Fundamentals

Abstract

The physical and structural fundamentals of polymorphism are introduced, including a review of the phase rule and the thermodynamic relations in polymorphs. The latter are used to introduce energy–temperature diagrams, leading to the definition of the concepts enantiotropism and monotropism describing the thermodynamic relationships between and among polymorphs with appropriate examples. The alternate representation of phase diagram in terms of pressure and temperature is also presented. These lead to a number of rules regarding the relationships between polymorphs and ways to understand and predict some important physical properties: the heat-of-transition rule, the heat-of-fusion rule, the entropy-of-fusion rule, the heat-capacity rule, the density rule, and the infrared rule. Structural aspects include the distinction between crystal form and crystal habit and methods for characterizing and comparing structures in polymorphic systems. Current developments are discussed that deal with the ramifications of nanoscale situations on structural concepts and thermodynamic relationships.