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Defying the Gibbs Phase Rule: Evidence for an Entropy-Driven Quintuple Point in Colloid-Polymer Mixtures
V F D Peters1, M Vis1,2, Á González García1,3
1Laboratory of Physical Chemistry, Department of Chemical Engineering and Chemistry & Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, Netherlands.
Abstract:
Using a minimal algebraic model for the thermodynamics of binary rod-polymer mixtures, we provide evidence for a quintuple phase equilibrium; an observation that seems to be at odds with the Gibbs phase rule for two-component systems. Our model is based on equations of state for the relevant liquid crystal phases that are in quantitative agreement with computer simulations. We argue that the appearance of a quintuple equilibrium, involving an isotropic fluid, a nematic and smectic liquid crystal, and two solid phases, can be reconciled with a generalized Gibbs phase rule in which the two intrinsic length scales of the athermal colloid-polymer mixture act as additional field variables.
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