A continuum thermodynamical approach to electrochemical systems

作者：Reis Martina Costa^*; Wang Yongqi; Maurizio Sacchi Bassi Adalberto Bono

来源：Journal of Mathematical Chemistry, 2014, 52(2): 441-463.

DOI：10.1007/s10910-013-0271-3

• Electrochemical systems
• Second law of thermodynamics
• Constitutive equations
• Non-equilibrium thermodynamics

This work focuses on formulating constitutive models for the bulk and double layer regions of an electrochemical system based on the fundamentals of modern continuum thermodynamics. Particularly, the constitutive models proposed accounting for transport phenomena in electrochemical systems by emphasizing the possibility of cross-coupling between two or more phenomena. Upon deriving a set of thermodynamic restrictions from the Muller-Liu approach of the second law of thermodynamics and axioms of constitutive theory, non-equilibrium quantities are examined in detail, and constitutive answers of the bulk and double layer regions are discussed. Moreover, the conditions for the thermodynamic equilibrium are evaluated for each region as well as the occurrence of dissipative mechanisms. Besides offering a proper formulation for non-equilibrium electrochemical systems, the approach described in this work can be easily extended to more complex chemical systems.

• 出版日期2014-2