Chapter 5

The Potential of Zero Charge

S. D. Argade and E. Gileadi

1. INTRODUCTION

1.1. What Is the Potential of Zero Charge?

When a metal is immersed in a solution of an electrolyte, a double
layer is set up at the interface, such that there can be an excess charge
on the metal side of the interface and an ionic atmosphere with a net
excess of one kind of ions in the solution side of the double layer,
to maintain electroneutrality over all of the system. The charge on
the metal per unit area is given by
(1)

where the summation is limited to the solution side of the double layer;
F is the Faraday; Zi is the charge of the ionic species i, including the
r
sign; and i is the surface excess of that component in the interphase,
in moles per unit area of the interface. The charge on the solution side
of the double layer qS is equal and opposite in sign to the charge on
the metal (qm = _qS).
Consider an ideally polarized electrode, i.e., an interface across
which charge transfer cannot occur. The Gibbs adsorption isotherm
at constant temperature and pressure can be written as
(2)

and hence the excess charge density on the metal is

( __
8u ) _ _qm (3)
8£ T.P,,,; -

87

E. Gileadi (ed.), Electrosorption

© Plenum Press 1967
88 S. D. Argade and E. Gileadi

where f.Li is the chemical potential of the species i; E is the electrode

potential; and a is the interfacial tension. In principle, one can deter-
mine the interfacial tension as a function of the electrode potential with
respect to some suitable reference electrode. The potential at which the
derivative (8aj8E)T.P'I-'i is zero corresponds to the situation where the
metallic side of the double layer has no excess charge. This potential
is defined as the potential of zero charge. It will be shown below that
the potential of zero charge is not a unique property of the metal, but
depends on the detailed composition of the whole system. Antropov
has suggested P] that a distinction should be made between the null
point of metals and the potential of zero charge. The former is meant
to be a property of the metal, while the latter would only be defined
for a system as a whole. The null point of a metal would be defined as
its potential of zero charge in a dilute aqueous solution, in the absence
of specific adsorption. While the concept of the null point of metals
is useful in bringing to light the dependence of the potential of zero
charge on all the components of an electrochemical system, it cannot
be considered a unique property of the metal. First, specific adsorption
of the solvent always occurs, and the null point hence may depend on
the solvent. Second, the absorption of gases in the metal may effect
its null potential. This has recently been verified [2] in the case of
absorption of hydrogen in Pt and may be expected to occur with
other metals and other gases (e.g., hydrogen in Fe, AI, Ti, Ni; oxygen
in Ag; nitrogen in Fe; etc.).

1.2. The Rational Scale of Potential

The potential of zero charge offers itself as a natural reference
point. This point of view was originally put forward by Frumkin [3]
and applied by Grahame [4] to devise a rational scale of potential and
was stressed further by Antropov [5]. The rational scale of potentials
is referred to the potential of zero charge as zero. Thus, measured
on any other scale, it will be given by

(4)

where E is the potential on the rational scale; E is the measured

potential; and Eq~o is the potential of zero charge on the same scale.
The potential expressed on the rational scale gives an approximate
idea regarding the charge on the electrode. This is most useful for solid
electrodes, where the dependence of charge on potential cannot be