60 Chronocoulometry : Application to the Study of Adsorption at an Electrode Solution Interface Robert A .

Osteryoung North American Aviation Science Center, Thousand Oaks, California 91360 In t r odu c t ion Chronocoulometry i s a term used t o describe a technique, ,developed jointly at North American Aviation Science Center and California Institute of Technologrlgin which t h e charge-time behavior o f a n electrode in a solution is observed. The electrode, initially at some potential E. where no current flows, has applied to it either a linear potential ramp orla potential step which results in t h e passage of charge across the, electrode interface. Ifthe resultant potential excursion is sufficient to bring the electrode potential into a region where a faradaic current flows, the charge passed will include a s the potencoulombs required to charge the electrical double layer, Qda'. and the fara aic chargepassed, tial c h a n g e d from E. t o a final potential, E QF, from time the p6tential excursion is inifiated at t = O until the measurement is made at some later time, t. Thus, the total charge passed,Qt,willbe (1.1 Q t = OF + Q d l The prime assumption in what follows is that the Q is essentially time I f Q;lis measured a s a function independent, while QF is a function of time. of time, a n d Q ( ) ,t is known, then the terms may be separated by 8lotting % . against the proper function o f time. In addition, if moles/cm of aspecles Ox are adsorbed at E. and react at E , an additional amount of charge, nFr, i f we a s h m e that t h i s - c i a r g e will likewise be time independent, will pass. then (1') Q t = QF + Q d l + n F r

Q then arises from a faradaic reaction where the reactant must diffuse F to the electrode to result in charge passage. Q and n F T represent charge non-diffusing hence time itaependent sources. which arises from ' d l must b e determined, then, by an independent procedure to permit evaluation of nFr. For instance, consider an electrode in a supporting electrolyte with The surface species Ox, at a potential Ei, when n o faradaic current flows. charge density, Q E ~ may be determined by using an extruded mercury drop or dropping mercury electrode. Now, consider the solution containing only Red at a concentration in solution or in an amalgam equal t o Ox. An electrode potential E is impressed. E is such that the reaction Ox+ne 4 Red would f occur and tf;e surface concentration o f Ox would be zero. (This is the condition that would prevail at the electrode surface at Ef in an experiment where only Ox i s initially in solution and the potential is changed to E with the f ' charge-time behavior recorded.) The charge density, QEf is measured. Howe v e r , since

then Q d l is k n o m regardless of how t h e potential is varied from E. t o Ef in the chronocou 1ome tr i c experimen t This ability to separate the faradaic and double layer charge, either by time-independence o f Q d l or by direct measurement of surface charge density, makes chronocoulometry particularly useful. 4,5,9-11 Chronocoulometry h a s been applied to the study o f e l e c t r o d e k i n 4v-5% and t o a study of a cntalytic reaction and other reactions in solutions to studies and determinations o f the extent of the a s r t 3,e,8-8,i9:lsf ~ t s ~ ~ c i c s which undergoes reaction at the electrode surface. principally to this latter problem that the remainder of the paper is addressed. I n particular, we shall consider the u s e of double-potential atop chronocoulometry a s a technique which permits an 'lins ii:iodouble layer corrcction even in t h e presence o f extensive adsorption.

Double Potential Step Chronocoulometr ) C o n s i d e r the redox couple, with :tandard potential Eo, Ox + n e 2 Red (2) bAn electrode at a potential E . , sufficiently anodic of Eo so n o current flows, At t=O, the is in a solution containing &cess supporting electrolyte and OX. potential is stepped t o a value Ef sufficiently cathodic of Eo so that the surface concentration of O x is immediately driven t o zero. Reaction 2 then 'proceeds to the right at a rate limited by diffusion of Ox t o the electrode. After a time, T , the potential is stepped back t o E . , which is sufficiently anodic so that the concentration of Red at the electrode surface is driven to 'zero. Again, the current is limited by the rate of diffusion of Red back to , t h e electrode surface. T h e Q-t behavior is observed. Initially w e consider neither Ox nor Red adsorbed. The faradaic charge 'during t h e forward step is given by the integral of the Cottrell equation i(t) = nF< Cox/Jn Jt

'
t

61

(3)
l w h e r e the symbols have their usual significance. For t > 7, t h e charpp m a y b e &L obtained by integration of current-time equations derived by Kambara. This ' yields
*\

Q(t

>

T)

2nFJTx

cox

Equation ( 4 ) contains no Q d l term because the electrode potential is back at \ i t s initial potential at t > 7 . charge, Q r , passedduring It is convenient, however, t o consider t h e t h e interval t > T , Qr=Q(r)-Q(t > 7 ) . T h u s

Jn

(Jt

(4)

+ ,fr Jt) will a) b e Thus, plots of U(t < 7) tM and Q VS. @ = and linear, b) have identical slopes ( 2 n f c x Cox/JV) proportional t o C ox' c ) have identical intercepts equal to Q If O x is adsorbed t o the extent ofdf'moles/cm2 and reacts at Ef, then

z.

(m

Q(t <
J,A

T)

2 K

cox

Jt

+ Q

dl

+ nFr

(5)

plot of U(t < T ) 2. tH will have the same slope a s in the absence of However, during t h e f o r adsorption, but the intercept will now be Q d l + nFr. ward step more Red is formed at t h e surface, and starts t o diffuse away than \, in t h e absence of adsorbed Ox i.e., Red is formed both from O x which was This, adsorbed on t h e electrode surface which diffuses to the electrode. qualitatively, will make the slope of the reverse step larger than in the absence o f adsorption of Ox, hence larger than t h e forward slope, which is \ unaffected by adsorption. 19920 Specifically, defining Qr a s before,

and

T h i s differs from Eq. 4 only'by the term nFr[l 2/n ~ i n - ~ m t ] arising from , Qdl here is t h e true double lnyer reoxidation o f initially adsorbed Ox. charging term in the presence of adsorptlon. Equation ( 6 ) may be simplified by approximating (1-2/n sin-'Tp) with a linear function of the form a,(@//JT) + . t o give a a nFr OnFJb;;; cox 1 + l o aonFTo + Qdl 0 + Qr = (6,)

Jn

Qc

62
where Qc f s the charge which has diff sed at t=T, (2nFJbor C J-t)/[n. from the intercepts o f Q(t < T ) ' t and Qr @ plots, nPf may be attained.

s.

E.

Hence,

OQ-OQ,

nFr=- 1-a

(7)

when OQ and OQ are the intercepts i n theoQ-axis o f the Q(t < T - ' 1t and Qr-@ The cogstants a and a l , although dependent on the expedimental timeplots. ratios used, can be mad: c l o s e to zero and unity, respectively. In short,

where S and S are the slopes of the reverse and forward plots, respectively, This may b e used t o establish an inter(Q er$erimentally, is Q(t=7)-0Q). Further, the double layer charging term is naf check on the procedure. given by OQr-ao0Q (9) Qdl 1-a

Figure 1 shows, qualitatively, the Q-t behavior expected without (a) and with ( b ) adsorption. Figure 2 show a n d a,@ plots for 1 mH Cd(I1) in 1 1 KNO and 0 8 E . A potential step from -200 to - 9 5 0 mV SCEwas KNO + 0.2 1 KSCN. f9 The points labelled Blank in A and B refer t o coulombs required to applied. charge the double layer in the Cd(I1) free base solutions. A summary of data is given i n Table I. I t is seen that a) the amount of Cd(I1) adsorbed decreases a s the initial potential is made more cathodic and b) the amount of Cd(I1) adsorbed rises to a maximum and decreases with increasing thiocyanate concentration. Figure 3 is a plot of n F T 2 . E obtained chronocoulometrically for Zn(1I) in 0 . 0 5 1 NaSCN + 0.95 1 NaNO This system is of interest because thepotention can be achieved at potential range for E. is such t h a 2 complete d tials prior to the Zn(I1) reduction wave. Also included in this figur%4 i s t h e amount of specifically adsorbed thiocyanate, as determined b y P a r s The straight line in the figure i s a plot of the slope of the forward Q-t The slope should be, and is, proportional t o the concenplot [Zn(II)]. tration of Zn(I1). Figure 4 is electronic chargelgather than potential, for thiourea in 1 M NaNO obtained by C a s e and Anson. T h e thiourea does not react, but give rise t a an anodic depolarization wave. T h e open circles a r e chronoe circles are from classical capacity m surements of coulometric data, Paraone and Symons" and t h e triangles from Schapink et a" , . This is the first instance where a direct comparison between chronocoulometry and claseical methods can be made, a n d the agreement is overwhelming1 Using essentially a coulostatic method, evidence for the validity of the assumption regsfding the rapidity of the reaction o f adsorbed material has been obtained. The chronocoulometric procedures appear to of fer real advantages in adsorption and kinetic studies. With the aid of sophisticated d a t a a q u i s systems, rapid and precise measurements o f parameters can be carried out. It is hoped that others will attempt to apply t o their problems what we conaider a very useful approach to studying electrode processes. Ref erences 1. R. A. Osteryoung, G. Lauer, and F. C. Anson, Anal. Chem., 1833 (1962). 2 . J. H. Christie, G. Lauer, R. A. Osteryoung, and F. C. Aneon, Ibid, 2, 1979 (1963). 3 . R. A. Osteryoung, G . Lauer, and F. C. Anson, J. Electrochem. Soc., 110, 9 2 6 (1963).

:-&'

the

""'

w" ''

z.

rz.

%?9,%

2,

E.

5.
6. 7.

J. H. Christie, G.

Lauer. and R. A.

Osteryoung. J. Electrochem. SOC., -.

F. C. Anson, Anal. Chem.,

9 3 2 (1964). R. A. Osteryoung and F. C.'Anson, I b i d 36, 975 (1964).

2,

J. H. Christie, Ibid

'0, 284
in press.

(1965).

70,

118, 127

18.

R. Koopmann, Ibid, 70, 121 (1966). R. Y. Murray and D. J. Gross, ,\rial. Chem., 38, 392 (1966). B. Epstein, Thesis Univ. of Calif., Riverside (1966). F. C. Anson and D. A . Payne, J. Electroanal. Chem. in press. 8 Case and F. C. Anson, J. Phys. Chem. . in press. J. H. Christie, R. A. Osteryoung, and F. C. Anson, J.Electroan.l.Chem.,

in press.

23

29

in press. T. Kambara, Bull. Chem. SOC. Japan, 3, 529 (1954). R. A. Osteryoung and R. L. Myers unpublished experiments. J. H. Christie and R. A. Osteryoung J. Phys. Chem. in press. R. Parsons Private Communication. P. C. Symons, Thesis, U. of Bristol, England, 1963. F. Y . Schapink, H. Oudeman, K. Y. Leu, and J. N. Helle, Trans. Faraday SOC., &, 415 (1960). R. A . Osteryoung and F. C. Anson, unpublished experiments. R. A. Osteryoung and G. Lauer, Anal. Chem., E, 1137 (1966). G. Lauer, F. C Anson, and R. A. Osteryoung . unpublished.

F. C. Anson, J. H. Christie, and R. A. Osteryoung, Ibid

Table I

I',
I

Data Summary for Adsorption of Cd(I1) from Thiocyanate Solutions nFrO pC/cm
2

Potential steps from

-200 -300) to -900 m V

2.S.C.E.

-400

L\ W N - I
i,
'
b

-05 E
-200

01 .

02 .

1
-400

[Cd( 1 1 ) ] E. =
02 .

-300
-0

-400
-0

-200 17.3

-300
1. 08 17.9

-400

-200 -300

-0

64 .
11.8 17.5

05 .
10 .

13.9
21.2

11.2

17.1

58 . 9.3

22.9 22.7

14.7 10.6 20.5 14.9

21.1

6.9
10.1 14.0

21.8

19.2
1.0

0.5
\

1
4.9 9.8

0.75 9.4 15.7

18.4

1
5.8 9.8
15.6

1
3.3 8.0
10.1

0.2

12.1

0-5
1 .o
IJ

18.4
24.4

10.8 14.2 16.1

7.5
12.8

13.4

16.9

8 . 3 5.1, 12.7 10.1 15.6 10.1

64

Fig.

2 5-

Fig.

65

20

il_

12O

c
I

i
LL
C

i
i,

-300 -400

-500

-600

-700

-000

-900

Fig. 3:

E i , m V vs SCE

'1