ELSEVIER ‘Fluid Phase Equilibria 148 (1998) 21-47 The evolution of multicomponent systems at high pressures: I. The high-pressure, supercritical, gas—liquid phase transition LF. Kenney * Joint Institute of the Physics of the Earth, Russian Academy of Sciences, Gas Resources, 15333 JFK Boulevard, Suite 160, Houston, TX 77032, USA Received 21 July 1997; accepted 27 January 1998 Abstract ‘The thermodynamic stability of n-octane has been investigated as a function of temperature, pressure, and degree of molecular clustering at supercritical temperatures. At low pressures, the free enthalpy is shown to be always lowest in the unassociated, gas state, and the system is, in that regime, robustly resistant to clustering. At high pressures, the free enthalpy of the unassociated, gas state exceeds that of the clustered, liquid state. At the pressure at which the values of the free enthalpies of the gas and liquid states become equal, the system becomes abruptly unstable, and will then spontaneously cluster into effective ‘cluster-polymers’, and undergo a phase transition to a liquid state. This phenomenon is a geometric effect, and occurs even at supercritical temperatures. The gas-liquid phase transition reported here is closely related to the Alder-Wainwright ‘2as—-solid phase transition, the onset of which is applied to approximate the optimal clustering parameter. This phase transition is of the class of entropically-driven phase transitions, characterized by an increase in spatial order accompanied by an increase in entropy, and manifests an inverted latent heat of transformation, analogous to adiabatic demagnetization, © 1998 Elsevier Science B.V. All rights reserved. Keywords: Theory; Chemical equilibria; Equations of state; Statistical mechanics 1. Introduction: the van der Waals critical state; and the Alder-Wainwright gas-solid phase transition at supercritical temperatures and pressures Approximately 140 years ago, J.D. van der Waals enunciated the first systematic analysis of the phenomenon of gas-liquid phase transitions and the equation of state which bears his name [1]. From his analysis, and directly from the van der Waals equation, follows the prediction of a critical state at specific values of pressure and temperature at which the density of every gas experiences large fluctuations, and for greater values of temperature the gas cannot condense, regardless of how great a * Corresponding author. E-mail: fk@ alum.miteda 0378-3812 /98 /$19.00 © 1998 Elsevier Science B.V. All rights reserved. PII $0378-3812(98)00194-02 ALF. Kenney / Fluid Phase Equilibria 148 (1998) 21-47 pressure might be applied. Every known fluid has indeed been observed to manifest a critical gas-liquid state, as predicted by the van der Waals equation, in the thermodynamic regime of modest temperatures and pressures characteristic of the near-surface of the Earth. Almost all fluids obey also the van der Waals equation of state modestly well in that same thermodynamic regime. However, it deserves to be noted that the predictions of a critical state by the van der Waals equation obtain from its properties as an equation of third degree in the variable of density. Similarly, the apparent prohibition of a phase transition at higher values of density is also a consequence of the cubic properties of that equation, Furthermore, it must be acknowledged that the van der Waals equation is not a fundamental one, nor is it even a phenomenological equation as is, for example, the famous Boltzmann transport equation [2]. The van der Waals equation is no more than an ad hoc statement based upon assumptions which seemed reasonable in 1870, The developments of atomic theory and statistical mechanics, have subsequently shown that the successes of the van der Waals equation obtain by accident from its reasonable approximation to general properties of fluids in regimes of dilute densities and low pressures. Such considerations must compel strong reservations about any suppositive prohibition of a gasliquid phase transition in thermodynamic regimes far outside the experiences which led to the enunciation of the van der Waals equation. Approximately a century later, the first serious, universal failure of the van der Waals prohibition of phase transitions at temperatures higher than that of the critical state was demonstrated by Alder and Wainwright [3-5] and Alder and Hecht [6] in their analysis of the hard-sphere gas whereby they established the existence of a density-dependent phase transition at high pressure and at density approximately 65% of the ‘close-packed’ value. That transition had earlier been suggested by analysis of the Kirkwood equation [7] which also has no solutions at densities higher than that of the Alder-Wainwright transition. The statistical mechanical problem of the hard-sphere gas was subse- quently examined extensively [8-19], and its analytical solution obtained in closed form indepen- dently by Wertheim [20] and Thiele [21], using a general formalism developed by Percus and Yevick (22]. The analysis of the hard-sphere gas applied both by Wertheim and Thiele develops slightly different equations of state depending upon whether the problem is addressed to define explicitly the pressure or the compressibility. However, both solutions are analytic and both give accurate predictions of the Alder-Wainwright results, falling closely each on opposite sides of the observed values. Although the Percus-Yevick procedure contains certain inconsistencies, the Wertheim—Thiele solution was later derived independently and consistently in a much simpler fashion by Reiss [11,23,24,26], Reiss and Tully-Smith [25] and Speedy and Reiss [27] who developed scaled particle theory. The formalism of scaled particle theory is based upon first principles and contains no adjustable parameters. A modified equation of state was developed later by Carnahan and Starling [28] which uses a rational combination of the pressure and compressibility solutions from Wertheim and Thiele and the solution from scaled particle theory, and which fits the observed values of density with good accuracy throughout the domain of that variable to the transition value. The analysis reported here draws upon the extensive literature of the Alder-Wainwright transition, and uses the Camahan-Starling equation throughout. The high-density Alder-Wainwright transition has been interpreted as a gas—solid phase transition That transition depends solely upon the entropic density terms which enter the partition function, and is independent of temperature. For the latter reason, the Alder-Wainwright gas-solid transition may occur in the supercritical regime. It is to be noted that neither of the Wertheim—Thiele equations (‘pressure’ or “compressibility’) predict a gas-liquid phase transition, nor similarly does the Carna-JE, Kenney / Fluid Phase Equilibria 148 (1998) 21-47 23 han-Starling equation. A gas-liquid phase transition is characterized by a vapor-liquid equilibrium line along which the partial derivative of pressure with respect to volume at constant temperature must vanish. Neither the Alder-Wainwright nor the Wertheim—Thiele equation admits a real solution for that constraint of the vapor-liquid equilibrium line. The principal reason why those equations do not predict a gas-liquid phase transition is because each represents the system solely as a gas phase. Both the Wertheim-Thicle and the Carmahan~Starling equations obtain from a restricted partition function in which have been summed only those members of the ensemble which pertain to the gas state. These aspects of the Wertheim-Thiele and the Carnahan-Starling equations are discussed in connection with the supercritical, high-pressure, gas-liquid phase transition in Section 7. In this article, the chemical potential and resulting Gibbs free enthalpy of the real fluid n-octane are examined as functions of temperature, pressure, and degree of molecular clustering. At low or modest pressures, the effects of the entropy are proportional to the temperature which is the dominant variable and determines the evolution of the system. At high pressures, the entropy depends upon the density of the system in a powerfully nonlinear fashion; and in thermodynamic regimes of pressures greater than approximately 10,000 atm, pressure becomes the dominant variable, and temperature relatively unimportant. Such results are consistent with the conclusions both of van der Waals and also of Alder and Wainwright. At low pressures, the entropy of the system is shown to be dominated by the contributions attributable to the molar abundance, or number of particles, and their random motion, which together may be called the entropy of disorder. At high pressures, the entropy is shown to be dominated by contributions attributable to the hard-core repulsive terms in the inter-molecular potential, which may be called the entropy of exclusion. For all temperatures and molar abundances, the entropy of exclusion is always negative, and that of disorder always positive. Therefore, there exists a critical bifurcation pressure below which the system evolves always toward dispersion and above which always toward concentration. These properties will be shown in a following article to be universal for all fluids and the causal agents of a high-pressure, supercritical, first-order, gas-liquid phase transition. Such are responsible also for the phenomena of high-pressure polymerization and agglomeration which will also be discussed in a following article. 2, The quantal partition function, pressure, and chemical potential of a real gas: the formalism of the simplified perturbed hard chain theory (SPHCT) To calculate the chemical potentials, and the entropy of a real gas or liquid in arbitrary regimes of temperature and pressure, it is necessary to have an explicit, general expression for the partition function of the system. The formalism of the simplified perturbed hard chain theory (SPHCT) generates from first-principles, statistical mechanical argument an analytic expression for the canoni- cal partition function, the derivation of which is independent of any specific regime of temperature or density [29-33]. Thereby, the expressions for the pressure and chemical potential of a fluid developed by the SPHCT are similarly valid in any regime of temperature or density, and hold for dense liquids equally as for dilute gases [34], Because the confidence with which any calculation is held depends upon an understanding of the basis for the validity of the formalism from which such was developed, that formalism is briefly reviewed here.