Vapor liquid electrolytes

Of course these requirements cannot be fulfilled simultaneously. For example, a low vapor pressure of the liquid electrolyte is obtained only by using more viscous dipolar aprotic solvents such as propylene carbonate, but high solvent viscosity generally entails a low conductivity. Nevertheless, a large number of useful solvents and electrolytes is available, allowing a sufficiently good approximation to an ideal electrolyte. 

The difficulties engendered by a hypothetical liquid standard state can be eliminated by the use of unsymmetrically normalized activity coefficients. These have been used for many years in other areas of solution thermodynamics (e.g., for solutions of electrolytes or polymers in liquid solvents) but they have only recently been employed in high-pressure vapor-liquid equilibria (P7). 

Conclusions The correlation of vapor-liquid equilibria in aqueous solutions of weak electrolytes is important for the separation of undesirable components from gases and liquids. The major problem in such correlations is the estimation of the activity... 

Two New Activity Coefficient Models for the Vapor-Liquid Equilibrium of Electrolyte Systems... 

Recently, there have been a number of significant developments in the modeling of electrolyte systems. Bromley (1), Meissner and Tester (2), Meissner and Kusik (2), Pitzer and co-workers (4, ,j5), and" Cruz and Renon (7j, presented models for calculating the mean ionic activity coefficients of many types of aqueous electrolytes. In addition, Edwards, et al. (8) proposed a thermodynamic framework to calculate equilibrium vapor-liquid compositions for aqueous solutions of one or more volatile weak electrolytes which involved activity coefficients of ionic species. Most recently, Beutier and Renon (9) and Edwards, et al.(10) used simplified forms of the Pitzer equation to represent ionic activity coefficients. 

To test the validity of the extended Pitzer equation, correlations of vapor-liquid equilibrium data were carried out for three systems. Since the extended Pitzer equation reduces to the Pitzer equation for aqueous strong electrolyte systems, and is consistent with the Setschenow equation for molecular non-electrolytes in aqueous electrolyte systems, the main interest here is aqueous systems with weak electrolytes or partially dissociated electrolytes. The three systems considered are the hydrochloric acid aqueous solution at 298.15°K and concentrations up to 18 molal the NH3-CO2 aqueous solution at 293.15°K and the K2CO3-CO2 aqueous solution of the Hot Carbonate Process. In each case, the chemical equilibrium between all species has been taken into account directly as liquid phase constraints. Significant parameters in the model for each system were identified by a preliminary order of magnitude analysis and adjusted in the vapor-liquid equilibrium data correlation. Detailed discusions and values of physical constants, such as Henry s constants and chemical equilibrium constants, are given in Chen et al. (11). 

A wide variety of data for mean ionic activity coefficients, osmotic coefficients, vapor pressure depression, and vapor-liquid equilibrium of binary and ternary electrolyte systems have been correlated successfully by the local composition model. Some results are shown in Table 1 to Table 10 and Figure 3 to Figure 7. In each case, the chemical equilibrium between the species has been ignored. That is, complete dissociation of strong electrolytes has been assumed. This assumption is not required by the local composition model but has been made here in order to simplify the systems treated. 

Another type of ternary electrolyte system consists of two solvents and one salt, such as methanol-water-NaBr. Vapor-liquid equilibrium of such mixed solvent electrolyte systems has never been studied with a thermodynamic model that takes into account the presence of salts explicitly. However, it should be recognized that the interaction parameters of solvent-salt binary systems are functions of the mixed solvent dielectric constant since the ion-molecular electrostatic interaction energies, gma and gmc, depend on the reciprocal of the dielectric constant of the solvent (Robinson and Stokes, (13)). Pure component parameters, such as gmm and gca, are not functions of dielectric constant. Results of data correlation on vapor-liquid equilibrium of methanol-water-NaBr and methanol-water-LiCl at 298.15°K are shown in Tables 9 and 10. 

Two activity coefficient models have been developed for vapor-liquid equilibrium of electrolyte systems. The first model is an extension of the Pitzer equation and is applicable to aqueous electrolyte systems containing any number of molecular and ionic solutes. The validity of the model has been shown by data correlation studies on three aqueous electrolyte systems of industrial interest. The second model is based on the local composition concept and is designed to be applicable to all kinds of electrolyte systems. Preliminary data correlation results on many binary and ternary electrolyte systems suggest the validity of the local composition model. 

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

Chen, C., H. I. Britt, J. F. Boston, and L. B. Evans, "Extension and Application of the Pitzer equation for Vapor-Liquid Equilibrium of Aqueous Electrolyte Systems with Molecular Solutes," AIChE J., 1979, 25, 820. 

The solubility of gaseous weak electrolytes in aqueous solutions is encountered in many chemical and petrochemical processes. In comparison to vapory-liquid equilibria in non reacting systems the solubility of gaseous weak electrolytes like ammonia, carbondioxide, hydrogen sulfide and sulfur dioxide in water results not only from physical (vapor-liquid) equilibrium but also from chemical equilibrium in the liquid phase. 

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. 

The comparison between measured and calculated results for vapor-liquid equilibria in aqueous systems of weak electrolytes confirms the applicability of van Krevelen 1s method for moderate temperatures and concentrations. The comparison also indicates that the procedure of Edwards, Maurer, Newman and Prausnitz yields reliable results also at temperatures around 100 °C therefore, it may be expected that it is also useful at higher temperatures where experimental material, necessary for checking that procedure, is not available... 

VAN AKEN et al. 0) and EDWARDS et al. (2) made clear that two sets of fundamental parameters are useful in describing vapor-liquid equilibria of volatile weak electrolytes, (1) the dissociation constant(s) K of acids, bases and water, and (2) the Henry s constants H of undissociated volatile molecules. A thermodynamic model can be built incorporating the definitions of these parameters and appropriate equations for mass balance and electric neutrality. It is complete if deviations to ideality are taken into account. The basic framework developped by EDWARDS, NEWMAN and PRAUSNITZ (2) (table 1) was used by authors who worked on volatile electrolyte systems the difference among their models are in the choice of parameters and in the representation of deviations to ideality. 

Table 1. Thermodynamic Framework of Representation of Vapor-Liquid Equilibria of Weak Electrolytes...

An application to one binary mixture of a volatile electrolyte and water will illustrate the choice of parameters H and K, an approach is proposed to represent the vapor-liquid equilibrium in the whole range of concentration. Ternary mixtures with one acid and one base lead to the formation of salts and high ionic strengths can be reached. There, it was found useful to take into account... 

Acetic Acid-Water Mixture. CRUZ (4) chose this example to illustrate his method of representation of vapor-liquid equilibria of volatile weak electrolyte and to show how to obtain simply from experimental vapor-liquid equilibrium data the significant parameters. ... 

CRUZ (7) equation for gE of binary electrolyte solution which incorporates a DEBYE - HUCKEL term, a BORN - DEBYE - MAC. AULAY contribution for electric work, and NRTL equation, can be used to represent the vapor-liquid equilibria of volatile electrolyte in the whole range of concentration. 

Appendix. Formalism of BEUTIER S Model of Volatile Weak Electrolytes Vapor-Liquid Equilibria... 

Figure 1. Schematic flow apparatus used for NH3-H20 (and electrolyte) vapor-liquid equilibrium measurements...

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. 

Volatile weak electrolytes, such as ammonia, carbon dioxide, and hydrohydrogen sulfide are of great interest in hydrometallurgy. The vapor-liquid... 

Very few generalized computer-based techniques for calculating chemical equilibria in electrolyte systems have been reported. Crerar (47) describes a method for calculating multicomponent equilibria based on equilibrium constants and activity coefficients estimated from the Debye Huckel equation. It is not clear, however, if this technique has beep applied in general to the solubility of minerals and solids. A second generalized approach has been developed by OIL Systems, Inc. (48). It also operates on specified equilibrium constants and incorporates activity coefficient corrections for ions, non-electrolytes and water. This technique has been applied to a variety of electrolyte equilibrium problems including vapor-liquid equilibria and solubility of solids. 

Generalized computer techniques for calculating vapor-liquid equilibria and solubility relationships in electrolyte systems are not readily available in the metallurgical industry. 

Equation 27 is similar to the solid-liquid equilibrium relation used for non-electrolytes. As in the case of the vapor-liquid equilibrium relation for HC1, the solid-liquid equilibrium expression for NaCl is simple since the electrolyte is treated thermodynamically the same in both phases. 

A review is presented of techniques for the correlation and prediction of vapor-liquid equilibrium data in systems consisting of two volatile components and a salt dissolved in the liquid phase, and for the testing of such data for thermodynamic consistency. The complex interactions comprising salt effect in systems which in effect consist of a concentrated electrolyte in a mixed solvent composed of two liquid components, one or both of which may be polar, are discussed. The difficulties inherent in their characterization and quantitative treatment are described. Attempts to correlate, predict, and test data for thermodynamic consistency in such systems are reviewed under the following headings correlation at fixed liquid composition, extension to entire liquid composition range, prediction from pure-component properties, use of correlations based on the Gibbs-Duhem equation, and the recent special binary approach. 

In this volume, we will apply the principles developed in Principles and Applications to the description of topics of interest to chemists, such as effects of surfaces and gravitational and centrifugal fields phase equilibria of pure substances (first order and continuous transitions) (vapor + liquid), (liquid 4-liquid), (solid + liquid), and (fluid -f fluid) phase equilibria of mixtures chemical equilibria and properties of both nonelectrolyte and electrolyte mixtures. But do not expect a detailed survey of these topics. This, of course, would require a volume of immense breadth and depth. Instead, representative examples are presented to develop general principles that can then be applied to a wide variety of systems. 

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. 

D. M. Austgen, G. T. Rochelle, X. Peng, et al., Model of vapor-liquid equilibria for aqueous acid gas-alkanolamine systems using the electrolyte NRTL equation, Ind. Eng. Chem. Res.,... 

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