Debye Model and the Primitive Model for Electrolyte Solutions

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Abstract
It is shown that the free energy terms arising from charge‐charge interactions in the Debye theory and in modern statistical‐mechanical treatments of electrolyte solutions can be brought into close agreement when it is borne in mind that the ``ionic diameter'' is an adjustable parameter of both theories. By considering the case of an ideal nonelectrolyte solution, it is shown that the imperfect gas (co‐volume) term in the modern theories is an artefact of the ``primitive model'' which cannot validly be included in comparisons with experimental data.