o f
a b o u t 15A i n t h i c k n e s s (28) ( a s s u m i n g F e 3+ as a p r e d o m i -
n a n t s p e c i e s ) . T h u s , t h e c h a r g e o f a b o u t 0.003 C / c m 2 cor-
r e s p o n d s to 1.1 9 10 -~ m o l / c m 2 o f F e 3+ a t p H = 9.4, i.e.,
l i t t l e F e 2+ is p r e s e n t . A s t h e s e r e s u l t s i n d i c a t e t h a t t h e
c o n c e n t r a t i o n o f F e 3§ p r e d o m i n a t e s o v e r t h a t o f F e 2+, t h e
f o r m e r is t a k e n as a c o n s t a n t , i n d e p e n d e n t o f p H . T h e ra-
tio o f Fe2+/Fe 3+ t h u s o b t a i n e d for d i f f e r e n t p H ' s is s h o w n
t (sec) i n Fig. 16. W h e n t h e p H i n c r e a s e s f r o m 7.0 to 9.4, t h e r a t i o
Fig. 15. Total charge QT obtained from current transient d e c r e a s e s f r o m 0.1 to 0.01, w i t h t h e s l o p e o f a b o u t - 0 . 3 5 .
Bore Iron
s e n t t h e o x i d a t i o n o f m e t a h i c F e to F e ~+, w h i l e t h e a r e a
a b o v e t h e l i n e r e p r e s e n t s t h e o x i d a t i o n o f F e 2+ to F e 3+ a t P a t h w a y . - - T h e p a t h w a y o f O~ r e d u c t i o n o n b a r e i r o n
the oxide-solution interface. has been derived from the rotating ring-disk analysis
The charges corresponding to the upper part of the ( T a b l e I). T h e i n t e r c e p t o f a b o u t 250, r e l a t e d t o t h e r a t i o
a n o d i c t r a n s i e n t s , Qu, w e r e c a l c u l a t e d for d i f f e r e n t p H ' s . o f t h e r a t e o f r e d u c t i o n w i t h o u t f o r m a t i o n o f H20~ to t h e
T h e i n t e g r a l o f t h e t r a n s i e n t Qu a r i s i n g f r o m t h e i n c r e a s e r a t e o f r e d u c t i o n i n v o l v i n g H~O2 as a n i n t e r m e d i a t e , i n d i -
o f t h e p H is s h o w n i n Fig. 16. T h e z e r o o f t h e c h a r g e c a t e s t h a t a b o u t 99% o f t h e O~ r e d u c t i o n c u r r e n t g o e s di-
c o o r d i n a t e is t a k e n as t h a t a t p H = 7. r e c t l y to f o r m O H - .
T h e c h a r g e Q, is u s e d i n t h e o x i d a t i o n o f f e r r o u s to fer- The 4e- pathway may proceed via formation of ad-
ric i o n s i n t h e r e a c t i o n sorbed peroxide or superoxide where these adsorbates
d o n o t l e a d to a s o l u t i o n p h a s e s p e c i e s .
F e O + O H - --->F e O O H + e- [VI] I f t h e p e r o x i d e s t a t e is i n v o l v e d , t h e r e a c t i o n p a t h w a y
w i t h t h e r a t e c o n s t a n t kl w o u l d b e d i f f e r e n t f r o m t h e
T h e r e a c t i o n [VI] m a y b e w r i t t e n i n a f o r m w h i c h in- s e r i e s p a t h w a y w i t h t h e r a t e c o n s t a n t s ks a n d ks i n re-
v o l v e s t h e (OH),d, as s p e c t to t h e a c t i v i t y o f t h e a d s o r p t i o n sites. T h u s , t h e ad-
sorbed peroxide will be further reduced before any

2ool -0008 V/NHE

appreciable desorption and diffusion in the solution
Occur.
T h e p a t h w a y i n v o l v i n g H202 as a n i n t e r m e d i a t e l e a d -
i n g to t h e s o l u t i o n p h a s e s p e c i e s p r o c e e d s a t a b o u t 100
t i m e s l o w e r r a t e , ks, o n t h e l e s s a c t i v e s i t e s . F u r t h e r , re-
d u c t i o n o f H202, k3, a p p e a r s to b e l i t t l e d e p e n d e n t o n t h e
e l e c t r o d e p o t e n t i a l (see Fig. 12). T h u s , t h e r a t e c o n s t a n t
k3 c a l c u l a t e d f r o m t h e s l o p e o f t h e ID/Ia vs. r -1/~ l i n e s (0.5
c m / s ) v a r i e s b y l e s s t h a n 2 for a n 0.15V c h a n g e i n p o t e n -
tial. T h i s i n d i c a t e s e i t h e r a p r o c e s s c o n t r o l l e d b y t h e dif-
f u s i o n o f H20~ to t h e s i t e s w h e r e it c a n b e r e d u c e d o r a
%%
slow chemical step preceding the fast electrochemical
reduction process.
100
T h e p a t h w a y o f O5 r e d u c t i o n o n b a r e i r o n c o n t r a s t s
w i t h t h a t o n p a s s i v e i r o n i n w h i c h t h e H202 is a p r o d u c t
of the reaction.
Discussion o f m e c h a n i s m s . - - I n o r d e r to d e t e r m i n e t h e
m e c h a n i s m s a n d r a t e - d e t e r m i n i n g s t e p for 4e- r e d u c t i o n
5
o f O2 o n b a r e i r o n , t h e k i n e t i c c r i t e r i a , Tafel slope, a n d re-
a c t i o n o r d e r w i t h r e s p e c t to O2, o b t a i n e d e x p e r i m e n t a l l y
i0 2 ( T a b l e I), a r e c o m p a r e d w i t h t h o s e d e r i v e d for m o s t p r o b -
a b l e m e c h a n i s m s ( T a b l e III).
T h e first s t e p o f t h e r e a c t i o n i n v o l v i n g O-O b o n d
b r e a k i n g is p r o b a b l y t h e a d s o r p t i o n o f O5 o n t h e s u r f a c e
i n s i d e - o n c o n f i g u r a t i o n (27).
pH
The reaction sequence can proceed either through the
Fig. 16. Q. and the ratio FeZ+/Fea+ on passive layer as a function of electrocatalytic pathway involving the bond breaking in
pH. t h e r a t e d e t e r m i n i n g s t e p ( m e c h a n i s m s A, B i n T a b l e III)
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 Vol. 133, No, 9 MECHANISM OF OXYGEN REDUCTION 1805

Table III. Proposed mechanisms for oxygen reduction on bare iron

Reaction pathway oE/o In i a log i/o log Po, 0 log i/opH

A) O2~a + e --> Oad + O~d 2RT/F 1 0

Oad + H20 -~ OHad + OH- RT/F 1 0
Oad + H20 + e- -> OHad + OH- 2RT/3F 1 0
OHad + e---* OH- 2RT/3F 1 -1
B) 02 + H20 + e- --> Oad + OHad + OH- 2RT/F 1 0
Oad + H20 + e---* OHad + OH- 2RT/3F 1 -1
OHad + e- --* OH 2RT/3F 1 -2
C) 0 2-~ Gad 4- Gad -- i 0
Oao + H20 + e- --~ OH,d + OH 2RT/F 0.5 0
OHad + e---+ OH 2RT/3F 0.5 -1
D) 02 + e- --~ 02 2RT/F 1 0
02- + H20 --* OHad + O~d + OH- RT/F 1 1
Oad + H20 + e- --> OHad + OH 2RT/3F 1 - 1
OHad + e- --* OH- 2RT/3F 1 -2
E) 02 + e- --~ 02- 2RT/F 1 0
02- + H20 --~ HO2ad + OH- RT/F 1 0
HO2a, + HzO + e --~ 2 OH,d + OH RT/F 1 -1
OHad + e- -* OH- RT/F 0.5 -2
F) 02 + e- -~ 02- 2RT/F 1 0
02- + H20 --> HO2.a + OH- RT/F 1 0
HO2ad + H20 + e--~ H2O2ad + O H 2RT/3F 1 -1
H202,d~ --~ 2 OH,d RT/2F 1 -2
OH~d + e- --* OH 2RT/5F 0.5 -2
G) 02 + H20 + e --+ O2H,d~ + OH- 2RT/F 1 0
O2H~d + H20 + e- --~ 2 OHa, + OH- 2RT/3F 1 - 1
OH~d + e---* OH RT/2F 0.5 -2

or t h r o u g h t h e f o r m a t i o n o f s u p e r o x i d e o r O2Had.~ in t h e c o n s i d e r s t h e e l e c t r o c a t a l y t i c p a t h w a y (A, B, T a b l e III)

r a t e - d e t e r m i n i n g s t e p ( m e c h a n i s m s D-G).
It c a n b e s e e n b y c o m p a r i s o n ( T a b l e s I a n d III) t h a t s i x
p a t h w a y s s a t i s f y t h e a b o v e c r i t e r i a if t h e first s t e p is rds.
To m a k e f u r t h e r p r o g r e s s t o w a r d d e t e r m i n i n g t h e de-
tailed pathway, the question of the participation of water
in the r a t e - d e t e r m i n i n g step and the potential e n e r g y
profile in t h e p r o c e s s s h o u l d b e c o n s i d e r e d .
I n r e s p e c t to t h e p a r t i c i p a t i o n o f w a t e r , t h e r e is s o m e
indication from the molecular orbital theory of metal-
d i o x y g e n c o m p l e x e s (31, 32) t h a t i n a s i d e - o n c o n f i g u r a -
t i o n o f a d s o r b e d o x y g e n (Griffith or B r i d g e ) , t h e r e is l e s s
capability of hydrogen bonding with water molecules
compared with the end-on (Pauling) configuration.
T h e m o s t l i k e l y p o t e n t i a l e n e r g y p r o f i l e f o r 02 r e d u c -
tion consistent with a rate-determining electron transfer
t o O~ ( T a b l e III) is g i v e n s c h e m a t i c a l l y i n Fig. 17. I f o n e
unlikely, b e c a u s e of the high e n e r g y of activation ex-
p e c t e d for s i m u l t a n e o u s c h a r g e t r a n s f e r a n d b o n d b r e a k -
ing in t h e r a t e - d e t e r m i n i n g step, the m o s t p r o b a b l e
mechanism would be
02 + e --->02 [VIII]
f o l l o w e d b y t h e c h e m i c a l (D, F) o r e l e c t r o c h e m i c a l (E)
O-O b o n d b r e a k i n g s t e p s .
Conclusion
T h e d i f f e r e n c e s i n t h e k i n e t i c s a n d p a t h w a y for 02 re-
d u c t i o n r e a c t i o n o n b a r e i r o n a n d p a s s i v e i r o n i n t h e in-
termediate pH range have been established.
1. T h e r a t e o f 02 r e d U c t i o n o n p a s s i v e i r o n is g r e a t e r
t h a n t h a t o n b a r e iron. T h e r e a c t i o n o r d e r w i t h r e s p e c t to
p H is - 0 . 4 o n t h e p a s s i v e l a y e r a n d z e r o o n t h e b a r e iron.
I n r e s p e c t to 02, t h e r e a c t i o n o r d e r o n b o t h s u r f a c e s is 1.
2. T h e 02 r e d u c t i o n p r o c e e d s t h r o u g h a 4e- p a t h w a y
w i t h l i t t l e H202 as a n i n t e r m e d i a t e o n t h e b a r e i r o n a n d
2e- p a t h w a y w i t h t h e f o r m a t i o n o f H202 as t h e p r o d u c t o n
t h e p a s s i v e layer.
3. T h e m o s t l i k e l y r a t e - d e t e r m i n i n g s t e p o n b a r e i r o n
i n v o l v e s t h e f o r m a t i o n o f 02% w h i l e o n t h e p a s s i v e l a y e r
it is o x y g e n c h e m i s o r p t i o n u n d e r T e m p k i n c o n d i t i o n s .
4. T w o m o d e l s f o r a d s o r p t i o n o f 02 m o l e c u l e s c o n s i s -
t e n t w i t h the data are s u g g e s t e d ; side-on a d s o r p t i o n
(Griffith or B r i d g e ) o n b a r e i r o n r e s u l t i n g in t h e 4e t r a n s -
f e r to w a t e r , a n d e n d - o n a d s o r p t i o n ( P a u l i n g ) o n t h e pas-
s i v e layer, w i t h f o r m a t i o n o f H202 as t h e e n d p r o d u c t .

Acknowledgments
T h e a u t h o r s a c k n o w l e d g e t h e s u p p o r t o f t h e Office o f
N a v a l R e s e a r c h u n d e r C o n t r a c t no. N0001480Co113.
T h e y a r e t h a n k f u l t o Dr. F r a n k H e r r f o r i d e n t i f y i n g t h e
INITIAL p r o b l e m s a n d f o r d i s c u s s i o n . T h e y a l s o w i s h to t h a n k
t h e i r c o l l e a g u e s , e s p e c i a l l y Dr. B. S c h a r i f k e r a n d Dr. A.
G o c h e v , for d i s c u s s i o n . P a r t i c u l a r t h a n k s are d u e to Dr.
A. J. A p p l e b y , Dr. A. D a m j a n o v i c , a n d P r o f . M. Hall, for
extensive discussion during the mechanism evaluation.
Dr. A p p l e b y is to b e p a r t i c u l a r l y t h a n k e d for a s u c c e s s -
FINAL
fully critical discussion of one of the authors' earlier
mechanisms.

M a n u s c r i p t s u b m i t t e d A u g . 30, 1985; r e v i s e d m a n u -
s c r i p t r e c e i v e d A p r i l 11, 1986.

Fig. 17. Potential energy profile for 02 reduction involving adsorp- Texas A&M University assisted in meeting the publica-
tion of reactants and product in rate-determining step. tion costs of this article.

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 1806 J. Electrochem. Soc.: E L E C T R O C H E M I C A L SCIENCE AND TECHNOLOGY S e p t e m b e r 1986

APPENDIX oV~r RT 1 o(Con-)D~

-l+x - - [A-12]
T h e p H in t h e d o u b l e l a y e r c a n be c a l c u l a t e d , u n d e r OV c~TF (Co.)DL OV
d i f f u s i o n c o n t r o l c o n d i t i o n s , as S u b s t i t u t i n g Eq. [A-12] into [A-11], w e can w r i t e
DnF a(Con-)DL CCTF
i- - - [(Co,-)OL- (Co~)~] [A-l]
oV RT
or
[(Co.-)OL- (Co.)B](CoH ).L
[A-13]
V i50) x[(CoH-)DL -- (Co~-).] - (CoH-)DL
(Co.-)~L = (Coil)~ [1 -- !
nFD(CoH-)~ J [A-2]
Thi~ gives t h e final e x p r e s s i o n for aT as
w i t h 50) = 1.61 9D 1/~ 90)-~n. vl/~, w h e r e t h e s e s y m b o l s h a v e
their usual meaning.
F r o m t h e e x p e r i m e n t a l r e s u l t (Table I), one can w r i t e aT=aA
( 1 - - X t(CoH)OL=(Co.)
(Co,-)DL ]
l a-141
i = ~ (Co~-)%L e x p (-- c~FV/RT) [A-3]
A t b u l k p H 8.4, in t h e Tafel region, in t h e a b s e n c e of a
w h e r e aT and x are t h e t r u e t r a n s f e r coefficients and reac- b u f f e r , t h e c o n c e n t r a t i o n of O H in t h e d o u b l e l a y e r
t i o n o r d e r for (OH-), r e s p e c t i v e l y . T h e a p p a r e n t and t r u e v a r i e s f r o m 10 5.4 to 10 4"~M. T h e c o r r e c t i o n for p H
t r a n s f e r coefficients are r e l a t e d by c h a n g e in t h e p r e s e n c e of b o r a t e b u f f e r can be o b t a i n e d
f r o m t h e e x p r e s s i o n for t h e b u f f e r c a p a c i t y (33)
C~AF (~TF 0 in (Coil)DL
-- + X [A-41 d[B] _2.303{ Ka'C'[H§ }
RT RT OV dp~ ~a + [H~ z [A-15]
F o l l o w i n g t h e similar c o r r e c t i o n for ~ g i v e n by B o c k r i s
w h e r e d[B] is t h e i n c r e m e n t of s t r o n g b a s e and K a and C
et al. (1), one can write for the c h a n g e of the O H - concen- are t h e d i s s o c i a t i o n c o n s t a n t a n d c o n c e n t r a t i o n of bo-
tration in the d o u b l e layer w i t h potential as rate, r e s p e c t i v e l y . Thus, t h e b u f f e r c a p a c i t y of b o r a t e so-
l u t i o n (0.0375M) at p H 8.4 is a b o u t 0.012 (34), w h i c h is
xRT (Coil)3 e q u a l to t h e c o n c e n t r a t i o n of s t r o n g b a s e (OH-) n e c e s -
V - V'qc= 0 -- O~T~-- I n (CoH-)DL "q~ [A-5] sary to i n c r e a s e t h e p H of t h e s o l u t i o n for o n e p H unit.
F r o m t h e p o i n t of v i e w of k i n e t i c s , it is k n o w n t h a t t h e
w h e r e V a n d V~=o are t h e p o t e n t i a l s o f t h e e l e c t r o d e w i t h b i m o l e c u l a r r e a c t i o n s in a q u e o u s s o l u t i o n s i n v o l v i n g H +
and without concentration polarization (~=0), or O H are c h a r a c t e r i z e d b y e x t r e m e l y h i g h rate c o n s t a n t
respectively. in t h e o r d e r o f 101~ 1/Ms (i.e., for NH4 § + O H - -~
To o b t a i n 0 in (CoH-)DL/OVin Eq. [A-4], one can w r i t e NH3H20; k = 4.10 TM1/Ms) (35).
Thus, o n e can c a l c u l a t e t h e rate of t h e r e a c t i o n
il -- (CoH-)DL1-- (CoH-)~ [A-6]
i (Co.-)OL - (CoR-)8 OH + H2B204--~ H20 + HB204- [A-I]
w h e r e suffix 1 r e f e r s to an a r b i t r a r i l y c h o s e n c o n s t a n t as V(M/ls) ~ 10.10 1/Ms 10 -~ M/l" 10 -2 M/l ~ 103 (M/Is). This
c u r r e n t d e n s i t y , and t h e c o r r e s p o n d i n g c o n c e n t r a t i o n of v a l u e is s e v e r a l o r d e r s of m a g n i t u d e h i g h e r t h a n t h e rate
O H - in t h e d o u b l e layer. of t h e f o r m a t i o n of OH in t h e d o u b l e layer.
T h e ratio of t w o c u r r e n t d e n s i t i e s i~ and i, c o r r e s p o n d - 1 10-4A/cm 2
i n g to s i t u a t i o n s in t h e d o u b l e layer, w h e r e t h e OH con- - - (M/cm2s) = ~ 5 9 10 -") M/cm2s
c e n t r a t i o n is (Co,-)~ a n d (Coil-), r e s p e c t i v e l y , a n d t h e nF 2 9 105 C / e q u i v
e l e c t r o d e p o t e n t i a l is V and V~, is g i v e n by
5 9 10 -1~ 107- 103 M/ls =- 5 M/ls

C , exp (V- VJ [A-7] It i m p l i e s no c h a n g e of t h e p H in t h e d o u b l e layer; c o n -

i ( O~-)DL [_ R T s e q u e n t l y , no c o r r e c t i o n is n e e d e d for t h e T a f e l slope.
F r o m Eq. [A-5], V - V~ can be o b t a i n e d as REFERENCES
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Electrocatalytic Reactivity of Hydrocarbons

on a Zirconia Electrolyte Surface
B. C. Nguyen,* T. A. Lin, and D. M. Mason**
Department of Chemical Engineering, Stanford University, Stanford, California 94305

ABSTRACT
An experimental survey of the electrochemical reactivity of five c o m m o n fuel species was made employing a solid ox-
ide electrolyte galvanic cell with porous Au and Pt electrodes in the temperature range 700~176 The electrolyte used
was Sc203-stabilized ZrO2 (SSZ). The fuel species electro-oxidized at the anode were: H2, CO, CH4, CH3OH, and C2H5OH.
Rates of reaction were determined coulometrically, SO that species other than H2 could have undergone an undetermined
a m o u n t of thermal dissociation during electro-oxidation. The concomitant reactivity of 02, which is reduced at the cath-
ode, was also investigated. The current-overpotential b e h a v i o r at both the cat h o d e and anode was found to be similar
w h e t h e r Au or Pt was used to form the porous electrodes. In the low o v er p o t en t i al range, the rate of charge transfer is
found to be rate determining for both the cathodic and anodic reactions. Activation enthalpies obtained from an analysis
of the data in this low overpotential range are also found to be similarly independent of the electrode materials. Reduction
of the electrolyte by current blackening leads to two to three orders of magnitude increase in both the cathodic and anodic
c urr en t density at a given overpotential. Again, the current overpotential characteristics obtained with Au and Pt elec-
trodes are very similar. Activation enthalpies obtained with the electrolyte in the b l a c k e n e d state do not deviate
significantly from those obtained with an unblackened electrolyte. These experimental observations are consistent with a
reaction m ech an i s m in which the major electrochemical steps occur at active sites on the electrolyte surface rather than
on the metal electrodes. The e l e c t r o c h e m i c a l reaction sites are h y p o t h e s i z e d to be o x y g e n vacancies with electrons
migrating along the electrolyte surface to or away from these active sites. Thus, an effective localized electronic conductiv-
ity of the electrolyte surface is postulated.

The cubic fluorite-type solid solutions obtained by re-
acting ZrO2 with alkaline earth or rare earth oxides such
as CaO, MgO, Y203, or Sc203 are stable over an e x t e n d e d
r a n g e of c o m p o s i t i o n and t e m p e r a t u r e (1). T h e s e oxide-
ion type solids are labeled with respect to the stabilizing
oxide, e.g., S S Z or YSZ, r e p r e s e n t i n g scandia (Sc203)- or
yttria (Y203)-stabilized ZrO2, r e s p e c t i v e l y . The h i g h an-
ion c o n d u c t i v i t y of t h e s e m a t e r i a l s is d u e to th e migra-
tion of o x y g e n ions via a v a c a n c y m e c h a n i s m . The vacan-
cies i n v o l v e d are o x y g e n v a c a n c i e s Vo~176 w h i c h are
created w h e n Zr02 is d o p e d with lower valent oxides; in
order to preserve the electrical neutrality of the solid, an
e f f e c t i v e c h a r g e of +2 results (2). O v e r th e last tw o dec-
ades, these stabilized ZrO2 c o m p o u n d s have f o u n d wide-
spread use as high t e m p e r a t u r e solid electrolytes in a va-
riety of practical devices such as: probes to m e a s u r e the
02 c o n t e n t of l i q u i d steel; o x y g e n sensors for c o m b u s -
tion processes and for closed loop control of a u t o m o b i l e
e x h a u s t systems; and electrically driven o x y g e n pumps,
electrolysis cells, and fuel cells (3, 4). A clear u n d e r s t an d -
ing of the nature of the electrode reactions is of scientific
i n t e r e s t as well as b e i n g i m p o r t a n t for t h e e n g i n e e r i n g
design of these devices.
* Electrochemical Society Student Member.
** Electrochemical Society Active Member.
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D u e to t h e initial i n t e r e s t in o x y g e n sen so r s and oxy-
gen pumps, the overpotential behavior of the O2 cathode
has been the subject of m a n y early investigations. These
s t u d i e s i n d i c a t e a lack of c o n s i s t e n c y w i t h r e s p e c t to
w h a t rate p r o c e s s e s are controlling. The f o l l o w i n g rate-
d e t e r m i n i n g steps for the r e d u c t i o n of 02 have been pro-
posed: (i) diffusion of atomic O t h r o u g h the body of the
m e t a l e l e c t r o d e (5); (ii) d i s s o c i a t i o n of 02 on t h e m e t a l
e l e c t r o d e s (6); (iii) d i f f u si o n of a t o m i c O on t h e electro-
lyte surface (7) or on the metal electrode surface (8); and
(iv) charge transfer across the electrode/electrolyte inter-
f a c e (9). The dissimilarity of these proposed m e c h a n i s m s
has b e e n a t t r i b u t e d to d i f f e r e n c e s in the r e s p e c t i v e ex-
p e r i m e n t a l c o n d i t i o n s e m p l o y e d such as t e m p e r a t u r e ,
Po2, and the electrode morphology.
C o m p a r e d to the 02 electrode, the behavior of the fuel
a n o d e has not r e c e i v e d m u c h attention. In an early
study, Weissbart et al. (10) m e a s u r e d the anodic current-
o v e r p o t e n t i a l b e h a v i o r at 800~176 in the f o l l o w i n g
fuel cell type system: H2 + H20, Pt/10 mole p er cen t (m/o)
CaO-ZrO2/Pt, air. Th ei r results i n d i c a t e that t h e electro-
lyte o h m i c r e s i s t a n c e was limiting. Etsell and F l e n g a s
(11) n o t e d c o n s i d e r a b l e a c t i v a t i o n o v e r p o t e n t i a l w i t h
electrocatalysis thus being limiting for the CO/CO2 reac-
tion. Stabilized ZrO2 electrolytes have been used in gal-