Hierarchy of equations for the surface tension of solids

Abstract

Of the four main equations in thermodynamics for the surface tension of condensed matter, i.e. the generalized and classical Lippmann equations and the Shuttleworth and Gokhshtein equations, only the classical Lippmann and Gokhshtein equations have been confirmed experimentally. The generalized Lippmann (Couchman–Davidson) equation is considered to be more universal, since three other equations could be derived from it. Although this fact has been widely accepted, it was recently reevaluated in two opposite ways. In the first approach, the experimental verification of the Gokhshtein equation should support the correctness of the generalized Lippmann and Shuttleworth equations. In the second approach, the incompatibility of the Shuttleworth equation with Hermann's mathematical structure of thermodynamics throws doubts upon all its corollaries, including the generalized Lippmann and Gokhshtein equations. However, both of these approaches are here shown to be erroneous, since the Gokhshtein equation cannot be correctly derived from any of the above-mentioned equations, and the opposite is also true: neither the generalized Lippmann nor Shuttleworth equations could be derived from the Gokhshtein equation.

Keywords:

• surface tension of solids
• generalized Lippmann equation
• Shuttleworth equation
• Gokhshtein equations
• thermodynamics

Acknowledgements

This work was started at the Institute of Physical Chemistry of Russian Academy of Sciences and then continued at the Center for Chemical Physics (CCP) of University of Western Ontario, Canada. The author thanks the participants of the CCP Seminar for valuable discussions.