Thermodynamics of Electrochemical Reactions

The thermodynamics of electrochemical reactions can be understood by considering the standard electrode potential, the potential of a reaction under standard conditions of temperature and pressure where all reactants and products are at unit activity. Table 1 Hsts a variety of standard electrode potentials. The standard potential is expressed relative to the standard hydrogen reference electrode potential in units of volts. A given reaction tends to proceed in the anodic direction, ie, toward the oxidation reaction, if the potential of the reaction is positive with respect to the standard potential. Conversely, a movement of the potential in the negative direction away from the standard potential encourages a cathodic or reduction reaction. 

Refs. [i] Parsons R (1974) Pure Appl Chem 37 503 [ii] Inzelt G (2006) Standard potentials. In Bard AJ, Stratmann M, Scholz F, Pickett Cf (eds) Inorganic electrochemistry. Encyclopedia of electrochemistry, vol. 7a. Wiley, Weinheim, chap 1 [in] Bard AJ, Faulkner LR (2001) Electrochemical methods, 2nd edn. Wiley, New York, chap 2, pp 52-53 [iv] Scholz F (2002) Thermodynamics of electrochemical reactions. In Scholz F (ed) Electroanalytical methods. Springer, Berlin... 

This chapter explains the fundamental principles and applications of electrochemical cells, the thermodynamics OF electrochemical reactions, and the cause and prevention of corrosion BY ELECTROCHEMICAL MEANS. SOME SIMPLE ELECTROLYTIC processes and the QUANTITATIVE ASPECTS OF ELECTROLYSIS ARE ALSO discussed. 

Scholz F (2010) Thermodynamics of electrochemical reactions. In Scholz F (ed) Electroanalytical methods, 2nd edn. Springer, Berlin, pp 11-31... 

However, this problem does not affect the thermodynamics of electrochemical reactions. The free energy of the solvated proton can be obtained from a thermodynamic argument, that of the adsorbed hydrogen atom from standard DFT, with or without a few water molecules. In this way, the free energy balance for the reaction can be calculated, and from this, the equilibrium potential can be obtained. The same principle can be employed for complicated reactions such as oxygen reduction, which contain many possible intermediate states. Chemical steps not involving charge transfer, such as the recombination reaction H2, can be treated by pure DFT, and for... 

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