A generalized enthalpy-based equation of state, which includes thermal electron excitations and non-equilibrium thermal energies, is formulated for binary solid and porous mixtures. Our approach gives rise to an extra contribution to mixture volume, in addition to those corresponding to average mixture parameters. This excess term involves the difference of thermal enthalpies of the two components, which depend on their individual temperatures. We propose to use the Hugoniot of the components to compute non-equilibrium temperatures in the mixture. These are then compared with the average temperature obtained from the mixture Hugoniot, thereby giving an estimate of nonequilibrium effects. The Birch–Murnaghan model for the zero-temperature isotherm and a linear thermal model are then used for applying themethod to severalmixtures, including one porous case. Comparison with experimental data on the pressure–volume Hugoniot and shock speed versus particle speed shows good agreement.