Viscous and thermodynamic behaviour of glass-forming organic liquids

Abstract

The free energy difference (ΔG) between an undercooled liquid and its corresponding equilibrium solid has been evaluated on the basis of a method involving Taylor series expansion of ΔG around its value at the equilibrium melting temperature. The resultant expression is shown to be capable of correctly estimating ΔG at temperatures as low as the glass transition temperature. The method is then enlarged to obtain the configurational entropy and used in conjunction with the Adam and Gibbs model to derive a novel expression for the viscosity of undercooled liquids. Most commonly used expressions for the temperature dependence of viscosity are shown to be approximations of the equation obtained in this study.