Thermodynamics of Interfaces Extended to Nanoscales by Introducing Integral and Differential Surface Tensions
As a system shrinks down in size, more and more molecules are found in its surface region, so surface contribution becomes a large or even a dominant part of its thermodynamic potentials. Surface tension is a venerable scientific concept, Gibbs defined it as the excess of grand potential of an inhomogeneous system with respect to its bulk value per interface area. The mechanical definition expresses it in terms of pressure tensor. So far, it has been believed the two definitions give always the same result. We show that the equivalence can break down for fluids confined in narrow pores. New concepts of integral and differential surface tensions, along with integral and differential adsorptions, need to be introduced for extending Gibbs thermodynamics of interfaces. We derived two generalized Gibbs adsorption equations.
董玮 教授(法国里昂高师)
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