Abstract
A mathematical treatment of the time-dependence of current-density/overpotential curves for the anodic metal dissolution and the cathodic Deposition processes (Me ⇋ Mez+ + ze−) under special conditions is given. The assumption has been made that the surface diffusion of ad-atoms (D, c0) and the transfer reaction (i0, α, z) are simultaneously rate-determining and that parallel “growth step lines” at a distance 2l (spiral growth on screw dislocations) and a dense concentration of kink sites—for which the equilibrium concentration of ad-atoms c0 always exists—are present. The potentiostatic step η → η* which includes the charging curve 0 → η and the discharge curve η* → 0 is treated through solving the partial differential equation for the surface diffusion with the required initial and boundary values. The theory of Fleischmann and Thirsk has thus been improved upon.An expanded and general definition of crystallization overpotential ηk, is given along with a discussion of the relationship between the total overpotential η and the crystallization overpotential ηk. The experimental determination of crystallization overpotential is further discussed.
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