The derivation of enthalpies, entropies and free energies of fusion an
d transition from DSC curves is discussed. Although the apparent locat
ion of a thermal event is much influenced by rate effects, isothermal
enthalpy changes are readily obtained by simple extrapolations. The co
rresponding entropies are always flawed by departures from reversibili
ty and data must be corrected by forcing data to obey the condition th
at DELTAG = 0 at a first-order transition. Free energy curves may then
be used to define the relative stabilities of different structures. P
rocedures are illustrated by examples from a series of liquid crystal-
forming materials that show widespread solid-state polymorphism.