Communications - Correlation Between Excess Entropy and Enthalpy Functions

QUITE generally an increase in the temperature tends to bring a system closer to ideality. It is reasonable as a first approximation to consider that the excess free energy will vary linearly with the temperature, or: where t may be defined as the "characteristic temperature" of the solution, or the temperature at which the system would become ideal if the results at T were linearly extrapolated. It must be emphasized that consideration of this hypothetical property is an appeal to intuition rather than an established physical concept. The order of magnitude of 7 for dilute solutions will depend on the nature of the solvent; a value of 3000° + 1000°K may be suggested for ordinary metallic solutions. In terms of free energy, entropy, and enthalpy first-order interaction coefficients, differentiation of the above equations with respect to composition leads to The concept of t offers a simple and plausible interpretation of Chipman and corrigan's3 recent empirical correlation between and a for a number of groups of ternary systems 1-24. The authors found that in each group the ratio was approximately constant. The corresponding calculated from their data by Eq. [4] are listed in Table I. The expected order of magnitude is obtained for 7. As noted by Darken,4 if a regular solution is not assumed, thus if utj) # 0, Chipman and Crrigan's results imply that, as T is increased, ultimately changes in sign, Fig. 1. Clearly Eq. [4] is valid only in a limited range of temperatures since at the temperature 7 at which the system becomes ideal not only should become null but also and . Thus, both and are functions of