Thermoosmosis of a near-critical binary fluid mixture: a general formulation and universal flow direction

TL;DR

This paper develops a theoretical framework for thermoosmosis in near-critical binary fluid mixtures, deriving formulas for flow direction and magnitude based on a coarse-grained free-energy approach, extending classical results.

Contribution

It introduces a universal formulation for thermoosmosis in near-critical binary mixtures, predicting flow direction independent of component adsorption, extending previous isothermal transport models.

Findings

Flow direction is opposite to temperature gradient near the lower critical point.

Derived explicit formula for thermal force density in adsorption layers.

Predicted universal flow behavior regardless of component adsorption.

Abstract

We consider a binary fluid mixture, which lies in the one-phase region near the demixing critical point, and study its transport through a capillary tube linking two large reservoirs. We assume that short-range interactions cause preferential adsorption of one component on the tube's wall. The adsorption layer can become much thicker than the molecular size, which enables us to apply hydrodynamics based on a coarse-grained free-energy functional. For linear transport phenomena induced by gradients of the pressure, composition, and temperature along a cylindrical tube, we obtain the formulas of the Onsager coefficients to extend our previous results on isothermal transport, assuming the critical composition in the middle of each reservoir in the reference equilibrium state. Among the linear transport phenomena, we focus on thermoosmosis -- mass flow due to a temperature gradient. We explicitly derive a formula for the thermal force density, which is nonvanishing in the adsorption layer and causes thermoosmosis. This formula for a near-critical binary fluid mixture is an extension of the conventional formula for a one-component fluid, expressed in terms of local excess enthalpy. We predict that the direction of thermoosmotic flow of a mixture near the upper (lower) consolute point is the same as (opposite to) that of the temperature gradient, irrespective of which component is adsorbed on the wall. Our procedure would also be applied to dynamics of a soft material, whose mesoscopic inhomogeneity can be described by a coarse-grained free-energy functional.