Analysis of Equilibrium Reactions using saturated Ca(OH)2

and NaCl solutions: Common-ion Effect, Diverse-ion Effect,

Solvent Polarity, and Temperature
Reginald Christian S. Bernardo
Institute of Chemistry, University of the Philippines, Diliman, Quezon City 1101 Philippines
Theoretical Physics Group, National Institute of Physics, University of the Philippines, Diliman, Quezon City 1101 Philippines

ABSTRACT
The equilibrium between Ca(OH)2(s) and its constituent ions in saturated solutions using distilled H2O, KCl, and
Ca(NO3)2 media have been analyzed using Titrimetric Analysis. The experimental value for the solubility product
constant of Ca(OH)2 in distilled H2O deviated from the accepted value by 456 %. Nonetheless, the experimental trend
for the molar solubility in the three media (Ca2+ < distlled H2O < KCl) agreed with theoretical prediction. Result shows
that the common-ion effect decreases solubility while diverse-ion effect increases solubility. On the other hand, the
equilibrium between NaCl(s) and its ions was analyzed to study the effect of solvent polarity and temperature on
equilibrium. It turns out experimentally that an increase in polarity and temperature favors the formation of the solid
solute, hence decreasing solubility. The unexpected decrease in solubility at high temperature was properly
accounted for and the sources of error for the whole experiment were discussed.
Introduction
The equilibrium between a salt and its
constituent ions is an interesting chemical
phenomenon with a wide variety of potential
applications. For example, the compounds
Ca3(PO4)2(s), forming the bulk of the human teeth and
bones, and CaCO3(s), responsible for the formation of
caves and sinkholes, are slightly soluble compounds
and dissociate only partially in aqueous solutions [1].
The principles of chemical equilibrium and solubility
can be applied to the sickening of erythrocytes and
can offer a bridge between the subjects of biology
and chemistry [2]. Potential applications also exist in
industries where the equilibrium reactions are
exploited to produce and extract particular chemicals
[3]. The equilibrium between a solute and its
component ions are important in the modern scientific
world and therefore effort must be given by both the
lecturers and students in understanding this
seemingly difficult, yet interesting and rewarding,
chemical concept [4, 5].
Consider a general equation representing
the chemical equilibrium between a slightly soluble
salt and its component ions:

() + ( ) + ( )
(1)
The equilibrium constant for these kinds of reaction is
called the solubility product constant Ksp. Based on
Eq. (1) this can be written as
= + .
(2)
The molar solubility s, defined as the number of
moles of salt dissolved to form a liter of saturated
solution, is directly related to the solubility product
constant [1]. In symbols, this relationship is given by
= ( ) +
(3)
for the equilibrium in Eq. (1). The solubility product
constants for several slightly soluble salts in particular
experimental conditions are tabulated in most
elementary chemistry textbooks [1, 3].
The factors that affect the equilibrium
reaction Eq. (1), and correspondingly its solubility
product constant and molar solubility, are the
following: presence of common and diverse ions,
temperature, and change in polarity of solvent. The
common ions are those ions that are induced in the
reaction and are a component of the salt. Using Le
Chateliers principle one can deduce that the
presence of common ions in a solution will tend the
reaction to go backwards, thus forming the solid salt
and decreasing solubility. On the other hand, diverse

ions are those ions that are induced in the reaction

are not an ion component of the salt. The presence of
diverse ions increases solubility by making the
interionic interactions between the salt component
ions and diverse ions significant [6]. In contrast, the
addition of polar molecules, such as ethanol, to the
equilibrium favors the formation of the precipitate
because the polar molecules react with water,
consequently reducing the amount of water that
dissolves the salt. The temperature affects the
equilibrium reaction because the solubility product
constant, like all equilibrium constants, is related to a
standard Gibbs free energy [1, 3]. At high
temperatures, it is expected that the endothermic
reaction will be favored.
In this experiment, the equilibrium reaction
between calcium hydroxide and its component ions
was analyzed to study the common- and diverse-ion
effects:
2 2+ ( ) + 2 ( ) (4)
In addition, the solubility product constant for the
partial dissociation of solid calcium hydroxide in water
was determined. The equilibrium reaction between
solid sodium chloride and its component ions was
used to qualitatively determine the effects of
temperature and change in solvent polarity on the
solubility:
+ ( ) + ( )
(5)
Methodology
For the determination of the solubility
product constant of Ca(OH)2(s) and the analysis of
common- and diverse-ion effects, a saturated calcium
hydroxide solution was prepared in three media:
distilled water, 0.5 M KCl, and 0.1 M Ca(NO3)2. The
preparation of the saturated solution in a medium
proceeded as follows. 60.0 mL of the medium was
transferred to a 250-mL beaker. While stirring, solid
Ca(OH)2 was added until the solution is saturated.
The stirring was continued for 5 minutes and then the
solution was left for 10 minutes. The suspension was
filtered using Whatman filter paper and a 25-mL
aliquot of the supernate was transferred to a 125-mL
Erlenmeyer flask. After adding 3 drops of 1 %
phenolphthalein the solution was titrated with 0.1 M
HCl until the phenolphthalein color disappears. Three
trials were done for each medium.

For the analysis of solvent polarity effect on

solubility, 1.0 mL of saturated NaCl solution was
transferred to a 6-inch test tube. 1.0 mL of 95 %
ethanol was then added into the test tube and the
observations were recorded. For the analysis of
temperature effect on solubility, another 1.0 mL
saturated solution was transferred to a 6-inch test
tube, but with NaCl solids. The test tube was placed
in a hot water bath and the observations were
recorded.
Results and Discussion
In the Ca(OH)2 solution that was prepared in
distilled water an average value of 9.85 mL of 0.1 M
HCl was needed to completely vanish the pink
phenolphthalein color. This amount of titrant is directly
related to the amount of OH- that was neutralized in
the titration process. And because it follows from Eq.
(4) that the molar solubility s of Ca(OH)2(s) is related to
the ion concentrations then the molar solubility and
solubility product constant Ksp can be calculated using
1
= []
(6)
2
and
= [2+ ] [ ]2 = 4 3 .
(7)
The experimental results suggest that the molar
solubility and solubility product constant of Ca(OH)2(s)
in water have the values 0.0197 M and 3.0610-5,
respectively. Based on the accepted value for the
molar solubility of Ca(OH)2(s) that is 5.510-6 the
experimental value has a percent error of 456 % [3].
The major source of error can be from the fact that
the work was divided among many experimentalists,
each contributing a different amount of error. The
laws of error propagation then imply that there will be
a larger error than if there was a single
experimentalist for the whole experiment. Another
possible major source of error is that the Ksp is
temperature dependent. The accepted value of Ksp for
Ca(OH)2 in water is at 25 degrees Celsius [3]. A
source of error can also be the experimental
limitations of the equipment, such as the 0.1 mL limit
in the volume of HCl that can be measured by the
burette. Also, a small error may come from the
approximations used in the analysis of data, i.e. that
the equilibrium concentration of the OH- is exactly the
amount of neutralized OH- by titration. A calculation
that takes into account that the phenolphthalein
indicator loses its visible pink color at pH = 8.2 shows
that the correction to the OH- concentration in

equilibrium is of the order 10-6. Although very small,

the correction has to be taken into account when the
dilution is large.
The molar solubilities of the saturated
Ca(OH)2 solution in KCl and Ca2+ media were
determined in the same manner as the molar
solubility of saturated Ca(OH)2 in distiller water. It
turns out, based on experimental results, that the
molar solubility of Ca(OH)2(s) in the KCl and Ca2+
media are 0.0217 M and 0.0119 M, respectively.
Thus, it is observed that the experimental trend in the
molar solubility of Ca(OH)2(s) in the three media is as
follows: Ca2+ < distiller water < KCl. This agrees with
what is predicted theoretically. Despite the large error
for the experimental solubility product constant, the
expected trend for common- and diverse-ion effects
was observed. In the saturated Ca(OH)2 in KCl media
the ionic strength was calculated to be 0.565 M.
Ethanol is known to be a molecule of high
polarity. It is therefore expected that the addition of
ethanol into the saturated NaCl solution would
decrease solubility and favor the formation of
precipitate. This was indeed observed in the
experiment. The highly polar ethanol molecules are
capable of hydrogen bonding with water. This
reaction between ethanol and water molecules
reduces the amount of water that dissolves the solute.
The dissociation of the solute into its component ions
is then less favored than its formation. Finally, it is
known that the solid NaCl is stable, that its energy is
relatively lower than when its component ions are
infinitely separated [7]. The dissociation of NaCl into
its component ions is therefore an endothermic
reaction and is favored at high temperatures.
However, experimental results showed that the
amount of solid NaCl increased when the saturated
NaCl solution was placed in a warm water bath. A
possible explanation to this is that the water bath
might have gotten too hot, thus evaporating some of
the aqueous part of the solution, and tending a
backward reaction. This follows using LeChateliers
principle.
Conclusion and Recommendations
The common-ion effect and diverse-ion
effect was studied using the equilibrium between the
solid calcium hydroxide, Ca(OH)2(s), and its
component ions. Experimental results showed that

the solubility product constant of Ca(OH)2(s) in water is

3.0610-5 which deviated from an accepted value by
456 %. Nonetheless, the experimental result for the
trend of solubility in solvents with common and
diverse ions agreed with theoretical predictions. The
major error was accounted by the fact that the
experimental work was divided in a large group of
experimentalists and that the Ksp is dependent on
temperature. Minor errors were attributed to the
limitation of the equipment used and the
approximations used in the analysis.
Moreover, the effect of solvent polarity and
temperature on solubility was analyzed using the
equilibrium between solid NaCl and its component
ions. The experimental result, that the solubility
decreased when the highly polar ethanol molecule
was added to the solution, agreed with theoretical
prediction. On the other hand, the experimental result
that at high temperature the solubility of the solid
NaCl increased disagrees with theoretical prediction.
This deviation from prediction was attributed to the
fact that some of the solvent may have evaporated in
the process and hence resulted in a backward
reaction.
To improve accuracy it is suggested that one
or two experimentalist work on the experimental
procedure. It is recommended for further study to
consider the use of other salt solutions. It is also
recommended to consider only a particular salt
solution and analyze extensively the effects on
equilibrium of a particular factor like the ionic strength.
Appendix: Sample Calculations
Consider Eq. (4) representing the equilibrium
between Ca(OH)2(s) and its component ions. By
constructing the ICE table
[Ca(OH)2(s)] [Ca2+]
[OH-]
I
0
0
C
+s
+2s
E
s
2s
one can show that in equilibrium the solubility s of the
Ca(OH)2(s) is related to the concentrations of Ca2+ and
OH- ions:
[2+ ] =
(A1)

[ ] = 2
(A2)
Eqs. (6) and (7) follow from Eqs. (A1) and (A2). The
equilibrium concentration of the OH- ions were
determined experimentally through titration. For

example, an average value of 9.85 mL 0.1 M HCl was

needed such that the phenolphthalein color vanishes
in the saturated NaCl solution in water. In this case
0.1 mmol
9.85 mL added

1 mmol 3 + added
1 mmol added

1 mL
1 mmol neutralized
1 mmol 3 + added

= 0.985 mmol neutralized

0.985 mmol in equilibrium (A3)
The OH- concentration in equilibrium is then 0.985
mmol/25.0 mL = 0.0394 M. Using Eqs. (A1) and (A2)
one arrives at the experimental values presented in
this paper. The same line of calculations led to the
experimental results for the molar solubility of the
saturated Ca(OH)2 solutions in the KCl and Ca2+
media. In these cases of KCl and Ca2+ media the
average amount of 0.1 M HCl titrant needed to
neutralize the corresponding saturated solutions were
10.87 mL and 5.97 mL, respectively.
The ionic strength given by [6]
1
=
2
(A4)
2 =1
where n is the number of ions, cj is the concentration
of each ion, and zj is the charge of each ion
represents the presence of all different ions present in
a solution. For example, experimental results in the
saturated Ca(OH)2 solution in the KCl media showed
an ionic strength of 0.565 M where the ions present in
the solution are OH-, Ca2+, K+, and Cl-. This is a useful
concept in discussing the diverse-ion effect and it
turns out that the solubility increases with increasing
ionic strength [6].
References
[1] Whitten, K.; Davis, R.; Peck, M.; Stanley, G.,
Chemistry, 8th edition, Thomson Brooks/Cole, 2007,
769-787.
[2] Martin, D.; Huheey, J.; J. Chem. Educ., 1972, 49,
177-178.
[3] Petrucci, R.; Herring, F.; Madura, J.; Bissonnette,
C., General Chemistry, Principles and Modern
Applications, Prentice Hall, 2010, 785-812.
[4] Bonomo, R.; Tabbi, G.;, Vagliasindi, L. J. Chem.
Educ., 2012, 89, 545-547.
[5] Letcher, T.; Battino, R. J. Chem. Educ., 2001, 78,
103-111.
[6] Carmody, W. R. J. Chem. Educ., 1959, 36, 125127.

[7] Feynman, R. P.; Leighton, R.; Sands, M., The

Feynman Lectures on Physics, Vol. 2, AddisonWesley Publishing Company, Inc., 8-3.
=