Theory of Solutions. II. Osmotic Pressure Virial Expansion and Light Scattering in Two Component Solutions

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Abstract
The method of the first paper (I) of this series can be used to provide a rigorous but relatively simple derivation of the McMillan‐Mayer osmotic pressure virial expansion and alternative expressions for the virial coefficients Bn. Exact relations are derived relating the Bn to the constant pressure coefficients Cn of Paper I. The initial slope in the usual plot (Hc/τ against c) of light scattering data obtained at constant p is shown to be 2B2—3v̄2°+b11+refrac tive index terms (where b11 is a cluster integral for solvent‐solute interaction) and not 2B2, as usually assumed. For hard spheres, this correction is very significant but it is not important if, as is usually the case, the effective solute size for intersolute interactions is large compared with the volume actually occupied by a solute molecule.

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