BNL 6422

DEC 3 On the Theory of Oxfdation-Reduction ReactiomInvolving Electron Transfer.

V. Comparison and Properties of Electrochemical and Chemical Rate Constants. 1
63 2
R. A. Marcus
Departments of Chemistry
Brookhaven National Laboratory
Upton, New York
and
Polytechnic I n s t i t u t e of Ekooklyn
Brooklyn 1, New York

Ahstract

Using a theory of e l e c t r o n transfers which takes cognizance of reorganiza-

t i o n of the medium outside the inner coordination s h e l l and of the ligands inside

it, r e l a t i o n s between electrochemical and related chemical rate constants a r e

deduced and compared with the experfmental data. A c o r r e l a t i o n i s found, without

the use of a r b i t r a r y parameters. Effects of w e a k complexes with added e l e c t r o l y t e s

a r e included under s p e c i f i e d conditione. The deductions o f f e r a way of coordinat-

ing a v a r i e t y of data i n t h e two f i e l d s , i n t e r n a l l y as well as w i t h each other, and

a way of p r e d i c t i n g r e s u l t s i n one f i e l d from those in another. For example, the

r a t e of oxidation o r reduction of a s e r i e s of rebated r e a c t a n t s by one reagent i s

correla’;ed with t h a t of another and w i t h t h a t of the corresponding electrochemical

redox reaction, under c e r t a i n s p e c i f i e d conditions. These correlktions may a l s o

provide a t e s t f o r distinguishing an electron from an atom transfer mechanism.

------
In recent gears many r a t e constants of electron t r a n s f e r reactions in solution and
at ~ some q u a n t i t a t i v e comparison of the data i n
electrodes have been m a ~ u r e d , 3 ’ and

the two f i e l d s now seems appropriate. As a guide we hall employ a theory formulated
in e a r l i e r papers.’ This theory yielded an expression f o r the r a t e s of each of these
@ processes, taking into consideration the solvent reorganization occurring outside t h e

inner coordination s h e l l of each r e a c t a n t p r i o r to‘ (and necessary f o r ) electron

transfer .Sa-%
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@- The t h e o r e t i c a l rate constant f o r e i t h e r process w a s given by Eqs. (l)-(3) 5CSS

-
k = Z e AF*/RT

where AF* = w + rn2X

and

I n Eq. (1)2 i s the c o l l i s i o n frequency of (hypothetica:L) uncharged species in

solution. I t w i l l be taken t o be ~ 1 0 1
' mole"
~ sec':L and ~ 14 c0
m sec"

f o r homogeneous and electrochemical reactions, respectively. w i s the work needed

t o bring the two r e a c t a n t s (or r e a c t a n t plus e l e c t r o d e ) together and 9is the

corresponding t e r m f o r t h e products. AF" i s the llstantiardflf r e e energy of the

elementary e l e c t r o n transfer s t e p i n the prevailing electrolyte medium. It is

-nF f o r t h e electrode case. (n = number of electrons transferred; Ya --
I

a c t i v a t i o n overpotential.) was given by Eq. (10) i n Etef. sc, which i s reproduced

i n Eq. ( 5 ) below.
Nore r e c e n t l y t h i s theory was extended t o include the e f f e c t of changes

(nq" below) in bond distances and bond angles b the brier coordination s h e l l
3'
of each reactant. Eqs. (1)t o (3) were again obtained with A now equal to:

A =x 0 + Ai (4
) depends on the s i z e and shape of the reactants. For s p h e r i c a l
o outer
p a r t i c l e s undergoing a homogeneous reaction,
0
i s given by F4. ( 5 ) below, and

f o r a s p h e r i c a l reactant undergoing an electrochemical reaction i t is one half t h a t

expression. .( ) i s given by E q . (6) where k and kp denote the f o r c e

inner
1 j J
constant of t h e 3" v i b r a t i o n a l coordinate i n a species involved i n the reaction when

t h a t species i s a r e a c t a n t and when it is a product, respectively. The summation i s

@ over both r e a c t a n t s i n the homoger,eous case and over the one r e a c t a n t in the electrode

one. A r a t h e r general expression f o r t h e inner s h e l l reorganization b a r r i e r i s given

i n Ref. $, b u t this one s u f f i c e s f o r t h e purpose of this paper.

 J J

a, and a2 a r e the r a d i i of the s p h e r i c a l p a r t i c l e s undergoing reaction, the h e r

coordination s h e l l of each p a r t i c l e being included in hhe estimation of a, and a2.

-r i s the mean distance between the centers of the r e a c t a n t s i n the a c t i v a t e d

complex. (We take r = a, + a2',) I n the electrochemical c:ase a, and a 2 a r e equal

and r i s twice the d i s t a n c e from the center of the reacting p a r t i c l e t o the elec-

trode surface, D and D a r e the square of the r e f r a c t i v e index and s t a t i c

OP S

d i e l e c t r i c constant, respectively.

For making the c o r r e l a t i o n desc-dbed in this paper,an e s s e n t i a l f e a t u r e of

where depends on the p r o p e r t i e s of p a r t i c l e 1 (size, force constants,

difference of corresponding equilibrium bond distances in r e a c t a n t and product

state) and not on those of p a r t i c l e 2. Similarly, depends only on p r o p e r t i e s

of 2,
r
i s the r term in Eq. (5). I n the e l e c t r x h e m i c a l case we f i n d

/A =A,.. Xr
II

el 2
than
where the value of Ar in 4. (8) will be equal t o o r l e s s / t h a t i n Ep. (7),
according as the reacting species can o r c a f n o t penetrate any bound layer of
solvent molecules adjacent to the electrode surface. 5 C

P a r t i c u l s r k v p e r t i n e n t t o the following arguments is :N. ( 9 ) , obtained frw,

3 F* 13 then linear i n A F o w i t h a slope of 0.5. When w and Wp a r e small,

@ i s seen t o be f o u r times t h e value of JFg when J F
0
= 0, i.e.
ir
4 ( L F " ) 0 say.

Thus, ;he above condition for l i n e a r i t y in A F o can be writtkn as:

1 F"/(> ~~~~j~~ ,C 2 ON
a condition o f t e n f u l f i l l e d i n p r a c t i c e . 6

--
Effec% of standard free energy of r e a c t i o n o r of overpotential on reaction r a t-
I_ e.

Two inmediate deductions may be d r a m from Eq. ( 9 ) wncn the work terms can
e i t h e r be made small, say by using high electrol.ybe concentration,or when Qiey a r e

e s s e n t i a l l y constant in the following v a r i a t i o n s : I n the redox r e a c t i o n of a s e r i e s

of related compounds with a given reagent s w h that AI?' i s essentFal3.y the only

parameter varied, a p l o t of DF
36
-
PS O F " and hence of log k -
vs log K

should be linear with a slope of 0.5 f o r A P o 3 s s a t i s f y k g Eq. (10). I n t!!e

electrocheraicd case, TAe correspondhg, plot of A F

-:c
--vs - nF 7 a (or of --iinPr I n k
-
vs electrode p o t e n t i a l ) should a l s o be linear with a s:Lope of G.5. Rie f i r s t

dedJc;ion, p r e d i c t e d first i n Elef. se, was r e c m d y con,'irined e x p e r h e n t a l l y :'or t h e

7
honcgmeous oxidation of Fe(1E) by a series of s u b s t i t x t e d ?e phenf3 i o n s , A g a i n ;
3
Lie slop of t h e electrochemical p l o ~of' :aIn 1; -JS e l e c t r o d e p o t e n t i a l i s the
n:
so-called electrochenical rltransfer A t apl recir-rble salt, c o t , m n t r a -
5
t i o n s crrwsfer c o e f f i c i e n t s have been found t o he nec:r 0.5 (0.b LO (I.&), b
l ~,TE-C-

m m t , with $he second deducticn.

dy arialogy, we shall c a l l t h e slope of cht, AFT'-vs - AF' p l o t '&e 'Ichemical

crmsfer c o e f f i c i e n t " of the reac tion.

Two deductions may a l s o be made on the direct relst,ion between electrochemical

and r e l a t e d chemical rabe constants:

Comparison of i s o t- o p i c exchange rate and correspondirig electrochendcal excharige ctrrcrit:

-or a i s o t o p i c exchange r e a c t i o n betweer i o n s differin,: only i n v E,~ SCE

l E r,Lte,

@ A F" = 0, w = wp, and hcnce m = -0.5 i n Eq. ( 3 ) + I n the "exchange c u r w r i t " or" she

correspon ling slectrochmiczik system ? = 0 by d s f i n i t i o n , and m =, -2.;. :i %he L . V ? K

/a
 t,erin w -2 i s small. The
\
A Is and A21:; i n Eqs. ( 7 ) and (8) are a l l eq!ril.
@ 4ccording t o t k c remarks following Fq. (a), it then follows t h a t

1%ex 6 2 ).. el, ( = cr < according as the r e a c t a n t can or cannot penetrate

the solvent layer adjacent t o th3 electrode). From a physical viewpoint, the

f a c t o r of two e n t e r s in the exchange system because two ions zr~d " h e i r solvation

s h e l l s are undergoing rearrtingemnt in forming t h e a c t i v a t e d complex while in the

electrochemical system there i s . b u t one such p a r t i c l e . I t thus f o l l o w +hat

it ><
,t.F
ex
6 2 A Fil wner, w and 2 a r e small h both ~e ex and e l experiments. From

E q , (1)we then expect t h a t < k e J d 1 3 ke1/10 4, where I(

ex
arid k
el
a r e i n units
-3 -1.I respectively.
ot' 1 mole sec anti cm sec Another f a c t o r tending t o favor the

ft)lt sign i s t h e existence, if any, of i n a c t i v e s i t e s on the electrode due, say,

t o any strongly absorbed foreign particles.

Nore r e c e n t l y i t has been concluded t h e o r e t i c a l l y t h a t under c e r t a i n condi-

tions n e i t h e r t h e above deduction of this9,TJkel r e l a t i o n nor t h a t of t h e 0.5

slopes of "she %- ; F% p l o t s should be affected i f one o r both of the reactants

form r e l a t i v e l y weak complexes w i t h otller ions. 9 (Ibe ,J : - ' ' f s a r e ;hen those

corresponding to the pseudo-rat.e constant,s, "constants'' which depend on *-.he

conren t r a t i o n s of these other ions. )

7-- 4 1

A comparison of ev'k JlO" arid kel/l& on the basia of e x i s t i n g e x p e r h e n l a 1

e
data i s g i v t n i n Pable I. A l l rate cofistanpls are pseudo-rate constants, their

use be:;17g justified under the conditions cibe3.9 h e q u a l i t a t i v e trend in both

and k i s seer, t o be *;he same, and t h e values i n the two columns are r e l a t i v e l y
kel ex
c l o s e t o each other, considering the f a c t t h a t approximations in the theory exber

eJgonentially (a f a i r e r comparison would be of AF''d2 and AF" >, that s t a t i o n a r y

E: el
electrodes (and t h e i r adsorption p r o b l m s ) ivere usuzlly necessa-y, and t h a t the

::ark terms may n o t have beeri n e g l i g i b l e . Ctker reaetjials f o r which the data are

@ nore fragmentary are described in iZppen4ix 1;.

Coaxparison of chernical and e l e c 'irochmical redox r;?t e s -- ---

of a s e r i e s of r e l a t e d rejlc t.ar,ts.

I n $his corrparison we shall. consider system i n which a constact reagent i: used

 - 6 -

@ i n the chemical system, and a constant electrode p o t e n t i a l Fn the electrochemical

one, t o oxidize or reduce a s e r i e s of r e l a t e d compounds. fin a s e r i e s of a given

charge type, the work terms a r e e i t h e r exactly or roughly constant in each of these

two systems.
*
FuTthermore, i f t h e AF I s a r e i n the region where they would depend

l i n e a r l y on 0 Fo, then according t o Eqs. (1)and ( 7 ) - t o ( 9 ) the r a t i o ksoln/kel

should be t h e same f o r each m e m b e r of the series: In both cases, the terms

Ll?"and, at a constant E, 7] ( = E - E " )
1, w i l l normally vary from member t o
member. ( A r e f e r s t o the constant reagent. } However, since s? F o equals

( - nFE" + constant) i n the series, one sees from Eqs. ( 7 ) t o ( 9 ) t h a t these

v a r i a t i o n s in A A F " and E" cancel when one compares values of (C; Fsoln-
* AFel),
it

12
t h a t i s of k /k Vlcek has r e c e n t l y observed t h a t t h e electroreduction and
s o h el'
the Cr dipy"2 reduction13 of Co(NH3)i3 and Co(NH ) (H 0)'3 had essentially the
3 3 5 2
same k /k f o r both Co compounds, (See Table II*) This experimental r e s u l t
s o h el
i s in agreernent with t h e above t h e o r e t i c a l dedixtiori. Presumably both E o and

d i f f e r e d i n the two conpounds. Lxtension of these comparative s t u d i e s t o other

Co compounds would of course be desirzble.

Similarly, the r a t i o ka /kb f o r each member of the s e r i e s oxidized o r

soh soh
reduced by two reagents, a and b, should be constant. This r e s u l t was found

experimentally f o r the CO(NH ) X (111) compounds reduced by V(H,O);* and C r dipy+3

3 5 3'
respectively, w i t h X being NH H20 and C 1-It3'' (Tzble 11.) fie restriction to
charge 3'
a given/type will n o t be important if the work terms are r e l a t i v e l y minor,The c ~ w . ? ~ P I : : ,
;hvC4v,*& L/ +i?
/>should accepted w i t h some reserve since the V ( I 1 ) reaction i s n o t necessarily

an "outer sphere" one, as Taube has pointed out.

 -
Sir3.t and s o l v e n t e f f e c t s .

The above colnparisons su,:gest, t h a t some of the i n t e r e s t i n g phenomena observed

ii i s o t o p i c exchange r e a c t i o i i s s h o u l d be looked for i n the corresponding e l e c t r o -

cheinical ones. F o r example,t;races of C1- ixhibit I'l(I> - T l ( T 1 1 ) isotopic

exchange but greater amounts catalyze i t . '' A e n i n , s u h t i t u t i o n of water by

isopropyl a l c o h o l decreased the rate of F e ( I 1 ) - ?e(III:) exchange 100 f o l d . If

....
Lhis f a c t o r could be due t,o thc enhanced couioinbic reyct:;3 i w . Lf riot, fhe E: lectro-
chemical excharige c u r r e n t may be reduced 1014 f o l d .
1t3
:!. S u t i n has suggesteLc uhlcitit w m l c ! al;~be in?,eresting t o s t u d y t h e e l e c t r o -

reduction of Co(TiH )<

3 ,
x (ii:i)wt1t.n x is a fumari.e ine~l-~yl
o r phenyl esLcr, LO see
T2
wha t,her this reductj.cn resembles :ocre eloscly a r e d u c t i c n by C r dipy, o r by V
+2
1
.
tiydrolysis of die ester accompanies t h e reduction i n t k s secoriti case ttis n o t ir. the

:'ir:,t.

Cross-reac cion r a t e c o n s t i r i t s :

whtre k and k are the i s o t o p i c exchar-ge r a t e c o n s t m t s i n systems 1 and 3 ,

11 22
w
11
arid w
22
are d e corresponding work terms, aid K
12
and w
12
42 denote the
equilibrium constant and the work terms of (11).
qd
~ q (12:~
. was d e r i v e d e?L*iier. tinder mrc. restrictivc a5sumpl;icr-1 ( k =
2
3 3
for
=IC<? negligiblt exrjonent,, Elver! i; axy o r a l l of the species i n (11) form weclG

csqlexes FiLh o%PLerions, (1%) shoultl s ~ i l hold

l f o r t h e pseudo krs, p r o v i d t d (11
 . 9 (ij) ~e coulombic contribution
the conditions l i s t e d earlier p r r v a i l ,

to w
12 + $2 - wll
- w 22 i s n e g l i g i b l e f o r each elementary electron transfer, and (ill)

the noncoulombic one (see below) i s e i t h e r e s s e n t i a l l y t,he same f o r each p a i r o r

vanishes. Ic?len t h e coulombic term i s no5 negligible, Eq. (12) i s t o be used f o r

each elementary e l e c t r o n trmsfer; i f a p a r t i c i p a t i n g complex i s very unstable,

3
I{ f o r t h i s s t e p i s t h a t computed ;.:hen a coordinate i s l'?rozenl't
12 -
F o r a somewhat more accurate comparison, k, Inmy be estimated from
12
kll anci k22
using the conpleie equations (1) t o (31, notim, that ;Al2 = '' A 11
(H<swever,the generalization t o weak complexes has riot been established f o r the case

where condition (10) does n o t hold.) When t h e work terms a r e n e g l i g i b l e , Eqs. (1)

to ( 3 ) yield:
I------
-
kl.2 - 4 kll. k22 ICL2
where

When r e a c t i o n (ll) i s one in which t h e reartarits a r e aquo ions which i r , t e - c h a x y

r) 7
charges, one would expect w = hf = VI = kq,>. JE work tern b (12) theln v x i s h e s .
1.2 12 11 CI.

C n t h e ol;her hand, wher, (11) is a reaction oetween an ion with hydrogen h o n j i n g

ligands and one w i t h organic ligands (e.g. Fe(Ii,,0)i2 + 1;e 0henf3j one z%oulde>.-,ect
1. 3
t h a t t h e noncoulombic contributions t o t,hc work ternis w i l l not cancel: ki
11 and w,6 L
3
m y have a t t r a c t i v e noncoulcmbic contrihu-ions and (id 12 + w'12 ) r c p u l s i v c one?. In

:his event t n ~ odeductions may be made: (i) k12 will be less than [k arid
con .ribu:io ;tl k22 5 2
/k13 a r e taken, the noncoulombic/to 2ke dark term :: :.
( : < I ~ ~ k ! ~~: i l i t 3 j ; : l err?%iosk1-2
e s s e n t i a l l y cancel i n the +3 31' +2 wi&l i i e ( & C \ +2 or +3
/ r a t i o \ e y g . > i f q2corresponds t o che reaction of Fe phen 3
A
. L '6
and k corresponds t o the r e a c t i o n of '?e phen
+3 Or +2
with another aquoion)
13 3
3a
Deduction ( i )may explair: the r e s u l t s of a comprison ol and kL2 &-"-1Y
1--"2;
;:- 1;
i
l

f o r t h e '-e+' - Ye hen+^ 3
sy:.tem. A value of a few kcal mole -1 f o r

+ bi*
D
- w,,)/2
would s u f f i c e t o explain the r e s u l t s . Deckction (ii) w s l s
(Wl2 12 - 5 1 / L

sugGeeted by a comparison of' k12/k13 witk AT

-3 7 2
made by K . SirtiriT-
1L 33
 - 9 -

@ A v a r i e t y of experimental t e s t s i n v o l v i n g the cross-relations i s now in progress

by U r . Sutin and collaborators.

18

Often i n t h e l i t e r a t u r e the r o l e of A F o (and hence of $2) has been ignored

i n explaining the values of c e r t a i n rate constants. Eq. ( 1 2 ) (or indeed Eqs. (1)

t o ( 3 ) ) i l l u s t r a t e s how important i t can be f o r ?,he p r e s e n t class of reactions.

Ligand-field e f f e c t s
The influence of l i g a n d f ' i e l d e f f e c t s on the r a t e s constants of redox reactions

and on other properties of complex ions has been the s u b j e c t of much i n t e r e s t . They

3' nqj and

are incorporated in the present theory; i n p a r t i c u l a r they influence k

Yo. Accordingly, the present approach converts discussions of ligand-field e f f e c t s

on k i n e t i c problems into a discussion of the problem of estimating k and

j'
8)
A?''. bloreover, according t o Eqs. (l), (7),/and ( 9 1 , these e f f e c t s cancel when c e r t a i n

c o r r e l a t i o n s of the. experimental data a r e made: the c o r r e l a t i o n s embodied i n chemical

and electrochemical t r a n s f e r c o e f f i c i e n t s of 0.5, i n the comparison of chemical and

electrochemical exchange tlcurrentsll, and i n Lhe conqariscw of cross and i s o t o p i c
exchmge r a t e constants.

-
One vs two electron t r a n s f e r s .

I n some reactions involving 2-electron redox reagents, i t has n o t been possible

-
t c decide whether the mechanism proceeds via two successive one-elec tron t r a n s f e r s

-
o r v i a one two-electron t r a n s f e r s . However, i t i s sometinzes possible t o d i s t i n g u i s h

be tween the two a l t e r n a t i v e mechanisms i n a corresponding electrochemical reaction.

For example, the Tl(I) - Tl(II1) electrochemical process has been found t o proceed
"g
-
v i a two one-electron transfers. From the electrochemical^ r a t e constants f o r the

Tl(1) - Tl(I1) and Tl(II1) - Tl(1) reactions, we have computed i n Appendix I a

r a t e constant which may be compared w i t h the homogeneous r a t e constant. Agreement

would be expected only i f the homogeneous r a t e constant proceeds v i a two one-electron

@
trsnsfers. The agreement i n Table I f o r t h i s comparisor, would appear t o favor t h i s

mechanism f o r the homogeneous reaction. Had the value f o r ,+/kex/l(ll' been

 - i0 -

L appreciably g r e a t e r than t h a t f o r kel/10

4 ( o r r e a l l y appreciably more than 10-fold

Zreater since thc: electrode was P t r a t h e r than Hg) one wou1.d have obtained evidence

:or the one two-elec tron homogeneous reaction instead.

Concluding remarks
The above c o r r e l a t i o n s o f f e r a possible way of systematizing and comparing
,.
experimental data both on electrochemical and on chemical clec tron t r a n s f e r

reactions. Some of the i s o t o p i c exchanges discussed e a r l i e r may n o t involve

electron t r a n s f e r and could involve atom trmsfer :instead. The e x t e n t of corre-

l a t i o n s such as those i n Table I may eventually provide a t a t of t h e mechanism,

a t l e a s t i n t h e cases of extreme discrepancy.

There are a v a r i e t y of other reactions f o r which t h e sxperimental electrochemical

and i s o t o p i c exchange r a t e c o n s h n t s could be compared, and of r e l a t e d reactions f o r

which chemical and electrochemical t r a n s f e r c o e f f i c i e n t s cculd be determined. Several

r e c e n t d e t a i l e d surveys of the literature3’‘ should be very. h e l p f u l f o r this purpose.

? o r e frequent collaboration between electrochemists and chemical k i n e t i c i s t s would be

useful f o r t h i s purpose .
Acknowledgement

I have benefitted considerably from the many stimulating discussions I have had

on t h i s subject w i t h D r . N. Suthn of Brookhaven National Laboratory. I am a l s o

p a r t i c u l a r l y indebted t o Drs. R. W. Dodson wcl J. Jordan fcir t h e i r very h e l p f u l

comments, and t o Dr. Dodson and h i s department f o r t h e i r holspitality during my s t a y

a t Brookhaven. i’his work was supported by t h e U.S. A’;c.niic Energy Commission, the

@ Mational Science Foundation and t h e Alfred P. Sloan Foundation, a support which I

deeply appreciate.
 - 11 -
'IABLE 1

8 COMPARISON OF' ISOTOPIC EXCHANGE AND ELF;(: IROCHEMICAI, U T E CONSTANTS

703 ONE-ELECTiiOR 'TRANSFEHS AT 25 OC

kelD 4 Electrode def.

1 x 10-5 Pt a

-2 x P t , See b
Ref. 13.
7 Pt C

ll x 10-7 Hg d

3 x 1 8 Hg e

2 x 1f8 Pt f

d
35 x Hg g

4
Assuming exchange proceeds -vi> GHO one-elec Lron t r a n s f e r s . Otherwise, value
i s an upper limit for the one-electron t r a n s f e r r a t e .
Exchange data: ( a ) def. ( b ) J. C. Slzeppard and A . C. Uahl, J. Am. Chem. SOC.
2, 1020 (1957); ( c ) J. Silverman and d . W. Dodson, J , phys. Chem. 846 (19.52); sy
i d ) K. V , Krishnmurty and A. C. b h l , J. Am, Chern. SOC. do, 5921 (1958); ( e )

DCdSOn, i- 2175 (1961).

-
I?. J. Meier and C. S. Garner, J. Phys. Chem. 56, 853 (195:2); ( f ) E. Roig and R,W.
b i d-65,
Zlectrochemical data: (a) iief. 8c; ( b ) def. 11 j ( c ) J . L . E . h d l e s and K.W.
Somerton, L'rms. Faraday SOC. b8, 937 11952); ( d ) def. c, J.E.B. dandles, Can. J.
Chem. z, 238 (1959), Ref. 8(i); ( e ) def. c:+note t h a t t h e corresponding
i m t o p i c exchange d a t a were i n s e n s i t i v e t o (H ), s o t h i s cumpacison covlld be made;
(f} Xef. 8g, See Appendix I.
All d a t a are c o r r e c t e d t o 2 5 O C and t o the c i t e d salt concentration l i s t e d under
Wedim.
 +2
X v+2 Sr dipy3

" 1 1 1
3
I I O 135 91 1211
2
c1- I.6Xlo3 1 5x103 -
JL

at E of 0.1 N calo.nel. electzode

 - 13-

Appendix I. A n analysis of t h e Tl(1) - Tl(II1) system.

I n Ref. 8g the following k l s were estimated a t th.e formal p o t e n t i a l of

T l ( 1 ) = Tl(II1) + 2e i n 1PI H C l O 25°C

4 at'
T~(III)+T~(II) -e kel = 3 x
32
cm see-'
Tl(1) +Tl(II)+ e k$ = 3.5 x 10-3 cm sec-1

We s h a l l designate A 1s by appropriate s u b s c r i p t s and l e t E"

ij
be the formal

h a l f - c e l l p o t e n t i a l ( i n lIvI H C l O a t 2 5 ° C ) of n(i)= T l ( j ) + ( j - i ) e (j7i).

(l),Cand@ 4
Equations /(9) then y i e l d , when t h e work terms a r e neglected,

-RT In k32/Z
el el = -+
4
732
4
, 132 - (Eol3
= Eo )
23

el
-RT I n k12/Z e l -- 712 , = E;j - E;* Y
4 4

since t h e t r a n s f e r c o e f f i c i e n t s a r e i n f a c t 9.$g s o Eq. ( 9 ) a p p l i e s , and since

the k ' s were given a t E o , r a t h e r than a t the unknown E" o r E"

13, 23 12
Noting f u r t h e r t h a t (E;3 - E b ) F i s AF", ;he llstandard" f r e e energy of

reaction ( A l ) i n the p r e v a i l i n g medium,

rl(III) + Tl(1L) = 2 T~(II),

one obtains

- AF"
--
-9T In kj2
e l k12/Z
el el 4.
4 2
(11,
However, i t can be shown from Qs/(7) and ( 8 ) that, the forward r a t e constant

of the homogeneous r e a c t i o n @ ) , kex , should be given by

-RT In kex/Z
soh - + 1;
-; + -. A ? ' "
8 2
$rl- Since Aex 6 2Xe1 i t then
/ f o l l o w s t h a t t o t e s t t h e thzory jK; should be compared wit4-h.
For t h i s reason t h e geometic mean of kel and k?; was used i n Table I.
32

Appendix 11. Comparisons i n other systems.

Yragmentary information e x i s t s about electroche-mica1 and chemical exchange r a t e s

i n a number of other systems:

 -4-

c;4 Co(NH 1+2,+3.

3 6 *

20th the electrochemical and chemical r i t e s are extremely small. l'he electro-

chemical reduction of Co(ITH )+' i n 0.14 21. 3C10 and 1.26 Pi MaClO a t 25°C nas a
36 4 4
r a t e constant of 2 . 1 x lo-' G c m sec -1 when the formal applied p o t e n t i a l E i s
vs 9.1 N calomel elecmode?'
0 - ( D i s the d i f f u s i o n c o e f f i c i e n t . ) Taking the
19
formal E
0
for the Co(NH ) +2y+3 system t o be - 0.1
d0.22 v o l t s vs N calomel,
3 12
the t r a n s f e r c o e f f i c i e n t t o be 0.67, and D N 19-' cm2 value or'
+,he
cf Q"5
ke1/lo4 at
7 a = 0 i s found

used, the value would have been 9 x loe1*.

$0 be 2 x If a t r a n s f e r coeSficient/haG been

i s o t o p i c exchange r a t e constants and e q u i l i b r i u n cons tants obL3ineo a t

'+Om
20
65"C, one may estimate khat
ex/#
J-- < +
5 x 19-11 i n c).lb !,i h a c -sot.
Presumably, theref ore, /- << 5 x 1c-l1 a t 2 5 0 ~ ,a resLclt consistent

with the above value of kel/104 .

a tely, the e l e c =rochertical t r e n s f e r coeT'ficient f o r oxidation was apparently 0.75,

a value s o d i f f e r e n t from 0.5 t h a t a comparison w i t h the exchange d a t a can be

questioned. (The magnitude of -the chemical t r a n s f e r c o e f f i c i e n t for the Ce(lV j

Fe phenf2 system i s of p a r t i c u l a r i n t e r e s t 2nd. i s under c u r r e n t inves5igation.l') Tne

3
vslue of J -ex is 7. in 0.8 Id 3 2SO4 a t 75°C.21

-
Cr(II) -Cr(III):

!he electrochemical exchange c u r r e n t f o r t h i s system has been measured a t

20°C i n 1 M KCI. where hydrolysis i s presuwbly a2preciable?2 Yfle value o l k el/10I:

23
Is 1.0 x lG-'. P o r n the i s o t o p i c exchange r a t e d3ta a t ;he lowest s c i d cancer,-

t r a t i o n studied (0.2 M HClC

L' 0.8 ki YaC10 ), one may E:stimate
4
a t 20°C.
 - 15 -

iieferences
---
1. Research performed in p a r t under the auspices. of the U.S.Atomic Energy
tie
Commission. Presented atisymposium on Mechanisms of Electrode deac tions:

142nd A.S.S. Yational Meeting, A t l a n t i c C i t j - , 1.962. For ?art I V s e e r e f . se;

Related papers are l i s t e d under ref.

2. Alfred P. Sloan Fellow. V i s i t i n g Senior S c i e n t i s t a t S.N.L. Present address:

Department of Chemistry, Folytechnic I n s t i t u t e of Brooklyn.

3. For d e t a i l e d reviews of homogeneous r e a c t i o n s , see (a) N . Sutin, Ann. Rev,

-
i.!uclear Sci. 12, 000 (1962) and ( b ) J . Iialpern, Quart. Revs. (London) -
15, 207

(1961).
4. For d e t a i l e d sulm.ry of e l e c t r o d e k i n e t i c data, see ( a ) N . Tanaka and R. Tanamushi,

t'r;inetic Parameters of Electrode 3eactiontt, a r e p o r t presented t o +he Cornmission

on Electrochemical Data of the Section of A n a l y t i c i l Chemistry of I.1J.P.A.C.

a t t h e I n t e r n a t i o n a l Congress of Pure md -4pplied Chexistry, ;/Iontrcal, 15'61.

Copie: a r c obixiinable from Id. Fischer, Cepar t m n t of Elec trochenzis try,

1n:;titute of Technology, Kar'Lsruhe, Germny; ( b ) J. Joi-dan, k.Xnalytical

bndbook, L. Meites, Ed., XcGraw41ill (1363).

5. 2. A . Plarcus (a) J. Chem. Phys. 24, 766 (1956;; (b) 0.EJ.R. i'echnical Fieport No. 1 2 .

-
P r o j e c t NR 051-331 (1957); ( c ) C a n . J. Chem. 37, 155 (1.9.59); ( d ) k a s . Symposium

ElccLrode Processes, E. Yeager, Ed. John Wiley and SOILS, N e w York (1961) p . 233;

-
( e ) T)iscussi,.ons Faraday SOC. 29, 2 1 (1960); ( f ) unpublished results f o r t h e

elect,rcr-i-?aical case, analogous t o those i n ( e ) .9r Eq. ( 5 ) of the present, paper,

which i s a convenient approximation t o the r e s u l t s obtained i n s e c t i o n s (ii)and

(iii)of r e f . se, will be discussed in de';ail elsewhere. As w i l l be p o i r t e d out in

ref. 9 , t h e r e i s also a r e l a t i v e l y ininor r e o r g a n z a t i o n term f o r ?;he surrounding

.A
e l e c t r o l f i e b u t one which does no% a l t e r the c o r r e l a t i o n s i n this paper. %cause of t h e
w apparent smallness, we have omitted it, in the present paper.;(g) Note on Zqs. (1) to
-L-
( 3 ) : I n a n o t a b i o n 4 charLge t o condaormw i t h r e f . ?e, w and w i n r e f , sc are now
w r i t t e n as w arid up, respectively. 'The f a c t o r of a in Eq. (8) of ref. sc i s now
incorporated in the p r e s e n t d e f i n i t i o n of f o r t h e electrode system, and tiert has
been replaced by its molar equivalent, the Faraday F. The values of 2 i n t h e
 - 16 -

p r e s e n t paper are t h e gas k i n e t i c values.

6. E.g., i n Ref. 7, the i n t e r c e p t of Fig. 2 y i e l d s (AFK)onb12 k c a l mole-?

(Ref. 7 gives A F
+ Is but A?" = A
F
'' - HT I n hZ/kT = , b F=I=-
2.8 kcal mole-'
5a
when the standard state i n AF' i s 1 mole l i t e r - ' ) . Since the l a r g e s t bo\
t h e r e was 1 2 k c a l mole-', (10)i s f u l f i l l e d . Again, i n electrochemical systems i n

whidnLhe t r a n s f e r c o e f f i c i e n t i s measured over an electrode p o t e n t i a l range of

Jt
perhaps 0.2 v o l t s from the equilibrium p o t e n t i a l , and i n which t h e t y p i c a l (bF )0)
(value of A F+' a t a 0 ) in Table I i s of t h e order of 7 kcal mole-l, condition

(10)i s
7 =

again f u l f i l l e d s i n c e j b F o / ( F9) I 0.2x23/'7.

rrl
0

7. K. H. Ford-Smith and N. Sutin, J. Am. Chem. SOC. - 83, 1830 (1961). fie d a t a
6
s a t i s f y condition @Q). I t is a s s y e d t h a t in t h e f i r s t approximation t h e sub-
s t i t u e n t s leave the k j ' s and A q J I s unaltered.
8. Oats a r c l a r g e l y but not e r , t i r e l y taken from def. 4(a).I'he t r a n s f e r c o e f f i c i e n t s
are
a r e either those of t h e reduction process or,(l-transfei* c o e f f i c i e n t of t h e
oxidation ste$ F e ( l I ) - F e ( I I I ) i n livl H SO 0.42,ayb 0.62, 0 0.61'; -4, -3
Fe(CN)6
2 4
d e
i n 111 K C 1 O.4SYC o.soYc and ( g r a p h i t e ) 0.5, j v ( I I ) - v ( I I l ~ )in l.M HClO,,0.52, 0.5of,-,
4
f c
0.57, and i n 1 M H,SO,, 0.1~6"; 'Tl(I)-rl(II)i n 1 M H C l O 0.5g; r l ( I I I ) - e r l ( i~n
11.I3C104 0.; . IC
A t l o w e r supporting e l e c t r o l v t e concentration: Fe(I1)-Fe (111) i n 0.1 M HC1OL,
0.78"; Cr(CJ!J)i3)-' in 0.2 M NaCN 0.67i(l'he exchange c u r r e n t i n the l a t t e r system
vas very s e n s i t i v e t o s a l t concentration. )

Low values are: Ce(II1) - Ce(1V) i n 1 N H 2 SO4' 0.2.#,b and Mn(I1) - Mn(II1)
i n 1s N H2SOlL, 0.28.a,b

( a ) R. Parsons, Handbook of Electrochemical Constants, Brtterworths, London (1959 j

( b ) K. J. Better, Electrochemische Iiinetik, Springer-Ver'Lag (1961); ( c ) 14. D. ?=Jnen

and W. PI. Smit, Rec. b a v . chim. -

79, 289 (1960); ( d ) A. Regner and J. i3alej:
Collection Czechoslov. Chem. Colununs. -
26, 237 (196a ( e ) K.M.Joshi, 2. Mehl and

3. darsons, itrans. Symposium Electrode Processes, E. Yeager, Ed., John Wiley and

Sons (1961), p. 249; ( f ) J.E.B. Randles, Can. J. Chem. --

37, 238 (1959); ( g ) H.

Catherino and J. Jordan, p r i v a t e communication; ( h ) J. Jordan and R. A. Javick,

-
F,lectrochinica Acta 6, 23 (1962); ( i )P. Delahay and M.Xleinerman, J. Am. .Chem. SOC.

-
8 2 , k5OY (19ho).
 - l? -

,e 9. R. A. Marcu (to b submitted) . 'the conditions imposed i n the derivation

were 'chat ( i )f o r every p a i r of reacting complexes the corresponding bF*
for e l e c t r o n t r a n s f e r between the p a i r i s in the l i n e a r A F o region described

e a r l i e r ; (ii)the added ions do not a c t as bridging groups t o any appreciable

extent; and (iii)d i s s o c i a t i o n of any complex does not c o n s t i t u t e an important

r e a c t i o n coordinate a t the i n t e r s e c t i o n surface of Ref. Se, though it can

occur before o r l a t e r .

If A and B denote d i f f e r e n t reactants, A' and C o r r e s P o n d ~ gP r o w * , x

UWd
*Y any ions forming complexes w i t h these species , condibion (i)i s f u l f i l l e d only i f the

standard f r e e energy of reaction of A Xm + B Yn$ APXm 3Vn, A F Z ,

+ satisfies

condition (la f o r every important mn p a i r , i.e. if [ AIi'&vAFLyo

( I6 2. If any Of

these complexes decomposes i n l e s s than a v i b r a t i o n a l period, AF,"y i s t o be computed

f o r a t'frozen" value of the unstable coordinate, the same value f o r both sides of the
above equilibrium. There i s some p o s s i b i l i t y t h a t f o r c e r t a i n deductions conditions
( i )and (2%) can be relaxed, a p o i n t which we s h a l l i n v e s t i g a t e further.

10. P. King, C.F. Deck and A.C.Wah1, 139th A.C.S. National. Meeting, (1961),
Abstracts, p. 30 R, and p r i v a t e communication. The v a h e in Table I is a long
exbrapolation which I made using their equation describing data in t h e 0.0025

t o 0.05 M KC1 region. A t 0.05 M K C 1 and corrected t o 2S0C, L-jiF e was

11. 2. Galus and R. N. Adams, Paper presented a t the1Y3ymposium on bchanisms of

Electrode Keactions , Q2nd A . C. S o National Meeting (1-962). These authors

found that i n a variety of electrochemical r e a c t i o n s Icelaveraged about 20-fold

less for a carbon paste electrode than it did f o r a p:Latinum one. Accordingly,

t h e i r kel f o r &IO '19'2(0.01 an sec.-l),which was obtained w i t h carbon paste,

4

e was increased by a f a c t b r of twenty,'to obtain the valiie c i t e d in Table I, so as

to permit its comparison w i t h the other systems.

12. A. A. Vlcek, in tW.xth I n t e r n a t i o n a l Conference on Coordination Chemistryt1:

I
S. Kirschner, Ed. Macmillan, w
a York (19611, p. 590.
 A , M. %wickel and H. Taube, DiscussionsFaraday SOC. 259, 42 (1960).

A. M. Zwickel and H. iaube, J. Am. Chem. S O ~ -

83,
. 793 (1961).
f3
--
.
Condition (10) i s f u l f i l l e d f o r the V+‘ - Co(NH3)6 reaction, Since
8
&” = - 8 k c a l mole-’, AF+’= 18 k c a l mole-’ whence ( F”)oN(18 + 7)

and AF0/(AF”) 1 1/3. I could not f i n d an 13” o r E-

1 for
0 2
+3
Cr d i ~ 3y + ~ ’ +so~ t, h a t condition (10)was not checked f o r the Cr dipy+*
3 - CO(NH~)~
- X(III), most of the
In t h e electrochemical reduction of Go(”
reaction.
3)5
t r t i n s f e r c o e f f i c i e n t s were near 0.5, though t h a t f o r K = NH was apparently 0.67.
3
16. G . Harbottle and R.W. Dodson, J. Am. Chem. SOC. -
7 3 , 2h42 ( 1 9 5 1 ) . 3’01’other

references t o anions which i n h i b i t Tl(1) - Tl(I11) exchange, s e e N. S u t h , def. 3a.

17 N. Sutin, J. Phys. Chem. -

64, 1766 (1960).
18. N. Sutin, private communication

19 W. !4. L a t h e r , Oxidation P o t e n t i a l s , Second e d i t i o n , Prentice-Hall, New Pork

(1952 1
20. D. R. Stranks, Discussions Faraday Society, 29, 73 (1950). -
21 0 79, 6353 (1957).
P. B. S i g l e r and B. J. Masters, J. Am. Chem. Soc, -

22. J. E. B. Randles and K. W, Sornerton. Trans. Faraday Soc. -

L8, 931 (1952).
23 76, 3826 (19sL).
A . Anderson and N. A . Bonner, J. Am. Chem. SOC. -