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640 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 March 1980

8. P e n n t u b e Plastics P r o d u c t Guide, Clifton Heights, 14. B. Miller, This Journal, 117, 491 (1970).
Pa., 19018 (1970). 15. B. Miller and R. E. Visco, ibid., 115, 251 (1966).
9. M. C. H. M c K u b r e and D. D. Macdonald, F i n a l R e - 16. H. Schlichting, " B o u n d a r y L a y e r Theory," M c G r a w
port, U.S. Dept. of E n e r g y Report, Contract Hill, New k o r k (1960).
EM-78-C-01-5159, Feb. 1980. 17. B. Miller, This Journal, 116, 1675 (1969).
10. B. Miller, This Journal, 116, 1117 (1969). 18. J. O'M. Bockris and A. K. N. Reddy, "Modern
11. M. C. H. M c K u b r e a n d D. D. Macdonald, S u b m i t t e d Electrochemistry," Plenum, N e w York (1970).
to This Journal.
12. Y. Beers, "The T h e o r y of Error," A d d i s o n - W e s l e y , 19. D. D. Macdonald, Atomic E n e r g y of Canada L i m -
Reading, Mass. (1962). ited Report 4139 (1972).
13. W. J. A l b e r y and S. Bruckenstein, Trans. Faraday 20. D. D. M a c d o n a l d a n d M. C. H. McKubre, To be
Soc., 62, 1946 (1966). published.

Factors Affecting the Electrochemical Responses of Metal


Complexes at Pyrolytic Graphite Electrodes Coated with Films
of Poly(4-Vinylpyridine)
Noboru Oyama* and Fred C. Anson*
Arthur Amos Noyes Laboratory, Cali$ornia Institute o~ Technology, Pasadena, California 91125

ABSTRACT
E l e c t r o c h e m i c a l responses from the r e d u c t i o n of Ru m (edta) coordinated
to films of high m o l e c u l a r w e i g h t poly ( 4 - v i n y l p y r i d i n e ) on p y r o l y t i c g r a p h i t e
electrodes w e r e s t u d i e d as functions of film thickness, t e m p e r a t u r e , s u p p o r t i n g
e l e c t r o l y t e composition, and solvent. Responses at filmed electrodes f r o m m e t a l
complexes t h a t do not coordinate to the films w e r e also examined. W i t h films
t h i c k e r t h a n ca. 1000A, the c u r r e n t responses a r e l i m i t e d b y the rates of molec-
u l a r motions w i t h i n the films. P e n e t r a t i o n of counterions, s e g m e n t a l motion of
sections of the p o l y m e r chains, and j u x t a p o s i t i o n i n g of pairs of a t t a c h e d m e t a l
complexes to facilitate i n t e r c o m p l e x electron t r a n s f e r w i t h i n the film or com-
binations of the t h r e e a r e suggested as l i k e l y c u r r e n t limiting p r o c e s s e s .

There has b e e n considerable c u r r e n t interest in t h e cylindrical stock (Tokai Electrode M a n u f a c t u r i n g Com-


p r e p a r a t i o n and p r o p e r t i e s of p o l y m e r - c o a t e d elec- pany, Limited, T o k y o ) . The disks w e r e sealed to t h e
t r o d e surfaces (1-12). E x a m p l e s of p o l y m e r coatings ends of glass tubing w i t h h e a t - s h r i n k a b l e polyolefin
t h a t have been described include nonelectroactive t u b i n g (Alfa Wire C o m p a n y ) to p r o d u c e an electrode
p o l y m e r s (1, 6), p o l y m e r s b e a r i n g r e p e a t i n g electro- a r e a of 0.2 cm. The glassy c a r b o n surface was polished
active groups (2, 3, 7, 8, 11), and electroinactive p o l y - w i t h silicon c a r b i d e p a p e r of successively finer g r a i n
meric coatings t h a t become electroactive w h e n m e t a l and finally w i t h 0.3# alumina. The polished s u r f a c e
complexes are a t t a c h e d to t h e m (4, 5, 7, 9). A m o n g the was w a s h e d w i t h excess w a t e r a n d methanol.
questions t h a t a w a i t definitive answers for such coat- P o l y ( 4 - v i n y l p y r i d i n e ) ( B o r d e n Incorporated, P h i l a -
ings is how electron t r a n s f e r is accomplished b e t w e e n delphia, P e n n s y l v a n i a ) was r e c r y s t a l l i z e d twice from
the electrode surface and electroactive sites p r e s e n t m e t h a n o l - d i e t h y l ether. ~ts a v e r a g e m o l e c u l a r weight
in the p o l y m e r i c films. was d e t e r m i n e d v i s c o m e t r i c a l l y (13) to be 7.4 X 105.
K a u f m a n a n d Engler (8) h a v e r e c e n t l y p r o p o s e d This was the p o l y m e r utilized in all e x p e r i m e n t s e x -
that electrons are conducted t h r o u g h r a t h e r thick films cept those associated w i t h Fig. 2. A q u o e t h y l e n e d i -
of a p o l y m e r i c p y r a z o l i n e b y electron t r a n s f e r b e t w e e n a m i n e t e t r a a c e t a t o r u t h e n i u m (III) was p r e p a r e d a n d
the electroactive groups w i t h i n the polymer. T h e y purified as p r e v i o u s l y described (9). Other chemicals
proposed t h a t such t r a n s f e r r e q u i r e d t h a t the sites of w e r e r e a g e n t g r a d e and w e r e used as received. A q u e -
e l e c t r o a c t i v i t y be mobile enough to achieve a p p r o p r i a t e ous solutions w e r e p r e p a r e d with t r i p l y distilled water.
j u x t a p o s i t i o n s of n e i g h b o r i n g sites in o r d e r for electron The s u p p o r t i n g e l e c t r o l y t e for most electrochemical
t r a n s f e r to occur. In addition, the p o l y m e r film m u s t m e a s u r e m e n t s in aqueous m e d i a was 0.2M CF3COONa
be porous enough to a l l o w p e n e t r a t i o n b y ions of the a d j u s t e d to the desired p H w i t h CF~COOH. Potentials
supporting e l e c t r o l y t e to m a i n t a i n e l e c t r o n e u t r a l i t y are quoted with respect to a sodium chloride s a t u -
w i t h i n the film. r a t e d calomel reference electrode ( S S C E ) .
In the p r e s e n t r e p o r t we address this and r e l a t e d The electrochemical i n s t r u m e n t a t i o n and p r o c e d u r e s
issues for films of p o l y ( 4 - v i n y l p y r i d i n e ) ( P V P ) a t - utilized have been described p r e v i o u s l y (9). W i t h
tached to p y r o l y t i c g r a p h i t e electrodes. The v e r s a t i l i t y electrodes b e a r i n g h e a v y coatings of P V P and RU m
of this p o l y m e r i c l i g a n d in anchoring t r a n s i t i o n m e t a l (edta) the q u a n t i t y of e l e c t r o c h e m i c a l l y active a t -
complexes to e l e c t r o d e surfaces ~was described r e - t a c h e d complex could not be d e t e r m i n e d r e l i a b l y b y
cently (9) and it seemed desirable to obtain m o r e i n - electronic i n t e g r a t i o n of v o l t a m m o g r a m s . F i g u r e 1
f o r m a t i o n on the electron t r a n s f e r p r o p e r t i e s of these shows an e x a m p l e of a v o l t a m m o g r a m for a coated
films which have electroactive groups ( m e t a l c o m - electrode and its a r e a as m e a s u r e d b y electronic i n t e -
plexes) i n t r o d u c e d into t h e m a f t e r t h e y have been gration of the c u r r e n t d u r i n g the potential scan. Note
a t t a c h e d to the g r a p h i t e surface. t h a t the slope of the i n t e g r a t e d c u r r e n t curve d o e s
not drop to b a c k g r o u n d levels even at potentials w e l l
Experimental n e g a t i v e of the p e a k potential. Significant c o n t r i b u -
P y r o l y t i c g r a p h i t e electrodes w i t h the graphitic tions to the c u r r e n t i n t e g r a l continue to a c c u m u l a t e
b a s a l planes exposed to the solutions w e r e p r e p a r e d at potentials f a r r e m o v e d f r o m the peak. F o r this r e a -
and t r e a t e d as p r e v i o u s l y described (9). Glassy c a r - son the quantities of r e a c t a n t s a t t a c h e d to p o l y m e r
bon electrodes w e r e p r e p a r e d b y cutting disks from l a y e r s were e v a l u a t e d b y i n t e g r a t i o n of the c u r r e n t
that passed w h e n the electrode p o t e n t i a l was s t e p p e d
~ Electrochemical Society Active Member.
Key words: polymers, modified electrode, surfaces. and h e l d a t a v a l u e well b e y o n d the v o l t a m m e t r i c
VoL 127, No. 3 ELECTROCHEMICAL RESPONSES 641
A
to the P V P coating was t h e n d e t e r m i n e d e l e c t r o c h e m i -
cally in 0.2M CF~COONa (pH 2.7) s u p p o r t i n g elec-
t r o l y t e b y the methods described in the E x p e r i m e n t a l
section. The e x t e n t of Ru m (edta) coordination d e -
p e n d e d on the a v e r a g e m o l e c u l a r w e i g h t o f t h e P V P
used to coat t h e e l e c t r o d e as shown in Fig. 2. T h e first
two points c o r r e s p o n d to t h e use of 4 - e t h y l p y r i d i n e
and 1 , 2 - b i s ( 4 - p y r i d y l ) - e t h a n e to coat t h e e l e c t r o d e .
N e i t h e r p r o d u c e d a surface w i t h m e a s u r a b l e affinity

0 ~,
I lo0/zC for R u m ( e d t a ) . W i t h p o l y m e r s of h i g h e r a v e r a g e
m o l e c u l a r w e i g h t t h e e x t e n t of binding of Ru m ( e d t a )
is assumed to reflect a n i n c r e a s e in t h e q u a n t i t y o f
P V P t h a t is p r e s e n t on the g r a p h i t e surface. P V P
samples w i t h a v e r a g e m o l e c u l a r weights in e x c e s s o f
I I i i i i i i i i i i i i 2 X 105 a r e c l e a r l y the most p o t e n t for p r e p a r i n g e l e c -
0.4 0.2 0 -0.2 -0.4 -0.6 -0.8
t r o d e coatings t h a t a c c e p t t h e l a r g e s t q u a n t i t i e s o f
E vs. SSCE, V R u In ( e d t a ) .
Fig. 1. A, voltammogram for the reduction of RutII (edta) at-
F i l m morphology.----Scanning electron m i c r o g r a p h s
tached to o coating of 2.3 X 10 - 7 moles cm - 2 of pyridine as
PVP on a pyrolytic graphite electrode. RuIII (edta) attachment was
of films of P V P on glassy carbon show the p o l y m e r to
that resulting when the PVP-coated electrode was exposed to a 5
be d i s t r i b u t e d s o m e w h a t u n e v e n l y w i t h islands o f
tamale solution of Rum (edta) at pH 3.9 for 15 rain. Supporting
p o l y m e r s u r r o u n d e d b y b a r e o r l i g h t l y covered a r e a s .
The uneveness a p p e a r s to increase w h e n R u IzI (edta)
electrolyte: 0.2M CF~COONa (pH = 2.85). Scan rate: 100 mV
sec - z . B, area under the voltammogram in A obtained by electronic
is coordinated to the polymer. A cross-sectional v i e w
integration of the current as the voltammogram was recorded.
of the l a y e r p r o d u c e d w h e n a m e t h a n o l i c solution con-
Background current and its integral are shown by the dashed lines.
taining 6 X 10 -~ moles c m - 2 of m o n o m e r i c p y r i d i n e
units was a l l o w e d to e v a p o r a t e on a glassy c a r b o n
surface is shown in Fig. 3. The a p p a r e n t thickness o f
p e a k p o t e n t i a l until the r a t e of charge a c c u m u l a t i o n the l a y e r is (8 __. 2) 104A w h i c h corresponds to a n
d e c r e a s e d to b a c k g r o u n d levels. effective density of only ca. 0.08 g / c m - ~ . Since the
To p r o v i d e electrode surfaces containing k n o w n density of b u l k p o l y ( 4 - v i n y l p y r i d i n e ) is 1.1 t h i s
quantities of a t t a c h e d PVP, m e a s u r e d aliquots of a could indicate t h a t the p o l y p y r i d i n e l a y e r is quite p o r -
stock solution of the p o l y m e r in m e t h a n o l w e r e c a r e - ous. However, the a p p a r e n t film thickness o b s e r v e d in
f u l l y t r a n s f e r r e d to the surface of a h o r i z o n t a l l y the SEM m a y not be an a c c u r a t e reflection of t h a t p r e -
m o u n t e d electrode w i t h a m i c r o l i t e r syringe. 1-4 m i c r o - vailing on the electrodes used in the electrochemical
liters of the solution s p r e a d u n i f o r m l y on p y r o l y t i c experiments. F o r example, s e v e r a l of the e x p e r i m e n t s
g r a p h i t e a n d w e l l - p o l i s h e d glassy c a r b o n surfaces to be described in w h a t follows indicate c l e a r l y t h a t
w i t h o u t overflowing, to p r o d u c e a visibly u n i f o r m film PVP films deposited on g r a p h i t e u n d e r some conditions
u p o n e v a p o r a t i o n of the solvent. To i n t r o d u c e Ru m b e h a v e e l e c t r o c h e m i c a l l y as if t h e y p r e s e n t e d ' a dense,
(edta) onto the electrode surfaces the resulting p o l y - i m p e r v i o u s d o m a i n to r e a c t a n t s seeking the electrode
m e r - c o a t e d electrodes w e r e i m m e r s e d in a 5 m m o l e surface. Thus, e x p o s u r e of films deposited f r o m m e t h -
aqueous solution of Ru m (edta) at p H 3.9 for 15 min. anol to the low pressures w i t h i n the SEM m a y cause
A f t e r a t t a c h m e n t of the c o m p l e x b y coordination to a l a r g e expansion of the film as r e s i d u a l t r a p p e d sol-
the p e n d a n t p y r i d i n e ligands in the p o l y m e r coating vent escapes f r o m the film, causing t h e m to a p p e a r less
(9), the electrodes w e r e w a s h e d r e p e a t e d l y w i t h water, dense. F o r this reason we do not r e g a r d the film d e n -
dried, and stored. This p r o c e d u r e is not w e l l calculated sities e s t i m a t e d f r o m SEM m e a s u r e m e n t s as r e p r e s e n -
to ensure a u n i f o r m d i s t r i b u t i o n of coordinated Ru In tative of electrode surfaces t h a t a r e n e v e r exposed to
(edta) t h r o u g h o u t the P V P layer. None of the electro- high vacuum.
chemical e x p e r i m e n t s p e r f o r m e d w i t h these coatings Coatings of PVP on glassy c a r b o n t h a t exceed ca.
of P V P - R u ( e d t a ) gave indications of h i g h l y aniso- 5 10 - s moles cm -2 ( e x p r e s s e d as m o n o m e r i c p y -
tropic film compositions b u t it w o u l d not be s u r p r i s - ridine units) a r e c l e a r l y visible w i t h o u t magnification.
ing to find t h a t m o r e of the a t t a c h e d complex resided The o r i g i n a l l y b l a c k surface becomes g r a y a n d t h e
n e a r the e l e c t r o l y t e / f i l m interface t h a n the e l e c t r o d e / glassy carbon loses its luster. W h e n Ru m (edta) is
film interface. coordinated to such h e a v y P V P coatings, a distinct
Scanning electron m i c r o g r a p h s w e r e o b t a i n e d w i t h and p e r s i s t e n t golden color develops on t h e e l e c t r o d e
a n ETEC C o r p o r a t i o n A u t o s c a n U-1 ( H a y w a r d , Cali- surface w h e n the R u ( I I I ) is r e d u c e d to R u ( I I ) . T h e
fornia) instrument. Electrodes were coated by the electrode can be cycled r e p e a t e d l y b e t w e e n potentials
p r o c e d u r e j u s t described. Cross-sectional views of that cause r e d u c t i o n a n d o x i d a t i o n of the r u t h e n i u m
coatings a p p l i e d to polished glassy c a r b o n electrodes
w e r e o b t a i n e d b y a p p r o p r i a t e m o u n t i n g of the elec-
t r o d e specimens in t h e microscope. I n this w a y the 4,0 1 I
thickness of the p o l y m e r i c l a y e r s could be estimated. 'E
(D

Results and Discussion 3.0-


0
E~ects of molecular weight on the adsorption of P V P E
on graphite.--To assess the d e p e n d e n c e of the m o l e c u - 0~'2. 0 -
l a r w e i g h t of the P V P on the e x t e n t of its a t t a c h m e n t 0
to p y r o l y t i c graphite, a set of P V P s a m p l e s f r a c t i o n -
x 1.0-
a t e d b y successive c r y s t a l l i z a t i o n f r o m m e t h a n o l solu-
tions to which increasing amounts of d i e t h y l e t h e r w e r e
a d d e d was p r e p a r e d and the a v e r a g e m o l e c u l a r weight 0 _~r" I I
of each fraction was d e t e r m i n e d v i s c o m e t r i c a l l y (13). 2.0 5.0 4.0 5.0 6.0
F r e s h l y cleaved p y r o l y t i c g r a p h i t e electrodes w e r e log (mol. WL)
exposed to 0.5% solutions of each fraction in m e t h a n o l
for 15 m i n followed b y w a s h i n g w i t h m e t h a n o l (for Fig. 2. Effect of the average molecular weight of PVP on its
15 rain) and e x p o s u r e of the r e s u l t i n g P V P coated attachment to graphite electrodes as reflected in the coordination
electrodes to a 5 m m o l e solution of R u n1 ( e d t a ) for of Rum (edta) to the polymer coatings under standard conditions
15 min. The a m o u n t of R u In (edta) t h a t c o o r d i n a t e d (see text for details).
642 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 March 1980

[ I I I I ] [ I I T I ' [ ' " ' " I I I I

A v :0.5Vs -I

0.2mA

N-
Z
W
0~
r~

i i i i i i i i 9 i I I i I

0.6 0.4 0.2 0 -0.2 -0.4 -0.6 -0.8


Fig. $. Scanning electron microgroph of a PVP coating on a
glassy carbon electrode. 6 X 10 - 7 moles cm - ~ of pyridine as PVP E vs. SSCE, V
was placed on the surface by evaporation of an aliquot of a Fig. 4. Cyclic voltammograms for RuzII (edta) attached to pyro-
methanolic solution. The calibration mark at the bottom of the lytic graphite electrodes coated with increasing quantities of PVP.
micrograph corresponds to 10 microns. PVP coatings were prepared by evaporation of measured aliquots of
solutions of the polymer in methanol. Rum (edtu) attachment
centers and the golden color fades and reappears cor- procedure as in Fig. 1. Quantity of pyridine introduced on surface
respondingly. S i m i l a r observations have b e e n made as PVP~ moles cm-2: A, 2.3 X 10-8; 13, 4.6 X |0-'7; C,
with polypyrazoline films (8). 2.3 X 10-~. Quantity of RuzII (edta) attached, moles cm-2: A,
2.4 10-9; B, 1.5 X I 0 - 7 ; C, ~>3 X 10 -7. Supporting electro-
Cyclic vo~tammetry and chronocouZometry.--Cyclic lyte: 0.2M CF3COONa (pH -- 4.2). Scan rate: 500 mV sec -z.
voltammograms obtained w i t h electrodes coated with
PVP to the extent of no more t h a n ca. 10 -8 moles cm - ~ 0.4 I I I I I I I I I
(of pyridine units) and then with Ru [H (edta), b y
exposure to a 5 mmole solution for 15 min, exhibit the 0.3 A
symmetrical shapes a n d l i n e a r dependence of peak
currents on scan rate expected for reactants that are 0.2
attached to electrode surfaces (14). I n addition, the
area u n d e r v o l t a m m o g r a m s for such coatings shows O.i
almost no dependence on scan rate. However, as shown
in Fig. 4, increasing the q u a n t i t y of P V P applied to 0
the electrode surface causes the shapes and peak cur- 0.5 I I I I I -- l I I I I
rents of the resulting v o l t a m m o g r a m s to change: at
first, increasing the q u a n t i t y of PVP on the electrode 0.4
surface causes the peak c u r r e n t to increase b u t still
heavier coatings produce diminished peak currents. At E 0.3
the same time the shape of the v o l t a m m o g r a m s b e -
comes less symmetric and they come to resemble volt- ,,=,0 2
ammograms for u n a t t a c h e d reactants that diffuse to the FF
CF
electrode surface. There is a corresponding change in O.l
the scan r a t e - d e p e n d e n c e of the peak currents. With (..)

light polymer coatings the peak currents are propor- 0 .... L.- [ L I I
tional to the scan rate (Fig. 5) as expected for attached 0.4 f I ' T f I I I l r

reactants (14) b u t with sufficiently heavy coatings,


the peak currents exhibit the p r o p o r t i o n a l i t y to the 0.5 C
square root of scan rate typical of diffusing reactants
(Fig. 5). The a p p a r e n t areas u n d e r the v o l t a m m o g r a m s 0.2
obtained with heavy p o l y m e r coatings show a strong
inverse dependence on scan rate a n d the i n t e g r a l of
the c u r r e n t that passes i n response to a potential step
from 0.7 to --0.7V grows r a p i d l y at first a n d t h e n con-
tinues to increase slowly for periods as long as 30 or 40 O0 5 I0 15 20 "'0 I00 200 500 400 500
min. F i g u r e 6 compares the charge consumed one m i n - I -I I
-I
ute after a potential step was applied with the charge (SCAN RATE) ~, (mVs):~ SCAN RATE, rnVs
r e q u i r e d to reduce all of the attached complex. With
Fig. 5. Peak currents for the three electrodes of Fig. 3 as a
sufficiently h e a v y coatings of PVP the charge consumed
function of scan rate and (scan rate) 1/~.
i n a fixed time i n t e r v a l is smaller t h a n with lighter
coatings even though the actual q u a n t i t y of Ru m (edta)
coordinated to the coating continues to increase as confirmed by spectroelectrochemical m e a s u r e m e n t s us-
heavier P V P coatings are applied. [This assertion was ing optically t r a n s p a r e n t graphite electrodes (15, 16).]
Vol. 127, No. 3 ELECTROCHEMICAL RESPONSES 643

I I occur. The c u r r e n t m a y be limited b y the rate at which


segments of the p o l y m e r chains w i t h i n the attached
layer can move out of the p a t h w a y of counterions en-
0.030
tering the film (18). (Note that such motion is re-
/ quired even if the p o l y m e r layer contains an a b u n d a n c e
/
of supporting electrolyte because an additional counter-
0.025 - / ion m u s t still be transported from the b u l k of the
O,J / solution to each site where a n additional charge is
IE /
to generated.)
o 0.015
/ Temperature dependence of the electrochemical re-
(..3 /
O sponse.--The diffusion of small molecules (and ions)
d o.oio- through polymeric matrices has received considerable
study (19-21). A p p a r e n t diffusion coefficients that
have been m e a s u r e d typically exhibit a n A r r h e n i u s
type of t e m p e r a t u r e dependence and the correspond-
0.005 -

ing activation process has been identified with seg-


m e n t a l motions w i t h i n the p o l y m e r (20). To evaluate
diffusional activation energies for the reduction of the
C Ru m (edta) complex attached to the polymeric layer
-8.0 -7.0 -6.0 -5.0 the t e m p e r a t u r e dependence of cyclic v o l t a m m e t r i c
log (Fpvp/moles crff 2) peak currents and chronocoulometric slopes were m e a -
sured. Figure 7B shows the cyclic voltammograms for
Fig. 6. Charge consumed by the reduction of Rum (edta) at- Ru m (edta) coordinated to a PVP layer on the elec-
tached to PVP-coated electrodes. ( ~ ) Charge consumed during trode surface at 5 ~ a n d 45~ The t e m p e r a t u r e de-
the first 60 sec following the application of a potential step from pendence of the peak currents is comparable to that
+ 0 . 7 to --0.7V. ( O ) Charge required for complete reduction of observed with freely diffusing Ru m (edta). However,
the attached complex at --0.7V. Supporting electrolyte: 0.2M since significant quantities of the attached complex
CF3COONa (pH = 4.2). RuIn (edta) attachment procedure as in can r e m a i n u n r e d u c e d u n d e r cyclic v o l t a m m e t r i c con-
Fig. 1. The charges required for complete reduction were obtained ditions (Fig. 4), the m a g n i t u d e of the peak c u r r e n t
by continuing the current integration until the rate of increase of does not provide a reliable measure of the a p p a r e n t
of charge matched background levels. diffusion coefficient. For this reason we used the slopes
of the linear chronocoulometric c h a r g e - ( t i m e ) w 2 plots
Straight lines were obtained for chronocoulometric shown in Fig. 7A as measures of the product of the
plots of the charge passed in response to the potential (square root of the) a p p a r e n t diffusion coefficient and
step against the square root of time. This behavior the concentration of the diffusing species. It is not
suggests diffusive t r a n s p o r t as the c u r r e n t - l i m i t i n g straightforward to obtain n u m e r i c a l values of the
factor. I n line with the proposals of K a u f m a n a n d a p p a r e n t diffusion coefficients from the slopes of the
Engler (8), both the motions of the anchored m e t a l plots such as those in Fig. 5C a n d 7A because the
complexes to achieve the proper juxtaposition for i n t e r - concentration of the "diffusing" species is not known.
complex electron transfer as well as diffusive supply of T h e - c o n c e n t r a t i o n of counterions in the b u l k of the
counterions to the sites where the attached complex solution is not the appropriate concentration to use
is to be reduced could be responsible for the observed because we observed no change in the m a g n i t u d e of
behavior. Both the attached Ru m (edta) and Ru II voltammetric peak currents w h e n the concentration
(edta) complexes are likely to be anionic at the pH of the supporting electrolyte was varied b e t w e e n 0.02
of the supporting electrolyte, 4.2 (17). Upon reduction, and 2.0M at constant pH.
the negative charge on the complex doubles so that Figure 8 shows the A r r h e n i u s plot of the slopes of
a cation m u s t be supplied to each a t t a c h m e n t site the chronocoulometric plots i n Fig. 6A from which a n
before the reduction of the attached Ru m (edta) can a p p a r e n t diffusional activation energy of 4.6 kcal per

A
5

ot 45oc\ /
a

I I I I I I I I I
,; 2'0 0.4 0.2 0 -0.2 -0.4 -0.6
(Time/sec) I/2 E vs. SSCE, V
Fig. 7. Temperature dependence of (A), charge-(time) 1/~ plots and (B), cyclic" voltammograms (sca~n rate: 200 mV s~~ - t ) for Rum
(edta) attached to electrodes coated with 2.3 X 10 - 6 moles cm - 2 of pyridine as PVP. Rum (edta) attachment procedure and supporting
electrolyte as in Fig. 2 except pH was 3.4.
644 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 March 1980

tions could serve to "plasticize" the coatings of P V P


on g r a p h i t e surfaces. T h e activation e n e r g y e v a l u a t e d
0.2 in Fig. 8 could then be r e g a r d e d as a m e a s u r e of the
b a r r i e r faced b y small segments of the P V P chains
as t h e y r e o r i e n t to j u x t a p o s e pairs of a n c h o r e d
R u ( e d t a ) complexes a n d to p e r m i t counterions to
o reach (or d e p a r t form) the sites w h e r e the electrode
co
Oh
0 reaction causes an increase (or decrease) in ionic
charge.
O4
O9 E~ect of solvent on the e~ectrochemical response.--
Changes in the solvent e m p l o y e d to conduct e l e c t r o -
chemical m e a s u r e m e n t s on Ru III (edta) coordinated to
P V P coatings can p r o d u c e d r a m a t i c differences in the
v -0.2 responses obtained. F i g u r e 8 shows the responses o b -
t a i n e d f r o m the same coating in five different solvents.
o The Ru III (edta) is r e n d e r e d v i r t u a l l y electroinactive
in acetonitrile a n d d i m e t h y l sulfoxide. The effect is
not the result of r e m o v a l of the complex from the s u r -
face because t r a n s f e r of electrodes t h a t give v e r y small
-0.4 - E A C T ~ 4.6 Kcol responses to an aqueous e l e c t r o l y t e i m m e d i a t e l y r e -
stores the electrochemical a c t i v i t y of the a t t a c h e d com-
plex.
In separate experiments with optically transparent
I I I I I I g r a p h i t e electrodes (15) we have found t h a t essen-
3.0 :5.2 :5.4 :5.6 t i a l l y all of the Ru m (edta) a t t a c h e d to PVP coatings
is electroactive in aqueous s u p p o r t i n g electrolytes w i t h
I / T x I0 5 p o l y m e r coatings s i m i l a r to those e m p l o y e d in Fig. 9.
Thus, these results show t h a t changes in solvent can
Fig. 8. Arrhenius plot of the slopes of the charge-(time) 1/2 lines cause a f u l l y electroactive film to become l a r g e l y i n -
in Fig. 7 relative to the slope at 298~ active.
Solvents t h a t diminish the e l e c t r o a c t i v i t y of com-
mole was calculated. This is a s o m e w h a t s m a l l e r v a l u e plexes a t t a c h e d to p o l y m e r coatings produce s i m i l a r
t h a n those r e p o r t e d for the diffusion of small molecules effects on electrode process involving u n a t t a c h e d r e -
w i t h i n solid p o l y m e r films (20) but it is s i m i l a r to actants: Fig. 10A shows a cyclic v o l t a m m o g r a m for
values o b s e r v e d for such films in the presence of p l a s - ferrocene at an uncoated p y r o l y t e g r a p h i t e electrode
ticizing agents t h a t facilitate s e g m e n t a l motions of in acetonitrile. Coating the electrode w i t h a m o d e r a t e l y
m o l e c u l a r chains w i t h i n p o l y m e r i c matrices (20). It h e a v y l a y e r of P V P (10 -7 to 10 -.8 moles cm -2 of
does not seem u n r e a s o n a b l e that acidic, aqueous solu- p y r i d i n e ) s o m e w h a t inhibits the ferrocene wave. If

.20
ol

Fig. 9. Solvent dependence of MeOH


steady-state cyclic voltammo-
grams for RuIII (edta) attached
to electrodes coated with 4.6 X
10 - 7 moles cm - 2 of pyridine as
I ot J

t--
PVP. Supporting electrolytes: Z ~OImA
H20, 0.2M CF.3COONa (pH = LLI
4.2); other solvents, 0.2M rY
NaCIO4. Scan rate: 200 mV rY EtOH
sec -1. RuIn (edta) attachment
procedure as in Fig. 2. A freshly
g ol
coated electrode was used in
each solvent. CH3CN
ol j

DMSO
ot
I I I I I I I 1 I I I I I I I I I I
0.6 0.4 0.2 0 -0.2 -0.4 -0.6 -0.8 -1.0
E vs. SSCE, V
VoI. 127, No. 3 ELECTROCHEMICAL RESPONSES 645

A compares cyclic v o l t a m m o g r a m s r e c o r d e d in four d i f -


ferent s u p p o r t i n g electrolytes w i t h i d e n t i c a l l y p r e -
p a r e d electrode surfaces. The p e a k c u r r e n t in the
e l e c t r o l y t e at p H 1.6 (curve B) is about twice as large
Z IO.I mA as those in the o t h e r electrolytes i n d i c a t i n g t h a t c h a r g e
Ld B t r a n s f e r t h r o u g h the film is facilitated b y p r o t o n a t i o n
of the p y r i d i n e groups. P r o t o n a t e d P V P chains no
d o u b t t e n d to s t r e t c h a p a r t to m i n i m i z e coulombic r e -
pulsions (23) and this w o u l d lead to a film t h r o u g h
i ot c which ions could move m o r e readily. As a result, seg-
m e n t a l motions w i t h i n the p o l y m e r l a y e r m a y also be
facilitated because the p e n e t r a t i o n of m a c r o m o l e c u l a r
I I I I I I I I I I i 1 I I I I I I solids b y l o w m o l e c u l a r w e i g h t species is k n o w n to
0.6 0.4 0.2 0 -0.2 -0.4 -0.6 -0.8 -I.0
E vs. SSCE, V p r o d u c e such effects (24).
Curves A and C in Fig. 11 h a v e r a t h e r s i m i l a r shapes
Fig. 10. Steady-state cyclic voltammograms for 1.3 mmele ferro- indicating t h a t changing the anion of t h e s u p p o r t i n g
cene at pyrolytic graphite electrodes in acetonitrile. Electrode pre- e l e c t r o l y t e from trifluoroacetate to b r o m i d e produces
treatments: A, freshly cleaved; B, coated with 4.6 X 10 - 7 moles only small effects. The change of s u p p o r t i n g e l e c t r o l y t e
cm - 2 of pyridine as PVP, soaked in 5 mmole RunI (edta) for 15 cation f r o m sodium to t e t r a m e t h y l a m m o n i u m (curves
rain, washed with H20 and acetonitrile. C, coated with 2.3 X 10 - 6 C and D) yields a more s y m m e t r i c a l v o l t a m m o g r a m .
moles cm - 2 of pyridine as PVP then as in B. Scan rate: 200 mV This m i g h t be the result of tess h y d r a t i o n of the l a t t e r
sec -1. Supporting electrolyte: 0.2M NaCIO4. cation with a c o r r e s p o n d i n g decrease in the e x t e n t of
s e g m e n t a l motion w i t h i n the p o l y m e r r e q u i r e d for its
Ru zH (edta) is a t t a c h e d to the coating, i n h i b i t e d r e - penetration.
sponses a r e o b s e r v e d for b o t h the a t t a c h e d c o m p l e x The suggestion t h a t the c u r r e n t e n h a n c e m e n t in
a n d ferrocene in the solution (Fig. 10B). W i t h h e a v i e r curve B of Fig. 11 results from an "opening up" of
coatings of PVP, the responses from both the a t t a c h e d the p o l y m e r i c s t r u c t u r e because of r e p u l s i v e i n t e r a c -
a n d the dissolved r e a c t a n t a r e s e v e r e l y i n h i b i t e d (Fig. tions among p r o t o n a t e d sites along the p o l y m e r chains
10C). That the w a v e for the dissolved ferrocene can receives a d d e d s u p p o r t f r o m the v o l t a m m o g r a m s in
be almost e l i m i n a t e d w i t h sufficiently h e a v y coatings Fig. 12. Curve A in Fig. 12 is a cyclic v o l t a m m o g r a m
of P V P indicates that the P V P films p r o d u c e d b y e x - for Fe In (edta) at an u n c o a t e d electrode. Curve B r e -
posure to this solvent are r e l a t i v e l y free of holes or sults w h e n t h e electrode is coated w i t h P V P and used
other defects that w o u l d allow the f e r r o c e n e to reach in the solution of F e m (edta) a t a pH w h e r e the P V P
t h e g r a p h i t e surface. Since the s u p p o r t i n g electrolyte is not significantly p r o t o n a t e d (25). The p o l y m e r l a y e r
w o u l d p r e s u m a b l y also be u n a b l e to p e n e t r a t e the film, a p p a r e n t l y cannot be p e n e t r a t e d b y the FeuI (edta)
it is not s u r p r i s i n g that r e a c t a n t s a t t a c h e d to such films complex. However, w h e n the p H is l o w e r e d to a value
should also e x h i b i t little or no electroactivity. S t r u c - w h e r e the P V P l a y e r is protonated, the e l e c t r o r e d u c -
tures of p o l y m e r i c films t h a t are compact enough to tion of Fe III (edta) is i m m e d i a t e l y r e s t o r e d (curve C).
i m p e d e the motion of s u p p o r t i n g electrolytes t h r o u g h W h e n Ru(NH3)63+ is substituted for the anionic Fe m
t h e m m i g h t also l a c k a d e q u a t e flexibility for the n e e d e d (edta) complex and the e x p e r i m e n t s repeated, curves
positioning of the r e d o x centers to accomplish electron D, E, and F in Fig. 12 are obtained. P r o t o n a t i o n of the
t r a n s f e r t h r o u g h the film. P V P film restores o n l y p a r t i a l l y the electrochemical
The swelling of p o l y m e r i c matrices b e a r i n g ionic response from the reduction of Ru (NH3) 63+ (curve F ) .
groups, e.g., ion exchange resins, b y exposure to a q u e - P r o t o n a t i o n of the p o l y m e r produces a m o r e porous
ous m e d i a (22) provides a f a m i l i a r e x a m p l e of the film b u t it is also h i g h l y p o s i t i v e l y c h a r g e d so that the
a b i l i t y of solvents to influence the d e n s i t y and t e x - t r i - p o s i t i v e r e a c t a n t e v i d e n t l y can t r a v e r s e it o n l y
t u r e of p o l y m e r i c m a t e r i a l s (20). It seems l i k e l y t h a t w i t h difficulty. This w o u l d account for the d r a w n - o u t
the differences a m o n g the v o l t a m m o g r a m s in Fig. 9 shape of v o l t a m m o g r a m F c o m p a r e d w i t h t h a t for t h e
can be a t t r i b u t e d in l a r g e m e a s u r e to variations in the anionic F e m (edta) complex in v o l t a m m o g r a m C.
s w e l l i n g tendencies a m o n g the solvents tested: A n a d d i t i o n a l factor t h a t could influence the ionic
conductivity of PVP l a y e r s is t h e increase in the q u a n -
EfJects o~ changes in supporting electrolyte.--Change tity of counterions w i t h i n the p o l y m e r i c m a t r i x t h a t
in the n a t u r e of the aqueous s u p p o r t i n g electrolytes m u s t a c c o m p a n y the i n t r o d u c t i o n of c h a r g e d sites.
in w h i c h the e l e c t r o c h e m i s t r y of a t t a c h e d Ru m (edta) Thus, the q u a n t i t y of anions t h a t a r e e l e c t r o s t a t i c a l l y
is o b s e r v e d p r o d u c e q u a n t i t a t i v e differences in the r e - held w i t h i n a p r o t o n a t e d P V P l a y e r will be r e l a t i v e l y
sponses o b t a i n e d r a t h e r t h a n the q u a l i t a t i v e differ- insensitive to the ionic s t r e n g t h of the s u p p o r t i n g elec-
ences arising from changes in the solvent. F i g u r e 11 t r o l y t e but h i g h l y sensitive to its pH. The m a g n i t u d e s
of v o l t a m m e t r i c p e a k c u r r e n t s and chronocoulometric
slopes for anchored reactants e x h i b i t s i m i l a r sensitivi-
ties which m i g h t be a n indication t h a t the counterionic
content of the p o l y m e r coatings controls the m a g n i t u d e
of the currents t h a t can t r a v e r s e them.
LLJ
(Z:
~ ~0.2 mA One is left w i t h two possible rationalizations for the
increased currents t h a t r e s u l t w h e n c h a r g e d sites are
i n t r o d u c e d into P V P films: increased p e r m e a b i l i t y
arising from stretching of the p o l y m e r chains b y re-
p u l s i v e electrostatic interactions among sites a n d / o r
i n c r e a s e d conductivity w i t h i n the p o l y m e r i c m a t r i x
0,6 0.4 0.2 0 - 0 . 2 - 0 . 4 - 0 . 6 - 0 , 8 - I . 0 O.S 0.4 0.2 0-0.2-0.4-o.g-0-8-I.0
resulting from a higher salt content. The d a t a p r e s e n t l y
E vs. SSCE, V
a v a i l a b l e do not allow a clear choice to be m a d e b e -
Fig. 11. Effects of supporting electrolyte on steady-state cyclic t w e e n these two rationalizations or rule out the possi-
voltammograms fort RUn I (edta) attached to electrodes coated b i l i t y t h a t both mechanisms a r e operative.
with 2.3 X 10 - 6 moles cm - 2 of pyridine a~ PVP. A, 0.2M If p r o t o n a t i o n of P V P films produces a m o r e open
CF~COONa (pH : 4.2). B, 0.2M CF~COONa plus 0.025M t e x t u r e t h e i n t r o d u c t i o n of o t h e r c h a r g e d ions into
CF3COOH (pH : 1.6). C, 0.2M NaBr (pH ~ $,.2). D, 0.2M the p o l y m e r m i g h t be e x p e c t e d to p r o d u c e s i m i l a r ef-
(CH3)4NBr (pH ~ 4.2). Scan rate: 200 mV sec -~. Rum (edta) fects. F i g u r e 13 d e m o n s t r a t e s t h a t the a t t a c h m e n t of
attachment procedure as in Fig. 2. Ru m (edta) to a P V P film does i n d e e d convert a
646 ft. 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 March 1980

A D
Fig. 12. Steady-state cycllc
voltommograms for 5 mmole
solutions of Fem (edta) or
Ru(NH3)6 8+ at pyrolytic graph-
ite electrodes under following /
conditions: A, D, freshly cleaved
electrode; supporting electrolyte, r-- B Io'lmA
0.2M CF3COONa at pH 5.4 (Fe)
E
or 6.0 (Ru). B, E, coated with
L.L.J ol o,L Jf
4.6 X 10 - ~ moles of pyridine as
PVP; supporting electrolyte as in
A, D. C, F, supporting electrolyte (.~
adjusted to pH 2.2 with /
CFsCOOH. The dashed line in |
curve C is the response at a T o olL_
freshly cleaved electrode a!
pH 2.2. The response fol
Ru(NH3)6 8+ showed no signifi-
cant pH dependence. Scan rate:
200 mV sec -z. I I I I I I I I I I I I I I I I I I I ! I I I I I I
0.4 0.2 0 -0.2 -0.4 -0.6 0.4 0.2 0 -0,2 -0.4 -0.6
E vs. SSCE, V
blocking l a y e r into one at w h i c h the F e ( C N ) e ~ - / 4 - charge t r a n s f e r m a y be possible b y suitable m a n i p u l a -
r e d o x r e a c t i o n can proceed. The cyclic v o l t a m m o g r a m tion of mass t r a n s f e r and charge t r a n s f e r rates a n d we
obtained at a n u n c o a t e d electrode (curve A) is a n - have such e x p e r i m e n t s u n d e r w a y . However, it m a y b e
nihilated b y the presence of an u n p r o t o n a t e d P V P w o r t h emphasizing two points in conclusion. (i) T h e
coating (curve B) b u t it reappears, in a s l i g h t l y dis- presence of electroactive r e d o x centers w i t h i n p o l y m e r
torted form, w h e n Ru m (edta) [a monoanion at p H films is no assurance t h a t the films will s u p p o r t charge
5.4 (17)] is coordinated to the p o l y m e r (curve C). In t r a n s f e r either to the a t t a c h e d r e d o x centers or to r e -
this case the d e n s i t y of b o u n d (anionic) charge is not actants dissolved in solution: P V P coatings containing
as high as t h a t resulting f r o m p r o t o n a t i o n of the p o l y - l a r g e quantities of coordinated Ru m (edta) n e v e r t h e -
m e r at low p H b u t the r e s t o r e d response is almost as less b e h a v e as insulating layers in certain nonaqueous
g r e a t as that o b t a i n e d at the uncoated electrode. The solvents (Fig. 10). (ii) Charge t r a n s f e r b e t w e e n dis-
coated electrode can also be u n b l o c k e d b y protonation, solved reactants and electrode surfaces covered w i t h
as in Fig. 12. thick (1-10 #m) P V P films can occur r a p i d l y even w h e n
The response o b s e r v e d for the F e (CN) 88-/4- couple the films do not have r e d o x centers a t t a c h e d to them:
in curve C of Fig. 13 can be u n d e r s t o o d s i m p l y in t e r m s p r o t o n a t i o n converts an insulating P V P film to one t h a t
of an increase in the p o r o s i t y of the film w h i c h allows does not i m p e d e the r e d u c t i o n of dissolved r e a c t a n t s
the r e a c t a n t to pass into the film m u c h m o r e r e a d i l y (Fig. 12).
t h a n was true u n d e r the conditions of curve B. H o w - Acknowledgments
ever, a second possible origin of the increased film The assistance of Prof. J. P. Revel a n d P a t Cohen in
conductance in this case (as contrasted w i t h curves C obtaining electron m i c r o g r a p h s is a c k n o w l e d g e d g r a t e -
and F in Fig. 12) is the transmission of electrons fully. Drs. A l a n R e m b a u m and Roger W i l l i a m s k i n d l y
t h r o u g h the film via the a t t a c h e d Ru m (edta) centers. p r o v i d e d the samples of f r a c t i o n a t e d P V P t h a t w e r e
That is, electron t r a n s f e r f r o m the g r a p h i t e to the used to o b t a i n the d a t a for Fig. 2. S e v e r a l p e r c e p t i v e
F e ( C N ) 8 8 - / 4 - couple m a y be m e d i a t e d b y electron comments and criticisms b y the r e v i e w e r s of a n e a r l i e r
t r a n s f e r among the a n c h o r e d r e d o x centers in the film. version of this m a n u s c r i p t h e l p e d us to f o r m u l a t e our
Distinguishing b e t w e e n these two m e c h a n i s m s of speculations m o r e clearly.
This w o r k was s u p p o r t e d b y the National Science
F o u n d a t i o n a n d the U.S. A r m y Research Office.

oF Manuscript s u b m i t t e d J u l y 23, 1979; revised m a n u -


script r e c e i v e d Oct. 15, 1979.
IomA A n y discussion of this p a p e r will a p p e a r in a Dis-
cussion Section to be p u b l i s h e d in the D e c e m b e r 1980
Z JOURNAL. A l l discussions for the D e c e m b e r 1980 Dis-
hi
cussion Section should be s u b m i t t e d by Aug. 1, 1980.
Publication costs oS this article were a~sisted by the
io California Institute of Technology.
REFERENCES
1. L. L. M i l l e r and M. R. V a n de Mark, J. Am. Chem.
Soc., 100, 639 (1978) ; J. Electroanal. Chem. Inter-
I I I l 1 I I I I I I I I I I facial Electrochem., 88, 487 (1978).
-0.6 -0.4 -0.2 0 0.2 0.4 0.6
E vs. S S C E , V
2. M. R. Van de M a r k and L. L. Miller, J. Am. Chem.
Soc., 100, 3225 (1978).
Fig. 13. Steady-state cyclic voltammograms for a 5 mmole solu- 3. A. Merz and A. J. Bard, ibid., 189, 3222 (1978).
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A Digital Simulation Model for


Electrochromic Processes at Electrodes
Benjamin Reichman and Allen J. Bard*
Department of Chemistry, The University of Texas at Austin, Austin, Texa~ 78712

and Daniel Laser


Department ol Chemistry, Te~ Aviv University, Ramat-Aviv, Israe~

ABSTRACT
C u r r e n t - p o t e n t i a l (i-E) curves for the electrochromic process at WO8 e l e c -
t r o d e s w e r e c a l c u l a t e d w i t h a digital simulation m o d e l which assigns the r a t e
of charge t r a n s f e r at the o x i d e / s o l u t i o n interface and the r a t e of diffusion of
h y d r o g e n into the b u l k of the film as m a j o r variables. The s i m u l a t e d i-E curves
a g r e e d well w i t h e x p e r i m e n t a l ones for different types of WO3 films and p r e -
dicted the o b s e r v e d d e p e n d e n c y of c u r r e n t on scan rate. The simulation r e -
q u i r e d k n o w l e d g e of the form of the electrochemical isotherm, which was o b -
t a i n e d e x p e r i m e n t a l l y , and a d j u s t m e n t of a charge t r a n s f e r r a t e constant, kf,
and the h y d r o g e n a t o m diffusion coefficient w i t h i n the film, Dm The best fit
was obtained w i t h kf ~- 9 10 -~ sec -1 ( m o l e / c m ~ ) - 2 a n d DH : 1 X 10 -9 to
2 X 10 - l ~ cm2/sec for the WO~ films p r e p a r e d by v a c u u m e v a p o r a t i o n and
kf -- 7.2 sec -1 ( m o l e / c m 3 ) - 2 and DH = 5 X 10 - s cm2/sec for WOz anodic
films. S i m u l a t e d p o t e n t i a l step results, w h i c h a r e s i m i l a r to the e x p e r i m e n t a l
curves at longer times b u t show some d i s c r e p a n c y in the short t i m e region,
a n d concentration profiles a r e also reported.

R e c e n t l y a g r e a t effort has been m a d e to u n d e r s t a n d (7-9) and film porosity (7-8) a p p e a r to p l a y i m p o r t a n t


the electrochromic process w h i c h occurs at WO3 elec- roles in d e t e r m i n i n g the response time of the WO~
trodes d u r i n g r e d u c t i o n and r e o x i d a t i o n and to con- electrodes. C r a n d a l l and F a u g h n a n (I0) discussed the
struct d i s p l a y devices based on this process (1-5). factors e n t e r i n g into the dynamics of the CB process
While it a p p e a r s clear t h a t the process involves f o r m a - at WO3 and c o m p a r e d values for the composition of
tion a n d o x i d a t i o n of h y d r o g e n tungsten bronzes, the the film w i t h time, o b t a i n e d d u r i n g p o t e n t i a l - s t e p e x -
d e t a i l e d m e c h a n i s m and a q u a n t i t a t i v e model of the periments, with c a l c u l a t e d values. T h e i r m o d e l as-
electrochromic process and the steps which g o v e r n the sumed that mass t r a n s f e r w i t h i n the film was v e r y
r a t e of the c o l o r - b l e a c h (CB) process have not been large and t h a t the r a t e - l i m i t i n g steps i n v o l v e d p r o t o n
resolved. Different WO8 films p r o d u c e d b y v a c u u m t r a n s f e r at the WO3/liquid interface and the b u i l d u p
e v a p o r a t i o n e x h i b i t different response times for color- of a "back emf" as the h y d r o g e n bronze formed. Good
ing and bleaching, even w h e n t h e y a r e p r e p a r e d b y a g r e e m e n t b e t w e e n the e x p e r i m e n t a l and calculated
s i m i l a r techniques (5). M o r e o v e r different types of values was o b t a i n e d in the short time region after
WO~ electrodes (e.g., anodic vs. e v a p o r a t e d films) the start of the coloring step or w h e n t h e coloring step
show significant differences in response time and elec- was m a d e at low potentials w i t h i n the e l e c t r o c h r o m i e
trochemical characteristics in the electrochromic r e - region. W i t h this model (5) the b l e a c h i n g process is
gion (6-8). The existence of w a t e r in the WO3 film l i m i t e d b y the "space charge" w h i c h is created b y ac-
c u m u l a t i o n of H + in the film. A r n o l d u s s e n (11) m e a -
* Electrochemical Society Active Member. sured exchange currents a n d t r a n s f e r coefficients for
Key words: electrode, interfaces, films.

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