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In binary systems of hydrogen and hydrocarbons, the fluid-phase thermodynamic behavior is unique in having the divergence of the critical curves to a high pressure region. The thermodynamic properties of the binary systems including hydrogen with methane, ethane, propane, and carbon dioxide were calculated from a Peng-Robinson equation of state (PR EOS). The mixing parameter of the present EOS has a functional form of temperature generalized by the critical temperatures of the hydrocarbons and carbon dioxide. Based on the corresponding states principle, the coefficients of the parameter were determined with a non-linear least squares fitting to the experimental critical points of the mixtures. The developed PR EOS shows good agreement with the experimental data of not only the critical points but also the phase equilibria. In the hydrogen binary systems, retrograde condensation is expected. The volumetric and enthalpy changes in this process were simulated for a hydrogen + carbon dioxide mixture of 0.55 mole fraction using the PR EOS at 270 K.

Thermodynamic Behavior of Hydrogen Binary Systems with Critical Curve Divergence and Retrograde Condensation