Alkyl chains acting as entropy reservoir in liquid crystalline materials.

The roles played by the conformational disordering of alkyl chains in determining the aggregation states of matter are reviewed for liquid crystalline materials from a thermodynamic perspective. Entropy, which is one of the most macroscopic concepts but which has a clear microscopic meaning, provides crucial microscopic information for complex systems for which a microscopic description is hard to establish. Starting from structural implication by absolute (third-law) entropy for crystalline solids, the existence of successive phase transitions caused by the successive conformational melting of alkyl chains in discotic mesogens is explained. An experimental basis is given for the "quasi-binary picture" of thermotropic liquid crystals, i.e., the highly disordered alkyl chains behave like a second component (solvent). A novel entropy transfer between the "components" of a molecule and the resulting "alkyl chains as entropy reservoir" mechanism are explained for cubic mesogens. Copyright 2003 The Japan Chemical Journal Forum and Wiley Periodicals, Inc., Chem Rec 3: 29-39; 2003: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.10046