Maxwell and van der Waals Revisited

Abstract

We utilize a modern continuum mechanic framework to reconsider an old problem for fluid interfaces, also addressed by Maxwell and van der Waals. We prove that their results need not be valid necessarily. This conclusion is arrived at as a consequence of questioning the existence of thermodynamic potentials and the validity of usual thermodynamic relations within unstable (spinodal) regions. One central result is that Maxwell's equal area rule needs not be valid and certain statistical models are shown to be internally inconsistent. Prescise conditions for the validity of Maxwell's rule and the variational theory of van der Waals established in terms of the coefficients defining the interfacial stress.