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The stable formation of ionic vacancy in a liquid solution was theoretically examined by means of a mean-field approximation based on Debye-Huckel’s framework. As the process of the vacancy formation, metal deposition from electrolyte solution was adopted, where anions associated with metallic ions adsorbed at electrical double layer were transcribed to the inner wall of the vacancy during the reaction. Then, it was concluded that since the formation energy of the vacancy is cancelled out by the electric work between the charged inner wall and its ionic atmosphere, the vacancy is stably self-organized. In copper deposition from potassium chloride solution and sulfuric acid solution, by measuring the partial molar volumes of the vacancies with gravity electrode, the radius of the vacancy theoretically predicted was experimentally validated.

Theory of Stable Formation of Ionic Vacancy in a Liquid Solution