Kyle, B. G. Phase Equilibrium The Engineering Handbook. Ed. Richard C.

Dorf Boca Raton: CRC Press LLC, 2000

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47
Phase Equilibrium
47.1 Pure-Component Phase Equilibrium 47.2 Phase Equilibrium in Mixtures 47.3 Perspective
The Clapeyron Equation The Clausius-Clapeyron Equation Vapor-Liquid Equilibrium (VLE) Liquid-Liquid Equilibrium (LLE) Solid Liquid Equilibrium (SLE)

Benjamin G. Kyle
Kansas State University

The best way to understand the rationale underlying the application of thermodynamics to phase equilibrium is to regard thermodynamics as a method or framework for processing experimentally gained information. From known properties for the system under study (information), other properties may be determined through the network of thermodynamic relationships. Thus, information about a system can be extended. The thermodynamic framework is also useful for conceptualizing and analyzing phase equilibrium. This allows extrapolation and interpolation of data and the establishment of correlations as well as evaluation and application of theories based on molecular considerations. For the most part, the variables of interest in phase equilibrium are intensive: temperature, pressure, composition, and specific or molar properties. The phase rule determines the number of intensive variables, F, required to define a system containing phases and C components.
F =C +2 (47:1)

The thermodynamic network also contains other intensive variables such as fugacity and the activity coefficient, which are necessary for computational purposes but possess no intrinsic value; they are simply useful thermodynamic artifacts. Specifically, the basis for the thermodynamic treatment of phase equilibrium is the equality of the fugacity of each component in each phase in which it exists.

47.1 Pure-Component Phase Equilibrium

Equilibrium between phases of a pure component can be visualized with the aid of Fig. 47.1, which shows areas in the pressure-temperature (PT) plane labeled S, L, and V and representing conditions where respectively solid, liquid, and vapor exist. In accordance with the phase rule, specification of two intensive variables (here, T and P) is required to define the state of the system.

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Conditions where two phases are in equilibrium are represented on this diagram by lines (such as ab, bc, and bd) and therefore only one variable need be specified. The intersection of three lines results in a triple point, where three phases are in equilibrium and no variables may be specified. Some systems exhibit more than one triple point. Figure 47.1 Pressure-temperature graph of pure-component phase equilibrium.

The Clapeyron Equation

For two phases in equilibrium, say the and phases, the equating of fugacities leads to the Clapeyron equation:
h h dP = dT (v v )T (47:2)

This equation relates the slope of a coexistence line on Fig. 47.1 (e.g., ab) to differences in molar enthalpy and molar volume and can be used to determine the value of one variable when all the others are known.

The Clausius-Clapeyron Equation

When one of the phases is a vapor, the number of variables in the Clapeyron equation can be reduced; the result is the Clausius-Clapeyron equation:
h d ln P 0 = d(1=T ) R (47:3)

If Eq. (47.3) is integrated under the assumption of constant h , the result is

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ln P 0 = c

h RT

(47:4)

where c is a constant of integration. Equations (47.3) and (47.4) relate the vapor pressure, P 0 , to temperature and the heat of vaporization or heat of sublimation, h , and predict that a plot of ln P 0 versus reciprocal of absolute temperature should be linear with a slope of h=R . Equations (47.3) and (47.4) find use in correlating, interpolating, and extrapolating vapor pressure data and in determining the heat of vaporization or sublimation from vapor pressure data. Despite some questionable assumptions made in arriving at Eqs. (47.3) and (47.4), the linear relationship has been found to hold over a wide range of temperature. In fact, the Antoine equation,
log P 0 = A B C+t (47:5)

which has been found to give excellent representation of vapor pressure data, can be seen to be an empiricized version of Eq. (47.4). Extensive compilations of Antoine parameters (A, B, and C) are available [Boublik et al., 1973; Reid et al., 1987].

47.2 Phase Equilibrium in Mixtures

There are two approaches to the treatment of phase equilibrium in mixturesthe use of an equation of state and the use of activity coefficients. The latter is developed here; the former is delineated by Kyle [1992] and also in Chapter 45 of this text.

Vapor-Liquid Equilibrium (VLE)

Although the activity coefficient approach can be used for systems at any pressure, it is predominantly applied at low to moderate pressure. Here, consideration will be restricted to low pressure. This method is based on the ideal solution model for representing the fugacity of a component in a solution. Unlike the pure-component fugacity, which can be easily calculated or estimated, it is usually not possible to directly calculate the fugacity of a component in a solution, and a modelthe ideal solution modelis therefore employed. This model is applied to both the vapor and liquid phases. It has been found to represent the vapor phase reasonably well and will be used here without correction. On the other hand, the model fits very few liquid-phase systems and needs to be corrected. The activity coefficient, i , is the correction factor and is expected to depend upon temperature, pressure, and the liquid-phase composition. The effect of pressure is usually neglected and activity-coefficient equations of demonstrated efficacy are used to represent the temperature and composition dependence [Reid et al., 1987]. Employment of the equal fugacity criterion along with these models yields the basic equation for treating vapor-liquid equilibrium,
P yi = Pi0 xi i (47:6)

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where P is the system pressure, Pi0 is the vapor pressure of component i, xi is its liquid mole fraction, and yi is its vapor mole fraction. Determination of Activity Coefficients Although methods for estimating activity coefficients are available (see Chapter 45), it is preferable to use experimental phase equilibrium data for their evaluation. The exception to this rule is when it is known that a system forms an ideal liquid solution and values are therefore unity. These systems, however, are rare and occur only when all the constituents belong to the same chemical family (e.g., paraffin hydrocarbons). Equation (47.6) is used to calculate i from experimental values of xi , yi , and P at a given temperature where Pi0 is known. Thus, for a binary system, for each component can be evaluated from a single VLE data point. Once a set of 1 , 2 , and x1 data has been determined from binary VLE data, it is customary to fit this data to an activity-coefficient equation. The Wilson equation, shown below for a binary system, is outstanding among equations of proven efficacy:
ln 1 = ln(x1 + x2 G12 ) + x2 ln 2 = ln(x2 + x1 G21 ) x1 G21 G12 x1 + x2 G12 x2 + x1 G21 G21 G12 x1 + x2 G12 x2 + x1 G21 (47:7)

(47:8)

The G values are empirically determined parameters that are expected to show the following exponential dependence on temperature:
G12 = a v2 12 ; exp v1 RT G21 = a v1 21 exp v2 RT (47:9)

where v1 and v2 are the liquid molar volumes of components 1 and 2, and a12 and a21 are empirically determined parameters. Some type of parameter estimation technique is used to determine the best values of G. This can easily be done on a spreadsheet using the optimization feature to find the parameters that minimize the following objective function:
n X i=1

(Qexp Qcal )2 i

(47:10)

where Q is defined as
Q = x1 ln 1 + x2 ln 2 (47:11)

In Eq. (47.10), Qexp is determined from Eq. (47.11) and values of 1 and 2 from experimental VLE data, while Qcal is determined at the same composition from Eq. (47.11) using Eqs. (47.7) and (47.8). The difference in these Q values and, consequently, the objective function [Eq. (47.10)]

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is a function only of the G values. Sensing a certain amount of circularity, one may well question the value of this procedure that uses experimental VLE data to determine parameters in the Wilson equation that will then be used to calculate VLE by means of Eq. (47.6). However, the procedure becomes more attractive when one recognizes that VLE data at one condition can be used to evaluate Wilson parameters that can then be used to calculate VLE at another condition. Or one might use the minimum amount of VLE data (one data point) to evaluate Wilson parameters and then proceed to calculate, via Eq. (47.6), sufficient data to represent the system. When no experimental information is available, activity coefficients may be estimated by the UNIFAC method, which is based on the behavior of functional groups within the molecules composing the solution rather than on the molecules themselves [Reid et al., 1987]. Azeotropes An azeotrope is the condition in which the vapor and liquid compositions in a system are identical. As the knowledge of the existence of azeotropes is crucial to the design of distillation columns, much effort has been expended in determining and compiling this information [Horsely, 1952, 1962]. These compilations represent a source of VLE data: values of T, P, and x1 , where xi = yi . At a specified T(or P) a value of can be calculated for each component via Eq. (47.6), the minimum data required to determine Wilson parameters. For an azeotrope in the 1-2 system, Eq. (47.6) can be employed to obtain
2 P10 = 0 P2 1 (47:12)

This equation is useful in estimating the effect of temperature (which is manifested as a corresponding change in pressure) on the composition of the azeotrope. The vapor pressure ratio depends only on temperature, whereas the values depend on temperature and composition. If one assumes that the ratio 2 =1 is independent of temperature and uses the azeotropic data point to evaluate Wilson parameters, the right-hand side becomes a known function of x1 , and, thus, a value of x1 can be determined from the vapor pressure ratio evaluated at any temperature. Computational Procedures The computations for VLE involving Eq. (47.6) cannot be directly executed because all of the necessary variables cannot be specified prior to the calculation. According to the phase rule, a system of two phases possesses C degrees of freedom. If the composition of a phase is specified at the expense of C 1 variables, there remains only one additional variable to be specifiedT or P. Because the quantities in Eq. (47.6) depend on T and P, it is necessary to adopt a trial-and-error computational procedure. If, for example, T and the xi values are specified, a value of P would be assumed and Eq. (47.6) used to calculate the yi values. If these calculated yi values all sum to unity, the assumed value of P would be correct: if not, other values of P would be assumed until this condition is met. A similar procedure would be used for a system described in different terms.

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Multicomponent Vapor-Liquid Equilibrium In order to effectively treat multicomponent systems, it is necessary to be able to represent activity coefficients as a function of temperature and composition for use in Eq. (47.6). The Wilson equation can be extended to any number of components and requires only two parameters (Gij and Gji ) for each binary pair that can be formed from the components of the system [Kyle, 1992]. A comprehensive study [Holmes and Van Winkle, 1970] has established the ability of the Wilson equation to calculate ternary VLE with acceptable accuracy from parameters obtained from the three constituent binary systems.

Liquid-Liquid Equilibrium (LLE)

When two liquid phases are in equilibrium, the equating of fugacities results in the following expression for each component:
i0 x0i = i00 x00 i (47:13)

where and distinguish the liquid phases. Because activity coefficients are required for each phase, calculations involving LLE are computationally intensive. These calculations entail either the computation of LLE from available information concerning activity coefficients or the use of LLE to obtain information concerning activity coefficients [Kyle, 1992].

Solid-Liquid Equilibrium (SLE)

For pure solid component i in equilibrium with a liquid solution containing component i, the equating of fugacities results in
RT ln xi i = Lmi (T Tmi ) T + cP i (Tmi T ) + T cP i ln Tmi Tmi (47:14)

where Tmi is the freezing point and Lmi is the heat of fusion of component i. Usually, the data for the evaluation of cP i are unavailable and only the first right-hand term is used. Figure 47.2 shows a phase diagram for a simple binary system where the curves AE and BE are represented by Eq. (47.14) with i equal to 2 and 1, respectively. The eutectic point E is merely the intersection of these two curves.

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Figure 47.2 Phase diagram for a simple binary system.

To apply Eq. (47.14) where liquid solutions are not ideal, it will be necessary to have access to enough experimental phase equilibrium data to evaluate parameters in the Wilson, or equivalent, activity-coefficient equation. When reliable parameters are available, it has been demonstrated [Gmehling et al., 1978] that good estimates of SLE can be obtained for systems of nonelectrolytes. Alternatively, SLE data can be used as a source of activity coefficient information for use in other types of phase equilibrium calculations involving a liquid phase. The solid phase can be either pure or a solid solution. For a given system, solid solutions will exhibit larger deviations from the ideal solution model than will liquid solutions, and, therefore, an activity coefficient will also be required for the solid phase. Thus, calculations for this type of system will require some experimental data for the evaluation of liquid- and solid-phase activity coefficients [Kyle, 1992].

47.3 Perspective
In this work the emphasis has been placed on delineating the rationale for the application of thermodynamics to phase equilibrium rather than on amassing a set of "working equations." Such a set would be useful in dealing with routine or standard problems; however, with the exception of pure components, there are few such problems in phase equilibrium. Each problem is defined by the nature of the system, what information is desired, and what information is available; judgments concerning the suitability of data and the fitting of data may also be involved. This endeavor can be regarded as information processing in which the activity coefficient provides the means by which information (experimental phase equilibrium data) at one condition is processed in order to generate information at other conditions.

Defining Terms
Eutectic point: The existence of two solid phases and a liquid phase in equilibrium at a temperature below the melting points of the pure solid components. Fugacity: A thermodynamic function that requires for its evaluation PVT data for a pure

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substance and PVT-composition data for a component in a mixture. It is often regarded as a thermodynamic pressure because it has the units of pressure and is equal to pressure for an ideal gas and equal to partial pressure for a component in an ideal gas mixture.

References
Boublik, T., Fried, V., and Hala, E. 1973. The Vapor Pressures of Pure Substances. Elsevier, Amsterdam. Gmehling, J. G., Anderson, T. F., and Prausnitz, J. M. 1978. Solid-liquid equilibria using UNIFAC. Ind. Eng. Chem. Fundam. 17(4):269273. Holmes, M. J. and Van Winkle, M. 1970. Prediction of ternary vapor-liquid equilibria from binary data. Ind. Eng. Chem. 62(1):2131. Horsely, L. H. 1952. Azeotropic Data. Advances in Chemistry Series, No. 6. American Chemical Society, Washington, D.C. Horsely, L. H. 1962. Azeotropic DataII. Advances in Chemistry Series, No. 35. American Chemical Society, Washington, D.C. Kyle, B. G. 1992. Chemical and Process Thermodynamics, 2nd ed. Prentice Hall, Englewood Cliffs, NJ. Reid, R. C., Prausnitz, J. M., and Poling, B. E. 1987. The Properties of Gases and Liquids, 4th ed. McGraw-Hill, New York.

Further Information
A comprehensive treatment of phase equilibrium consistent with this work and a list of sources of phase equilibrium data is available in Kyle [1992]. A vast quantity of various types of phase equilibrium data is available in the Dortmund Data Bank via the on-line service DETHERM provided by STN International. See Reid et al.[1987] for a detailed explication of the UNIFAC method for estimating activity coefficients and for comprehensive lists of sources of experimental data and books about phase equilibrium.

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