A treatment of solvent effects in the potential theory of electrolyte solutions

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Abstract
The potential theory of electrolyte solutions is extended to non-ideal solvents using the Kirkwood hierarchy of integral equations. Two closures are considered in the statistical mechanical analysis. The first closure, which is equivalent to that of Debye and Hückel, implies a dielectric constant of 1 + x (x = 4π∑σμσ 2ρσ kT, μσ dipole moment, ρσ dipole number density) and Debye shielding in the ion-dipole, dipole-dipole potentials of mean force. The second closure leads to the Onsager expression for the dielectric constant and predicts that the primitive model potential of mean force at infinite solute dilution is modified by a damped oscillatory term. Within this closure the analysis given here is restricted to those values of x such that Onsager's dielectric constant is less than 5·603.

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