SOLUBILITY EQUILIBRIUM OF CALCIUM HYDROXIDE

A.J.A. ESCOTO
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
14 MARCH 2017
MAE CRISTE D. FAJICULAY

ABSTRACT
The experiment aimed to determine the Ksp of calcium hydroxide and explain the effects of
temperature, presence of common and diverse ions, and solvent polarity on the solubility of
sparingly soluble salts. The experiment prepared different suspensions of calcium hydroxide in
different media. The values of solubility and solubility product constant were determined through
the titration data. The effect of temperature was established, at low temperature, solubility
increases and at high temperature, solubility decreases. Also, it was able to determine the
experimental molar solubility and Ksp of calcium hydroxide. Ksp obtained was 3.95 x 10-7, with
69.6% error. The effect of the presence of diverse ions was also established, the addition of diverse
ion tend to increase the solubility of calcium hydroxide. The experiment failed to establish the
effect of presence of common ions and the change in solvent polarity.

INTRODUCTION number moles of solute in 1 L of saturated

Solubility is the ability of a substance to
dissolve in water. On the other hand,
solubility equilibrium refers to the
equilibrium between the dissolved salt
(ions) and undissolved salt that usually
exists in a saturated solution or a solution
of a sparingly soluble salt.8 The equilibrium
can be represented in the form
AxBy(s)  xAy+(aq) + yBx-(aq) (1)
Hence, we can derived the equilibrium
constant expression for this equilibrium
equation as
Ksp = [Ay+]x [Bx-]y (2)
solution (moles per liter), is used.8 The
molar solubility can be obtained through
𝑠 =
[𝐴𝑦+ ]
=
[𝐵𝑥− ]
(3)
𝑥 𝑦
For this experiment, the solubility of the
sparingly soluble compound calcium
hydroxide, Ca(OH)2 was analyzed. The
equilibrium equation is represented by
Ca(OH)2 (s)  Ca2+ (aq) + 2OH- (aq) (4)
Once equilibrium has been established and
the solid removed, the concentration of
hydroxide can be easily determined via
acid/base titration.

The solid state is removed from the The solubility constant product and the
equilibrium constant expression since the molar solubility can be determined from
activity of a pure solid is 1. The solubility equations (2) and (3), respectively.
product constant, Ksp, is the constant for the
equilibrium established between a solid Ksp = [Ca2+] [OH-]2 (5)
solute and is ions in a saturated solution.5
[𝐶𝑎 2+ ] [𝑂𝐻 − ]
𝑠 = 1
= 2
(6)
To calculate the actual solubility of the salt,
the molar solubility, which is defined as the Ksp = [s] [2s]2 (7)
 the equilibrium system. Ionic strength can
The Gibbs free energy, ΔG ̊, is related to the greatly influence the ionic atmosphere.
equilibrium constant (Ksp) by Ionic strength, μ, is a measure of the total
concentration of ions in solution.
ΔG ̊ = -RT lnKsp (8)
1
𝜇= ∑ 𝑐 𝑧2 (11)
2 𝑖 𝑖 𝑖
where R is the thermodynamic constant (R
= 8.3145 J mol-1 K-1) and T is the absolute
where ci is the concentration of the ith
temperature in Kelvin.10
species and zi is its charge. The sum extends
over all ions in solution.2
To find the Gibbs free energy (ΔG ̊) changes,
this equation is used
The energy balance of intermolecular forces
between solute-solute, solvent-solvent and
ΔG ̊ = ΔH ̊ - TΔS ̊ (9)
solute-solvent molecules controls solubility.
The simple rule is “like dissolves like” and it
where T is the absolute temperature.3 We
is based on the polarity of the systems.9
assume that ∆H° and ∆S° do not change
significantly over small temperature
The purpose of the experiment was to
ranges.5
determine the solubility product constant of
calcium hydroxide and explain the effects of
There are factors affecting the solubility of
temperature, presence of common and
salt in aqueous solutions such as
diverse ions, and solvent polarity on the
temperature, presence of common ions,
solubility of sparingly soluble salts.
presence of diverse ions and change in
solvent polarity.
METHODOLOGY
The van’t Hoff equation (10) describe that
The experiment in determining the molar
equilibrium constants vary with
solubility of calcium hydroxide was done in
temperature such that it depends upon the
various conditions. Also, the experiment
relative magnitudes and the signs of the
used the laboratory technique titration.
standard enthalpy change (∆H°) and
Different media was prepared in each 250-
standard entropy change (∆S°) associated
mL beaker such that
with the equilibrium.3

∆𝐻 ∆𝑆 Table 1. Components of different media

ln 𝐾 = − 𝑅𝑇 + 𝑅
(10) Component Condition
A 50 mL distilled Room
where ΔH the enthalpy of the reaction (in KJ water temperature*
mol-1), ΔS the entropy of the reaction (in J B 50 mL distilled Heated*
mol-1K-1) and R is gas constant, 8.314 J mol- water
1K-1.
C 50 mL distilled In cold water
water bath*
Common-ion effect is whenever weak D 50 mL 0.10 M Room
electrolyte and a strong electrolyte CaCl2 temperature
containing a common ion are together in E 50 mL 0.50 M Room
solution; the weak electrolyte ionizes less KCl temperature
than it would if it were alone in solution.1 F 45 mL distilled Room
water + 5 mL temperature
The diverse ion effect is more commonly 95% ethanol
called the salt effect. The numerical value of *Temperatures must be recorded
a Ksp based on molarities will vary
depending on the ionic atmospheres.2 The titration setup was set first and
Diverse-ion effect is simply adding burettes were rinsed with the titrant, which
uncommon ions, which are different from is the 0.10 M HCl. After the preparation of
the different medium, calcium hydroxide
was added to each beaker until a saturated
solution was obtained. The suspensions
were stirred for five minutes and left for ten
minutes. Afterwards, the suspensions were
filtered, in medium B and C, receiving flasks
must have the same temperature as the
suspensions. A 25mL aliquot filtrate was
drawn from the suspension and was
transferred to a 125-mL Erlenmeyer flask.
Then, 3 drops of 1% phenolphthalein was
added. Moreover, the analyte was titrated
until the color vanishes to colorless. In each
medium, two trials were performed.
color change was pink to colorless,
happened when pH changes.
Solubility is the molar concentration while
Ksp is the product of molar concentrations.8
So both can be used to find one another
because there is a relationship between the
solute's molarity and the solubility of the
ions.
The solubility of each medium was
computed by obtaining first the OH-
concentration and substituting to equation
(6). Then, equation (7) was used to obtain
the Ksp values.

RESULTS AND DISCUSSION Table 2. Summary of calculated data

Average molar Average Temperature
In the preparation of set-up, burettes were solubility Ksp (in K)
rinsed with HCl, to remove impurities, (in M)
which may react to the titrant or on the A 0.0052 5.39 x 10-7 304.65
analyte and also to remove traces of water B 0.0023 5.56 x 10-8 327.15
in burettes that may affect the titrant’s C 0.0063 1.04 x 10-6 278.15
concentration. D 0.0088 2.71 x 10-6 At room
E 0.0049 4.67 x 10-7 temperature
In the preparation of the analyte, the
F 0.0135 9.83 x 10-6
suspensions made were filtered to remove
the solids. The filtrate must be clear, since
The table shows the different average molar
the presence of any solid Ca(OH)2 may
solubility and solubility product constant.
interfere with the saturation concentration
This also shows that solubility and
of OH- ions. The collected filtrate must be
solubility product constant varies with
prevented to the exposure of air because
different condition.
carbon dioxide acts as an acid and may
neutralize OH.
In media A, B, C, showed how temperature
affects the solubility of Ca(OH)2. Table 2
In medium A, B, C, receiving flasks when
shows that in medium B, which has the
filtering has the same temperature as the
highest temperature, also have the lowest
suspension to maintain the condition of the
Ksp and lowest solubility. While in medium
medium.
C, which has the lowest temperature, was
the other way around.
Two trials were performed to show if the
results are consistent.
To compute for the Ksp at 298 K, the results
obtained was plot based on the van’t Hoff
The experiment used titration technique to
equation (9).
know the OH- concentration at the
equilibrium of the reaction studied. Hence
the reaction was

HCl(aq) + OH- (aq) → H2O(l) + Cl- (aq) (12)

The molar solubility of Ca(OH)2 is half of the

OH- concentration found by titration.3

Phenolpthalein was used as an indicator to

determine the endpoint of the titration. The
Figure 1. Linear plot based on the van’t
Hoff equation
The figure shows the relationship of lnKsp
versus 1/T of the different temperature
done in media A, B, and C. The graph has a
coefficient of determination or the r2 as
0.84682. This implies that the data obtained
were somehow good because it was fitted in
the linear relationship of lnKsp and 1/T.
Furthermore, using the trendline equation
y = 5227.8x - 32.284 (13)
which according to van’t Hoff equation (10),
∆𝐻
the slope is equal to − 𝑅 and the y-
∆𝑆
intercept is equal to . Therefore, ∆H is
𝑅
equal to -43.46 KJ mol-1 with literature
value5 of -986.1 KJ mol-1, which gave a
104.4% error. While ∆S is equal to -268.41 J
mol-1K-1 with literature value5 of 83.39 J
mol-1K-1, which gave a 421.9% error.
Using equation (9), ∆G can be obtained as
equal to 36.53 KJ mol-1 with literature
value2 of -898.5 KJ mol-1 which gave a
104.1% error.
The dissolution reaction was exothermic (∆
= -43.46 KJ mol-1), so increasing the
temperature results in a stress on the
products side from the additional heat.1 At
low temperature, dissolution heat
elimination was favored and thus the
solubility equilibrium constant and
solubility of dissolution of Ca(OH)2 were
increased. Subsequently, at high
temperature, solubility equilibrium
constant and solubility were decreased.
Furthermore, the value of Ksp at 298 K can
be determined using equation (8). Ksp
obtained was 3.95 x 10-7 at room
temperature. The literature value10 for Ksp
Ca(OH)2 is 1.3 x 10-6 which gave a 69.6%
error. The experimental solubility was 4.62
x 10-3 M.
In medium D, common ion effect was
exhibited through the addition of CaCl2.
According to Le Chatelier’s principle, the
addition of common-ion shifts the
equilibrium of a slightly soluble compound
toward undissolved compound, causing
more precipitate, thus the solubility of the
compound is reduced.5 Comparing the
treated data to the experimental value, the
solubility of Ca(OH)2 in medium D was
increased. The result was opposed to Le
Chatelier’s principle.
In medium E, diverse ion effect or the salt
effect was exhibited through the addition of
KCl. The addition of diverse ions is also
called the inert electrolyte effect. The inter-
ionic interactions play a role. The ionic
atmosphere attenuates the attraction
between ions since each ion-plus-
atmosphere contains less net charge.1
Effective concentrations become smaller
than the stoichiometric concentration. This
means that higher concentrations must
appear in the solution before the
equilibrium is established, thus solubility
increases.5
In medium F, change in solvent’s polarity
was exhibited through mixing distilled
water and 95% ethanol. Like other alcohols,
ethanol has a non-polar carbon chain
connected to a polar OH group or hydroxyl
functional group. This group is capable of
forming hydrogen bonds with the same
hydroxyl functional group also found in the
water.6 So when ethanol was mixed with
water, the solution made has less polarity
compared to distilled water. Decrease in
polarity resulted in weak dissociation,
because it reduces the chance to break the
attraction of an ionic substance.7 Thus,
solubility was lowered. Comparing the
treated data to the experimental value; the
solubility of Ca(OH)2 in medium G was
increased. The result did not satisfy the
aforementioned principle.
Experimental errors obtained in the
experiment were incompletely or over
saturating the suspensions, improper
filtration, solid Ca(OH)2 remnants on the
analyte and exposure of the aliquot filtrate
to the air.
CONCLUSION AND RECOMMENDATION
The experiment established the effect of
temperature and presence of diverse ions
on the solubility of calcium hydroxide. The
experimental solubility equilibrium
constant was determined as 3.95 x 10-7,
with 69.5% error. In exothermic dissolution
reaction, at low temperature, Ksp and
solubility increases and at high
temperature, Ksp and solubility decreases.
The addition of diverse ions increases the
solubility of a sparingly soluble salt.
Meanwhile, the experiment failed to show
the other different factors affecting the
solubility of salt in aqueous solutions such
as the presence of common ions and the
change in solvent polarity.
The experiment can be further improved by
saturating each suspension properly to
attain equilibrium. Also, by filtrating the
suspension twice, clear filtrate should be
obtained to ensure no solid calcium
hydroxide would interfere to the saturated
concentration OH ions. Lastly, avoiding the
exposure of the aliquot filtrate to the air, so
that OH- ions will not be neutralized by the
carbon dioxide in the air.
REFERENCE
[1] Brown T., LeMay H., Bursten B.,
Murphy C., Woodward P.,
Chemistry: The Central Science,
Twelfth Edition; Prentice Hall.
2011
[2[ Ch. 7 Systematic Treatment of
Equilibrium.
http://chem320.cs.uwindsor.ca/Note
s_files/320_l07.pdf (Updated Oct. 10,
2011; Slides 20-350
[3] Determination of Ksp, ΔG ̊, ΔH ̊ and ΔS ̊
for Ca(OH)2. Chemistry 221.
http://mhchem.org/223/pdfLabs223
/DetKsp.pdf (accessed March 19,
2017)
[4] Euler, W., Kirschenbaum L., Ruekberg,
B. Determination of Ksp, G , H , and
S for the Dissolution W of Calcium
Hydroxide in Water. Journal of
Chemical Education. 2000. 1039-
1040.
http://homepages.dordt.edu/~fictori
e/pchem/caoh2_jce_v77_2000_p1039
.pdf (accessed March 20, 2017)
[5] Petrucci, R., Herring, F., Madura, J., &
Bissonnette, C. General chemistry:
Principles and Modern Applications
10th ed. Pearson Education South
Asia Pte. Ltd., Philippines. 2010
[6] Recitation Notes for Experiment 3
Crystallization. The University of
Texas and Dallas. 2011
https://www.utdallas.edu/~scortes/
ochem/OChem_Lab1/recit_notes/reci
t_exp3_cryst.pdf
(accessed March 26, 2017)
[7] Samaro, A., Solubility and Distribution
Phenomena. 2015
https://www.slideshare.net/arijabuh
aniyeh/solubility-physical-pharmacy
(accessed March 27, 2017)
[8] Solubility Equilibrium. Nassau
Community College Faculty
Website.https://faculty.ncc.edu/Link
Click.aspx?fileticket=smTKdcQlPY4%
3D&tabid=1903 (accessed Marcg
18,2017)
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Chem 351 Laboratory. University of
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2017)
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Ninth Edition; Finch, M, Brooks/Cole
(Cengage Learning). 2014
APPENDIX

Raw Data
Trial 1 (in mL) Trial 2 (in mL)
Vana Vtit Vana Vtit
A 25 2.5 20 2.1
B 25 0.9 12.5 0.7
C 25 3.5 25 2.8
D 25 4.3 24 4.3
E 25 2.5 22 2.1
F 25 7.0 22 5.7

Calculation

Experimental molecular solubility for

different media

Mol H+ = Mol OH-

MtitVtit = MOH- VOH-

(0.10 M HCl)(0.0025 L) = (MOH-)(0.25L)
MOH- = 0.1 M
MCa2+ = 0.005 M
s = 0.005 M

Ksp = [s] [2s]2

Ksp = [0.005] [0.1]2
Ksp = 5.0 x 10-7
y = 5227.8x - 32.284

∆𝐻
5227.8 = −
𝑅

∆H = -43.46 KJ mol-1

∆𝑆
− 32.284 =
𝑅
∆S = -268.41 J mol-1K-1

ΔG ̊ = ΔH ̊ - TΔS ̊
ΔG ̊ = 34.02 KJ mol-1 – (298 K) (3.01 J mol-
1K-1)

ΔG ̊ = 36.53 KJ mol-1

ΔG ̊ = -RT lnKsp
36.53 KJ mol-1 = -(8.3145 J mol-1 K-1)(298K)
lnKsp
Ksp = 3.95 x 10-7