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Using a minimal algebraic model for the thermodynamics of binary rod--polymermixtures, we provide evidence for a quintuple phase equilibrium; an observationthat 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 phasesthat are in quantitative agreement with computer simulations. We argue that theappearance of a quintuple equilibrium, involving an isotropic fluid, a nematicand smectic liquid crystal, and two solid phases can be reconciled with ageneralized Gibbs phase rule in which the two intrinsic length scales of theathermal colloid--polymer mixture act as additional field variables.

Defying the Gibbs Phase Rule: Evidence for an Entropy-Driven Quintuple Point in Colloid-Polymer Mixtures