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A comprehensive model for calculating phase equilibria and

thermophysical properties of electrolyte systems

P. Wang, A. Anderko*, R.D. Young and R.D. Springer
OLI Systems Inc.
108 American Road
Morris Plains, NJ 07950, USA

ABSTRACT

A thermodynamic model has been developed for calculating phase equilibria and
other properties of multicomponent electrolyte systems. The model has been designed to
reproduce the properties of both aqueous and mixed-solvent electrolyte systems ranging
from infinite dilution to solid saturation or pure solute limit. The model incorporates
formulations for the excess Gibbs energy and standard-state properties coupled with an
algorithm for detailed speciation calculations. The excess Gibbs energy model consists of
a long-range interaction contribution represented by the Pitzer-Debye-Hückel expression,
a second virial coefficient-type term for specific ionic interactions and a short-range
interaction term expressed by the UNIQUAC equation. The accuracy of the model has
been demonstrated for common acids and bases and for multicomponent systems
containing aluminium species in various environments.

*
Author to whom correspondence should be addressed. E-mail: aanderko@olisystems.com

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Also. THERMODYNAMIC MODEL The thermodynamic framework has been developed (6) by combining an excess Gibbs energy model for mixed-solvent electrolyte systems with a comprehensive treatment of chemical equilibria. caloric and volumetric properties of electrolytes in water. it is applied to systems containing aluminum in various aqueous environments. double salts. self-consistent treatment of speciation and phase equilibria is of utmost importance for realistic simulation of electrolyte systems. (5).g. we examine the applicability of this model to selected systems that are related to hydrometallurgical processes. Such solutions are challenging for computational models because of their complex chemical behaviour and strong nonideality. the model is used to represent the properties of fundamentally important acid-water and base-water solutions. Thus. Rather than focusing on particular processes. or mixed solvents. (3). A characteristic feature of electrolyte systems is the fact that phase equilibria and other thermodynamic properties are often inextricably linked to speciation equilibria. Various models for electrolyte solutions have been reviewed by Zemaitis et al. those with more than one distinct solvent and mixtures in which a given component may continuously vary from being a solute to being a solvent (e. speciation. a general. the model is capable of representing phase equilibria in multicomponent inorganic systems containing multiple salts. INTRODUCTION Electrolyte thermodynamics is of great importance for the simulation and optimization of hydrometallurgical processes. In many processes... The model is referred to as the mixed-solvent electrolyte (MSE) model because it is equally valid for classical aqueous systems. acids. (1). Rafal et al. speciation-related properties such as pH. In this study. are of primary importance. which may be due to ion pairing. the excess Gibbs energy is expressed as 2 of 15 . and bases (7). In many industrial processes. organic. In this framework. Complex phase behavior such as formation of multiple hydrated salts. multicomponent electrolyte solutions are encountered at high concentrations under diverse conditions of temperature and pressure. Recently. we select systems that provide a stringent test for the model. in acid-water mixtures). oxidation-reduction potential. The model is valid for salts from infinite dilution to the fused salt limit and for various completely miscible inorganic systems (such as acid-water mixtures) over a full concentration range. First. Then. This model was shown to reproduce simultaneously vapor-liquid equilibria. acid-base reactions. Pitzer (2). complexation and other phenomena. or the presence of eutectic points can be accurately represented. solid-liquid equilibria. etc. Loehe and Donohue (4) and Anderko et al. speciation-based thermodynamic model has been developed for mixed-solvent electrolyte solutions (6). distribution of complexed or hydrolyzed species.

The long-range interaction contribution is calculated from the Pitzer-Debye- Hückel formula (8. GMR is referred to as the middle-range term.. 9) expressed in terms of mole fractions and symmetrically normalized. only the basic features of the model are summarized here. ex ex ex GUNIQUAC G combinator G residual ial = + (4) RT RT RT with the combinatorial and residual terms expressed as: ex G combinator ial   φ Z θ  =  ∑ ni  ∑ x i ln i + ∑ q i x i ln i  (5) RT  i  i xi 2 i φi  3 of 15 .     ex G DH   4 Ax I x  1 + ρI x1 2  = − ∑ ni  ln (2) RT i  ρ  0  ∑ x i [ 1 + ρ I x .i ( ) 12  ]  i  where the sum is over all species. respectively. i. (1) was discussed in detail by Wang et al. i.e. Ix. (1) by differentiation following standard thermodynamic definitions. therefore.0) and Ax is given by 32 1  e2  Ax = (2πN A d s )1 2   (3) 3  4πε 0 ε s k B T    where ds and εs are the molar density and the dielectric constant of the solvent. For brevity. ex G ex G LR G ex G ex = + MR + SR (1) RT RT RT RT ex ex where G LR represents the contribution of long-range electrostatic interactions. Activity coefficients are obtained from eq.i0 denotes the ionic strength when the system composition reduces to a pure component i. The derivation of eq. For the short-range interaction contribution to the excess Gibbs energy.. primarily ionic (i. the UNIQUAC equation (10) is used. (6) and.e. ρ is related to the hard-core collision diameter (ρ = 14. Ix is the mole fraction-based ionic strength.. ion-ion and ion-molecule) interactions and G SR ex is a short-range contribution resulting from intermolecular interactions.e.i0 =½ zi2. Ix. GMR ex represents specific.

Z is a constant with a value of 10.ij T + c2.ij T + b2. ex G residuall     = − ∑ ni  ∑ q i xi ln ∑ θ jτ ij  (6) RT  i   i  j    where qi xi θi = (7) ∑qjxj j ri x i φi = (8) ∑ rj x j j  a ji  τ = exp −  (9) ji  RT    where qi and ri are the surface and size parameters.ij + c1. The short-range parameters are used primarily for interaction between neutral molecules. The UNIQUAC model has been extensively verified for systems composed of neutral molecules.ij / T (13) In practice. the parameters bij and cij are calculated as functions of temperature as bij = b0. For electrolyte systems encountered in hydrometallurgy. for the species i. respectively.ij + b1. In general.ij / T (12) cij = c0. The middle-range interaction contribution is calculated from an ionic strength- dependent. the middle-range contribution is by far the most important. the middle-range parameters are used to represent ion-ion and ion- neutral molecule interaction. symmetrical second virial coefficient-type expression (6): ex G MR   = − ∑ ni ∑ ∑ xi x j Bij (I x ) (10) RT  i i j where Bij (I x ) = B ji (I x ) . aij is the binary interaction parameter between species i and j (aij ≠ aji). Bii = B jj = 0 and the ionic strength dependence of Bij is given by Bij (I x ) = bij + cij exp(− I x + a1 ) (11) where bij and cij are adjustable parameters and a1 is set equal to 0. 4 of 15 .01.

It should be noted that standard-state properties calculated from the model of Helgeson et al. γ a ⋅ γ b ⋅ ... (1) are symmetrically normalized and based on the mole fraction scale.. µi0. data of the following type may be included in the regression of model parameters: 1. = cC + dD + . and (ii) the molality-based standard-state chemical potentials are converted to a corresponding mole fraction-based quantity.   A B A B  with ∆G 0 = ∑ν i µ i0 (16) i where µ i0 is the standard-state chemical potential of species i. In particular.. (6). At the same time.. the sum is over all species participating in the chemical reaction. 5 of 15 . The standard-state chemical potentials for aqueous species are calculated as functions of temperature and pressure using the Helgeson-Kirkham-Flowers equation of state (11). Chemical equilibrium calculations require the standard-state chemical potential. Evaluation of model parameters The parameters of the model are determined on the basis of various kinds of experimental data. The parameters of this model are available for a large number of aqueous species including ions. for a chemical reaction: aA + bB + .. are based on the infinite-dilution reference state and on the molality concentration scale. (1) are converted to those based on the unsymmetrical reference state. especially in completely dissociated systems. i. the activity coefficients obtained from eq. Speciation effects due to the formation of ion pairs and complexes are explicitly taken into account using chemical equilibria. as described by Wang et al. Thus. (14) with positive values for the species on the right-hand side of the equation and negative values for those on the left-hand side. γ Cc ⋅ γ Dd ⋅ . for all species together with activity coefficients..  − = ln Ca Db ⋅  (15) RT  x ⋅ x ⋅ .. To make the speciation calculations consistent. Osmotic coefficients (or activity of water) in aqueous solutions and activity coefficients.. the following conversions are performed: (i) the activity coefficients calculated from Eq. and neutral species (12-15). associated ion pairs..e.. Vapor-liquid equilibria 2. (14) the equilibrium conditions can be determined from ∆G 0  x c ⋅ x d ⋅ .. at infinite dilution in water. and ν i is the stoichiometric coefficient of species i in Eq.

At low and moderate temperatures. Figure 1 shows vapor-liquid equilibria for the system HCl – H2O at various temperatures. cannot approach the critical locus too closely. 3. The horizontal lines connect the compositions of two coexisting phases and show the equilibrium pressure of a three-phase liquid-liquid-vapor system. RESULTS AND DISCUSSION In this study.9⋅Tc. In concentrated electrolyte systems. The use of multiple data types is important to ensure the accuracy of model parameters. Unlike in the case of hydrochloric acid. therefore. Heats of mixing and dilution 8. Thus. the volatility of sulfuric acid is very small and the partial pressure of water in this system is close to the total pressure. which is indicated by horizontal lines. Data that reflect ionic equilibria in solutions. such as acid/base dissociation and complexation constants 5. The combined model is typically applicable for temperatures up to 0. Solubility of salts in water and other solvents 4. 300 °C. Among these types of data. we first apply the model to fundamental systems that often determine the electrolyte environment in practical hydrometallurgical systems. Heat capacities. whichever applies. Properties of electrolytes at infinite dilution. Below the three-phase pressure. solid-liquid equilibrium data can be used to constrain both the excess Gibbs energy and the properties of solid phases that are in equilibrium with the liquid phase. caloric data (heat of mixing or dilution and heat capacities) are useful to determine the temperature dependence of model parameters. this system shows liquid phase splitting. Whereas vapor-liquid equilibrium data directly constrain the excess Gibbs energy. This makes it possible to make reliable predictions of solubilities well outside of the temperature range of experimental solubility data. the model has been successfully applied up to 500 °C for concentrated sulfuric acid solutions as described below. In 6 of 15 . Figure 1 shows the compositions of coexisting vapor and liquid phases. Densities 7. the properties of relatively dilute aqueous systems can be represented up to ca. For example. The experimental data cover the concentration ranges from infinite dilution in water to the solubility or fused salt limit. Figure 2 shows vapor-liquid equilibria in the sulfuric acid – water – sulfur trioxide system. vapor-liquid equilibria and salt solubilities are of paramount importance. the critical temperature is typically higher and the model may be valid well beyond 300 °C. such as pH measurements 6. where Tc is the critical temperature of the mixture. This is due to the fact that the excess Gibbs energy model is valid only for liquid-like systems and. The correct representation of vapor-liquid and liquid-liquid equilibria demonstrates that the model accurately predicts the nonideality of hydrochloric acid solutions. For example.

In view of the stoichiometric relation SO3 + H2O = H2SO4. the mole fraction of sulfur trioxide is used as a concentration variable. calculations have been made for a large number of binary and multicomponent systems containing aluminum. Figure 6 shows the solubility of solid phases in the binary system Al2(SO4)3 – H2O. At temperatures between ca.Figure 2. The model accurately predicts the topology of the phase diagram. Figure 3 shows solid-liquid equilibria in the system NaOH – H2O as a function of temperature. the ice . An example of such calculations is shown in Figures 6 and 7. This allows us to show the behavior of oleum mixtures (SO3 – H2SO4) in addition to that of sulfuric acid (H2SO4 – H2O) on one plot.e. In this case. While Figure 4 illustrates the solubility behavior of aluminum at strongly alkaline conditions... enthalpies of dilution and heat capacities in addition to solid-liquid equilibria. The parameters obtained by fitting the thermodynamic properties of this system and the Na2SO4 – H2O binary were further used to calculate the solubility behavior of the ternary mixture Al2(SO4)3 – Na2SO4 – H2O.5 in Figure 2. The results are shown in Figure 7. multiple hydrated solid phases are observed.. Both the temperature and pH dependence of solubility are accurately reproduced by the model. 300 °C and 500 °C. The pH effect on the phase behavior is of particular interest here because of a shift in the pH dependence as the temperature is increased from ca.g. pure H2SO4 corresponds to x(SO3) = 0.NaOH⋅7H2O eutectic) and congruently melting solid hydrate phases (e. It should be noted that the model reproduces other properties such as vapor-liquid equilibria. 100 to 290 °C. sodium hydroxide (expressed as weight % of Na2O) and water. NaOH⋅3.5H2O and NaOH⋅H2O) at temperatures ranging from ca –40 °C to 300 °C. It is noteworthy that the model accurately reproduces the behavior of the system ranging from pure water to pure sulfur trioxide at temperatures from 0 °C to approximately 300 °C. At the conditions shown in this figure. Such double salts are common in many mixed electrolyte systems and can be accurately predicted by the model. the model correctly reproduces the phase behavior of concentrated solutions. After verifying the performance of the model for fundamental electrolyte systems. Figure 4 shows the solubility behavior of mixed systems containing aluminum oxides or hydroxides (expressed as weight % of Al2O3). AlNa(SO4)2). Figure 5 shows a solubility diagram for aluminum species at pH values ranging from 1 to 11. Of particular interest is the prediction of solubilities in systems containing multiple salts. boehmite (AlOOH) is the stable phase. A particular advantage of the model is its ability to reproduce the properties of multicomponent systems on the basis of a limited amount of data. including eutectic points (e.g. 7 of 15 . It is noteworthy that the ternary phase diagram shows the presence of a solid phase that does not occur in either of the binary subsystems (i. The model accurately reproduces this behavior for temperatures ranging from 0 °C to at least 200 °C (which is the upper limit of experimental data). The characteristic solubility maximum in this system is due to a transition between the stability of aluminum hydroxide or oxyhydroxide solid phases at lower alkalinities and sodium aluminate at higher alkalinities.

Schrage (25).0E-05 1.9 1.Calculated and experimental vapor-liquid equilibria in the sulfuric acid/oleum system as a function of the mole fraction of SO3.5 0. Literature data are taken from Gmitro and Vermeulen (23).0E-04 1.0E+01 100ºC 1.1 0.3 0.0 x SO3 Figure 2 . Experimental data are from references (16-22).01 0.0E-02 1. atm 0. and Giazitzoglou and Wuster (26).8 0.9 1 x (HCl) Figure 1 .1 0.7 0. atm 1.0E+02 300ºC 200ºC 1. 8 of 15 . 1. The horizontal lines at high pressures connect the compositions of two coexisting liquid phases.0E-01 0ºC P.0E-03 1. 100 10 -20C -10C 5C 15C 25C 35C 45C 1 Pressure.001 0.1 0.0E-08 0.0E+00 50ºC 25ºC 1.6 0.0E-07 1.0001 0 0.5 0.4 0.2 0.6 0.0E+03 500ºC 400ºC 1.8 0.2 0.0 0.7 0.3 0. Brand and Rutherford (24).0E-06 1.4 0.Calculated and experimental vapor-liquid equilibria in the HCl – H2O system.

45 40 200 C 35 Al(OH)3 (s) or AlOOH(s) 30 Na2 O.2H2O 40 NaOH.H2O 50 NaOH.3.Representation of solubilities of solids in the ternary system Al2O3 – Na2O – H2O. C Figure 3 – Calculated and experimental solubility of NaOH in aqueous solutions as a function of temperature. weight % 60 NaOH. Experimental data are taken from references (27) and (28).4H2O 20 NaOH. 9 of 15 .7H2O 10 Ice 0 -40 -20 0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 Temperature.2.5H2 O Al2O3 wt% 25 110C 20 95C 15 50C 10 30C 5 25C 0 0 10 20 30 40 50 60 70 Na2O wt% Figure 4 . The experimental data are from references (29-36).5H2 O 30 NaOH. 100 90 80 NaOH 70 NaOH.Al2 O3.

The experimental data are from references (27) and (39-43). 60 50 wt% Al2(SO4)3 40 Al2 (SO4 )3 .E-05 1. The experimental data are from references (37) and (38).E-08 1. 10 of 15 .3 C 1.E-07 1.E+01 1.5 C 1.E-06 1.E+00 150 C 1.E-01 203.E-10 0 1 2 3 4 5 6 7 8 9 10 11 12 pH Figure 5 – Representation of the solubility of boehmite (AlOOH) in 0.E-04 290. 1.E-09 1.E-02 250 C 101.16H2 O 30 20 ice 10 0 -20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 t/C Figure 6 – Calculated and experimental solubilities of aluminum sulfate as a function of temperature.03 m NaCl as a function of pH.2 C 1.E-03 m (AlOOH) 1.

tin. eutectic points formed by salt hydrates and ice. acids and bases in wide concentration and temperature ranges.and second-group elements. bases and salts of first. the model has been shown to be very useful for reproducing complex solid-liquid equilibrium diagrams.16H2 O 35 30 wt% Al2 (SO4 )3 25 AlNa(SO4 )2 . The model has been verified for a large number of systems including common acids. and iron.10H2 O 0 0 5 10 15 20 25 30 35 wt%-Na2SO4 Figure 7 – Calculated and experimental solubility of solids in the system Al2(SO4)3 – Na2SO4 – H2O. double salts. The model is based on a combination of an excess Gibbs energy formulation with a treatment of standard-state properties and an algorithm for comprehensive speciation calculations. etc. congruently melting solid phases. In particular.12H2 O 20 Na2 SO4 15 25C 30C 10 0C 5 Na2 SO4 . 40 Al2 (SO4 )3 . Work is in progress on developing model parameters for a large class of systems that are of interest in hydrometallurgy. the model can be extended to even higher temperatures (up to 500 °C) as long as the system of interest is subcritical. In favorable cases. The model is valid for aqueous systems ranging from infinite dilution to molten salts or pure acids at temperatures from the freezing point to 300 °C. which may involve multiple hydrates. CONCLUSIONS A recently developed comprehensive mixed-solvent electrolyte model has been applied to calculate phase equilibria in multicomponent systems containing salts. It is also applicable to organic and organic – salt mixtures. The experimental data are from Linke and Seidell (27). aluminum. 11 of 15 .

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