# Relativity, thermodynamics, and cosmology by Richard C. Tolman

By Richard C. Tolman

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6(a), the stability criterion, eq. (83) or eq. (84), is violated in the region between B and C in Fig. 6(b). The system then phase-separates in the region between A and D, keeping B / xB = 0, saving the system from violating eq. (83). The region between A and B and that between C and D are meta-stable. While eq. (83) is satisfied in these regions, the value of G = nB B + nW W can be shown to be larger than that for the sum of two separate phases. Similar to the Maxwell construction for 44 Fig. II-6(a) to II-6(b) (µ BE - µ B*) or RT ln(x B) µ BE - µ B* 0 RT ln(x B) (a) 0 1 xB Fig.

The excess partial molar enthalpy of 2-butoxyethanol (BE) in BE−H2 O at 25 C. The open circles are the measured data by Siu & Koga (1989). The line is calculated by the foursegment fit by Douheret et al. (1989). Broken line is calculated using the Abbott-van Ness fitting, E eq. (III-3). Clearly both fittings are not satisfactory for calculating HBE , although the fit for HmE looks almost acceptable (see Fig. III – 3). If we titrate W instead of B, we obtain HWE . Fig. III-6 shows the results of such E measurements for 2-butoxyethanol BE −H2 O at 25 C, HBE , the excess partial molar E enthalpy of BE.

Editor-in-chief), Copyright (2005), John Wiley & Sons. however, the amount of the i-th component, ni , must be perturbed by a small but finite amount ni and the resulting change in the excess enthalpy, H E is determined at the constant pressure. This corresponds to approximating the slope of the tangent at P with the slope of the cord QR in Fig. 4. The goodness of this approximation could be checked by reducing the size of ni and seeing if the resulting quotient H E / ni converges to a constant value.