Abstract
The electrode charge is one of the most fundamental concepts in electrochemistry. However, ambiguousness often comes to its definition as specific adsorption occurs. In this review, three types of electrode charges, the metallic excess charge, the free charge, and the total charge, are discriminated via a modelistic description at the metal/solution interface, and the relationships between them are formulated. The total charge is proved to be the thermodynamic charge in a general Lippmann equation. Based on this equation, thermodynamic analysis can be performed to estimate the adsorbate coverage, then the free charge can be derived. As an example, manipulation has been made on a previous work in the (bi)sulfate adsorption system, the surface charging relations are obtained, displaying nonmonotonic relationships. In addition, a modeling study for specific adsorption is introduced and exemplarily performed in the (bi)sulfate adsorption system.
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