471

J. Electroanal. Chem., 256 (1988) 471-475

Elsevier Sequoia S.A., Lausanne - Printed in The Netherlands

Preliminary note

Kinetic study of electrode processes by ac quartz

electrogravimetry

S. Bourkane, C. Gabrielli l and M. Keddam

LP 15 du C.N.R.S. “Physique des Liquides et Electrachimie”, Tout 22-4, Place Jussieu,
75252 Paris Cea’ex 05 (France)

(Received 10 October 1988)

INTRODUCTION

The use of a quartz crystal for measuring small mass changes (of the order of
10M9 g) is well established in vacuum or in a free atmosphere [l]. The principle of
this quartz microbalance is based on the property of the resonance frequency of a
quartz crystal to vary in a proportional way with small changes of the mass of a
foreign substance deposited on one of its sides. Hence, by measuring the change of
the frequency of an oscillator into which the quartz is inserted, the change of the
mass can be detected and evaluated. It seems that Nomura and Iijima [2] were the
first to apply this technique to an electrolytic medium for analytical purposes in
1981. A few years later, Bruckenstein and Shay [3] and practically at the same time
Kanazawa and co-workers [4] used this technique for electrochemical kinetic stud-
ies.
During gold oxidation in perchloric medium, the simultaneous recording of the
current-voltage voltammogram, the quantity of electricity-voltage curve and the
mass-voltage curve allowed Bruckenstein to weigh one adsorbed oxygen monolayer
(20 ng) on the gold surface. In the same way Kanazawa showed that during the
reduction of a conducting polymer film the charge compensation is carried out by
diffusion of the lithium ions in the polymer and not by diffusion of the perchloric
ions in the solution.
All the previous results have been obtained by quasi-steady-state techniques, i.e.
the recording of the variation of the quartz resonance frequency; hence the mass
variation under experimental conditions changes. In this Note it will be shown how
the same principle can be used in order to obtain dynamic information about the

l To whom correspondence should be addressed.

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mass changes. A sinusoidal perturbation of the electrolysis current which flows

through the electrode allows the classical impedance and a new mass-voltage
transfer function to be obtained simultaneously.

EXPERIMENTAL

Copper is deposited in sulfate medium (0.5 M CuSO, + 0.5 M H,SO,) on one of

the electrodes of a quartz crystal resonator, which is called the working crystal. The
latter is inserted in an oscillator which has to be tuned so that it oscillates even
when the crystal resonator is strongly damped by the electrolytic solution. Processing
of the oscillating signal gives the change of the resonance frequency of the working
crystal and hence the change in the mass of copper deposited on the quartz
electrode.
The scheme of the oscillator was chosen such that the resonator can be grounded.
This allows the working electrode to be connected to the ground. In this case the
electrochemical arrangement is easier to operate than when the working electrode is
floating [5].
The modulation of the resonance frequency Af related to the sinusoidal perturba-
tion of the current AZ about the steady-state polarization current Z, is analyzed by
means of a transfer function analyzer (Solartron-Schlumberger 1254) which allows
the classical impedance to be obtained at the same time (Fig. 1) from the processing
of the frequency of the working oscillator f, =fO’ + cut+ Af. First the difference
with the frequency of a reference oscillator f, (f, =&‘) using the quartz crystal in
free air is performed. Then the resulting frequency is converted to a voltage which
can be high-pass filtered in order to eliminate the continuous offset due to f, -fo/
and the frequency drift LYZrelated to the continuous mass change of the electrode
due to the constant current I, (Faraday’s law). The experimental arrangement

Fig. 1. Scheme of the experimental arrangement used for measunng the mass-voltage transfer function m
a galvanostatlc regime.
 413

I
REAL PART /-Cl
Fig. 2. Impedance of the copper during deposition at 200 PA in 0.5 M CuSO, +0.5 M H,SO,.

allows mass-voltage transfer function measurements between 0.1 and 100 Hz to be

carried out.
In Figs. 2 and 3 are given the impedance and the mass-voltage transfer function
measured at I, = 200 PA during copper deposition at ambient temperature.
It can be shown that for an AT cut quartz crystal with a 6 MHz resonance
frequency the theoretical sensitivity is
hf/Am = 0.081 Hz cm’ ng-’ (1)

-02
C

REAL PART151

Fig. 3. Mass-voltage transfer function (dm/dE), measured for the same conditions as in Fig. 2.
As the frequency-voltage converter gives a voltage Vt = 10 V for a 100 kHz
frequency excursion

Al’,/Af= 1O-4 V Hz-’ (2)

Hence, the theoretical sensitivity of the whole measurement channel is
A&/Am = 0.081 x lo5 g-’ cm2 V (3)
i.e. for the active surface of the quartz electrode (S = 0.312 cm*)
Am/A& = 3.85 x low5 g V-i (4)

DISCUSSION

In a simplistic approach it is assumed that the cupric ion discharges directly on

the electrode:
Cu*+ f 2 e” -+ Cu (5)
Therefore
dm/dt = (A/2F) Ir (6)
if I, is considered as positive for a cathodic process, where A is the molar mass of
copper (A = 63 g mole’) and F = 96500 C mall’, and hence

m(f) = (Aj2F)J’Ir dt (7)

0
If I, is kept constant
m(t) = (A/2F)l,r (8)
which is an expression of Faraday’s law. The perturbation of the current by a small
quantity AZ leads to a mass change Am and a voltage change AE. Equation (7)
gives

m(f) + Am(t) = (A/2F)l’(I, + AI,) dt (9)

where the mass change is

Am(t) = (A/ZF)i’ AI,(t) dt 00)

i.e. in the frequency domain

Am(f) = (A/2F)(l/N) AZ,(f) (11)

As A E = R, AI, where R, is the charge transfer resistance
Am/AE = (A/2F)(l/~~)(l/R~) 02)
However, the charge transfer resistance R, has to be associated with the non-faradaic
components: R,, the electrolyte resistance and C,, the doubIe-layer capacity, in
order to obtain the full equivalent circuit of the electrode.
 475

The measured quantity in the low frequency range is then

R
gi(,+o)=&d~o).--“-R,+R, (13)

As an example the experimental conditions which give the results depicted in Figs. 2
and 3 are considered. From Fig. 2, R, = 77 s2 and R, = 46 Q which gives
A/ILFoR, = 1.14 x 10v6 g/V at 1 Hz. From Fig. 3

Im( Am/AV) = 4.3 x lo-’ g/V (141

i.e.

Im( Am/AE) = 1.15 X low6 g/V (1%

where Re(x) and Im(x) are the real and imaginary parts of the complex quantity x.
These values show a good agreement between A/2FcoR, and Im( Am/AE) as
predicted above.
However Re(Am/AV) # 0 is not in agreement with the oversimplified model
considered previously. Consequently this value shows the presence of an adsorbed
reaction intermediate whose relaxation has been ignored.
This technique is able to reveal the presence of adsorbed reaction intermediates
and to study their kinetics even when their role is not very obvious from the
impedance analysis.

REFERENCES

1 E. Lu and A.W. Czandema, Applications of Piezoelectric Quartz Crystal Microbalances, Methods and
Phenomena, Vol. 7, Elsevier, Amsterdam, 1984.
2 T. Nomura and M. Iijima, Anal. C%im. Acta, 131 (1981) 97.
3 S. Bruckenstein and M. Shay, J. Electroanal. Chem., 188 (1985) 131.
4 J.H. Kaufman, K.K. Kanazawa and G.B. Street, Phys. Rev. Lett., 53 (1984) 2461.
5 S. Bourkane, thesis, to be submitted.