Article

pubs.acs.org/jchemeduc

Ion Association versus Ion Interaction Models in Examining

Electrolyte Solutions: Application to Calcium Hydroxide Solubility
Equilibrium
M. Isabel Menéndez and Javier Borge*
Departamento de Química Física y Analítica, Universidad de Oviedo, C/Julián Clavería 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
coefficients to treat the saturated solution of calcium hydroxide (and by
extension, all electrolyte solutions) and the inadequacy of any general or
nonspecific equation (such as the Debye−Hückel limiting law or Davies
equations) to calculate activity coefficients 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 coefficients 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

M ost electrolyte solutions cannot be adequately repre-

sented by ideal and dilute ideal solutions due to the
presence of electric charge: they are the examples of nonideal
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
solutions, where the use of activities instead of concentrations is sign that do not form a true chemical bond between them) was
necessary. Activity coefficients are introduced as correction introduced. This latter idea was initially ranked as a cunning
factors that transform concentrations into activities. The argument to reproduce, with greater accuracy, experimental
thermodynamic representation of electrolyte solutions (thermo- data related to the electrolyte solutions (electrical conductivity
dynamic model) requires (i) an itemization of the solutes measurements, basically). However, in a few years, exper-
present (speciation or chemical model, answer to what species imental evidence confirmed their existence. Figure 1 shows
are there in the solution?) and (ii) a methodology to estimate
different chemical models for the particular case of calcium
activity coefficients (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 thermody-
namic 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 appro-
priate for upper-level physical chemistry students.

■ THERMODYNAMIC MODELS
Chemical Models
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).
Speciation of electrolyte solutions is controversial from the very
beginning.1 Arrhenius’s original proposal was to assume that
the strong and weak electrolytes do not dissociate completely.
© XXXX American Chemical Society and
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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
2 Basic
Debye−Hückel theory is the simplest approach for calculating
activity coefficients in electrolyte solutions. Its foundations and
limitations can be found elsewhere.3,4 Essentially, the activity
coefficient 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, ε), and the ionic strength of the
solution, I. The activity coefficient of a neutral species is unity.
Figure 2A outlines the modus operandi of the Debye−Hückel
Figure 2. (A) Modus operandi of the Debye−Hückel 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 coefficient
of species i (with charge zi) in a particular solvent (ε) and at a
particular temperature (T) only depends on I, a global property not
affected 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
specific 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.
theory, which yields activity coefficients valid only for very low
(≤0.01 mol kg−1) ionic strengths. Many other semiempirical
functions based on the same parameters have been described in
the literature to estimate activity coefficients at higher ionic
strengths (the documentation accompanying the computer
program Aqueous Solutions5 contains an exhaustive enumer-
ation of such functions). The Davies equation (valid for ionic
strengths up to 0.1 mol kg−1), originally proposed in 19386 and
revised in 1962,7 is one of the most popular equations.
Henceforth, activity coefficients calculated via Debye−Hückel,
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 coefficients 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
specific 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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Article
As previously stated, a thermodynamic model is any
combination of a chemical model and a model to calculate
activity coefficients. Scientific literature classifies thermody-
namic models in four major groups (see Table 1).11
Table 1. Classification of Thermodynamic Models
Thermodynamic Model Chemical Model Activity Model
Free ions Ionic strength
Association Free ions + ion pairs Ionic strength
Interaction Free ions Ion interaction
Mixed Free ions + ion pairs Ion interaction
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.
Different 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 = f−1(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)
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 coefficients
of the species involved.14 However, throughout the history of
this Journal, many articles devoted to the study of solubility
equilibrium have appeared15−23 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 different formulas (mainly the Debye−Hückel law
and the Davies equation) to calculate activity coefficients. 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 affected 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.
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 × 10−6. Note that the
uncertainty associated with log10K° generates a range of
possible values for K°(298.15 K) comprised between 4.07 ×
10−6 and 6.46 × 10−6. The NBS Tables of Chemical
Thermodynamic Properties25 provides ΔrG°(298.15 K) =
30.422 kJ mol−1 for the solubility equilibrium of Ca(OH)2,
where ΔrG° is the standard reaction Gibbs energy (see “The
standard equilibrium constant” in the Supporting Information).
Then, K°(298.15 K) = 4.6794 × 10−6, 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 × 10−3 mol kg−1. 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 influence 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
Although out of Table 1, the simplest way to obtain a first
approximation to the solubility product comes from the ideal
solution model where solute−solvent interactions are very
similar to solvent−solvent 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 fulfilled 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 × 10−5 (see
“Predicting solubility product from solubility: ideal solution
model” in the Supporting Information):
K m(T , p , m) = ∏ (mB/m°)υ B
= 3.09 × 10−5
B (2)
where the index B refers to species in solution, m° is the
standard molality, and υB denotes the stoichiometric number.
Taking as “right” value that proposed by the NIST Database
(5.13 × 10−6), 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 verified.
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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,
ΔrG°(298.15 K) = −7.576 kJ mol−1. 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 coefficients) yields a solubility product
of 5.57 × 10−6 (“Predicting solubility product from solubility:
association model” in the Supporting Information):
K mγ(T , p) = ∏ (mBγB/m°)υ B
= 5.57 × 10−6
B (4)
where γB is the activity coefficient (molality scale) of the
substance B. Using the NIST Database value for the solubility
product (5.13 × 10−6), 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 × 10−6.
K mγ(T , p) = ∏ (mBγB/m°)υ B
= 6.90 × 10−6
B (5)
The percentage relative error, with respect to the NIST
Database value (5.13 × 10−6), 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 offered by the ion association method.
A MATLAB script (s2k.m) for the calculation of Kmγ(T,p), or
Km(T,p,m), for the three cases just described has been included
in the Supporting Information.
■
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 different salts and at different 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.
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
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 different
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 different literature sources display different 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 10−10.
Calculations are performed using PHREEQC version 3 and
NIST equilibrium constants (input files have been included in
the Supporting Information).
Figure 3 shows four continuum lines corresponding to
different chemical models tested for the solution, along with the
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.
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
D dx.doi.org/10.1021/ed4004589 | J. Chem. Educ. XXXX, XXX, XXX−XXX
Article
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 different 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 effect 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 different 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 specific
interactions Pitzer’s model. PHREEQC version 3 code provides
the Ca(OH)2 solubility at different 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.
■ CONCLUSIONS
This article presents a step forward in the pedagogical approach
of physical chemistry to real situations. Both the Debye−
Hückel limiting law and any of its semiempirical extentions are
instructional models useful to get acquainted with the
calculation of activity coefficients 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
(specific ion interaction theory). The first 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.
■
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
Journal of Chemical Education Article

model; MATLAB script to calculate calcium hydroxide
solubility product from solubility values; PHREEQC version
3 input files; predicting solubility from solubility product;
association model; influence of equilibrium constant of the
weakest ion pairs. This material is available via the Internet at
http://pubs.acs.org.
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■
Reference Database 46. NIST Critically Selected Stability Constants of
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AUTHOR INFORMATION Institute of Standards and Technology: Gaithersburg, MD, 2004.
Corresponding Author (25) Wagman, D. D.; Evans, W. H.; Parker, V. B.; Schumm, R. H.;
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*E-mail: jborge@uniovi.es.
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