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SOLUBILITY EQUILIBRIUM OF CALCIUM HYDROXIDE

Z. Uchida1, L.Dela Cruz1
1
Department of Chemical Engineering,, College of Engineering,, University of the Philippines, Diliman,

Quezon City 1101 Performed 1 October 2019; Submitted 8 October 2019

ABSTRACT

This experiment aimed to determine the solubility product constant, Ksp of Ca(OH)2 (s) and explored the effects temperature,
common and diverse ions, and solvent polarity on the solubility of sparingly soluble salt. Saturated solutions of Ca(OH)2 (s) were
prepared in six different media. Solutions were prepared by adding Ca(OH)2 (s) in each medium while stirring vigorously until no
more solid dissolved. After letting it settle, filtration was done to acquire the supernatant from each medium and was titrated with
0.10M HCl. The Ksp of Ca(OH)2 (s) at 298K was determined to be 2.35 x 10-5 with 327.27% deviation from the literature value of
5.5 x 10-6. The experiment was successful in looking into the effects of temperature, common ion and diverse ion on the solubility
of sparingly soluble salt since the gathered data was parallel to what was described by the literature. However, the effects of solvent
polarity shown in the experiment was different from what was stated by the literature. This experiment can be improved by keeping
the temperature constant as much as possible throughout the experiment and practicing proper filtration and titration techniques.

Introduction
As such, the Ksp expression for (6) can be written as:
Sparingly soluble salts partially dissociate into its constituent
Ksp = [Ca2+][OH-]2 (7)
ions when placed in water until equilibrium is established
between the compound and its ions [1]. This dissociation
Thus, the Ksp of Ca(OH)2 can be expressed in terms of its
process can be represented by the general, hypothetical
molar solubility (s) as:
reaction:
Ksp = 4s3 (8)
AxBy(s) ⇌ xAy+(aq) + yBx-(aq) (1)
The [OH-] in (7) can be determined using acid-base titration
Like other equilibrium, the extent to which the dissolution
with HCl.
reaction occurs is expressed by the magnitude of the
equilibrium constant [2]. Determining this equilibrium
HCl(aq) + OH-(aq) → H2O(l) + Cl-(aq) (9)
constant will indicate how soluble the solid is in a solvent.
The solubility product constant, Ksp , is the constant for the
The molar solubility of Ca(OH)2 is half of the OH-
equilibrium established between a solid solute and its ions in
a saturated solution[3]. For (1), Ksp is denoted as: concentration obtained by titration.

Ksp = [Ay+]x[By-]y (2) Also, like other equilibrium constants, Ksp varies linearly with
temperature [1]. This dependence on temperature of the
Moreover, Ksp is also related to the molar solubility of solubility constant is mathematically demonstrated by the
the sparingly soluble salt. Molar solubility, (s) is van’t Hoff equation:
defined as the number of moles of the salt dissolved to
𝛥𝐻 𝛥𝑆
form a liter of saturated solution [1]. By stoichiometry, ln 𝐾𝑠𝑝 = − + (10)
𝑅𝑇 𝑅
the molar solubility of the hypothetical compound
AxBy (s) can be expressed as: Where 𝛥𝐻 is the enthalpy change of the reaction, 𝛥𝑆 is the
entropy change, and R is the gas constant 8.314 J/mol•K
[Ay+] = xs; [Bx−] = ys (3)
The primary objective of this experiment is to determine the
Expressing Ksp in terms of molar solubility (s) we Ksp of the saturated Ca(OH)2 solution. Furthermore, this
obtain: experiment will also explore the effects of different factors
.Ksp = (xs)x(ys)y (4) such as temperature, presence of common and diverse ions,
x y (x+y)
Ksp = (x y )s (5) and solvent polarity on solubility of sparingly soluble salts.

In this experiment, the solubility of calcium hydroxide Methodology (TNR 10, Bold)
(Ca(OH)2 ) is determined, as suggested in the reaction:

Ca(OH)2 (s) ⇋Ca2+ (aq) + 2OH- (aq) (6)

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Saturated Ca(OH)2 solutions were prepared in six 250-mL
beakers to simulate the effects of different conditions.
The first 3 beakers were filled with 50 mL distilled water. 50
mL of CaCl2 was added in the fourth beaker while 50 mL of
KCl was added in the fifth beaker. To the last beaker, 45 mL
distilled water and 5 mL 95% ethanol were mixed.
The solutions were prepared by adding Ca(OH)2 solid in each
medium while stirring vigorously until no more solid
dissolves. The 2 beakers with distilled water as solvent were
placed in different environments: one in a hot bath, and the
other in a cold bath. Room temperature was obtained as well
as the temperatures of both hot and cold bath.
After letting it settle, the suspension was then filtered to
receiving flasks to separate solids from the supernatant. The
suspensions generated from the ones placed in the baths were
placed in a flask of the same temperature. 25 mL aliquot of
the resulting solution was then drawn and transferred to an
150 mL Erlenmeyer flask. Using 1% phenolphthalein as
indicator, the solutions were titrated with 0.10 M HCl until
pink color became fade pink.
Table 2. Values of Molar solubility (s) and Ksp for varying
temperatures
Table 2 showed that Molar solubility (s) of Ca(OH)2
decreased as temperature increased. Thus, the dissolution of
Ca(OH)2 is an exothermic reaction. Increasing the
temperature results in a stress on the products side from the
additional heat. Le Châtelier's principle predicts that
the system shifts toward the reactant side in order to alleviate
this stress. By shifting towards the reactant's side, less of the
solid is dissociated when equilibrium is again established,
resulting in decreased solubility [4].
Furthermore, the solubility product constant Ksp is heavily
dependent on the temperature, as shown in equation (10), the
thermodynamic nature of the reaction can be deduced from
solving the Ksp of the solutions when subjected to different
temperatures.
-10 𝐾sp vs Temperature
0.003 0.0032 0.0034 0.0036 0.0038
-10.5
ln Ksp

Results and Discussion -11 y = 2130.3x - 17.806

Volume of Titrant R² = 0.9564
Medium (mL) Molar Solubility (s)
-11.5
A 9.1 0.0182 1/T
B 7.3 0.0146 Figure 1. Graph of ln Ksp vs. 1/T
C 10.6 0.0212
D 7.2 0.0144 As shown in Figure 1, the graph of Ksp versus temperature
E 8.3 0.0166 was linearize using equation (10). The obtained R2 value of
the line is close to 1 thus, the data exhibits high linearity.
F 9.3 0.0186
Using the function y = 2130.3x – 17.809 determined from
Table 1. Volume of HCl needed for titration and the
the graph in Figure 1, Ksp at 298K can be calculated. The
corresponding molar solubility in each media.
Ksp at 298K extracted from the function is 2.35 x 10 -5. The
literature value for Ksp of Ca(OH)2 (s) at 298K is 5.5 x 10-6 [3].
Table 1 summarizes the data obtained from the titration of the This signifies 327.27% deviation.
saturated Ca(OH)2 solutions versus 0.10 HCl. The volume of
the titrant was used in calculating the molar solubility of In addition, the calculated 𝛥𝐻 and 𝛥𝑆 values from the
Ca(OH)2 for each medium using equations (6) and (9). function in Figure 1 are -17.33 kJ/mol and -144.83 J/mol•K
respectively. The negative value of 𝛥𝐻 indicates that the
reaction is indeed exothermic. Literature values for the
For the first three media, in which the saturated solutions 𝛥𝐻 and 𝛥𝑆 of Ca(OH)2 (s) are -16.7 kJ/mol and -157.99 J/
were placed in different environments (i.e. hot, cold, room mol•K respectively [3]. Percent error for 𝛥𝐻 and 𝛥𝑆 are
temperature), the effect of change in temperature was 3.77% and 8.32% respectively.
explored.
Another condition affecting solubility in the experiment
observed was the effect of common and diverse ions on the
Temperature Molar Calculated
system.
Medium (K) solubility (s) Ksp
A 302.65 0.0182 2.41143E-05 Medium Solvent Used Molar Solubility
B 323.15 0.0146 1.24485E-05 A distilled water 0.0182
C 277.15 0.0212 3.81125E-05 D 0.10M CaCl2 0.0144
E 0.50M KCl 0.0166
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distilled water +
F 5% ethanol 0.0186
Conclusion and Recommendations
Table 3. Solvent used for different media and the
corresponding molar solubility (s) The calculated solubility product constant Ksp of Ca(OH)2
was 2.35 x 10-5 which deviates from the literature value by
On the effects of the presence of common ions, the molar
327.27%. However, the experiment successfully discovered
solubility of medium A and D in table 3 can be compared. It
the effects of temperature on sparingly soluble salts. The
was observed that the molar solubility is less with the
calculated thermodynamic quantities (𝛥𝐻 and 𝛥𝑆) were
presence of common ions.
3.77% and 8.32% away from the true value and the reaction
According to Le Châtelier s Principle, an equilibrium mixture was supported by the literature as exothermic.
responds to a forced increase in the concentration of one of
In the effects of the presence of common ion, the solution did
its reactants by shifting in the direction in which that reactant
show a decrease in the solubility of the sparingly soluble salt
is consumed [3]. The addition of the common ion shifts the
just as the theoretical result determined. Moreover, the
equilibrium of a slightly soluble ionic compound toward the
observed effect of the presence of diverse ion increased its
undissolved compound, causing more to precipitate. Thus,
solubility just as the literature stated.
the solubility of the compound is indeed reduced[3].
However, in the experiment. the effect of solvent polarity to
On the other hand, the effect of diverse ions on
the solubility of Ca(OH)2 did not follow what was determined
solubility is governed by the ionic strength it provides
by the literature. In the experiment, a decreased polarity must
to the reaction system. Ionic strength, µ, is defined as:
have resulted to a lesser solubility.
1
𝜇 = ∑ 𝑐𝑖 𝑧𝑖2 (11) This experiment can be improved by making sure that the
2
temperature of the hot bath, ice bath, and room temperature
where ci is the molarity of ion i, zi is its charge, and the
is held constant. To avoid deviation from the constant
summation is over all ions present in the system.
temperature, receiving flasks during filtration must be of the
Table 3 shows that the molar solubility of medium E is same temperature with the solutions and titration must be
greater than of medium D. The calculated ionic strength of done quickly but with most accuracy. It is also recommended
the solvent used in medium E is 0.5M while medium D has a to filter solution at least twice to ensure that no solid will be
ionic strength of 0.25M. This is mainly caused by having a transferred to the flask used for titration. This will directly
solvent of greater concentration in medium E (0.50M) affect the concentration of the analyte.
compared to the solvent used in medium D (0.10M).

Diverse ions tend to increase rather than decrease solubility.

As the total ionic concentration of a solution increases,
interionic attractions become more important. For the ions
involved in the solution process, this means that higher
concentrations must appear in solution before equilibrium is
established thus, the solubility increases[2] .

Finally, the effect of solvent polarity to the solubility of

Ca(OH)2 was observed. Distilled water mixed with 5%
ethanol resulted to an increase in molar solubility as shown
in Table 3. The result is rather unprecedented since water is
more polar than ethanol, the addition of 5% ethanol decreased
the polarity of the solvent. Decreasing the polarity of the
solvent, lowered the capability of the solvent to dissolve ionic
salts [5]. This is due to the unfavorable interaction of the
nonpolar components of ethanol to the ions present in the
solution as it will only lead to repulsion [3].

The errors that affected the results could be that the

temperature was not held constant throughout the
experiment. This may be the reason why the calculated Ksp
had a very high percent error. Also, filtration was done once
which allowed some of the tiny solids to transfer with the
supernatant in the flask for titration. Lastly, some of the
mediums were over titrated.
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References

[1] General Chemistry II Laboratory Manual. Institute of Chemistry. University of the Philippines, Diliman, Quezon City.
[2] Brown, T.L., LeMay, Jr., H.E., Bursten, B.E., Murphy, C.J., Woodward, P.M., Stoltzfus, M.W. (2015). Chemistry the central
science 13th ed. United States of America: Pearson Education.
[3] Bissonnette, C., Herring, F. G., Madura, J. D., Petrucci, R. H. (2011). General chemistry: Principles and modern applications
10th ed. Canada: Pearson Education
[4] Tran, E., Liu, D. (2019). Solubility and Factors Affecting Solubility. Retrieved from
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Supplemental_Modules_(Physica
l_and_Theoretical_Chemistry)/Equilibria/Solubilty/Solubility_and_Factors_Affecting_Solubility
[5] Bodner Research Web (n.d) Solubility and Complex-Ion Equilibria. Retrieved from
http://chemed.chem.purdue.edu/genchem//topicreview/bp/ch18/soluble.php

Appendix

A. Tables and Figures

Volume of Titrant
Medium (mL) Molar Solubility (s)
A 9.1 0.0182
B 7.3 0.0146
C 10.6 0.0212
D 7.2 0.0144
E 8.3 0.0166
F 9.3 0.0186
Table 1. Volume of HCl needed for titration and the corresponding molar solubility in each media.

Temperature Molar Calculated

Medium (K) solubility (s) Ksp
A 302.65 0.0182 2.41143E-05
B 323.15 0.0146 1.24485E-05
C 277.15 0.0212 3.81125E-05

Table 2. Values of Molar solubility (s) and Ksp for varying temperatures

Medium Solvent Used Molar Solubility

A distilled water 0.0182
D 0.10M CaCl2 0.0144
E 0.50M KCl 0.0166
distilled water +
F 5% ethanol 0.0186
Table 3. Solvent used for different media and the corresponding molar solubility (s)
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-10 𝐾sp vs Temperature

0.003 0.0032 0.0034 0.0036 0.0038

-10.5

ln Ksp
-11 y = 2130.3x - 17.806
R² = 0.9564

-11.5
1/T

Figure 1. Graph of ln Ksp vs. 1/T

B. Sample Calculations

Calculation of Ksp
HCl(aq) + OH-(aq) → H2O(l) + Cl-(aq) *Mol HCl= mol OH-

MEDIUM 1:
Mol HCl = 0.10M HCl x 0.0091 L = 9.1 x 10-4
Mol OH- = 9.1 x 10-4

Ca(OH)2 (s) ⇋Ca2+ (aq) + 2OH- (aq)

Mol HCl /2 = Mol Ca2+ = 4.5 x 10-4

[OH-] = 9.1 x 10-4 / 0.025 = 0.0364M [Ca2+] = s; [OH-] = 2s

[Ca2+] = 4.5 x 10-4 / 0.025 = 0.0182 s = 0.0182
Ksp = 4s3 = 2.41 x 10-5

Calculation of 𝛥𝐻 and 𝛥𝑆

y= 2130x – 17.806
- 𝛥𝐻/𝑅 = 2130
𝛥𝐻 = -17.33 kJ/mol
𝛥𝑆 = −17.806 x 8.314 = -145.66 J mol-1K-1

@ T=298K

LnKsp= 2130 (1/298) – 17.806

Ksp = e-10.65834899 = 2.35 x 10-5

Ionic strength
1
𝜇 = ∑ 𝑐𝑖 𝑧𝑖2
2
(CaCl2) 𝜇 = ½ (0.1) (2)2 + ½ (0.1) (-1)2 = 0.25 M
(KCl) 𝜇 = ½ (0.5)(1)1 + ½(0.5)(-1)2 = 0.5M