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Electrochemistry and Corrosion on Homogeneous and Heterogeneous Metal Surfaces

  • William H. Smyrl
Part of the Comprehensive Treatise of Electrochemistry book series (AN, volume 4)

Abstract

The driving force for a reaction is the change in Gibbs free energy, AG, for reactants to products. Mathematically this may be expressed by
$$ \Delta G = \mathop{\sum }\limits_{{products}} G - \mathop{\sum }\limits_{{reac\tan ts}} G $$
(1)
The summation signs are used as a general notation to indicate that all reactants and products are included in the calculation. From the nature of the free energy function, this calculation applies to initial (reactants) and final (product) states, and is independent of intervening states. The reaction may be investigated under controlled reversible conditions such as in an electrochemical cell, or under irreversible conditions such as in corrosion, and the same total free energy change (ΔG) will be appropriate. A quite general predictive capability may be applied to specific corrosion reactions since all the available thermodynamic data may be used for corrosion calculations directly. This enables the position of final equilibrium of the corrosion system to be established. The thermodynamic calculations have the limitation that no information of the rate of the reaction is provided, only what the final state will be for the process. Another limitation of the thermodynamic treatment is found when there are multiple reactions in a corrosion system but none are dominant, so that the final state is not well known. The limitations will not be described further here, but the influence of kinetics on corrosion behavior is significant and is the subject of the remaining sections. However, this section will briefly describe the sources of thermodynamic data and procedures for using it, since this remains a powerful resource despite the limitations.

Keywords

Corrosion Rate Corrosion Potential Corrosion Current Density Cathodic Reaction Cathodic Protection 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© Springer Science+Business Media New York 1981

Authors and Affiliations

  • William H. Smyrl
    • 1
  1. 1.Sandia LaboratoriesAlbuquerqueUSA

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