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We derive the phase diagrams and spinodals of binary liquid systems with anisotropic interactions, such as hydrogen‐bonded molecules. The work is based on the four‐particle cluster variation method, using a different potential for different contact points. It is shown that the introduction of a cluster larger than previously used by Barker and Fock, leads to a considerable improvement in the shape of the phase diagram and avoids some of the difficulties encountered in their calculation. Phase diagrams are displayed for various choices of the parameters: the number of contact points, the interaction potential, and the order of the approximation.

Coexistence and spinodal curves in directionally bonded liquids using the four-cluster approximation