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By Tolman R.C.

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1). For a fluid described appropriately by such an equation of state, the expressions for the molar internal energy, u, and the molar entropy, s, have the following form [34] u = cv T − a , v s = cv ln T + R ln(v − b) . 28) The heat capacity at constant volume, cv , of the van der Waals fluid does not depend on volume. Employing this result and Eqs. 28), one can obtain a relationship for the chemical potential, µ, which can be expressed generally as µ = u − T s + pv . 29) Then, taking into account the condition of phase equilibrium for liquid and vapor Eq.

A detailed consideration of the critical behavior of systems in the presence of exciting fields is given in Ref. [30]. One can suppose with sufficient foundation that the spatial inhomogeneity of the system near the critical point is not only an accompanying effect of the influence of external fields but an essential feature having a significant impact on the results and determining the return to classical critical indices in the immediate vicinity of the critical point. Taking into account this effect, it is possible to understand the mechanism of the second crossover assuming that a highly correlated fluctuational state of the substance (corresponding to a nonclassical Ising-type behavior) is incompatible with the existence of externally induced strong density gradients.

3)) for the substances shown in Fig. 4 are given: temperature T0 , pressure p∗ , exponent c, mean square errors of the determination of these parameters, σ (p∗ ) and σ (c), and also the values of the initial slope of the melting curves, (dp/dTSL )T0 , calculated by using the Simon approximation. In the last few decades, the possibility was realized to make experimental investigations on crystal–melt phase transitions at pressures above 104 MPa and at temperatures exceeding 1000 K. The application of the above discussed traditional methods of melting temperature measurement using thermocouples is impossible under such conditions since the material of the thermocouple would also melt.

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