Abstract
The relationship between the work function of the substrate+adsorbate system and the underpotential shift is derived from a thermodynamic argument. An alternative explanation of the correlation formulated in the literature between the underpotential shift and the work function difference of the metals involved is proposed. A simple model is used to illustrate the meaning of the equations derived. Abrupt adsorption-desorption behaviour is predicted for those electrochemical systems where the work function shows a pronounced minimum as a function of the coverage, provided that this is a first-order contribution to the chemical potential of the system.
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