Predicting miscibility gaps in reciprocal liquids

Abstract

There is a strong correlation between the appearance of liquid miscibility gaps in reciprocal phases and the standard Gibbs energy of the reciprocal reaction, Δ°G. The associate solution model does not predict such a correlation but the two-sublattice model does. Physically, the critical temperature of a reciprocal miscibility gap is related to Δ°G and is also affected by the presence of short range order. The latter effect can be estimated from Δ°G using the conformal solution theory which was developed for reciprocal systems with univalent ions. In that approximation the short range order effect is described with a reciprocal parameter. The estimate of that parameter for systems with different valencies is now discussed. The calculated phase diagram may be reasonable for low values of the reciprocal parameter, relative to Δ°G, but is not satisfactory for large values because two asymmetric miscibility gaps will appear when the critical temperature has been suppressed to 3 4 of the value predicted without a reciprocal term. An alternative form of the reciprocal term is now proposed, which does not produce the splitting into two miscibility gaps.