Multicomponent solutions, vapor-liquid

In their correlation, Chao and Seader use the original Redlich-Kwong equation of state for vapor-phase fugacities. For the liquid phase, they use the symmetric convention of normalization for y and partial molar volumes which are independent of composition, depending only on temperature. For the variation of y with temperature and composition, Chao and Seader use the equation of Scatchard and Hildebrand for a multicomponent solution ... 

Prausnitz, "Vapor-Liquid Equilibria in Multicomponent Aqueous Solutions of Volatile Weak Electrolytes," AIChE J., 1978, 24, 966. 

This interaction between physical and chemical equilibria complicates considerably the description of vapor-liquid equilibria in multicomponent aqueous solutions. The development of thermodynamic correlations for those equilibria is also hindered by the limited experimental material available on that subject. 

This contribution describes and compares three procedures for representing vapor-liquid equilibria in multicomponent aqueous solutions of volatile weak electrolytes. Starting from the basic thermodynamic relations, the approximations and simplifications applied by van Krevelen, Hoftijzer and Huntjens ( ), Beutier and Renon (2) and Edwards, Maurer, Newman and Prausnitz (3) are discussed the necessary information for using these correlations is compiled. Results calculated with these procedures are discussed and compared with literature data. 

To calculate the multicomponent vapor-liquid equilibrium, equilibrium constants for chemical reactions 1-9 are taken from literature in comparison to the original publication, in the present work different numerical values for the second dissociations of hydrogen sulfide and sulfur dioxide were chosen (cf. Appendix III). Henry s constants are evaluated from single solute solubility data without neglecting Poynting corrections ... 

It is evident from the title of this symposium that as a result of recent requirements to reduce pollutant levels in process wastewater streams, improved techniques for predicting the vapor-liquid-solid equilibria of multicomponent aqueous solutions of strong and/or weak electrolytes are needed. In addition to the thermodynamic models necessary for such predictions, tools have to be developed so that the engineer or scientist can use these thermodynamic models correctly and with relative ease. 

Despite these apparent weaknesses, within the context of a general purpose system for predicting the vapor-liquid-solid equilibria of multicomponent aqueous solutions, GCES as a tool succeeds remarkably well as will be seen in a few illustrations after the following description of the software structure and use. 

Until the advent of computers, multicomponent distillation problems were solved manually by making tray-by-tray calculations of heat and material balances and vapor-liquid equilibria. Even a partially complete solution of such a problem required a week or more of steady work with a mechanical desk calculator. The alternatives were approximate methods such as those mentioned in Sections 13.7 and 13.8 and pseudobinary analysis. Approximate methods still are used to provide feed data to iterative computer procedures or to provide results for exploratory studies. 

T. J. Edwards, J. Maurer, J. Newman, et ah, Vapor-liquid equilibria in multicomponent aqueous solutions of volatile weak electrolytes, AIChE /., 1978, 24, 966-976. 

In Chap. 6 we treated the thermodynamic properties of constant-composition fluids. However, many applications of chemical-engineering thermodynamics are to systems wherein multicomponent mixtures of gases or liquids undergo composition changes as the result of mixing or separation processes, the transfer of species from one phase to another, or chemical reaction. The properties of such systems depend on composition as well as on temperature and pressure. Our first task in this chapter is therefore to develop a fundamental property relation for homogeneous fluid mixtures of variable composition. We then derive equations applicable to mixtures of ideal gases and ideal solutions. Finally, we treat in detail a particularly simple description of multicomponent vapor/liquid equilibrium known as Raoult s law. 

The vapor pressure curve forms the basis for the description of vapor-liquid equilibrium for a pure fluid. As the temperature increases, the vapor pressure curve for the vapor-liquid situation ends at the critical pressure. In the case of a binary or multicomponent solution, the critical point is not necessarily a maximum with respect to either temperature or pressure. It is then possible for a vapor or liquid to exist at temperature or pressures higher than the critical pressure of the mixture. At constant temperature, it is then possible for condensation to take place as the pressure is decreased. At constant pressure, condensation may take place as the temperature is increased. Vaporization can take place at constant temperature as the pressure is increased and decreased. This unusual behavior can be useful in some process situations, for example, in the recovery of natural gas from deep wells. If the conditions are right, liquefaction of the product stream is possible. At the same time, the heavier components of the mixture may be separated from the lighter components. 

Now we will use the ideal solution model to develop a mathematical description of vapor-liquid equilibrium in a multicomponent solution. We will make the assumption that we have a system that is separated into a coexisting vapor and liquid phase. The vapor phase will be assumed to behave like an ideal gas, while the liquid phase will be assumed to behave as an ideal solution. 

The activity coefficient of a component in a mixture is a function of the temperature and the concentration of that component in the mixture. When the concentration of the component proaches zero, its activity coefficient approaches the limiting activity coefficient of th component in the mixture, or the activity coefficient at infinite dilution, y . The limiting activity coefficient is useful for several reasons. It is a strictly dilute solution property and can be used dir tly in nation 1 to determine the equilibrium compositions of dilute mixtures. Thus, there is no reason to extrapolate uilibrium data at mid-range concentrations to infinite dilution, a process which may introduce enormous errors. Limiting activity coefficients can also be used to obtain parameters for excess Gibbs energy expressions and thus be used to predict phase behavior over the entire composition range. This technique has been shown to be quite accurate in prediction of vapor-liquid equilibrium of both binary and multicomponent mixtures (5). 

These three approaches have found widespread application to a large variety of systems and equilibria types ranging from vapor-liquid equilibria for binary and multicomponent polymer solutions, blends, and copolymers, liquid-liquid equilibria for polymer solutions and blends, solid-liquid-liquid equilibria, and solubility of gases in polymers, to mention only a few. In some cases, the results are purely predictive in others interaction parameters are required and the models are capable of correlating (describing) the experimental information. In Section 16.7, we attempt to summarize and comparatively discuss the performance of these three approaches. We attempt there, for reasons of completion, to discuss the performance of a few other (mostly) predictive models such as the group-contribution lattice fluid and the group-contribution Flory equations of state, which are not extensively discussed separately. 

The Wilson equation is widely used for many nonpolar, polar, and associated solutions in vapor-liquid equilibrium systems. It is often best for hydrogen-bonded substances. For multicomponent solutions, it makes effective use of binary-solution parameters to give good results, but it cannot predict the liquid immiscibihty phenomena. 

The BP and SR methods for vapor-liquid contacting converge only with difficulty or not at all for separations involving very nonideal liquid mixtures (e.g., in extractive distillation) or for cases where the separator is like an absorber or stripper in one section and a fractionator in another section (e.g., a reboiled absorber). Furthermore, BP and SR methods are generally restricted to the very limited specifications stated above. More general procedures capable of solving ail types of multicomponent, multistage separation problems are based on the solution of all the MESH equations, or combinations thereof, by simultaneous correction (SC) techniques. 

Table 2.4-4 Adsorbed solution theories for the description or prediction of multicomponent adsorption equilibria. In the light gray area new theoretical models are listed. The theories in the double-framed area require experimental data of binary adsorptives. VLE denotes vapor liquid equilibrium. The meaning of VAE is vapor adsorbate equilibrium...

When a multicomponent mixture forms nearly ideal liquid and vapor solutions, and the ideal gas law holds, the K values and relative volatility can be readily estimated from vapor pressure data. Such K values are referred to as ideal or Raoult s law K values. Then, the SF for vapor-liquid separation operations employing an ESA (partial evaporation, partial condensation, or distillation) is given by... 

Chandrasekaran SK, King CJ. Multicomponent diffusion and vapor-liquid equilibria of dilute organic components in aqueous sugar solutions. AIChE J. 18(3) 513-520, 1972b. 

OPl. Edwards, T.J., G. Maurer. J. Newman and J.M. Prausnitz, "Vapor-Liquid Equilibria in Multicomponent Aqueous Solutions of Volatile Weak Electrolytes", AIChE J., 24. 966 (1978)... 

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