General continuum analysis of transport through pores. I. Proof of Onsager's reciprocity postulate for uniform pore

Abstract

The nonelectrolyte (Js) and volume (Jv) flux across a membrane is usually described in terms of two equations derived from the theory of irreversible thermodynamics: (see article) where delta c and delta P are the concentration and pressure difference; omega and Lp are the diffuse and hydraulic permeability; and sigma s and sigma v are the reflection coefficients. If Onsager's reciprocity postulate is assumed, it can be shown that signa s and sigma v are equal. This is an important assumption because it allows one to apply the continuum theory relationship between sigma s and the pore radius to experimental measurements of sigma v. In this paper, general continuum expressions for both the Jv (a new result) and Js equation will be derived and the equality of sigma s and sigma v proved. The proof uses only general hydrodynamic results and does not require explicit solutions for the drag coefficients or, for example, the assumption that the solute is in the center of the pore. The proof applys to arbitrarily shaped solutes and any pore whose shape is independent of axial position (uniform). In addition, new expressions for the functional dependence of omega and sigma on the pore radius are derived (including the effect of the particle lying off the pore axis). These expressions differ slightly from earlier results and are probably more accurate.