ELECTRODICS 1237

In terms of the diffusion-layer concept (Section 7.9.9), this condition becomes

It is obvious that the concentration gradient has a maximum value for Placing
this limit upon Eq. (7.202) produces
This maximum-concentration gradient corresponds to a maximum or limiting
current density denoted by and given from (7.202) and (7.205) by
For a given electronation reaction, this is the maximum attainable current density. The
reaction cannot go faster than because the transport process in the electrolyte bulk
is incapable of supplying the electron acceptor to the interface at a faster rate.
The concept of a limiting current density is of great practical importance. Table
7.11 shows some typical experimental limiting current densities for four energy
producers employing oxygen (where the calculation of limiting current density is more
complicated than that of (7.206).
7.9.10.1. Polarography: The Dropping-Mercury Electrode. The propor-
tionality between and [cf. Eq. (7.206)] constitutes the basis of polarography, a
powerful electroanalytical technique introduced by Heyrovsky. The essential part of
the polarographic setup (Fig. 7.98) is a dropping-mercury electrode consisting of a
glass capillary tube out of which mercury converges at the rate of a drop every few
seconds. To the solution is added a large excess (~1 M) of a substance termed an
indifferent electrolyte because its ions do not participate in, or are indifferent to, the
1238 CHAPTER 7
charge-transfer reaction at the drop/solution interface. In contrast, the species A under
polarographic analysis exists in the solution at a very small concentration
This wide disparity in the concentrations of A and the indifferent electrolyte ensures
that the ions of the indifferent electrolyte carry the migration current and that any
transport of species A occurs by a process of pure diffusion.
In a polarographic experiment, a potential difference E is applied across the cell
consisting of the dropping-mercury electrode and a nonpolarizable interface (e.g., a
calomel electrode). In response to this potential difference, a current density i flows
across the drop/solution interface. As each drop grows and falls, however, the surface
area of the drop also grows, and then becomes effectively zero when the drop falls.
Thus, the instantaneous current (current density times surface area) shows fluctuations,
but the mean current is a unique function of the potential difference across the
drop/solution interface, and therefore of that across the cell.
The relationship between the mean current and the potential (Fig. 7.99) will now
be derived. Suppose that at the drop/solution interface, an electronation reaction:
is driven by the imposition of a constant potential, E. The reaction results in
the depletion of A in the interfacial region, and therefore in the diffusion of A toward
the drop/solution interface. Let it be assumed that the species D produced by the
ELECTRODICS 1239
electrode reaction is soluble either in the electrolyte or in mercury (i.e., D is an
amalgam-forming metal). Then, since there is generation of D in the interfacial region,
there will be a diffusion of D away from the drop/solution interface either toward the
electrolyte or into the mercury.
It is clear that since the mercury drop approximates a sphere, the theory of
spherical, and not linear, diffusion might have to be used. However, detailed consid-
erations accessible in monographs show that if the electrodic reaction is driven for a
sufficiently short time (t < a few seconds) and if the mercury-drop radius is not too
small (r > 0.05 cm), then the equations of linear diffusion can be used with validity.
Thus, the partial differential equations for the diffusion of A and D are [see Ficks
second law; cf. Eq. (4.32)]
The initial conditions are
i.e., before the imposition of the potential difference E, the concentrations of A and D
for any x are and zero, respectively.
The first boundary condition to be satisfied by solutions of the differential
equations (7.207a) arises from the fact that the only source for the material D is the
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electrodic transformation of A by the reaction For each mole of A reacting
at the interface (i.e., at x = 0), one mole of D is produced; hence, the sum of the fluxes
of A and D at x = 0 must be equal to zero:
The second boundary condition involves a relation between the concentrations of
A and D and the potential E. The simplest relation is obtained by (initially) assuming
that there is charge-transfer equilibrium at the interface (x = 0), in which case the
Nernst equation (7.47) can be applied:
where and are the activities and activity coefficients of the species A and
D, respectively.
Finally, the situation far away from the drop can be assumed to be unperturbed
by the reaction Thus, one has
Before attempting to solve the differential equations (7.207a) in the context of the
initial and boundary conditions (7.207b)(7.207e), two variables, and will
be defined thus:
and
In terms of these two variables, the differential equations (7.207a) and the initial and
boundary conditions (7.207b)(7.207e) become
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The corresponding Laplace transforms of equation (7.210a) are
and
These total differential equations can be combined with the initial condition (7.210b)
and solved. The result is
The integration constants and must be zero in order to satisfy the boundary
conditions (7.210e), in which case
To evaluate and it is necessary to use boundary conditions (7.210c)and(7.210d),
which after Laplace transformation are
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If equations (7.212a) and (7.212b) are used in (7.213a) and (7.213b), the integration
constants and turn out to be
where
Thus, the solutions of the total differential equations are
and
It is known, however, that the Laplace transform (see Table 7.12) of erfc is
hence
or
and
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At time t, the instantaneous current is given by Ficks first law:
where is the surface area of the drop at time t. It is necessary, therefore, to get an
explicit expression for the concentration gradient at the interface. This
expression is obtained by differentiating Eq. (7.216a) with respect to x and then setting
x = 0 in the result. Thus, with
the result of the differentiation is
Combining Eqs. (7.217) and (7.218), one obtains
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since the current, when i.e., when is equal to the
limiting current,
By eliminating between Eqs. (7.220b) and (7.207) one obtains the required
current-potential relation:
where is termed the half-wave potential because the versus E curvethe
polarographic waveis of the form shown in Fig. 7.98 and when i.e.,
when has attained half the wave height The potential also corresponds to an
inflection point in the versus E curve, for it may be shown that the second derivative
of the versus E curve is equal to zerothe criterion for an inflection pointwhen
The half-wave potential (Table 7.13) might be called a pseudo-fundamental
quantity in polarographic analysis since, in the absence of disturbing factors, particu-
larly the heat of amalgam formation, it should be equal to the standard electrode
potential [Eq. (7.221a)]. It was once thought that by determination of the half-wave
potential and the assumption that this potential corresponded to the standard thermo-
dynamic potential of the reaction at the mercury/solution interface, a qualitative
identification of the species in solution could be made. However, the approximations
involved in Eq. (7.221) reveal this as untrue; thus, the identification of the half-wave
potential as the standard thermodynamic electrode potential depends not only upon
the neglect of amalgam formation between the product D and the mercury but also
upon the assumption made in Eq. (7.221) that the activation overpotential is negligible.
It may well be true that for a number of reactions, is negligible at the current
densities obtained in polarographic analysis. However, it is too gross an assumption
to allow polarography anything but a historical claim to applications in qualitative
analysis.
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Quantitative analysis is, however, possible since, in Eq. (7.221), the existence of a
limiting current density and its relationship to the concentration of species undergoing
electronation are unaffected by the approximations involved. However, as Eq. (7.206a)
shows, is a function of time and as t rises, the diffusion-controlled current decreases
toward zero. This is one disadvantage of working at a stationary electrode. Another
disadvantage is the effect of impurities that accumulate at the surface. In order to avoid
these difficulties, a dropping-mercury electrode is used where each drop extends only over
a short time, which is determined by the flow rate v. The same law of nonstationary linear
diffusion can be applied; however, a correction must be made for the variation of the
surface area with time. The surface area can be calculated, on assuming perfectly
spherical drops, as follows. The weight of the drop at time t is given by
where r and d are the radius and density of the mercury drop, respectively.
Then,
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and, at 25 C,
The thickness of the diffusion layer, as first shown by Ilkovic, will be changed in
that instead of Eq. (7.204), one has now for an expanding spherical drop
From Eqs. (7.206), (7.222), and (7.223), the limiting current at time t is given by
This equationin which i is in amperes, v in grams per second, t, in seconds, in
square centimeters per second, and in moles per cubic centimeteris known as the
Ilkovic equation.
7.9.11. The Steady-State CurrentPotential Relation under
Conditions of Transport Control
The concept of limiting current density permits a simple derivation of a relation
between the steady-state concentration overpotential and the current density i if the
reaction is such that other forms of overpotential are negligible. One starts from the
expression for the concentration overpotential [cf. Eq. (7.198)]
the electronation current density is given by
and one can write
or