Right and wrong near critical endpoints

The implications of convexity (or thermodynamic stability) for isothermal density (or composition) phase diagrams near critical endpoints are investigated. In particular, Schreinemakers' rules for the geometry of three coexisting phases in a space of densities are refined and extended physically to apply at and in the vicinity of a critical endpoint. Seemingly plausible phase diagrams are presented which violate the extended rules (and, in most cases, the Second Law of Thermodynamics). The requirements of convexity, supplemented for Ising-related systems by the Griffiths-Kelly-Sherman inequalities, also restrict the signs of important expansion coefficients of thermodynamic scaling functions for criticality and provide bounds on universal critical amplitude ratios. (C) 2002 American Institute of Physics.