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Chapter 5

MIXED POTENTIAL
THEORY

5.1 INTRODUCTION
This chapter is confined to analyze the complex aqueous corrosion phenomenon
using the principles of mixed-potential, which in turn is related to the mixed
electrode electrochemical corrosion process. This theory has been introduced
in Chapter 3 and 4 as oxidation and reduction electrochemical reactions. Basi-
cally, this Chapter is an extension of the principles of electrochemistry, in which
partial reactions were introduced as half-cell reactions, and their related kinet-
ics were related to activation and concentration polarization processes. The
principles and concepts introduced in this chapter represent a unique and yet,
simplified approach for understanding the electrochemical behavior of corrosion
(oxidation) and reduction reactions in simple electrochemical systems.
Both Evans and Stern diagrams are included in order to compare and ana-
lyze simple and uncomplicated electrochemical systems. The concept of anodic
control and cathodic control polarization is also introduced. In addition, the
predetermined corrosion circuit is included in order to analyze corrosion using
an electrochemical device containing an external circuit.

5.2 MIXED-ELECTRODE POTENTIAL


Electrochemical corrosion systems can be characterized using the kinetic para-
meters previously described as Tafel slopes, exchange and limiting current den-
sities. However, the mixed potential theory requires a mixed electrode system.
This is shown in Figure 5.1 for the classical pure zinc electrode immersed
in hydrochloric (HCl)acid solution [1,8-9]. This type of graphical representa-
tion of electrode potential and current density is known as Evans Diagram for
representing the electrode kinetics of pure zinc.
156 CHAPTER 5. MIXED POTENTIAL THEORY

The Evans diagram requires anodic and cathodic straight lines and the cor-
rosion potential and the corrosion current density point located
where hydrogen reduction line and zinc oxidation line
converge. Furthermore, the exchange current densities and the open-circuit
potentials for hydrogen and zinc are necessary for completing the diagram as
shown in Figure 5.1 for a simple electrochemical system..
In fact, this type of potential-current density diagram can be developed
for any solid material in contact with an electrolyte containing one or more
oxidizing agents such as etc..As a result, the corrosion potential
and the corrosion current density can be determined from the diagram (Figure
5.1).In addition, connecting the and provides the shown straight lines,
which are accompany by their respective overpotential equation. With regard
to the point in Figure 5.1, the potentials and current densities are
equal since this point represents electrochemical equilibrium.
On the other hand, Stern [10] used eq. (3.38) to draw anodic and cathodic
nonlinear polarization curves, which provide a more realistic representation of
the electrode kinetics of an electrochemical system. Evans (straight lines) and
Stern (solid curves) graphical methods are illustrated in Figure 5.2 for a cor-
roding hypothetical metal M immersed in an corrosive medium containing
and oxidizers [6,13].