Equations of state virial

The macroscopic dense gas modeling approaches include van der Waals family of equation of states, virial family of equation of states, and non-classical approaches. The mo-lecular/theoretical approaches and considerations contribute not only to more comprehensive models but also provide insight bringing forth sound parameters/terms to the macroscopic models. Computer simulation (molecular) can also be used to directly compute phase behavior wifli some success. The virial family of equation of states finds limited use in supercritical applications due to the necessity for a large number of terms and... 

Small molecules versus macromolecules Kinetic representation of pressure Derivation of ideal gas law PT diagram of small molecule pure substance PT diagram of polymer van der Waals cubic equation of state Virial equation of state... 

This chapter presents a general method for estimating nonidealities in a vapor mixture containing any number of components this method is based on the virial equation of state for ordinary substances and on the chemical theory for strongly associating species such as carboxylic acids. The method is limited to moderate pressures, as commonly encountered in typical chemical engineering equipment, and should only be used for conditions remote from the critical of the mixture. 

Numerous empirical equations of state have been proposed but the theoretically based virial equation (Mason and Spurling, 1969) is most useful for our purposes. We use this equation for systems which do not contain carboxylic acids. 

The virial equation of state is a power series in the reciprocal molar volume or in the pressure ... 

This chapter uses an equation of state which is applicable only at low or moderate pressures. Serious error may result when the truncated virial equation is used at high pressures. 

The Virial Equation of State, Pergamon Press, Oxford (1969)... 

Enthalpies are referred to the ideal vapor. The enthalpy of the real vapor is found from zero-pressure heat capacities and from the virial equation of state for non-associated species or, for vapors containing highly dimerized vapors (e.g. organic acids), from the chemical theory of vapor imperfections, as discussed in Chapter 3. For pure components, liquid-phase enthalpies (relative to the ideal vapor) are found from differentiation of the zero-pressure standard-state fugacities these, in turn, are determined from vapor-pressure data, from vapor-phase corrections and liquid-phase densities. If good experimental data are used to determine the standard-state fugacity, the derivative gives enthalpies of liquids to nearly the same precision as that obtained with calorimetric data, and provides reliable heats of vaporization. 

VPLQFT is a computer program for correlating binary vapor-liquid equilibrium (VLE) data at low to moderate pressures. For such binary mixtures, the truncated virial equation of state is used to correct for vapor-phase nonidealities, except for mixtures containing organic acids where the "chemical" theory is used. The Hayden-0 Connell (1975) correlation gives either the second virial coefficients or the dimerization equilibrium constants, as required. 

IF BINARY SYSTEM CONTAINS NO ORGANIC ACIDS. THE SECOND VIRTAL coefficients ARE USED IN A VOLUME EXPLICIT EQUATION OF STATE TO CALCULATE THE FUGACITY COEFFICIENTS. FOR ORGANIC ACIDS FUGACITY COEFFICIENTS ARE PREDICTED FROM THE CHEMICAL THEORY FOR NQN-IOEALITY WITH EQUILIBRIUM CONSTANTS OBTAINED from METASTABLE. BOUND. ANO CHEMICAL CONTRIBUTIONS TO THE SECOND VIRIAL COEFFICIENTS. 

Real gases follow the ideal-gas equation (A2.1.17) only in the limit of zero pressure, so it is important to be able to handle the tliemiodynamics of real gases at non-zero pressures. There are many semi-empirical equations with parameters that purport to represent the physical interactions between gas molecules, the simplest of which is the van der Waals equation (A2.1.50). However, a completely general fonn for expressing gas non-ideality is the series expansion first suggested by Kamerlingh Onnes (1901) and known as the virial equation of state ... 

The same result can also be obtained directly from the virial equation of state given above and the low-density fonn of g(r). B2(T) is called the second virial coefficient and the expansion of P in powers of is known as the virial expansion, of which the leading non-ideal temi is deduced above. The higher-order temis in the virial expansion for P and in the density expansion of g(r) can be obtained using the methods of cluster expansion and cumulant expansion. 

A2.3.2.2 EQUATIONS OF STATE, THE VIRIAL SERIES AND THE LIQUID-VAPOUR CRITICAL POINT... 

It is detemrined experimentally an early study was the work of Andrews on carbon dioxide [1], The exact fonn of the equation of state is unknown for most substances except in rather simple cases, e.g. a ID gas of hard rods. However, the ideal gas law P = pkT, where /r is Boltzmaim s constant, is obeyed even by real fluids at high temperature and low densities, and systematic deviations from this are expressed in tenns of the virial series ... 

Figure A2.3.4 The equation of state P/pkT- 1, calculated from the virial series and the CS equation of state for hard spheres, as a fimction of q = where pa is the reduced density.

Figure A2.3.10 Equation of state for hard spheres from the PY and FfNC approximations compared with the CS equation (-,-,-). C and V refer to the compressibility and virial routes to the pressure (after [6]).

The CS pressures are close to the machine calculations in the fluid phase, and are bracketed by the pressures from the virial and compressibility equations using the PY approximation. Computer simulations show a fluid-solid phase transition tiiat is not reproduced by any of these equations of state. The theory has been extended to mixtures of hard spheres with additive diameters by Lebowitz [35], Lebowitz and Rowlinson [35], and Baxter [36]. 

Virial equation represents the experimental compressibility of a gas by an empirical equation of state ... 

The volumetric properties of fluids are conveniently represented by PVT equations of state. The most popular are virial, cubic, and extended virial equations. Virial equations are infinite series representations of the compressibiHty factor Z, defined as Z = PV/RT having either molar density, p[ = V ), or pressure, P, as the independent variable of expansion ... 

The virial equations are unsuitable forhquids and dense gases. The simplest expressions appropriate (in principle) for such fluids are equations cubic in molar volume. These equations, inspired by the van der Waals equation of state, may be represented by the following general formula, where parameters b, 9 5, S, and Tj each can depend on temperature and composition ... 

Cubic equations, although simple and able to provide semiquantitative descriptions of real fluid behavior, are not generally useful for accurate representation of volumetric data over wide ranges of T and P. For such appHcations, more comprehensive expressions with large numbers of adjustable parameters are needed. 7h.e simplest of these are the extended virial equations, exemplified by the eight-constant Benedict-Webb-Rubin (BWR) equation of state (13) ... 

Although PVT equations of state are based on data for pure fluids, they are frequently appHed to mixtures. 7h.e virial equations are unique in that rigorous expressions are known for the composition dependence of the virial coefficients. Statistical mechanics provide exact mixing rules which show that the nxh. virial coefficient of a mixture is nxh. degree in the mole fractions ... 

Mixing mles for the parameters in an empirical equation of state, eg, a cubic equation, are necessarily empirical. With cubic equations, linear or quadratic expressions are normally used, and in equations 34—36, parameters b and 9 for mixtures are usually given by the following, where, as for the second virial coefficient, = 0-. 

SemiempiricalRelationships. Exact thermodynamic relationships can be approximated, and the unknown parameters then adjusted or estimated empirically. The virial equation of state, tmncated after the second term, is an example of such a correlation (3). 

The PirialExpansion. Many equations of state have been proposed for gases, but the virial equation is the only one having a firm basis in theory (1,3). The pressure-expHcit form of the virial expansion is... 

Virial Equations of State The virial equation in density is an infinite-series representation of the compressiDility factor Z in powers of molar density p (or reciprocal molar volume V" ) about the real-gas state at zero density (zero pressure) ... 

The application of cubic equations of state to mixtures requires expression of the equation-of-state parameters as func tions of composition. No exact theory like that for the virial coefficients prescribes this composition dependence, and empirical mixing rules provide approximate relationships. The mixing rules that have found general favor for the Redhch/Kwong equation are ... 

Gamma/Phi Approach For many XT E systems of interest the pressure is low enough that a relatively simple equation of state, such as the two-term virial equation, is satisfactoiy for the vapor phase. Liquid-phase behavior, on the other hand, may be conveniently described by an equation for the excess Gibbs energy, from which activity coefficients are derived. The fugacity of species i in the liquid phase is then given by Eq. (4-102), written... 

Evaluation of 9 is usually by Eq. (4-196), based on the two-term virial equation of state, but other equations, such as Eq. (4-200), are also applicable. The activity coefficient Jj is evaluated by Eq. (4-119), which refates In Jj to G /RT as a partial proper. Thus, what is required for the hquid phase is a relation between G /BT and composition. Equations in common use for this purpose have already been described. 

The two values kp and k are usually not very different, and kp is not strongly composition dependent. Nevertheless, the quadratic dependence of Z — a/RT) on composition indicated by Eq. (4-305) is not exactly preserved. Since this quantity is not a true second virial coefficient, only a value predicted by a cubic equation of state, a strict quadratic dependence is not required. Moreover, the composition-dependent kp leads to better results than does use of a constant value. 

Other volume-explicit equations of state are sometimes required, such as the compressibility equation V = zRT/P or the truncated virial equation V= (1 -i- B P)RT/P. The quantities z a.ndB are not constants, so some land of averaging will be required. More accurate equations of state are even more difficult to use but are not often justified for kinetic work. 

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