Fluidity: a general theory.
The equation varphi = B(V - V(o))/V(o), which reproduces the fluidity of simple liquids accurately over ranges between freezing and boiling points, is here shown to hold to pressures of at least 500 atm, and nearly to critical volumes. Fluidity can vary continuously above the critical region into that of compressed gas, where the parameter B becomes a function of temperature.The parameter V(o) is a "corresponding states" fraction of the critical molal volume. It is identical with the molal volume of the solid only in cases where molecules are free to rotate as they do in the liquid.Parameter B is a measure of the extent to which the external momentum that produces viscous flow is absorbed by the molecules of the liquid. Such damping can result from molecular mass, e.g., Ne, Ar, Kr; flexibility, normal alkanes; or rotational inertia, SiBr(4) against SiCl(4).
Department of Chemistry, University of California, Berkeley, Calif. 94720.
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Hildebrand
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Lamoreaux