电化学（天津大学） Ch_4_thermo_May_2010.pdf

Chapter 4: Thermodynamics of Electrochemical Systems 1. Gibbs free energy defining the spontaneous direction of chemical reactions 2. Chemical potential, the Gibbs equation and equilibria 3. Activity of ions 4. Electrode standard potentials 5. The Nernst equation 6. Pourbaix diagrams, region of aqueous electrochemistry and corrosion 7. Concentration cells 8. Alloy plating 9. Heat of electrochemical reactions 10. Electrodes of the second kind 11. Reference electrodes 12. Liquid Junction potentials 4-1 Chapter 4: Thermodynamics of Electrochemical Systems Thermodynamics is the study of equilibria states. Thus, it provides us information on systems which do not carry current. Thermo applies also to pseudo-steady states, i.e., systems whose response time is faster (shorter) than the imposed change (perturbation), and therefore if the reaction is fast, thermo will still apply. However, electrochemical systems are often characterized by sluggish electrode kinetics and slow diffusion, hence; one should apply themodynamic analysis with care to such systems, since it can be misleading. Accordingly, thermo indicates that we cannot plate zinc out of acidic solutions, the lead acid battery cannot exist, and that we cannot plate InSb, GaAs and other compounds from aqueous solutions – all of which are wrong. Nonetheless, thermo provides the ‘base line’ – i.e., the ideal or the basis from which we start to analyze our system. This relates primarily to the standard potential, direction of spontaneous reactions, energy content in chemicals, etc. We focus our discussion on electrochemical systems, i.e., systems involving ionic species in contact with electrodes. Energy Expressions used in thermo:  G = Gibbs Free energy  A = Helmholtz free energy We can determine the change in Gibbs Free energy of a system undergoing