Article pubs.acs.

org/jchemeduc

Ion Association versus Ion Interaction Models in Examining Electrolyte Solutions: Application to Calcium Hydroxide Solubility Equilibrium
M. Isabel Menen dez and Javier Borge*
Departamento de Qumica Fsica y Analtica, Universidad de Oviedo, C/Julian Clavera 8, 33006 Oviedo, Spain
S Supporting Information *

ABSTRACT: The heterogeneous equilibrium of the solubility of calcium hydroxide in water is used to predict both its solubility product from solubility and solubility values from solubility product when inert salts, in any concentration, are present. Accepting the necessity of including activity coecients to treat the saturated solution of calcium hydroxide (and by extension, all electrolyte solutions) and the inadequacy of any general or nonspecic equation (such as the DebyeHuckel limiting law or Davies equations) to calculate activity coecients of 1:2 electrolytes, our results uncover (i) how the inclusion of ion pairs in the last mentioned equations makes them adequate for low ionic strength solutions and (ii) the need of sophisticated models, such as the ion-interaction Pitzer equations, for calculating the activity coecients when ionic strength is high. In addition, we have developed a set of MATLAB scripts and propose the use of the free code PHREEQC version 3 to perform all the calculations described in the article. The tasks proposed here can be complemented with the experimental determination of the solubility of calcium hydroxide in water along with the experimental checking of its solubility in aqueous salt solutions during several lab sessions. Experimental guidance is provided as Supporting Information. KEYWORDS: Upper-Division Undergraduate, Physical Chemistry, Computer-Based Learning, Textbooks/Reference Books, Aqueous Solution Chemistry, Precipitation/Solubility, Thermodynamics

ost electrolyte solutions cannot be adequately represented by ideal and dilute ideal solutions due to the presence of electric charge: they are the examples of nonideal solutions, where the use of activities instead of concentrations is necessary. Activity coecients are introduced as correction factors that transform concentrations into activities. The thermodynamic representation of electrolyte solutions (thermodynamic model) requires (i) an itemization of the solutes present (speciation or chemical model, answer to what species are there in the solution?) and (ii) a methodology to estimate activity coecients (activity model, answer to how can we deal with their nonideality?). There are as many thermodynamic models as combinations can be formed between chemical and activity models. We present the full spectrum of thermodynamic models and apply some of them to study of the solubility of calcium hydroxide in water and in aqueous salt solutions of any concentration. The models and experiments are appropriate for upper-level physical chemistry students.

However, some years later, total dissociation of strong electrolytes was recognized and, almost simultaneously, the ion pair notion (an association of two solvated ions of opposite sign that do not form a true chemical bond between them) was introduced. This latter idea was initially ranked as a cunning argument to reproduce, with greater accuracy, experimental data related to the electrolyte solutions (electrical conductivity measurements, basically). However, in a few years, experimental evidence conrmed their existence. Figure 1 shows dierent chemical models for the particular case of calcium

THERMODYNAMIC MODELS

Chemical Models

Speciation of electrolyte solutions is controversial from the very beginning.1 Arrheniuss original proposal was to assume that the strong and weak electrolytes do not dissociate completely.
2013 American Chemical Society and Division of Chemical Education, Inc.

Figure 1. (A) The simple chemical model (only free ions); (B) one possible intermediate model (free ions and some ion pairs); (C) the complex model (free ions and all possible ion pairs). Published: December 5, 2013
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dx.doi.org/10.1021/ed4004589 | J. Chem. Educ. 2014, 91, 9195

Journal of Chemical Education hydroxide saturated solution in presence of an inert salt (a salt that does not present any ion common to those produced in the dissolution of Ca(OH)2) represented by NaCl: from those considering just solvated isolated ions (Figure 1A) to those where isolated ions coexist with all possible ion pairs (Figure 1C) passing through intermediate cases where only some ion pairs are considered (Figure 1B).
Activity Models

Article

As previously stated, a thermodynamic model is any combination of a chemical model and a model to calculate activity coecients. Scientic literature classies thermodynamic models in four major groups (see Table 1).11 Table 1. Classication of Thermodynamic Models
Thermodynamic Model Basic Association Interaction Mixed Chemical Model Free Free Free Free ions ions + ion pairs ions ions + ion pairs Activity Model Ionic strength Ionic strength Ion interaction Ion interaction

DebyeHuckel theory2 is the simplest approach for calculating activity coecients in electrolyte solutions. Its foundations and limitations can be found elsewhere.3,4 Essentially, the activity coecient of an ion, i, is a simple function of the charge of the ion, zi, the temperature, T, the nature of the solvent (through its relative permittivity, ), and the ionic strength of the solution, I. The activity coecient of a neutral species is unity. Figure 2A outlines the modus operandi of the DebyeHuckel

Figure 2. (A) Modus operandi of the DebyeHuckel theory (ionic strength activity model) and (B) the Pitzer methodology (ion interaction activity model). In (A) white circles represent ions and empty circles neutral molecules. In this model, the activity coecient of species i (with charge zi) in a particular solvent () and at a particular temperature (T) only depends on I, a global property not aected by the nature of the ions but only on their charge (zj) and concentration (mj). In (B) green and orange circles represent ions of opposite charge, so black and white lines correspond to repulsive and attractive interactions, respectively, modulated, in each case, by the specic nature of the ions. In short, ion interaction activity models perform a microscopic description of the interactions much more detailed than that performed by the ionic strength activity models.

Note that the application of the simplest possible combination (free ions + ionic strength activity model) is very restricted (only to extremely dilute solutions). The mixed model is the most complex (note that the most sophisticated descriptions are used for both chemical and activity models) and will not be implemented in this article. The usefulness of a thermodynamic model is based on the quality with which it reproduces the available experimental data. Dierent thermodynamic models are used to calculate the solubility product of calcium hydroxide (eq 1) from experimental measurements of its solubility (K(T) = f (s)) and the solubility from the solubility product (s = f1(K(T))), where the function f is the mathematical representation of the thermodynamic model. K(T) is the standard equilibrium constant (see the The standard equilibrium constant in the Supporting Information).
Ca(OH)2 (s) Ca 2 +(aq) + 2OH(aq)
(1)

theory, which yields activity coecients valid only for very low (0.01 mol kg1) ionic strengths. Many other semiempirical functions based on the same parameters have been described in the literature to estimate activity coecients at higher ionic strengths (the documentation accompanying the computer program Aqueous Solutions5 contains an exhaustive enumeration of such functions). The Davies equation (valid for ionic strengths up to 0.1 mol kg1), originally proposed in 19386 and revised in 1962,7 is one of the most popular equations. Henceforth, activity coecients calculated via DebyeHuckel, Davies, or similar formulas will be referred to as the ionic strength activity model. There is another model, opposite to the above one, to calculate activity coecients in electrolyte solutions. It treats, one-by-one, the interactions of each solute species, B, with all others. This proposal has its origin in the principle of the specic interactions of ions,8 and Pitzer equations9,10 are a practical realization of this new procedure. Figure 2B outlines the modus operandi of the Pitzer methodology, which will be referred to as the ion interaction activity model.
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It has been established that the determination of solubility products from solubility measurements is not an adequate method to get accurate solubility products, mainly due to the need of using a particular model to evaluate activity coecients of the species involved.14 However, throughout the history of this Journal, many articles devoted to the study of solubility equilibrium have appeared1523 with the goal of obtaining equilibrium constants from solubility measurements. In most of them, authors encourage the use of activities instead of concentrations (Ramette15 advocates this idea with special vehemence) and they follow nearly the same outline: choose a particular chemical compound, measure its solubility in water, and apply dierent formulas (mainly the DebyeHuckel law and the Davies equation) to calculate activity coecients. The pedagogical value of this approach is indisputable, but it is not possible to obtain good solubility products without using advanced thermodynamic models, as we shall show later. The reverse relationship between solubility product and solubility, expressing the solubility as a function of the solubility product, is also interesting not only from a pedagogical viewpoint but also for its numerous applications in real-life problems where solubility is strongly aected by the presence of other ions. Real-life problems are more appealing for undergraduate learners as they allow them to appreciate the capability of physical chemistry to solve such practical issues. To the best of our knowledge, only the paper of Willey23 deals with the prediction of solubility from solubility products at salt aqueous solutions, a complex system more similar to real ones than simple pure aqueous solutions. Again, the application of advanced thermodynamic models is mandatory to obtain correct values of the solubility.
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Journal of Chemical Education

PREDICTING SOLUBILITY PRODUCT FROM SOLUBILITY As the solubility product of Ca(OH)2 and its solubility in water at several temperatures are available in the literature, students should look for this information to assess the quality of their results. The NIST Critically Selected Stability Constants of Metal Complexes Database24 is a source of outstanding quality to get values of K(T). The value of the solubility product of Ca(OH)2 is presented (at 298.15 K) as log10K = 5.29(10), which implies K(298.15 K) = 5.13 106. Note that the uncertainty associated with log10K generates a range of possible values for K(298.15 K) comprised between 4.07 106 and 6.46 106. The NBS Tables of Chemical Thermodynamic Properties25 provides rG(298.15 K) = 30.422 kJ mol1 for the solubility equilibrium of Ca(OH)2, where rG is the standard reaction Gibbs energy (see The standard equilibrium constant in the Supporting Information). Then, K(298.15 K) = 4.6794 106, a value within the range predicted by the NIST Database. Like any physical quantity derived from an experiment, there is not one single value for the solubility of calcium hydroxide in water at 298.15 K. The classic study, par excellence, on this subject was carried out by Johnston and Grove26 in 1931. The proposed value was 19.76 103 mol kg1. It seems that several factors such as the aggregation state of the solid (crystalline solids do not behave like amorphous ones; particle size is also a critical factor) or the preparation method of the saturated solution inuence the experimental value. It is worth mentioning that the solubility of calcium hydroxide in water decreases with temperature, a fairly infrequent behavior. In the Supporting Information, a procedure for the experimental determination of calcium hydroxide solubility in water in a student lab is outlined. The time needed to carry out this procedure is 4 h.
Ideal Solution Model

Article

Ca 2 +(aq) + OH(aq) CaOH+(aq)

(3)

The NIST Database result for the equilibrium constant of eq 3 is presented (at 298.15 K) as log10K = 1.30(10). This implies K(298.15 K) = 20.0. Note that the uncertainty associated with log10K generates a range of possible values for K(298.15 K) comprised between 15.8 and 25.1. Using the NBS Tables, rG(298.15 K) = 7.576 kJ mol1. Then, K(298.15 K) = 21.25, a value within the range predicted by the NIST Database. In this case, it is necessary to consider simultaneously the two equilibria: solubility (eq 1) and association (eq 3). The application of the association model (using the Davies equation to calculate the activity coecients) yields a solubility product of 5.57 106 (Predicting solubility product from solubility: association model in the Supporting Information):
K m(T , p) =

(mBB/m)
B

= 5.57 106
(4)

where B is the activity coecient (molality scale) of the substance B. Using the NIST Database value for the solubility product (5.13 106), the percentage relative error is 8.61%, which means that ionic association models generate accurate solubility product values in water.
Interaction Model

For the present case, Pitzer model generates a solubility product of 6.90 106.
K m(T , p) =

(mBB/m)
B

= 6.90 106
(5)

Although out of Table 1, the simplest way to obtain a rst approximation to the solubility product comes from the ideal solution model where solutesolvent interactions are very similar to solventsolvent interactions and the size and shape of solute and solvent molecules are also similar. These conditions mean that enthalpy and volume of mixing are zero, which are never fullled by electrolyte solutions. The application of the ideal solution model to the saturated solution of Ca(OH)2 yields a solubility product of 3.09 105 (see Predicting solubility product from solubility: ideal solution model in the Supporting Information):
K m(T , p , m) =

The percentage relative error, with respect to the NIST Database value (5.13 106), is 34.48% (although this value falls to 6.79% if the comparison is made with the upper limit proposed by the NIST Database). For the problem we are solving now, that is, prediction of Ca(OH)2 solubility product from its solubility in water, values provided by Pitzer model are similar to those oered by the ion association method. A MATLAB script (s2k.m) for the calculation of Km(T,p), or Km(T,p,m), for the three cases just described has been included in the Supporting Information.

(mB/m)
B

= 3.09 105
(2)

where the index B refers to species in solution, m is the standard molality, and B denotes the stoichiometric number. Taking as right value that proposed by the NIST Database (5.13 106), the percentage relative error of Km is 501.59%. This large error clearly indicates that the ideal solution model is inadequate to represent the saturated solution of Ca(OH)2.
Association Model

In water, ions coming from Ca(OH)2 dissolution can form the CaOH+ ion pair. The formation of the CaOH+ ion pair in saturated solutions of calcium hydroxide through eq 3 has been experimentally veried.
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PREDICTING SOLUBILITY FROM SOLUBILITY PRODUCT Up to now we aimed to predict the solubility product of calcium hydroxide from its solubility in water. Now we proceed to a more applied issue where the aim is the prediction of Ca(OH)2 solubility, not only in water but in aqueous salt solutions, of any concentration, based on its solubility product. This procedure is customary in professional practice, such as in pharmaceutical industry to know how the solubility of a drug changes in the presence of other species, and is also important in the study of the variation of the solubility of calcium carbonate in the presence of carbon dioxide (the solubility of calcium carbonate in fresh and salt water is a crucial parameter for the development of all living beings with external shells). Terms salting-in and salting-out stand for the solubilization and precipitation, respectively, of a substance due to salt addition to water. For our particular system, in 1931 Johnston and Grove experimentally studied the variation of Ca(OH)2 solubility in presence of dierent salts and at dierent concentrations. A procedure for the experimental determination of calcium hydroxide solubility in aqueous salt solutions in a students lab is outlined in the Supporting Information.
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Journal of Chemical Education Recently, the freely distributed program PHREEQC version 3 has been published as a tool for chemical speciation.27 It is a professionally oriented code ready to run under both Linux and Microsoft Windows operating systems, which allows the use of the two theoretical approaches tested in this work (association and interaction models). The software was designed to handle much more complex systems than Ca(OH)2 in presence of NaCl, but it is easy to use to solve the teaching problems and, at the same time, provides a professional experience to the undergraduate students.
Association Model

Article

We focus on the Davies semiempirical equation combined with the ion pair formation to predict Ca(OH)2 solubility. The cases where the inert salt NaCl is present in the solution at dierent concentrations is examined. The NaCl salt makes possible the formation of up to four ion pairs between its ions and those coming from Ca(OH)2 dissolution: CaOH+, CaCl+, NaOH, and NaCl (association among more than two ions and chemical reactions yielding new species are avoided). A literature search indicates that these four ion pairs have been detected and their association constants (obtained from NIST Database24) are 20.0, 2.51, 1.26, and 0.50, respectively. It is worth mentioning that dierent literature sources display dierent values for the association constants of the weakest pairs. Particularly, for the pair NaOH, Koryta et al.28 give a value of 0.20 and the value, by default, provided by the program PHREEQC version 3 is 1010. Calculations are performed using PHREEQC version 3 and NIST equilibrium constants (input les have been included in the Supporting Information). Figure 3 shows four continuum lines corresponding to dierent chemical models tested for the solution, along with the

measurements. Yellow, green, and purple lines were obtained considering an additional ion pair each time. It is evident that results worsen considerably, mainly at high ionic strengths. When all possible ion pairs are taken into account, six simultaneous equilibria coexist in the solution (including calcium hydroxide solubility equilibrium and the autoionization of water), so chemical complexity is high and the solution of the six coupled equations is strongly dependent on the values of the standard equilibrium constants used. As mentioned above, completely dierent values for the association constants of the weakest pairs can be found in the literature and choosing one or the other fully determines the outcome. Calculations with equilibrium constants other than NIST values (not displayed) show dramatic changes in yellow, green, and purple lines and indicate that the only stable fact is that neglecting the eect of the weakest ion pairs (in this case the most uncertain) yields the best results. The correct use of association models involves the knowledge of accurate association constants of all the possible ion pairs. If dubious values are employed, calculated results may be not fully trustful. To corroborate this idea, we include two new calculations in the Supporting Information. As the number of dierent ion pairs in a solution is increased, the use of the association model is more and more complicated.
Interaction Model

Next step in the prospect of calculating accurate Ca(OH)2 solubilities at high ionic strengths is the use of the specic interactions Pitzers model. PHREEQC version 3 code provides the Ca(OH)2 solubility at dierent NaCl concentrations displayed in the dashed blue line in Figure 3. Pitzer results are close to experimental data and to those obtained by the best association model. However, Pitzer results could be obtained in a straight way, so we propose that this model is adequate to predict calcium hydroxide solubility in salt aqueous solutions when the ionic strength is high.

Figure 3. Variation of the solubility of Ca(OH)2 in the presence of NaCl. Blue dots are the experimental data obtained by Johnston and Grove. The solid lines are the theoretical results obtained by applying the association model (red, CaOH+; yellow, CaOH+ + CaCl+; green, CaOH+ + CaCl+ + NaOH; purple, CaOH+ + CaCl+ + NaOH + NaCl). The dashed blue line is the theoretical result obtained by applying the interaction model.

CONCLUSIONS This article presents a step forward in the pedagogical approach of physical chemistry to real situations. Both the Debye Huckel limiting law and any of its semiempirical extentions are instructional models useful to get acquainted with the calculation of activity coecients in electrolyte solutions, but useless to solve real problems. This article describes two possible alternatives to the academic treatments: a relatively simple one (ionic association theory) and a more advanced one (specic ion interaction theory). The rst alternative is subject to the tentative selection of ion pairs relevant in the solution, whereas the second alternative only needs the parameters of the ions in the solution. Calcium hydroxide, a sparingly soluble substance, has been used to illustrate all concepts presented through the prediction of its solubility product from its solubility and the reverse process, the calculation of its solubility even at high ionic strengths. Computational tools are provided to perform all calculations described.

experimental data (blue dots) obtained by Johnston and Grove. As CaOH+ ion pair shows an association constant much larger than those for the remaining ion pairs, we start our test of the association models by including only this one. The red line in Figure 3 indicates that the association model with the strongest ion pair does not deviate very much from experimental
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ASSOCIATED CONTENT

S Supporting Information *

The standard equilibrium constant; experimental determination of calcium hydroxide solubility in water and in aqueous salt solutions: chemicals, hazards, instrumentation and lab guide; predicting solubility product from solubility: ideal solution model; predicting solubility product from solubility: association
dx.doi.org/10.1021/ed4004589 | J. Chem. Educ. 2014, 91, 9195

Journal of Chemical Education model; MATLAB script to calculate calcium hydroxide solubility product from solubility values; PHREEQC version 3 input les; predicting solubility from solubility product; association model; inuence of equilibrium constant of the weakest ion pairs. This material is available via the Internet at http://pubs.acs.org.

Article

AUTHOR INFORMATION

Corresponding Author

*E-mail: jborge@uniovi.es.
Notes

The authors declare no competing nancial interest.

REFERENCES

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dx.doi.org/10.1021/ed4004589 | J. Chem. Educ. 2014, 91, 9195