SOLUBILITY EQUILIBRIUM OF CALCIUM HYDROXIDE

J. M. R. CIRIO
DEPARTMENT OF MINING, METALLURGICAL AND MATERIAL ENGINEERING, COLLEGE OF
ENGINEERING
UNIVERSITY OF THE PHILIPPINES , DILIMAN, QUEZON CITY, PHILIPPINES
DATE PERFORMED : MARCH 29, 2016

ABSTRACT
This experiment aims to determine the solubility product constant (Ksp) of calcium hydroxide by titrimetry and
the effect of temperature to the molar solubility and the solubility product constant, as well[1]. To assess the effect of temperature on
the solubility of Ca(OH)2, three media were used: distilled water at room temperature (30 C), at a heated temperature (71 C)
and at a cold water bath (9C). To be able to calculate the Ksp, the saturated solutions were filtered and 15mL of the aliquot were
titrated using 0.1M hydrochloric acid. The obtained data were then used to calculate for the concentrations of OH- and Ca2+,
wherein the value of the latter (Ca2+) also corresponds to the molar solubility of the compound [2]. The molar solubility was then
used to calculate the Ksp of the different media. Using the temperature and the Ksp of the media A, B and C, a linear plot (lnKsp
vs. 1/T) was constructed with the equation y=105.88x-11.771 and r2 value of 0.007. The Ksp at 298K was then calculated
using the function. The Ksp computed was 1.102x10-5 which has 100.38% defiance from the literature value of 5.5x10-6. This
experiment can be improved by accuracy in the saturated solution preparation as well as in titration techniques.

INTRODUCTION
Sparingly soluble salts are partially
dissociated to form its ions and undergo an
equilibrium reaction when placed in water [1]:
(s) + (aq) + ()

(1)

From this reaction, the equilibrium

constant, Keq, can be also considered as the
))
solubility product constant, Ksp, of the ionic solid.
The relationship of the ionic solid and its ions,
when quantified, is the Ksp [1].

[
+ ] [ ]

[]

(2)

where [+] and [] are the activities of the

ions, which is derived from
+ =

+ [ + ]

For ideal cases, + approaches 1 while

A is approximately equal to 1 mol L-1.

+ ]
Therefore, [
and [ ] [ ] .
+ ] [
Also, a = 1 for pure solids and liquids. Thats why
concentrations are also considered to be used in
computing the Equilibrium constant [1].
In this experiment, the equation of the Ksp was
written as:

where aAy+ is the activity of Ay+, + is the activity

coefficient, [ + ] is the equilibrium concentration
of + , and A is the concentration for the
reference state of + .

(3)

[ + ] [ ]

(4)

Ksp is also related to the molar solubility

of the sparingly soluble salt [2]. Molar solubility, (s)
is defined as the number of moles of the salt
dissolved to form a liter of saturated solution. By
stoichiometry, a saturated solution of (s)
has:

[ + ] = xs ; [ ] = ys
There are specific factors which cause
changes in the Molar solubility and to the Solubility
product constant, also. These are the temperature,
common ions presence, diverse ions presence, and
solvent polarity change [1].
Temperature affects solubility because
Ksp, as with all equilibrium constants, varies with
temperature, T, according to the vant Hoff
equation [4]:
=

(7)

Where and are the enthalphy and entropy

changes for the reaction, repectively, and R is the
gas constant, 8.314 J/K-mol.
The effect of common-ions is an
application of the Le Chateliers principle. It states
that when a common ion is added into the solution
of dissociated solids, the result would be towards
the precipitation of the dissolved solid [4]. The
effect of adding an ion common to one already in
equilibrium in a solubility reaction is to lower the
solubility of the salt. This arises from the solutions
shifting equilibrium which actively balances the
reaction system in order to attain and maintain an
equilibrium state. In this case, it is the addition to
the product side that needs to be removed by
formation of the original solid.
The diverse-ion on the other hand deals
with the interionic interactions of the ions present
in the solution. This is the opposite of the
common-ion effect. Adding an uncommon ion
tend to increase solubility. As the ionic
concentration or strength of the solution then rises,
these interionic contacts becomes stronger until
these interactions are not negligible. Due to the
increase attractions, the activities of the
participating ions or their effective concentration
become lesser causing a considerable increase in
solubility [4].

1
= 2
2

Where is the molarity of ion , is its charge,

and the summation is over all ions present in the
system.
The change in solvent polarity can also be
observed. Two substances with similar
intermolecular forces are more likely to be soluble
with each other like dissolves like [4].
In this experiment, the solubility product
constant, Ksp, of calcium hydroxide, Ca(OH)2, was
obtained using titration. Titration is the process in
which a solution of one reactant, the titrant, is
carefully added to a solution of another reactant,
and the volume of titrant required for complete
reaction is measured [3]. The equilibrium reaction
of Ca(OH)2 can be expressed as,
()2 (s) 2+ (aq) + 2 () (9)
From this expression, the Ksp of ()2
can be represented by,
[2+ ][ ]2

(10)

where [2+ ] and [ ] are equilibrium

concentrations of 2+ and , respectively [5].
This experiment aims to determine the
solubility product constant (Ksp) of calcium
hydroxide by titrimetry and the effect of
temperature to the molar solubility and the the
solubility product constant, as well.
METHODOLOGY
Six small groups were formed. Each group was
assigned to prepare a specific medium in a 250-mL
beaker. Each medium was labeled using letters AF. Table 1 indicates the composition and their
respective volumes of the different media.
Table 1. Required volume for each media.
Medium

The effect of diverse ions on solubility is

governed by the ionic strength it provides to the
reaction system. Ionic strength, , is defined as:

(8)

Composition and Volume

50 mL Distilled Water (Room
Temperature, 30C)

B
C

50 mL Distilled Water (Heated, 70C)

50 mL Distilled Water (Cold water bath,
9C)
D
50 mL 0.10 M CaCl2 (RT)
E
50 mL 0.50 M KCl (RT)
F
45 mL Distilled Water + 5 mL 95%
ethanol (RT)
After preparing the media, the Ca(OH)2
solid was added to each medium while stirring
vigorously until no more solid dissolves. There was
no specific amount of Ca(OH)2 solid because even
an independent amount of this is added, the excess
solid, when it reaches the point of saturation, will
be seen suspended. The stirring of the media
continued for 5 minutes and they were left to
suspend for another 10 minutes. The suspensions
of each medium were filtered using a 3 and 1 filter
paper.
The receiving flasks for the suspensions
prepared in media B and C were set to have the
same temperature as the suspensions. This done to
prevent the change in temperature when the
suspensions are transferred. The aliquot of the
filtrate with the amount of 15 mL was drawn and
transferred to a 125-mL Erlenmeyer flask. To the
aliquot, 3 drops of 1% phenolphthalein were
added. It was then titrated with 0.10M HCl until the
phenolphthalein color vanished to colorless. The
titrant volume was recorded. Another trial was
performed for each medium.
RESULTS AND DISCUSSIONS
In this experiment, the solubility of
Ca(OH)2 was investigated upon. The initial part of
the experiment involved the determination of the
solubility product constant and molar solubility of
Ca(OH)2 through titration. Solid Ca(OH)2 was
added in six different media until the solvent could
no longer dissolve the solid upon further addition,
indicating the saturation of the mixture.
Careful filtration must be observed as to
remove all the precipitate because certain errors can
arise if excess precipitate would be included in the
aliquot. Upon the addition of the phenolphthalein,
the solutions turned pink which exhibit the
presence of OH- ions. Phenolphthalein is an
indicator which turns pink to point out basicity, and

colorless when in acidic solution. The equivalence

point of the titration process is specified by the
drop before the solution turns colorless.
Using the data recorded from the
experiment and the I.C.E. table, the values of the
molar solubility for each medium were calculated.

Table 2. Molar Solubility

Media

Vtitrant
1st
2nd
Trial
trial
4.8
5.0
4.0
3.8
3.7
4.0
4.6
4.6
4.2
4.7
2.9
3.5

A (H2O RT)
B (H2O H)
C (H2O C)
D (CaCl2)RT
E (KCl)RT
F (H2O+eth)

Molar
Solubility
0.01633
0.01300
0.01283
0.01533
0.01483
0.01067

The values obtained for the molar

solubility were then used to calculate the Ksp for
the Media A, B and C.

Table 3. Solubility Product Constants of

Media A, B and C.
Media and
Molar
Ksp ( 4s3)
Temperature Solubility (s)
( )
0.01633
1.742
A ()
0.01300
0.879
B ()
0.01283
0.845
C ()
Using the calculated Ksp for the different
temperatures, a linear plot based on the vant Hoff
equation was constructed.

Figure 1. lnKsp vs. 1/T

ln Ksp vs. 1/T

-10.8
-11 0
-11.2
-11.4

0.001

0.002

0.003

y = 105.88x - 11.771
R = 0.007

0.004

-11.6
-11.8

The equation of the line is y=105.88x 11.771 and

the R squared value is 0.007.

Using the function constructed, the Ksp at

298K was calculated with the value of
1.102105 . And with the literature value of
5.5106[1], the percent error reached 100.38%.
The experimental value of the and
were also calculated using the same function and
using the vant Hoff equation. The values of the
and are -880.286 J/mol and -97.864 J/Kmol, respectively. The literature value of the is
-986.17J/mol [6], which means that when calculated
the deviance is 10.74% while the literature value for
the is 83.39 J/K-mol [6], which means that
when computed, the deviance is 217.36 %. The
reason why the percent error for the entropy was
so large is that although the dissolution of the ions
Ca2+ and 2OH- increases the entropy as you might
expect, the ordering of the water molecules around
these ions decreases the entropy. It turns out that
in this case the latter entropy effect dominates, so
that overall the entropy decreases.
The errors could have risen from: the
impurities of the reagents, inconsistent ambient
temperature, poor titration techniques, change in
temperature (from the cold water bath or from the
hotplate to the titration process, there may have
been a large change in temperature) and etc.
CONCLUSIONS AND
RECOMMENDATIONS
The conducted experiment was both a
success and a failure. An experimental Ksp yield of
1.102105 in water was attained with a 100.38%
error from the literature value of 5.5x10-6 [1].
This experiment was performed using the
titration technique. Using titration, the molar
solubility of the Ca(OH)2 of different media were
calculated. Thus, the Ksp of the three specific
media were also determined. However, by plotting
the values of the natural logarithm of Ksp vs.
1/Temperature and applying linear regression, the
equation of the line was found to be y = 105.88x11.771 with a linearity coefficient of R2 of 0.007
which shows that the calibration is not completely

valid because it is not even close to the ideal value

which is 1. This results mean that the effect of the
errors were great that they have altered the results.
But on the bright side, the experimental had a
small deviance which means that the equation of
the line is near to the ideal equation of the line.
To gather more accurate results for the
former part of the experiment, it is recommended
to conduct a thorough and strict filtration and
titration process so as to avoid excess precipitate.
Moreover, thermal conditions should also be
parallel with the set-up conditions. Finally, the
transfer of reagents through pipetting could either
add or deduct a small but significant amount of
solvent hence the results are altered.
REFERENCES
[1] Petrucci, R., Herring G. Madura J., Bissonnette
C. General Chemistry: Principles and Modern
Applications 10th Ed. Pearson Publishing Inc.
Canada.2011
[2] Chang, R. Chemistry 8th Edition Student Study
Guide. The McGraw-Hill Companies. 2001.
[3] Whitten, K. et. al Chemistry. Brooks/Cole,
Cengage Learning: Canada, 2010.
[4] Solubility and Factors affecting it. Retrieved on
April
4,
2016
from
http://chemwiki.ucdavis.edu/Core/Physical_Che
mistry/Equilibria/Solubilty/Solubility_and_Facto
rs_Affecting_Solubility
[5] Solubility product constant. Retrieved on April
4,
2016
from
http://www.chemteam.info/Equilibrium/calcKsp-from-titration-data.html
[6]Oxtoby, David W; Pat Gillis, H; Campion, Alan

(2011). Principles of Modern Chemistry. p. 547

Appendix
WORKING CALCULATIONS
Note: The following equations and sample calculation exhibit the calculations and equations used to solve for
the data found in the data table.
In the experiment, [OH-] and [Ca2+] are to be solved from the titration data. Here,
titrant (0.1 M HCl) added to the analyte solution containing the Ca(OH)2 solution.

is the amount of

(11)
(12)
Table 1. Solvolysis of Ca(OH)2
Ca(OH)2
Initial
-Change
-+x
Equilibrium
-+x

+2x
+2x

Molar Solubility of Ca(OH)2 = s = x

Keq = Ksp = [Ca2+][OH-]2
= (x)(2x)2 = 4x3 = 4s3

(14)

SAMPLE CALCULATIONS
Media

Vtitrant
1st
2nd
Trial trial
4.8
5.0

A (H2O
RT)
B (H2O H)
C (H2O C)
D
(CaCl2)RT
E (KCl)RT
F
(H2O+eth)
(Media A)

[ ] =
[2 +] =

(B)

()[+]
,
[]

[ ] =

4.9

3.8
4.0
4.6

3.9
3.85
4.6

4.2
2.9

4.7
3.5

4.45
3.2

(15)

= 0.0326667 M

= 0.016333

2
()[+]

Average

4.0
3.7
4.6

(.)[.]

s = [Ca2+] = 0.016333

(.)[.]
(15)

(13)

= 0.026 M

[2 +] =
(C)

[]
2

[ ] =
[2 +] =

(D)

(E)

()[+]

(F)

[ ] =
[2 +] =

(.)[.]

=
,
2

(15)

= 0.01283 M

()[+]

,
[]
2

[ ] =
[2 +] =

s = [Ca2+] = 0.013

[]

[ ] =
[2 +] =

= = 0.013 M

s = [Ca2+] = 0.01283M

(.)[.]
(15)

= 0.0306667 M

= 0.015333
()[+]

,
[]

s = [Ca2+] = 0.015333

(.)[.]
(15)

= 0.0148333

2
()[+]

,
[]
2

(.)[.]
(15)

= 0.0213333 M

= 0.0106667

s = [Ca2+] = 0.0106667

Ksp = 4s3 = 4(0.0163333)3 = 1.74294x10-5

Ksp of (B)

Ksp = 4s3 = 4(0.0130000)3 = 8.78800x10-6

Ksp of (C)

Ksp = 4s3 = 4(0.0128333)3 = 8.45431x10-6

Temperature (K)
303.15
344.15
282.15

= 0.0296667 M

s = [Ca2+] = 0.0148333

Ksp of (A)

Media
A
B
C

= 0.025667M

1/T (K-1)
0.003298697015
0.00290570972
0.003544214071

Ksp
1.74294x10-5
8.78800x10-6
8.45431x10-6

Y=105.88x-11.7711
Ksp at 298 K =

%error =

||

|5.5106 |

105.88= -

%error =

= 1.102111052x10-5
|5.5106 1.1025|

-11.771=

1
)11.7711
298

||

= +

%error =

105.88(

x 100 % =

x100= 100.38%

Y=105.88x-11.771

= 105.88(8.314) = 880.28632 J/mol

||

|986.17(880.28632)|

||

|986.17|

x 100 % =

x100= 10.74%

= (11.771)(8.314) = 97.864094 J/K-mol

||

|83.39(97.864094)|

||

|83.39|

x 100 % =

x100= 217.38%

lnKsp
-10.95795975
-11.6421234
-11.68084141