Relaxation and Two-dimensional Phase Transitions in the Electrical Double Layer

The excess entropy of formation and the characteristic relaxation times of the electrical double layer at the interface between the metal and electrolyte solution have been determined by the laser temperature jump method, consisting in the measurements of the electrical signal of an electrochemical cell on heating a metallic electrode by nanosecond laser pulses. The combination of the laser temperature jump data and data obtained by electrochemical methods shows that the orientational rearrangement of the solvent monolayer and the adsorption of surfactants occurring when the electrode potential and the solution composition are altered have the character of two-dimensional first- and second-order phase transitions.
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