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Abstract
The excess free energy Aex for solutions of isotopes is discussed. We consider the volume dependence of the free energy and integrate over the concentration weighted molar volume isotope effect, but under the constraint of constant g(r*). The result is significantly different than results from integration along the isothermal equilibrium path employed by previous authors. Both internal and external modes can make important contributions to Aex. This is exemplified by treating solutions of 36Ar/40Ar, C6H6/C6D6, H216O/H218O, and H2O/HDO.
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