Kinetics of Electrochemical Processes

Abstract

We consider the electrochemical process shown by the formula

$$M\, \mathbin{\lower.3ex\hbox{$\buildrel\textstyle\rightarrow\over {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}}$}} \,M^{n + } \, + \,ne$$

((3.1))

where $\mathbin{\lower.3ex\hbox{$\buildrel\textstyle\rightarrow\over {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}}$}}$ indicates reversibility. According to the theory of chemical processes, the reaction rate which can be measured from the outside is the difference between the forward reaction rate $\vec \upsilon$ and the backward reaction rate $\mathord{\buildrel{\lower3pt\hbox{$\scriptscriptstyle\leftarrow$}}\over \upsilon }$, i.e.,

$$\upsilon = \overrightarrow \upsilon - \overleftarrow \upsilon$$

((3.2))

The reaction will proceed in the forward direction when υ<0, and vice versa. It is clear that

$$\begin{array}{*{20}c} {\overrightarrow \upsilon = \overleftarrow \upsilon = \upsilon _0 ,} & {at} & {\upsilon = 0} \\ \end{array}$$

((3.3))

υ₀ is the exchange reaction rate at equilibrium.