On the extrapolation behavior of empirical equations of state

Generally, the extrapolation behavior of empirical equations of state is regarded as poor, but it can be shown that state-of-the-art equations of state yield reliable results well beyond the range where they were fitted to experimental data. During the past years a new generation of highly accurate equations of state which yield reasonable results even up to the limits of chemical stability of the considered substances has been developed. In this paper, the positive influence of recent methods for the development of equations of state on their extrapolation behavior is discussed. The influence of the mathematical structure on the extrapolation characteristics is analyzed and requirements for a reasonable behavior up to extreme temperatures and pressures are formulated. As possible ways for assessment of the extrapolation behavior of an equation of state, comparisons with experimental data at very high pressures and temperatures and with theoretically predicted features of the so-called “ideal curves” of a fluid are discussed. Finally, the current status of our knowledge of the extrapolation behavior of empirical equations of state is summarized and its shortcomings are pointed out.

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