Chronocoulometry

A Convenient, Rapid and Reliable Technique for Detection and Determination of

Adsorbed Reactants
Fred C. Anson
Arthur Amos Noyes Laboratones, D~visionof Chemfstryand Chem~alEngineering,' Calffornla lnstltute of Technology, Pasadena,
CA 911%
Robert A. Osteryoung
Department of Chemistry. Acheson Hall, State University of New York, Buffalo, NY 14212

All of the interesting action in electrochemistry takes place

a t the interface between the conducting (usually solid) elec-
trode and the (usually liquid) electrolyte solution. This is
where ionic current is transformed into electronic current by
an electrode reaction. The electrode/electrolyte interface in
any electrochemical cell often exhibits chemical propert~es
that differ substantially from those observed in the bulk of the
electrode and in the electrolyte solution far from the interface.
One particularly interesting property of many electrode1
electrolyte interfaces is their tendency to attract and retain
reactants. The phenomenon is often described in terms of the
"adsorntion" of reactants at electrode surfaces. Considerable
effort has been expended to devise metods for measuring the Fiaure 1. Tvoicai
,, steadv-state current-ootential curve for the reduction of a
quantity of any reactant that may be adsorbed a t the elec- reactant at an electrode surface. Reduction currents are plotted upward and the
trodelelectrolyte interface. The problem is not trivial because potential becomes more negative to the right.
the quantities whose magnitudes it is desired to measure
typically lie in the range between 10-l2 to 1 0 - L h o l efor each
cm2 of interface.
Our interest in measuring the quantities of reactants ad- As the potential is made still more negative, the current
sorbed on electrodes was stimulated initially by a publication eventually levels off at a limiting value where every reactant
of Breiter and Gilman (1)in which the amount of a reactant, molecule that reaches the electrode is immediately re-
methanol, adsorbed on platinum electrode surfaces was esti- duced.
mated from the areas under current-ootential curves (vol-
~

At potentials in the plateau region the current is limited by

tammograms) obtained when the electrode potential was the rate at which the reactant is supplied to the electrode
scanned across the ranre where oxidation of both adsorbed surface. If the experimental conditions are arranged so that
and unadsorbed methanol proceeded. Initially, we also utilized the reactant is transported to the electrode surface by means
the areas of voltammetric current-uotential curves to measure of linear diffusion (i.e., unstirred solution, flat electrode) an
the quantities of adsorbed reactants ( 2 , 3 )but soon realized equation originally derived by Cottrell (6) can he used to
that the same information could be obtained more simply, calculate the current that flows a t any time after application
reliably, and rapidly by stepping rather than scanning the
of the potential step as a result of the reduction of the reac-
electrode potential while measuring the electric charge that tant.
flows in response to the potential step (4). Measurement of
For example, if the electrode potential is stepped from a
the time dependence of the flow of charge constitutes the value (i.e., E l in Fig. 1)where no reaction is proceeding to a
procedure that now is known as chronoconlometry. While the value on the limiting current plateau (Ez in Fig. 11, the re-
technique has proved useful in a variety of electrochemical
sulting current is given by eqn. (1):
measurements besides the evaluation of reactant adsorption
(51, we will focus on this single application for which the
technique was originally devised.
Electrode Reactions Controlled by the Supply of Reactant where F is the Faradav (96.487 coulombs per equivalent). n
to the Electrode Surface
In Figure 1is shown a typical current-potential curve (re-
reactant in the bulk of the solution (mole cm-9, D is the
corded under steady-state conditions) for the reduction of a
reactant's diffusion coefficient (em2 ss'), and t is the time
reactant at an electrode surface (extension to oxidation re-
actions is straightforward). Nu current flows until the po-
tential reaches values near the reduction potential of the
reactant whereupon there is a rather sharp onset of current. ' Contribution No. 6684.

Volume 60 Number 4 April 1983 293

 Cottrell current
+
Z
W
LZ
LZ
3
U
I I 0
I I
I I (TIME 1''
I I

O ! '. Figure 3. Chronacoulometric plots of charge versus (time)'? The dashed,

iI C
horizontal line represents the charge response obtained in the absence of
reactant. Line 1 results if the reactant is not adsorbed. Line 2 results with the
i
I Same concentration of an adsorbed reactant. The dotted extensions of lines 1
and 2 indicate that the intercepts of chronocoulometricplots are usually obtained
W
0 by linear extrapolation from the shortest times at which reliable data are avail-
u able.
a
I
U transported to the electrode surface by diffusion (7). Suppose
some of the reactant is adsorhed a t the electrode/electrolyte
interface while the electrode is restine at notentialE,..(Fig. .
" 1).
When the potential is stepped to E2all o? the adsorhed reac-
tant will he reduced essentiallv instantaneouslv because i t is
TIME
Figure 2. Temporal behavim of me elemode potential, current, and charge in
chronocoulometric experiments. (A) The electrode potential is stepped from give rise to an extra burst of charge as soon as the electrode
El to E, at time = (I: (8) The current that flows in response to the potential step potential is stepped to Ez, hut thereafter the chronocoulo-
(solid curve). The dashed curve is the current obtained when the experiment is metric response will be unaffected by the adsorption of the
repeated in the absence of reactant: (C) The time-integrals of the two curves reactant. Thus, the total charge in the presence of adsorhed
in 8. reactant will obey eqn. (4) instead of eqn. (3)

follow in^ the notential steo. Fianre 2A deoicts the notential

step that is applied to the eiectride and 2 ~ s h o w thk
s current
that results. The current is actnallv com~osedof two com-
ponents: The Cottrell current gi;en b; eqn. (1) plus a
"charging current," i,, that flows to charge up the capacitance
that is always present in electrode/electrolyte interfaces. The
charging current, which can be observed by applying the po-
tential step in the ahsence of the reactant, is shown as the
dashed curve in Figure 2B. the charging current decays much
more rapidly than the Cottrell current and becomes zero once
the interfacial capacitance has become fully charged.
The total charge passing through the electrode is the time
integral of the two current components:
Q = J'FnAcb (z)
D
+ 112
ddt Si,dt
where 0, is the charge flowine into the interfacial canacitance
response in the absence of reactant.
According to eqn. (3), plots of Q versus t1I2 should he linear
with intercepts of Q, and slopes proportional to the concen-
tration of the reactant. This behavior is shown by line 1 of
Figure 3 and has been observed experimentally in a large
number of cases.
The charge increases in chronocoulometric experiments
with the square root of time because additional reactant is
Q = 2FnACb );;(Dt 112
+ Q, + Qads (4)
where Qads is the extra charge produced by the adsorbed
reactant. Under these conditions plots of Q versus (time)l/2
will have intercepts that exceed Q, by an amount of charge
equal to Qsds. This behavior is shown in line 2 of Figure 3. The
slope is unaffected by the adsorbed reactant. The values of
Qads are direct measures of the quantity of reactant adsorhed
because of Faraday's Law
where r is the quantity of adsorbed reactant in moles. It is this
simple, direct relationship hetween the experimentally ac-
cessible parameter, Qsds, and the quantity i t is desired to
measure, r, that makes the technique of chronocoulometry
(2) as attractive as it is.
Double Potential Step Chronocoulometry
As shown clearly in Figure 3, to obtain Q.a. from the in-
tercept of a chronocoulometric plot of Q versus t'J2 it is nec-
essary to know or measure Q,. This presents no problem when
the adsomtion of a readant nroduces little or no change in- thr
~-~~
interfacial capacitance so that the value of Q, measured in a
-~
"blank" experiment in the ahsence of reactant (dashed line
in Fig. 2C) applies to measurements in the presence of the
adsorbing reactant. However, frequently adsorption of a
reactant produces significant changes in the interfacial ca-
pacitance so that values of Q, evaluated in the absence of the
reactant do not apply when the reactant is present.
This difficulty can sometimes be overcome by double po-
tential step chronocoulometry in which the electrode potential

294 Journal of Chemical Education


TIME
Figure 4. Temporal behavior of: (A) potential, (B) cunent, and (C) charge in double
potential step chronocoulometry
Flgure 5 Chronocoulometrlc plots for double potential-step chronocoulometry
Llnes 1 and 2 correspond to no adsorption of the reactant or product Lmes 3
and 4 correspond to reactant but not product adsorption
is returned to its initial value hefore the experiment is ter-
minated ( 8 ) . Figure 4 depicts the potential-, current- and
charge-time responses obtained in such a double potential-step
experiment for cases where the product of the electrode re-
action is re-oxidized when the potential is returned to its initial
value. The ~harge-(time)'/~ plot of the data acquired during
the first potential step (Fig. 5, line 1) is, of course, identical
to that obtained in a single-step experiment. So long as neither
the reactant nor the product of the electrode reaction are
Figure 6.Chronocoulometric charge-(time)"2 plots for the reduction of Cd(l1)
at a mercury electrode (0.032 cmZ).The suppotting electrolyte was 0.1 FNaN03
+
for line 1 and 0.5 FNaN03 0.5 F NaNCS for lines 2-4. The concentrations
ot Cd(1l) were (1.2) 0.2; (3) 0.5; (4) 1.0; (5) 2.0 mM.
Figure 7. Concentration dependence of the adsorption of Cd(l1) on mercury
+
electrodes from 0.5 FNaNO* 0.5 FNaNCS electrolyte. The initial electrode
potential was -0.2 V versus a saturated calomel reference electrode.
adsorbed, the charge, Q,, (Fig. 4) that passes following the
+
second potential step is a linear function of [.r1I2 ( t - T ) ' / ~
- tlJz], where T is the duration of the first step. The corre:
sponding plot for data acquired during the second potential
step is shown in line 2, Figure 5. In cases where the reactant
but not the product of the electrode reaction is adsorbed, for
example in the reduction of a variety of dl0 metal complexes
to metal amalgams at mercury electrodes (9),the intercept
of the chronocoulometric plot for the reverse step (after a
Volume 60 Number 4 April 1983 295
small wmrctim 1s ;lpp~ic;d111,Il prwides u direct lniusure d
Q,.in r l i v p ~~+, i , : <~ , j u d , ~ , dr hn u i l w ~(11,.
~ 11 I This iemue
of douhlepotential-step chronocoulometry makes it partic-
ularly attractive for measuring the quantities of adsorbed
reactants. Converselv. when the two chronocoulometric nlots
have equal (and opposite) slopes and intercepts, as in lines 1
and 2 in Figure 6, this may usually be taken as good evidence
for the absence of reactant (or product) adsorption. Under
favorable conditions intercepts of chronocoulometric plots
can be measured with a precision of f0.5 X --
which corresponds to an uncertaintv in r of E 5 X 10-12 mole
cm-2 (for a &electron reactant):
Experimental Example
One of the first systems to which chronocoulometry was
applied to measure reactant adsorption was that of Cd(II) in
supporting electrolytes containing thiocyanate anions (11).
A set of chronocoulometric cha~ge-(tirne)'/~ plots for this
system are shown in Figure 6. Instead of the total charge, Q ,
these plots show Q - Q" versus t1I2 where the values of Q, in
~ ~
i w h nice w i w c\.;~lu;ltedby miun: 18ftheh u l d e potential step
prutedt~rede~rrrihrda l x w . 'l'hus, rhe inrercept uieach otthe
linch in Flgun, 6 i: O,,,,. Sote that i n the pure nitrate sup-
paning elecrrol)-re (line 1 in Fi:. (il rne line pnsses rhrvunh rhe
oririn
" >h~\ving -
t ~ > I ('11~111
I is not ~ l ~ t e r r t ~
electrolyte. In the mixed nitrate-thiocyanate electrolyte,
~ l ~ l \in
~ this
however, there is quite substantial adsorption that increases
296 Journal of Chemical Education
with the concentration of Cd(Ii). A plot of Q a d s versus [Cd(II)]
which represents a type of adsorption isotherm for this system
is shown in Figure 7. It is the relative ease with which such
isotherms can be constructed from the results of chronocou-
lometric experiments that has led to the popularity of this
technique for accurate measurements of adsorption of a wide
variety of electroactive substances.
Acknowledgment
coul ~ m - ~ The initial development of chronocoulometry was the result
of collaborative research involving the authors, J. H. Christie
and G. Lauer. The research was supported, in part, by the
National Science Foundation, the U. S. Army Research Office,
and Rockwell International Corporation.
Literature Cited
(1) Breiter. M.. and Gilrnan, S., J.Electrochem. Soc., LO?, 672 (1962).
(2) Osteryoung,R.A..Lauer,G., 8ndAnson.F. C.,Anoi. Cham..34,1833 (1962).
(31 Osteryoung, R. A , Lauer, G., and Anson, F. C., J. Electrochem. Soc., 110, 926
(1963).
(4) Christie, J. H.,Anson,F. C.,Lauer. G.,snd Osteryoung,R.A.,Anol.Chem.35.1979
(1963).
(5) Bard, A. J., and Faulher, L. R., "Electroeherniesl Methods? John Wiley +"d Sans.
Inc.,NY, 1980, p. 199 if.
(6) Cottrell, F. G., 2.Physik. Chem., 42,386 (1902).
(7) Reference ( 5 ) , ~ h5..
( 8 ) An3on.F. C.,Anol. Chrm.,38,54 (1966).
~ ~ ~ l ~ o r
(9) Ansun, F. C.,Accts. Chem R e r , 8,4W (1975) and references tberein.
(10)l ~Christie,
t ~ ~ J.l H.. Oslwyuung, R. A , and Anson, F. C.. J Elerfroonol. Chem., 13, 236
,-...,.
,7967)
(11) Anson, F. C., Chriatie. J. H., and Osteryoung, R. A., J El~ctroonal.Chrm., 13, 343
(1967).