Lecture 14: Electron Transfer Reactions with Associated Chemical Reactions

Introduction
The discussion so far has assumed that the limiting factor in electrode reactions is primarily
one of mass transport. However, in reality the effect of electrode kinetics is often important
– or even critical in for example corrosion. In other cases both the effect of mass transport
and electrode kinetics are important. Electrode kinetics have been discussed by Dr Marken
in former lectures.

Moreover, in many cases, this electrochemical step takes place in tandem with a chemical
reaction. These reactions are important, as altering scan rates in a cyclic voltammetry
experiment allows one to (in principle) determine life times of intermediates.

So, up to now we have considered situations where either the mass transport to the
electrode or the rate of electron transfer are the rate limiting step. Now life gets a little more
complex..

The E mechanism and the effect of ko

The EC mechanism

Reactant O undergoes an electron transfer (E), immediately followed by a chemical

reaction (C). So this reaction is known as an EC mechanism.

If we consider facile electron transfer kinedtics, the rate of the electron transfer reaction is
determined by Fick's 2nd law:

However, since the product R is being used up by the couple chemical step, the overall
rate of production of R must also include a term to reflect this.

The effect of such a coupled reaction, providing the kinetic chemical rate constant kEC is
high enough, is that the reverse electron transfer reaction (above a reduction) is
suppressed:

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 E mechanism (diffusion controlled) EC mechanism (high kEC)
However, the observed CV will depend on the scan rate. At high scan rate, if kEC is not too
large, then the reverse (oxidation reaction might still be seen, since the chemical reaction
step might be relatively slower than the electron transfer for the oxidation reaction.

This effect can be clearly seen here:

low kEC

The ECE mechanism

The ECE mechanism stands for: Electron transfer, Chemical reaction, Electron transfer.
Like the EC mechanism, the CV obtained for a specific system is strongly dependent on
the chemical rate constant kECE. Two separate electron transfer steps are involved. They
may or may not be both observable as reversible waves on the CV, for the reasons just
given.

The first step is similar to the EC process. However now the product for the chemical
reaction (S) is also electrochemically active. The figure below shows the voltammogram for
an ECE mechanism where the product (S) is more difficult to reduce than the starting
material (O).

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The above CV would be for a system with a facile and uni-directional chemical reaction
step. Hence, the second re-oxidation step (R→O) is not seen, since S is not chemically
reduced in any quantity to R.
If the chemical step is reversible, then two separate electron transfer waves may be seen:

This is a real experiment. p-nitrosophenol is first reduced via an electron transfer reaction
(top right on CV I). From here two things can happen. At fast scan rate, intermediate I can
be re-oxidised back to II. Alternatively (and often simultaneously), some of I will
dehydrolyse in the chemical step to form the ketone intermediate IV. This then undergoes
reversible oxidation to form p-aminophenol III.

Since the second electron transfer step depends on how much of the intermediate I is
chemically converted to intermediate IV, the peak currents here are strongly affected by the
scan rate. At very high scan rate, the chemical reaction and second electron transfer step
can be effectively suppressed by rapid re-conversion of I back to starting material II, the p-
nitrosophenol.

The EC' mechanism

This is an important variant of the EC mechanism. In this case the C' refers to a catalytic
chemical reaction step which drives the electron transfer reaction, thus increasing the rate
of electron transfer, which is observed as an increase in peak current (oxidation or
reduction, depending on the system under study).

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In this situation, one of the products of the second step, the chemical reaction, is the
original starting material O. So the system is autocatalytic: the faster the chemical reaction,
the more starting material O is made, which is reduced to form R in the electron transfer
step, which forms further O.

The EC' reaction is the basis of the reaction used in glucose biosensing. Diabetics have to
keep a careful check on their blood glucose. They do so usually using an electrochemical
sensor.

Schematically, the glucose sensor works like this:

Glucose is enzymatically oxidised to gluconic acid by glucose oxidase (GOD). The electron
removed by the GOD is used to reduce a mediator (usually a ferrocene compound). This
mediator is then re-oxidised at the electrode surface. Since every electron transferred at
the electrode surfaced corresponds (stochiometricaly) to 1 glucose molecule being
oxidised, it is possible, by measuring the electron transfer current to determine the
concentration of glucose in a solution (after calibrating the system with known
concentrations).

The system can be considered as a number of separate reactions in related equilibrium:

At electrode surface: Fc(CO2)H Fc+(CO2)H + e- E

Fc+(CO2)H + GOD- Fc (CO2)H + GOD C'

GOD + Glucose GOD- + Gluconic acid C'

Arguably, the system is more an EC'C' reaction, with two chemical steps regenerating
reactant each time, but the principle remains the same.

THE CV obtained from EC' reactions shows an irreversible nature (as with the EC
mechanism), but importantly, shows an increase in the limiting current (the current at
maximum applied potential) with increasing concentrations of the chemical reactant (Y in
the generic scheme, glucose in the glucose biosensor).

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This is shown here:

Error!

Commercial glucose biosensor