Activity coefficients Pitzer equations

An individual-ion, activity-coefficient formula (Equation 5) derived by Millero and Schreiber (14) from the work of Pitzer (15) was used in the amended WATEQ and fit models ... 

The individual-ion activity coefficients for the free ions were based on the Macinnis (18) convention, which defines the activity of Cl to be equal to the mean activity coefficient of KCl in a KCl solution of equivalent ionic strength. From this starting point, individual-ion activity coefficients for the free ions of other elements were derived from single-salt solutions. The method of Millero and Schreiber (14) was used to calculate the individual-ion, activity-coefficient parameters (Equation 5) from the parameters given by Pitzer (19). However, several different sets of salts could be used to derive the individual-ion activity coefficient for a free ion. For example, the individual-ion activity coefficient for OH could be calculated using mean activity-coefficient data for KOH and KCl, or from CsOH, CsCl, and KCl, and so forth. 

This review should cover more than one of these sources as they do not always present the same complexes. In those cases where there are differences, a choice of values will have to be made. This decision can be aided by a literature search which often will yield articles detailing work done to identify the ionic and molecular species in solution. Articles may be found describing modeling efforts similar to the one desired. Such articles are becoming increasingly common and they often use one of the activity coefficient modeling equations presented in Chapters IV and V. The Pitzer formalism, in particular, is frequently used. 

Estimate Pitzer s electrolyte activity coefficient model by minimizing the objective function given by Equation 15.1 and using the following osmotic coefficient data from Rard (1992) given in Table 15.5. First, use the data for molalities less than 3 mol/kg and then all the data together. Compare your estimated values with those reported by Rard (1992). Use a constant value for in Equation 15.1. 

Can the species activity coefficients be calculated accurately An activity coefficient relates each dissolved species concentration to its activity. Most commonly, a modeler uses an extended form of the Debye-Hiickel equation to estimate values for the coefficients. Helgeson (1969) correlated the activity coefficients to this equation for dominantly NaCl solutions having concentrations up to 3 molal. The resulting equations are probably reliable for electrolyte solutions of general composition (i.e., those dominated by salts other than NaCl) where ionic strength is less than about 1 molal (Wolery, 1983 see Chapter 8). Calculated activity coefficients are less reliable in more concentrated solutions. As an alternative to the Debye-Hiickel method, the modeler can use virial equations (the Pitzer equations ) designed to predict activity coefficients for electrolyte brines. These equations have their own limitations, however, as discussed in Chapter 8. 

In applying this equation to multi-solute systems, the ionic concentrations are of sufficient magnitude that molecule-ion and ion-ion interactions must be considered. Edwards et al. (6) used a method proposed by Bromley (J7) for the estimation of the B parameters. The model was found to be useful for the calculation of multi-solute equilibria in the NH3+H5S+H2O and NH3+CO2+H2O systems. However, because of the assumptions regarding the activity of the water and the use of only two-body interaction parameters, the model is suitable only up to molecular concentrations of about 2 molal. As well the temperature was restricted to the range 0° to 100 oc because of the equations used for the Henry1s constants and the dissociation constants. In a later study, Edwards et al. (8) extended the correlation to higher concentrations (up to 10 - 20 molal) and higher temperatures (0° to 170 °C). In this work the activity coefficients of the electrolytes were calculated from an expression due to Pitzer (9) ... 

About the same time Beutier and Renon (11) also proposed a similar model for the representation of the equilibria in aqueous solutions of weak electrolytes. The vapor was assumed to be an ideal gas and < >a was set equal to unity. Pitzer s method was used for the estimation of the activity coefficients, but, in contrast to Edwards et al. (j)), two ternary parameters in the activity coefficient expression were employed. These were obtained from data on the two-solute systems It was found that the equilibria in the systems NH3+ H2S+H20, NH3+C02+H20 and NH3+S02+H20 could be represented very well up to high concentrations of the ionic species. However, the model was unreliable at high concentrations of undissociated ammonia. Edwards et al. (1 2) have recently proposed a new expression for the representation of the activity coefficients in the NH3+H20 system, over the complete concentration range from pure water to pure NH3. it appears that this area will assume increasing importance and that one must be able to represent activity coefficients in the region of high concentrations of molecular species as well as in dilute solutions. Cruz and Renon (13) have proposed an expression which combines the equations for electrolytes with the non-random two-liquid (NRTL) model for non-electrolytes in order to represent the complete composition range. In a later publication, Cruz and Renon (J4J, this model was applied to the acetic acid-water system. 

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. 

In this paper, two new models for the activity coefficients of ionic and molecular species in electrolyte systems are presented. The first is an extension of the Pitzer equation and is covered in more detail in Chen, et al. (11). 

The interaction parameters are weak, linear functions of temperature, as shown in Table 5, Table 6 and Figure 6. These tables and figure show the results of isothermal fits for activity coefficient data of aqueous NaCl and KBr at various temperatures. The Pitzer equation parameters are, however, strongly dependent on temperature (Silvester and Pitzer, (23)). 

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. 

The derivative equations for osmotic and activity coefficients, which are presented below, were applied to the experimental data for wide variety of pure aqueous electrolytes at 25°C by Pitzer and Mayorga (23) and to mixtures by Pitzer and Kim (11). Later work (24-28) considered special groups of solutes and cases where an association equilibrium was present (H PO and SO ). While there was no attempt in these papers to include all solutes for which experimental data exist, nearly 300 pure electrolytes and 70 mixed systems were considered and the resulting parameters reported. This represents the most extensive survey of aqueous electrolyte thermodynamics, although it was not as thorough in some respects as the earlier evaluation of Robinson and Stokes (3). In some cases where data from several sources are of comparable accuracy, a new critical evaluation was made, but in other cases the tables of Robinson and Stokes were accepted. 

Pitzer et al (1972, 1973, 1974, 1975, 1976) have proposed a set of equations based on the general behavior of classes of electrolytes. Pitzer (1973) writes equations for the excess Gibbs energy, AGex, the osmotic coefficient activity coefficient Y+ for single unassociated electrolytes as... 

Generally, agreement has been found between our correlations and those of Pitzer, and others (1972, 1973, 1974, 1975, 1976) and Rard, and others (1976, 1977). Many of our correlations agree fairly well with Robinson and Stokes, (1965) and Harned and Owen, (1958) but in most cases a much larger data base and more recent measurements have been incorporated into the evaluations. It has been observed that agreement with Pitzer s equations is found below moderate concentrations (several molal), but often deviate at higher concentrations where the Pitzer equations do not contain enough parameters to account for the behavior of the activity (or osmotic) coefficient. 

The Pitzer equation for single electrolytes with the value of parameters collected in several publication may be used as a compact source of activity coefficient data. From the values y° yj. thus obtained, one may calculate, for example, (/, / ) values using Eq. (6.1). 

Equations for single ion activity coefficients [4], osmotic coefficients [17], and other thermodynamic quantities [28], as well as applications in different cases (e.g., H2SO4 and H3PO4 solutions) have been given by Pitzer and coworkers [4,20]. 

One method takes into account the individual characteristics of the ionic media by using a medium-dependent expression for the activity coefficients of the species involved in the equilibrium reactions. The medium dependence is described by virial or ion interaction coefficients as used in the Pitzer equations and in the specific ion interaction model. 

Numerous studies on the thermodynamics of calcium chloride solutions were published in the 1980s. Many of these were oriented toward verifying and expanding the Pitzer equations for determination of activity coefficients and other parameters in electrolyte solutions of high ionic strength. A review article covering much of this work is available (7). Application of Pitzer equations to the modeling of brine density as a function of composition, temperature, and pressure has been successfully carried out (8). 

In Equation 8-6, y is the activity coefficient of an ion of chaige z and size a (picomeiers, pm) in an aqueous solution of ionic strength p. The equation works fairly well for p 0.1 M. To find activity coefficients for ionic strengths above 0.1 M (up to molalities of 2-6 mol/kg for many salts), more complicated Pitzer equations are usually used.7... 

Figure 18.4 Comparison of activity coefficients at T = 298.15 K for three different electrolytes as calculated from Pitzer s equations (solid lines) with the experimental results (symbols).

Figure 18.5 Graph of (a) the osmotic coefficient and (b) the activity coefficient for NaCl(aqueous) at p = 0.1 MPa as a function of temperature. The curves were obtained by using temperature-dependent coefficients in Pitzer s equations. The dotted line is for r=273.15 K and the dashed line is for T = 298.15 K. The solid lines are for T= 323.15, 373.15, 423.15, 473.15, 523.15, and 573.15 K, with both and 7 decreasing with increasing temperature.

The log K values shown in Figure 18.10 are the values that best reproduce all of the heat of mixing curves.v The J1 values are obtained by estimating initial values using the activity coefficients for NaCl(aq).16 These initial values of Jy are then readjusted, as the value for Km is optimized, by adjusting the coefficients of Pitzer s equations, whose form is described in the previous section. Pitzer s equations are, of course, internally consistent so that adjustments to the activity or osmotic coefficient parameters result in adjustments to the thermal parameters (L, L2, 4>J, or J2), and hence, to the heat effects. 

K. S. Pitzer, Ion Interaction Approach Theory and Data Correlation , Chapter 3 of Activity Coefficients in Electrolyte Solutions, 2nd Edition, K. S. Pitzer, Editor, CRC Press, Boca Raton, 1991. Parameters for many electrolytes are summarized in this reference. The equations and parameters can also be found in K. S. Pitzer, Thermodynamics, Third Edition, McGraw-Hill, Inc., New York, 1995. 

There are alternative methods for estimating the temperature dependence of the equilibrium constant. One can use Pitzer s theoretical approach to estimate activity coefficients, which will be discussed in the following section, for the constituents of a reaction (Eqs. 2.13 and 2.16) coupled with experimental measurements of the molalities to estimate activities and the equilibrium constant directly at various temperatures. Alternatively, one can estimate the temperature dependence with the theoretical equation... 

Note that the equations for estimating the pressure dependencies of 7 and aw (Eqs. 2.87 and 2.90) depend on the Pitzer equations (Eqs. 2.76, 2.80, and 2.81) but this is not the case for the pressure dependence of the equilibrium constants (Eq. 2.29) the latter equation is based entirely on partial molar volumes at infinite dilution, which are independent of concentration. Also, compared to the pressure-dependent equation for the equilibrium constant (Eq. 2.29), the pressure equations for activity coefficients (Eq. 2.87) and the activity of water (Eq. 2.90) do not contain compressibilities (K) because the database for these terms and the associated Pitzer parameters are lacking at present (Krumgalz et al. 1999). The consequences of truncating Eqs. 2.80 and 2.81 for ternary terms and Eqs. 2.87 and 2.90 for compressibilities will be discussed in Sect. 3.6 under limitations. 

Equations 2.87 (activity coefficient), 2.88 (density), and 2.90 (activity of water) are all indirectly dependent on the temperature and pressure dependence of B v, B v, BC2), and Cv (Eqs. 2.76, 2.80, and 2.81). Table B.10 (Appendix B) lists the temperature dependence of these volumetric Pitzer parameters. The pressure dependence of these parameters were evaluated with the density equation (Eq. 2.88). All three terms in the denominator of Eq. 2.88 are temperature and pressure dependent. The density of pure water (p°) as a function of temperature and pressure is evaluated with Eqs. 3.14-3.16 and 3.20. Similarly, the molar volume of ions as a function of temperature and pressure is calculated by... 

This assumption limits application of the latter chemistries to low pressures. Activity coefficients for aqueous-phase gases (CO2, O2, and CH4) are calculated using the Pitzer equation for neutral species (Eq. 2.42). Activity coefficients for aqueous acids are calculated using the Pitzer equations for ions (Eqs. 2.40 and 2.41). For the case of HC1, the Henry s law constant is given by... 

Earlier, when discussing historical development, we mentioned that different workers have used different equations to describe the Debye-Hiickel constant (A, Eq. 2.35) as a function of temperature. For example, at 0°C, the value of this constant is 0.3781, 0.3764, and 0.3767 kg1/2 mol-1/2 for the FREZCHEM, Archer and Wang (1990), and Pitzer (1991) models, respectively. At NaCl = 5 m and 0 °C, the calculated mean activity coefficients using these three parameters evaluated with the FREZCHEM model are 0.7957, 0.7995, and 0.7988, respectively. The largest discrepancy is 0.48%, which is within the range of model errors for activity coefficients (Table 3.5). 

Table 1.5. Pitzer equation activity coefficients (based on Nagy, 1988).

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