Abstract
The thermodynamic stability limits of specific adsorption at the polarized liquid metal/ electrolyte solution interface are studied. Here the reversible starting and disappearance of the electroadsorption effects at a threshold potential are revealed, which are the result of Gibbs stability violation. The stability limits are determined by the bifurcation manifold of the critical states for which determinant of matrix of a second differential of the surface pressure equals zero. The equations of the critical states are equivalent to the spinodal equations used in the theory of phase transitions. The conception developed beneath will help provide to interpretate the anomalies of electrocapillary effects through the catastrophe theory.
Highlights
OverviewDifferent kinds of the surface phenomena can be examined at the liquid-liquid interface when one of they serves as an idealy polarisable electrode
The interface characteristics undergo qualitative changes, permitting to presume a peculiar wetting transition
Where q = q − q0 is a change of charge density on an electrode in a surfactant electrolyte, E is electrode potential mesuring relative cation reversible reference electrode, Γ is an adsorption of a surfactant component at the interface and μ is its chemical potential
Summary
Different kinds of the surface phenomena can be examined at the liquid-liquid interface when one of they serves as an idealy polarisable electrode. The explanation to the observed class of phenomena should be sought in the interconnection between the problems of the solution components’ surface activity and adsorptive phases’ stability at the polarized interface. The problems of stability of surface phases were studied in connection with wetting transitions [4,10] within the framework of the model functional’s methods. The matter of stability of surface phases on the polarized interface of the liquids has its own specificity, connected with the main role of electrode potential. The purposes of this research are to carry on an investigation of the ranges of stability of an adsorptive state at the polarized interface of metal - electrolyte solution, to examine the interface tension and other measured qualities close to them, to establish the connection with the wetting transitions, and to formulate the proper criteria
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