\Tala Alrashid

Student number :1006265391

Lab Section 0101
CHM110
Lab partner: Anastajiha Avramovic

Experiment 5:

DETERMINATION OF THE KSP AND STANDARD THERMODYNAMIC

PARAMETERS FOR DISSOLVING Ca(OH)2

TA: Rodica Pecheanu

Date of lab: November 18th , 2019

Date submitted: November 25th , 2019
Introduction
Calcium hydroxide is a compound characterized by a soft white powder, obtained from a
combination of lime and water through an exothermic reaction, called slacking (1). It is slightly
soluble in water, and its solubility tends to decrease with increasing temperature. The effects of
temperature on solubility will be further studied in this experiment.

It is commonly used in mortar, cements, calcium salts, paints, and pH regulating. However, when
using calcium hydroxide, it is important to measure the appropriate concentrations to prevent the
substance from attaining toxic levels (1). A saturated solution of calcium hydroxide in an
equilibrium is represented as the following:
Ca(OH)2(s) = Ca+2(aq) +2OH-(aq)
Purpose
The purpose of this experiment is to perform an acid-base titration in standardized HCl to
evaluate the solubility of calcium hydroxide as a function of temperature (room temperature, 60˚-
80˚, and boiling point) in order to find ∆H˚, ∆S˚and ∆G˚. The value of Ksp will be determined at
three different temperatures by measuring each hydroxide concentration through titration means.
This experiment provides an understanding of the relationship between the Ksp and ∆H˚, ∆S˚and
∆G˚, as well as evidence regarding solubility of calcium hydroxide at different temperatures
Ca(OH)2(s) = Ca2+(aq) +2OH-(aq) (1)
Ksp = [Ca2+][OH-]2 (2)
∆G˚ = - RT lnK = ∆H˚ - T ∆S˚ (3)
Experimental Method
(refer to CHM110 course manual book from page 81-83)
1- Inside the fume hood, transfer approximately 2 g of Ca(OH)2 into a 250mL beaker, then
add 100mL of distilled water and stir at room temperature for 15 minutes. Let the solid of
the compound settled by leaving undisturbed for a few minutes, then measure the
temperature of the solution using a thermometer.
2- Add a piece of fluted filter paper to the funnel into a dry 250mL Erlenmeyer flask in
order to filter the solution of calcium hydroxide and obtain a saturated solution.
3- To determine the concentration of hydroxide in the solution, an acid- base titration will
be performed. Using a volumetric pipette measure out 5.0mL of the saturated calcium
 hydroxide solution into a 125mL Erlenmeyer flask. Phenolphthalein indicator will be
used to indicate the endpoint of the solution through colour modification. Record the
initial and final liquid readings on the burette.
4- To prepare a saturated solution at 60˚-80˚, place the flask with 10.0 mL of solution on a
hot plate and insert a thermometer to measure the temperature, and try to maintain a
stable temperature. Then repeat steps 2-3 with the heated solution
5- To achieve the boiling point temperature, apply step 4, the proceed with step 2-3.
Data collected
Table 1.0: summary of the results
Test 1 (˚C) T (K) Volume [OH-](M) [Ca+2](M) Ksp (M) lnKsp 1/T (K)
# Average of HCl
(mL)
1 21.6˚C 294.75K 9.7 mL 3.88 x 10-2 1.94 x 10-2 2.92 x 10-5 -10.44 1/294.75K

2 21.6˚C 294.75K 10.23 mL 4.092 x 10-2 2.046 x 10-2 3.41 x 10-5 -10.28 1/294.75K

3 65˚C 338.15K 17.73 mL 3.46 x 10-2 1.73 x 10-2 2.23 x 10-5 -10.71 1/338.15K

4 94˚C 367.15K 9.96 mL 1.992 x 10-2 9.96 x 10-3 3.95 x 10-6 -12.44 1/367.15K

Graph 1.0: relationship between lnKsp vs 1/T

ln Ksp vs 1/T (K-1) for dissolution of

Ca(OH)2
0
0 0.0005 0.001 0.0015 0.002 0.0025 0.003 0.0035 0.004
-5
ln Ksp

y = 2627.7x - 19.157
-10
R² = 0.7684

-15
1/T(K-1)

Table 1.1: data results for thermodynamics parameter, ∆H˚and ∆S˚

Slope (-∆H˚/R) 2627.7
Intercept (∆S˚/R) -19.157
∆H˚ -21373.7Jmol-1K-1 or -21.37kJ/mol
∆S˚ -159.27Jmol-1K-1
Table 1.2: data results for Gibbs Free Energy, ∆G˚
K ∆G˚
294.75 25029.86 J/mol or
25.029 kJ/mol
294.75 25191.66J/mol or
25.191 kJ/mol
Average of 1 & 2 25110.76J/mol or
25.11kJ/mol
338.15 30109.87 J/mol or
30.1kJ/mol
367.15 37150.8J/mol or
37.15 kJ/mol

Sample Calculations
To find the Ksp value of Ca(OH)2
1- Use CHClVHCl = COHVOH in order to find the concentration of hydroxide.
We are given the concentration of HCl, 0.0002M, the volume of HCl and the volume of OH
(same as the volume of the calcium hydroxide solution).
For 21.6˚C, [OH-]…
CHClVHCl = COHVOH
(0.02M)(9.7mL) = COH(5mL)
[OH-] = 3.88 x 10-2 M
Use the molar ratio of calcium and hydroxide to find [Ca+2]:
[Ca+2] = (3.88 x 10-4 M)/2
= 1.94 x 10-2 M
Thus, Ksp of Ca(OH)2 is…
Ksp = [Ca+2][OH-]2
= 2.92 x 10-5
lnKsp = ln(2.92 x 10-11)
= -10.44
 2- To find the standard enthalpy change, ∆H˚, we use the slope of graph 1.0 and the
equation lnKsp= -∆H˚/R
Substitute the slope, m, in lnKsp and R= 8.134Jmol-1K-1
2627.7 = -∆H/(8.134Jmol-1K-1)
∆H˚ = -21373.7118 Jmol-1K-1 or -21.3kJ/mol

3- To find the entropy change, ∆S˚, we use the intercept (+/- b) of graph 1.0 and the
equation lnKsp= ∆S˚/R
Substitute the intercept, +/- b, in lnKsp and R= 8.134Jmol-1K-1
-19.157= ∆S˚/(8.134Jmol-1K-1)
∆S˚ = -159.27 Jmol-1K-1
4- To find ∆G˚ use the equation ∆G˚= -RTlnKsp
For 294.75K…
∆G˚ = -(8.134Jmol-1K-1)(294.75K)(-10.44)
= 25029.86 J/mol or 25.029 kJ/mol
5- Calculating the deviation percentage
|experimental value – theoretical value|/theoretical value *100
For ∆G at room temperature...
|25.029 – (-985.2)|/(-985.2) *100 = 97.8%
Discussion
The solubility product constant, also known as Ksp signifies the equilibrium between the
solid and its ions in a solution. Factors such as temperature and pressure (only in gases) affect the
value of Ksp. Notably, in most solids, the Ksp value increases with temperature, allowing the
dissociation of bonds and intramolecular forces between molecules. However, according to the
collected data, the Ksp value decreases as the temperature gets higher (65˚C= 2.22 x 10-5; 94˚C=
3.95 x 10-6) , thus the solution of calcium hydroxide at room temperature has a greater solubility
property than the solution at higher temperatures (65˚C and 94˚C). These findings confirm the
theory stating that the solubility of calcium hydroxide decreases with temperature (2).
Moreover, the data enabled the evaluation of the enthalpy, entropy, Gibbs free energy as
a function of the temperature and the Ksp. The enthalpy, ∆H˚, of a reaction indicates whether the
reaction is endothermic (absorbed energy) or exothermic (release of energy) (3). Consequently,
the value of ∆H˚ can be negative (exothermic) or positive (endothermic). The entropy of a
reaction indicates whether particles are moving freely (disordered) or if the system has become
ordered, they are indicated by a positive or negative sign, respectively. The enthalpy and entropy
of a system are correlated to the ∆G˚ , indicating whether the reaction is spontaneous or not (3).
The dissolution of calcium hydroxide is favoured at room temperature; hence the
solubility of the compound is inversely proportional to the temperature. When calcium hydroxide
is dissolved in water, an exothermic reaction occurs, meaning energy is released by the system.
The net entropy of the system is temperature-dependant, so the entropy of calcium hydroxide
will decrease with increasing temperature (2). Lastly, considering that the reaction is exothermic
and undergoes a decrease in entropy, the Gibbs free energy value of calcium hydroxide is
nonspontaneous at high temperature and spontaneous at low temperature.
According to the results, the solution of calcium hydroxide undergoes an exothermic
reaction (-21.37kJ/mol). The reaction results in a negative entropy, denoting that the disorder of
the system has decreased, implying that there is a formation of a solid. The Gibbs free energy
value can be found by utilizing equation 3, thus the final results show that ∆G˚>0 at all three
temperatures (294.75K = 25.11kJ/mol; 338.15K = 30.1kJ/mol; 367.15K = 37.15kJ/mol). These
findings conclude the reaction is in fact nonspontaneous within these thermodynamic conditions,
meaning that it does not favour the formation of products.
The theoretical value of Ksp, ∆G, ∆H and ∆S at STP were compared to the experimental
values (4). The deviation percentage of the average Ksp is 28%, ∆H is 97.8%, ∆S is 90.9%, ∆G
(room temperature) is 97%, ∆G (65˚C) is 96% and ∆G (boiling point) is 95.8%. The deviation
percentages are significant numbers, proposing that certain experimental errors occurred. As
shown in graph 1.0, the coefficient of regression is 77%, suggesting that there are points on the
graph that could potentially change the slope or intercept if they were removed. Other sources of
error are mentioned in the sources of error section of the lab. However, the deviations can be
justified by the differences in temperatures, leading to a different Ksp and thermodynamic values
when compared to that of STP. Since the provided literal values of the thermodynamic
parameters are given at a standard temperature and pressure conditions, it is evident that the
obtained values will deviate from it.
The technique of separation or filtration is important in this experiment because it
separates the precipitate particles from the solution in order to isolate the dissolved solution. The
concentration of the remaining solution is measured to find the value of Ksp. In fact, the heated
solution will have less supernatant compared to the solution at room temperature. If the solution
is not filtered, the presence of precipitate in the solution would alter the endpoint because excess
HCl will be added to neutralize the calcium hydroxide precipitate, leading to invalid Ksp and
thermodynamic values. The physical and chemical properties of calcium hydroxide reveal that its
solubility decreases as the temperature increases, therefore it is important to filter the heated
solution because once it cools down the solubility increases, thus the remaining solution would
be greater than anticipated, resulting with the same Ksp as the solution at room temperature.
Therefore, the solution is filtered before it is cooled down to maintain a constant temperature and
to prevent the increase of solubility of the compound.

Sources of Error
 Incorrect estimate of measurements of the volumes (mistakes on the burette or pipette or
any instrument)
 If heated saturated solution of calcium hydroxide is not filtered right away, the
temperature of the solution can alternate (not constant).
 Incorrect reading of temperature on thermometer due to contact of the instrument and the
burette, thus it measures the temperature of the burette and not the solution.
 Air bubbles in the burette could have led to incorrect reading of HCl volumes, leading to
invalid calculations for concentration.
 Endpoint errors, meaning that the indicator, phenolphthalein, did not change colour once
introduced to the neutral solution due to the presence of CO2 in the solution.
Learning Objectives
 Manipulating the Ksp equation for Ca(OH)2 and determining its value using the
concentrations of OH- obtained from titration.
 Dissolved CO2 could alter the pH of the solution, thus resulting in an incorrect endpoint.
 Handling instruments and chemicals with dexterity and caution, such as the heat plate,
calcium hydroxide and hydrochloric acid.
 The solubility of Ca(OH)2 was favourable when the temperature is at room temperature.
 Phenolphthalein was the appropriate indicator for this experiment because it functions
efficiently in a solution with a pH ranging between 8.3-10.0.
Conclusion
To conclude, the solubility of calcium hydroxide decreases with increasing temperature,
this observation was made by evaluating the Ksp value of a calcium hydroxide solution at
different temperature (room temperature, 60˚-80˚, and boiling point). Using the Ksp values, we
plotted a graph illustrating the relationship between lnKsp and 1/T. The slope and intercept aided
in solving for the thermodynamic parameters. These calculations led to conclude that the
dissolution of calcium hydroxide is an exothermic reaction, the system becomes more ordered,
and the reaction is nonspontaneous. This experiment used acid-base titration as way to measure
the concentration of hydroxide in the dissolved solution, it is an efficient and non-expensive
method to obtain the desire values. It is important to note that filtration at higher temperature
prevents the solution from dissolving the precipitate and helps maintain a constant temperature.
References
(1) Poe, J. CHM 110 Course Manual; Erindale College University of Toronto Mississauga:
Mississauga, ON, 2019; p 81-83.
(2) Lohninger, H. Calcium Hydroxide.
https://chem.libretexts.org/Bookshelves/Inorganic_Chemistry/Supplemental_Modules_(I
norganic_Chemistry)/Descriptive_Chemistry/Elements_Organized_by_Block/1_s-
Block_Elements/Group__2_Elements%3A_The_Alkaline_Earth_Metals/Z%3D020_Che
mistry_of_Calcium_(Z%3D20)/Calcium_Hydroxide (accessed Nov 23, 2019).
(3) AP* Edition of CAMPBELL BIOLOGY - Pearson - MAFIADOC.COM.
https://mafiadoc.com/ap-edition-of-campbell-biology-
pearson_5a1e24a21723ddbd7069ecf7.html (accessed Nov 23, 2019).
(4) (3) R. Rumble, J. Handbook of Chemistry and Physics 100th Edition.
http://www.hbcponline.com/ (accessed Nov 23, 2019).