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Since the data required to produce these are experimentally more readily accessible, the diagrams based on the Gibbs free energy are more commonly in use, and will be described in some detail here (Grunenberg et al. 1996). The utility of these diagrams is that they contain a great deal of information in a compact form, and provide a one page visual and readily interpretable summary of what can be complex interrelationships among polymorphic modifications. As their utility is recognized these diagrams should become more widely used for the characterization of polymorphic systems and the phase relationships among various polymorphs (Henck and Kuhnert-Brandst¨atter 1999).

1992; Sato and Suzuki 1986). g. Keller and Cheng 1998; Lotz 2000; Rastogi and Kurelec 2000). g. Calleja et al. 1993; Chunwachirasiri et al. 2000), which of course is one of the driving forces for the development of new polymeric materials. Although not referenced specifically, many of the principles and examples presented in subsequent chapters apply equally well to many of the polymorphic molecular systems. 2 Fundamentals Of course, one cannot ignore the physics, and, in particular, one has to pay due respect to thermodynamic considerations .

The enthalpies of transition ( Ht ) or fusion ( Hf ) appear at the corresponding temperatures as the vertical differences between the appropriate H curves. The energy vs temperature diagram for a monotropic relationship between two polymorphs is shown in Fig. 5. In this case, however, the free energy curves do not cross at a temperature below the two melting points. Hliq Energy HII HI GII GI Gliq 0 mpII mpI Temperature [K] Fig. 5 Energy vs temperature (E/T ) diagram for a monotropic dimorphic system.

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An introduction to crystal chemistry by Robert Crispin Evans

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