The role of the critical compressibility factor in the equation of state for the critical fluid

Based on the literature data of PVT measurements, the amplitudes of the equations of the critical isotherm D0(Zk), the critical isochore Г0(Zk), the phase boundaries В0(Zk) are expressed in terms of the critical factor of compressibility of the substance Zk=PkVk/RTk in the entire fluctuation region near the critical point. By doing so, a phenomenological method has been used for calculating the values of the critical exponents of the fluctuation theory of phase transitions based on the introduction of small parameters into the equations of the fluctuation theory. It has been shown that, within the limits of the PVT measurement errors, these dependences D0(Zk) and В0(Zk) on the compressibility factor are linear, and Г0 practically does not depend on the compressibility factor Zk. The relationship of these amplitudes with the amplitudes a and k of the linear model of the system of parametric scale equations of state of substance near the critical point has been established. It has been shown that the dependences k(Zk) and а(Zk) are also linear in the entire fluctuation region near the critical point. The obtained dependences k(Zk) and а(Zk) agree with the known relationship between the amplitudes of the critical isotherm D0(Zk), critical isochore Г0(Zk), phase boundaries В0(Zk) Aerospace Institute of the National Academy of Sciences of Ukrainewithin the framework of the system of parametric scaling equations. The relations а(Zk), k(Zk) make it possible, on the basis of a linear model of the system of parametric scale equations of state of substance, to determine such important characteristics of the critical fluid as the temperature and field dependences of the correlation length Rc(T,m) and the fluctuation part of the thermodynamic potential Ф(T,m) in the entire fluctuation region near the critical point. Then, based on the form of the fluctuation part of the thermodynamic potential Ф(T,m)~Rc(T,m)-3, the results obtained allow one to calculate the field and temperature dependences of the thermodynamic quantities for a wide class of molecular liquids in the close vicinity of the critical point (DP<10-3, Dr<10-2, t<10-4), where precision experiments are significantly complicated, and its can also be used when choosing the conditions for the most effective practical application of the unique properties of the critical fluid in the newest technologies.

Thermodynamic Derivation of Scaling at the Liquid–Vapor Critical Point

With the use of thermodynamics and general equilibrium conditions only, we study the entropy of a fluid in the vicinity of the critical point of the liquid–vapor phase transition. By assuming a general form for the coexistence curve in the vicinity of the critical point, we show that the functional dependence of the entropy as a function of energy and particle densities necessarily obeys the scaling form hypothesized by Widom. Our analysis allows for a discussion of the properties of the corresponding scaling function, with the interesting prediction that the critical isotherm has the same functional dependence, between the energy and the number of particles densities, as the coexistence curve. In addition to the derivation of the expected equalities of the critical exponents, the conditions that lead to scaling also imply that, while the specific heat at constant volume can diverge at the critical point, the isothermal compressibility must do so.