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COEFICIENTES DE FUGACIDAD Liquid activity coefficient methods for phase equilibrium calculations differ at a fundamental level from equation

of state (EOS) methods. In EOS methods, fugacity coefficients (referring to an ideal-gas state) are computed for both vapor and liquid phases. In activity coefficient methods, the reference state for each component in the liquid phase is the pure liquid at the temperature and pressure of the mixture. It is often more convenient and accurate to use this approach when the liquid phase is a mixture of components which do not differ greatly in volatility; it is also often easier to describe strongly nonideal systems with a liquid activity coefficient model than with an equation of state. The thermodynamics of liquid mixtures within an activity coefficient framework is covered in standard textbooks, a few of which are referenced at the end of this section. The activity coefficient is introduced in the way the fugacity of component i in the liquid phase is written: = Donde: = fugacity of component i in liquid phase = standard-state liquid fugacity of component i = mole fraction of component i in liquid = liquid-phase activity coefficient of component i (1)

The standard-state fugacity

is defined as that of the pure liquid i at the approaches

temperature and pressure of the mixture. With this definition,

one in the 1. The standard-state fugacity may be related to the vapor pressure of component i as follows: = Donde: P = system pressure = vapor pressure of component i at the system temperature R = gas constant T = system temperature = liquid molar volume of component i at T and P (2)

= fugacity coefficient of pure component i at temperature T and pressure .

The exponential term in Equation (2) is the Poynting factor which accounts for the effect of pressure on the liquid fugacity. If the pressure does not exceed a few atmospheres, this correction can generally be neglected. Since liquid volumes do not depend greatly on pressure, Equation (2) can be simplified to = (3)

When liquid activity coefficients are used, any method may be used to compute the vapor-phase fugacity. An ideal gas is often assumed, but in general vapor fugacities may be written as: = donde: = fugacity of component i in vapor phase yi = mole fraction of component i in vapor = fugacity coefficient of component i in vapor For an ideal gas, the fugacity coefficient is one, but it may also be computed from an equation of state or other correlation. Equations (1) and (4) are fundamentally different in the way they describe liquid and vapor fugacities, respectively. The two equations do not in general "match" at the vapor-liquid critical point, where vapor and liquid phases become indistinguishable. Phase equilibrium calculations near a vapor-liquid critical point must be carried out with some other method such as an equation of state. The familiar vapor-liquid K-value is defined as the ratio of yi to xi, and can be obtained by combining Equations (1) and (4): = (5) (4)

At low and moderate pressures, the Poynting correction is often ignored and Equation (5) becomes (5a) Unless there is vapor-phase association (as is the case with carboxylic acids, for example), the fugacity coefficients may also be ignored at low and moderate pressures. Equation (5) then simplifies to

(5b) For most low-pressure systems, the regression of experimental vapor-liquid equilibrium data will produce essentially the same parameters if equation (5a) or (5b) is used in place of the full equation (5). This is not necessarily the case at higher pressures and for systems where vapor-phase nonideality is important. Significant errors can be introduced when the regression and calculations using the regressed parameters employ differing sets of simplying assumptions. In general, calculations should be performed using the same assumptions about vapor fugacities and the Poynting factor as those employed in fitting the parameters. An important exception to this rule is the case where parameters were fitted at low pressure but the calculations are at a substantially higher pressure; in such a case it is best to employ nonideal vapor-phase fugacities and the Poynting correction in the calculation even if they were not used in the original fit.

Liquid activity coefficients are derived from expressions for the excess Gibbs energy of a liquid mixture. The defining equation is (6)

donde: = excess Gibbs energy of liquid mixture ni = moles of component i in liquid The following sections describe the expressions available for describing liquid-phase activity coefficients. ECUACION DE MARGULES Required Pure Component Properties Vapor pressure Temperature

Use at or near temperatures where parameters were fitted The oldest empirical correlations for liquid activity coefficients, such as the Margules equation (1895), are derived from simple polynomial expansions. The most popular form of the Margules equation was proposed by Redlich and Kister (1948). When that expansion is truncated after the quadratic term, the resulting three-parameter correlation is known as the four-suffix Margules equation. The resulting expression for the activity coefficient is: (7)

donde:

Thus, for each ij binary pair in a multicomponent system, the parameters are aij, aji, and dij. No temperature dependence is included in this implementation; one should therefore be cautious about using this equation at temperatures differing substantially from the range in which the parameters were fitted. ECUACION DE VAN LAAR Required Pure Component Properties Presin de Vapor components Components: Use for chemically similar

Another old correlation which is still frequently used is the van Laar equation. It may be obtained by discarding ternary and higherorder terms in an alternative expansion of the excess Gibbs energy (known as Wohl's equation), though that is not how van Laar derived it originally. The resulting expression for the activity coefficient is:

donde:

Two parameters, aij and aji, are required for each binary. As with the Margules equation, no method is included for making the parameters temperature dependent. It should also be noted that the van Laar equation, because of its functional form, is incapable of representing maxima or minima in the relationship between activity coefficient and mole fraction. In practice, however, such maxima and minima are relatively rare.

ECUACION PARA SOLUCIONES REGULARES Required PureComponent Properties: Vapor pressure Liquid molar volume Solubility parameter Components Not valid for polar components and solutions containing fluorocarbons Hildebrand defined a regular solution as one in which the excess entropy vanishes when the solution is mixed at constant temperature and constant volume. This is nearly the case for most solutions of nonpolar compounds, provided the molecules do not differ greatly in size. The excess Gibbs energy is then primarily determined by the attractive intermolecular forces. Scatchard and Hildebrand made a simple assumption relating mixture interactions to those in pure fluids; the result is a simple theory in which the activity coefficients are a function of pure-component properties only. The important property is the solubility parameter, which is related to the energy required to vaporize a liquid component to an ideal gas state. The activity coefficient expression is (9)

donde: = liquid molar volume of component i = solubility parameter of component i There are no adjustable parameters in regular solution theory. It is useful for mixtures of nonpolar components, but it should not be used for highly nonideal mixtures, especially if they contain polar components. Solubility parameters have been tabulated for numerous compounds, and these parameters are included for most components in PRO/II's library. TEORIA DE FLORY-HUGGINS Required Pure Component Properties: Vapor pressure, Liquid molar volume Solubility parameter ComponentS: Best for components which are chemically similar and which differ only in size (e.g. polymer solutions) The Flory-Huggins model may be considered a correction to the Regular Solution Theory for the entropic effects of mixing molecules which differ greatly in size. It is therefore suitable for polymer/solvent systems, especially if the molecules involved are nonpolar. In this simplest implementation of the theory, there are no binary parameters. The activity coefficient expression is

(10)

donde: = activity coefficient from regular solution theory = liquid molar volume of component i = liquid molar volume of solution ECUACION DE WILSON Required Pure Component Properties: Vapor pressure, Liquid molar volume Components: Useful for polar or associating components in nonpolar solvents and for completely miscible liquids The Wilson equation was the first to incorporate the concept of "local composition." The basic idea is that, because of differences in intermolecular forces, the composition in the neighborhood of a specific molecule in solution will differ from that of the bulk liquid. The two parameters per binary are, at least in principle, associated with the degree to which each molecule can produce a change in the composition of its local environment. The expression for the activity coefficient is:

(11) donde: (when unit of aij is K) (when unit of aij is KCAL or KJ) (when unit of aij is NODIME) and is the liquid molar volume of component i.

aij represents a characteristic energy of interaction between species i and j. While there is no explicit temperature dependence in the Wilson equation's parameters, the derivation is such that the equation may be used with some confidence over a wider range of temperatures than either the Margules or van Laar equations. It is also much more successful in correlating mixtures containing polar components. The Wilson equation cannot describe local maxima or minima in the activity coefficient. Its single significant

shortcoming, however, is that it is mathematically unable to predict the splitting of a liquid into two partially miscible phases. It is therefore completely unsuitable for problems involving liquid-liquid equilibria. ECUACION DE NRTL Required Pure Component Properties: Vapor pressure Components: Useful for strongly nonideal mixtures and for partially immiscible systems The NRTL (non-random two-liquid) equation was developed by Renon and Prausnitz to make use of the local composition concept, while avoiding the Wilson equation's inability to predict liquid-liquid phase separation. The resulting equation has been quite successful in correlating a wide variety of systems. The expression for the activity coefficient is: (12) donde: (when unit is K) (when unit is KCAL or KJ) , Three parameters, tij, tji, and aij = aji are required for each binary. These parameters may be made temperaturedependent as described above. If tij is to be represented with only one constant, it has been found empirically that better results over a range of temperatures are obtained if only bij is used and aij = cij = 0. The a parameter does not vary greatly from binary to binary, and it is often satisfactory to fix it at 0.3 for vapor-liquid systems and 0.2 for liquid-liquid systems. ECUACION UNIQUAC Required PureComponent Properties: Vapor pressure, van der Waals area and volume Components: Useful for nonelectrolyte mixtures containing polar or nonpolar components and for partially miscible systems The UNIQUAC (universal quasi-chemical) equation was developed by Abrams and Prausnitz based on statistical-mechanical considerations and the latticebased quasichemical model of Guggenheim. As in the Wilson and NRTL equations, local compositions are used. However, local surface-area fractions are used as the primary composition variable instead of volume fractions. Each molecule i is characterized by a volume parameter ri and a surface-area parameter qi.

The excess Gibbs energy (and therefore the logarithm of the activity coefficient) is divided into a combinatorial and a residual part. The combinatorial part depends only on the sizes and shapes of the individual molecules; it contains no binary parameters. The residual part, which accounts for the energetic interactions, has two adjustable binary parameters. The UNIQUAC equation has, like the NRTL equation, been quite successful in correlating a wide variety of systems. The expression for the activity coefficient is:

(13)

(14)

(15)

donde: (when unit is K) (when unit is KCAL or KJ)

Awi = van der Waals area of molecule i Vwi = van der Waals volume of molecule i Two parameters, Uij and Uji, are required for each binary; they may be made temperature dependent as described above. If no temperature dependence is used for Uij, better results over a range of temperatures are normally obtained by using aij and setting bij = 0.

UNIFAC

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