Electrochemical Experiments in Systems Far from Equilibrium

In Chap. 2 9 we presented a thermodynamic and stochastic theory of chemical reactions and transport processes in non-equilibrium stationary and transient states approaching non-equilibrium stationary states. We established a state function h, which for systems approaching equilibrimn reduces to AG. Since Gibbs free energy changes can be determined by macroscopic electrochemical measurements, we seek a parallel development for the determination of by macroscopic electrochemical and other measurements. 

We begin with a discussion of two kinds of experiments and then, in the next chapter, turn to the development of the thermodynamic and stochastic theory to connect with these experiments. There are very few thermodynamic measurements on complex open reaction systems (see [2] as one example). 

2 Measurement of Electrochemical Potentials in Non-Equilibrium Stationary States 

When chemical species come into equilibrium with an electrode in an open circuit, the potential between the electrode and a reference electrode is related to the potential difference of the half reaction occurring at the electrode. If no 

We studied the autocatalytic minimal bromate reaction, which can be oscillatory, but was studied in a bistable regime. A proposed mechanism for this reaction, and participating species, are listed in Table 10.1. 

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