INTEGRATED CONCEPTS IN EQUILIBRIUM

R.C. CAAL
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
DATE PERFORMED: 20 MARCH 2015
INSTRUCTORS NAME: IRINA CASTAOS

ABSTRACT
The experiments objective was to determine the solubility product constant
(Ksp) of calcium hydroxide (Ca(OH)2) through the use of titration. The Ca(OH) 2
solution was prepared by dissolving solid calcium hydroxide in three different
media, distilled water, potassium chloride solution or calcium chloride solution, until
it became saturated. The solution was then filtered and the supernate titrated with
hydrochloric acid. The titration was used to calculate for the equilibrium hydroxide
concentration, and in turn, the equilibrium calcium ion concentration, K sp, and
solubility of Ca(OH)2. A solubility product constant of 1.22x10 -5 for Ca(OH)2 in
distilled water was found, with a 75.71% difference to the literature value, K sp =
5.5x10-6. The effect of diverse and common ions were also studied, with K sp values
of 5.06x10-5 and 1.87x10-7 from 0.500M KCl and 0.100M Ca2+, respectively.

INTRODUCTION
Sparingly soluble ionic salts
partially dissociate in water to form
ions.
This
partial
dissociation
establishes equilibrium between the
undissolved solid and its ions in the
form:
AxBy(s) xAy+(aq) + yBx-(aq) (1)
As
with
other
equilibrium
reactions, the extent to which this
reaction occurs is measured by the
equilibrium constant. Because the
equilibrium reaction set up in equation
1 involves the dissolution of a solid,
the equilibrium constant measures
how soluble it is in water, and is called
the solubility product constant, K sp.
As
with
all
equilibrium
constants, Ksp can be written as the
concentrations of products over the

concentrations of reactants (all at

equilibrium). However, solids are not
included in the equilibrium expression.
Therefore, based on the expression in
equation 1, Ksp is simply
Ksp = [Ay+]x [Bx-]y

(2)

The solubility product constant

can also be related to the molar
solubility of the sample. Molar
solubility (s) is the number of moles of
solute dissolved in 1 Liter to form a
saturated solution of the solute. Its
relation to the concentration can be
written as
[Ay+] = xs; [Bx-] = ys
(3)
To get the relationship between
molar
solubility
and
Ksp,
the

expressions in equation 3 can be

substituted into equation 2, giving
Ksp = (xs)x(ys)y; Ksp = (xxyy)xs+y
(4)

bath. The effect of these factors on the

solubility of the substance was
observed through the amount of solid
left in the test tube.
RESULTS AND DISCUSSION

In the experiment, the K sp of

calcium hydroxide (Ca(OH)2) was
determined with the use of titration.
The effect of temperature, polarity and
common and diverse ions on solubility
was also tested.

Following the template set up in

equation 1, the equilibrium reaction
for the experiment is as follows:
Ca(OH)2(s) Ca2+(aq) + 2OH-(aq)
(5)

METHODOLOGY
Part I: Determination of Solubility
Product
Constant
and
Molar
Solubility of Ca(OH)2
75 mL of the assigned medium
(distilled water, 0.5 M KCl or 0.1 M
CaCl2) was transferred to a 250-mL
beaker.
While
stirring,
calcium
hydroxide (Ca(OH)2) solid was added
to the solution until it became
saturated. After stirring for a further
five minutes, it was left to settle. After
ten minutes, the suspension was
filtered through two layers of fluted
filter. A 25-mL aliquot of the supernate
was drawn and transferred to a 125mL Erlenmeyer flask. Upon transfer,
1% phenolphthalein was added to the
solution, and then titrated with 0.1 M
HCl until it became colorless. Two trials
were performed for each medium.
Part II: Effect of Solvent Polarity
and
Temperature
on
Phase
Equilibrium
Three six-inch test tubes were
filled with one mL saturated sodium
chloride (NaCl) solution, with NaCl
solids, each. The first test tube was
kept as a control. In the second test
tube, one mL of 95% ethanol was
added. The third test tube and its
contents was placed in a warm water

And
from
that,
the
expression can be written as:
Ksp = [Ca2+][OH-]2

Ksp
(6)

With [Ca2+] and [OH-] as the

equilibrium concentrations of calcium
and hydroxide ion, respectively.
To get the value of the solubility
product constant, the equilibrium
concentrations of the calcium and
hydroxide ions are needed. The
concentration of hydroxide ion can be
computed for using the equation for
titration,
MHClVHCl= MOHVOH

(7)

The calcium ion concentration

can be obtained using the mole ratio
observed in equation 5 giving.
[Ca2+] = [OH]/2
(8)
Using equations 7 and 8, the
computed [OH-] for distilled water,
potassium chloride, and calcium ion
solution were 0.029 M, 0.0466 M, and
0.0256 M respectively. Following that,
the [Ca2+] concentrations were found
to be 0.0145 M, 0.0233 M and 0.0128
M respectively.
Ksp can also be expressed in
terms of molar solubility, s. The
relationship between s and Ksp is

established in equation 3, with s being

equal to the concentration of the ion
divided by the moles of ion. In the
equilibrium expression in equation 5,
calcium ion only has one mole, thus
making the molar solubility equal to its
concentration. And using equation 8,
we can concluded that s is equal to
half
of
the
hydroxide
ion
concentration. These relationships can
be summarized as the equation below.
s = [Ca2+] = [OH-]/2
(9)
Combining equations 6 and 9
gives us the relationship between the
equilibrium constant and solubility.
Ksp = (s)(2s)2 = 4s3

(10)

The knowledge of solubility

product constant and solubility can be
applied in different procedures, such
as for the purification and precipitation
of salts.
However, there are other
factors beside concentration the can
affect the solubility of a salt. Some of
these
include
the
temperature,
polarity of solvent, the common-ion
effect and the diverse-ion effect.
If a reaction is exothermic, the
addition of more heat reduces the
solubility; if it is endothermic, it
increases solubility. These cases follow
Le Chateliers principle, with heat
being a product or reactant of the
reaction. In the experiment, the test
tube containing the NaCl solution and
solids was placed in a warm water
bath. It was observed that the amount
of solid in the test tube decreased,
implying an increase in solubility.
If the solvent used on a
nonpolar salt is also nonpolar, the
solubility is higher as compared to if a
polar solvent was used. This follows
the concept like dissolves like,
meaning species with the same

intermolecular forces can dissolve

each other.
Sodium chloride is an ionic
compound, while ethanol is slightly
polar. Because of this, ethanol can
slightly dissolve the NaCl, though not
enough for it to be easily noticeable.
This is what happened during the
experiment.
The common ion effect is when
a solution that contains a common ion
to the salt is added to the mixture, and
the solubility is reduced. This is
because it shifts the established
equilibrium
in
equation
5;
the
concentration of the ions increase,
prompting the reaction to move
backwards and produce more solid to
compensate. This can be seen in the
experiment, with CaCl2 garnering the
lowest molar solubility (0.0128 M), and
thus the lowest solubility product
constant (8.39x10-6).
However, these values do not
yet take into consideration the
addition of calcium ions in the
solution. Given that the CaCl 2 solution
has a concentration of 0.100M an ICE
table can be constructed as such:

Table 1. ICE Table of Ca(OH)2(s) in

CaCl2 medium
I
C
E

Ca(OH)2
-

Ca2+
0.100
+s
0.100+
s

OH+2s
2s

From this table, the following

equation can be surmised:
Ksp(theoretical) = (0.100+s)(2s)2
(11)
Using equations 10 and 11, the
value for s is equal to 3.60x10 -3, and
the value for Ksp is equal to 1.87x10-7.
The diverse ion effect is when
solutions with noncommon ions are
added to the solution. The addition of
these spectator ions affects the
effective
concentration
of
the
participating ions such that when the
total ionic concentrations become
higher, the ionic interactions are no
longer negligible. When this happens,
the spectator cation (in this case, K +)
tends to surround the participating
anion (OH-) and vice versa with the
spectator
anion
(Cland
Ca2+,
respectively). This decreases the
concentrations of the ions, prompting
the production of more and increasing
solubility. The ionic strength can be
measured using this equation,
n

1
c 1 z 12

2 i=1

(12)

Where c is the concentration,

and z is the charge of the ion. The
diverse ion effect typically has only a
small effect on the solution.
For
the
experiment,
the
theoretical general trend for solubility
would be 0.100M Ca2+ < distilled water
< 0.500 M KCl. The results obtained
are consistent with the theory, with

Ca2+ having Ksp = 1.87x10-7, water

having Ksp = 1.22x10-5, and KCl having
Ksp = 5.06x10-5.

CONCLUSION AND
RECOMMENDATION

REFERENCES

Based on the results obtained,

the experiment failed to determine the
equilibrium solubility constant of
Ca(OH)2, though it was able to show
the trend of solubility given different
media, with common and diverse ions.
The experiment had a 121.81%
error when comparing the theoretical
and experimental Ksp of calcium
hydroxide. This large error is mostly
due to the errors that occurred during
the procedure.
The first error was that the
analyte volume was neither accurate
nor consistent. The procedure was to
use 25 mL for two trials though in the
actual experiment, the first trial had
more than 25 mL, and the second trial
had less than 25 mL. This affected the
calculated
concentrations
and
solubility. Another error is that the
solutions used were contaminated.
When doing the experiment, the
analyte was already a pink color
before the addition of phenolphthalein.
The experiment could have
been more successful if the solutions
were not contaminated and were
measured out using more accurate
apparatus. The temperature at which
the experiment was being conducted
could also have been recorded, since
equilibrium constants are dependent
on temperature.

[1] Brown, T.L., LeMay, H.E. Jr.,

Bursten, B.E., Murphy, C.J., Woodward,
P.M., Stoltzfus, M.W. Chemistry the
Central Science 13th ed. Pearson
Education Inc., New Jersey. 2014.
[2] Petrucci, R.H., Herring, F.G.,
Madura, J.D., Bissonnette, C. General
Chemistry Principles and Modern
Applications 10th ed. Pearson Canada
Inc., Toronto. 2011.
[3]
Ophardt,
C.
(2003)
Temperature/Pressure on Solubility.
Retrieved March 25, 2015, from
http://www.elmhurst.edu/~chm/vchem
book/174temppres.html.
[4] Rosenberg, J.L., Epstein, L.M.
College Chemistry 7th ed. McGraw-Hill
Inc, New York, 1990.
[5] Study Material, Chemistry, Ionic
Equillibrium, Applications Solubility
Product. (2011). Retrieved March 26,
2015, from
http://www.emedicalprep.com/studymaterial/chemistry/ionicequillibrium/applications-solubilityproduct.html
[6] Clark, J. (2011). Solubility Product
and the Common Ion Effect. Retrieved
March 26, 2015 from
http://www.chemguide.co.uk/physical/k
sp/commonion.html

APPENDIX
Calculations
Preparation of KCl medium

0.5 M KCl=

x moles
.250 L

x = 0.125 moles

0.125 moles=x grams

x = 9.31875 grams

mole
74.55 grams

Calculation for [OH-] based on titrimetric analysis

MHClVHCl = MOH-VOH
Distilled water:
Trial 1
(0.1)(8) = x(25)
x = 0.032M

Trial 2
(0.1)(6.5) = x(25)
x= 0.026M

0.500M KCl:
Trial 1
(0.1)(11.5) = x(25)
x = 0.046M

Trial 2
(0.1)(11.8) = x(25)
x= 0.0472M

0.100M Ca2+:
Trial 1
(0.1)(6.5) = x(25)
x = 0.026M

Trial 2
(0.1)(6.3) = x(25)
x = 0.0252M

Average Values:
Distilled water: 0.029M
0.500M KCl: 0.0466M
0.100M Ca2+: 0.0256M
Calculation for [Ca2+]

2+

2+

1 mol Ca : 2 mol OH ; [Ca ] =

OH

Distilled water:
Trial 1
[Ca2+] = 0.032/2 = 0.016M

Trial 2
[Ca2+] =0.026/2 = 0.013M

0.500M KCl:
Trial 1
[Ca2+] = 0.046/2 = 0.023M

Trial 2
[Ca2+] = 0.0472/2 = 0.0236M

0.100M Ca2+:
Trial 1
[Ca2+] = 0.026/2= 0.013M

Trial 2
[Ca2+] = 0.0252/2 = 0.0126M

Average Values:
Distilled water: 0.0145M
0.500M KCl: 0.0233M
0.100M Ca2+: 0.0128M
Calculation of Ksp

Ksp = [Ca2+][OH-]2; where [x] is concentration

Distilled water: (0.0145)(0.029)2 = 1.22 x10-5
0.500M KCl: (0.0233)(0.0466)2 = 5.06x10-5
0.100M Ca2+: (0.0128)(0.0256)2 = 8.39x10-6
To account for common ion effect
Ksp(theoretical) = (0.100+s)(2s)2
5.5x10-6 = (0.400s2+ 4s3)
s = 3.6x10-3 = [Ca2=]

[OH-] = 7.2 x 10-3

Ksp = [OH-]2[Ca2+] = 1.87x10-7

Calculation for experimental

molar solubility

Calculation of theoretical molar

solubility

s = [Ca2+] =

OH

Distilled water: 0.0145M

0.500M KCl: 0.0233M
0.100M Ca2+: 0.0128M

Ksp = [Ca2+][OH-]2
Ksp = s(2s)2
Ksp = 4s3
5.5x10-6 = 4s3
s = 0.0177 M

Calculation of ionic strength ()

n

1
2
c1 z1

2 i=1

1
2

( (0.0233*(2)2)+ (0.0466*(-

1)2 + (0.500)(1)2 + 0.500(-1)2) =

0.5699 M

Percent Error and Percent Difference

Percent Error
(|Theoretical actual|/theoretical)*100
= % error

Percent Difference

theoreticalactual
100
theoretical+actual
=%

5.5 x 1061.22 x 105

100
=121.81
2
6
5.5 x 10
difference

5.5 1051.22 106

100 =7
5
5.5 10 +1.22 106
2