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Basic Thermodynamics of Electrified Interfaces

G.G. Láng, in Encyclopedia of Interfacial Chemistry, 2018

Introduction and Basic Concepts

A “thermodynamic system” is a part of the physical world CONSTITUTED by a significantly large number of particles (i.e., ATOMS, molecules, or ions). A “homogeneous thermodynamic system” is defined as the one whose intensive thermodynamic properties are constant in SPACE. If a portion of a thermodynamic system behaves in this way throughout all its volume, it is called a “phase,” that is, the term “phase” is used for a region that is chemically and structurally homogeneous. According to a more general definition, a “phase” is a region of (spatially) constant or continuously changing physical (intensive thermodynamic) and chemical properties.

A “heterogeneous system” can involve more than one phase, and the passage through the interface among two phases leads to a discontinuous variation of one or more intensive functions, such as concentrations, DENSITY, and electric POTENTIAL.