ATENEO

DE MANILA UNIVERSITY
Ch 46.5 Applied Physical Chemistry Laboratory
1st Sem. 2014-15

Determination of , , , and of Ca(OH)2

for the Dissolution of Calcium Hydroxide in Water
Experiment No. 6



INTRODUCTION

The solubility of hydroxides is easily determined by titration. From the molar solubility,
the solubility equilibrium constant, Ksp can be calculated and from this the Go for the
dissolution of the material can be determined. Using Go at two different temperatures
and noting that the Ho and So are relatively invariant over small temperature ranges,
the enthalpy and entropy changes can also be estimated. With knowledge of these
constants, the Go and Ksp can be calculated at any temperature between 0oC and 100oC.
Note that what is being calculated in this experiment is the apparent, not
thermodynamic equilibrium constant since it is based on concentrations rather than
activities; further ion-pairing and ionic strength effects and activities are being
neglected, which would not be the case in a more rigorous approach of an advanced
course.

Reaction. The solubility of an ionic substance in a solvent can be thought of as a
reaction where the solid dissolves into ions in solution. In this experiment, the solubility
of calcium hydroxide will be determined, as suggested in the reaction below;

Ca(OH)2(s)
Ca+2(aq) + 2OH-(aq)
(1)

Once equilibrium has been established and the solid removed, the concentration of
hydroxide can be easily determined via an acid base titration. Hydrochloric acid will be
used to find the concentration of OH-(aq).

HCl(aq) + OH-(aq)
H2O(l) + Cl-(aq)
(2)

Determination of , , , and . The concentration of the hydroxide ion in a
saturated solution of Ca(OH)2 is found by titration with standardized hydrochloric acid.
Since HCl is a strong acid and H+ and OH- react with 1:1 stoichiometry, we may write

!"# !"# = !" ! !" !
(3)

Where !"# and !" ! are molarities and !"# and !" ! are the volumes of the acid and
hydroxide solutions, respectively. The molar solubility od the salt is then just half of the
hydroxide ion concentration. The apparent equilibrium constant for the equation (1),
Ksp, is found from the mass action expression in equation (4).

(4)
!" = !! ! !

The calcium ion concentration is half the hydroxide ion concentration determined by
titration. The Gibbs Free Energy, Go, is related to the equilibrium constant (Ksp) by
equation (5)

! = !"
(5)

Where R is the gas constant (R = 8.314 J/mole-K) and T is the absolute T in Kelvin.

To find the enthalpy (Ho) and entropy (So) changes, equation (6) is used:

! = ! !
(5)

Where, again, T is the absolute temperature. We assume Ho and So do not change
significantly with temperature which is usually true for this small temperature change.
Using free energies Go, found for two different temperatures, Ho and So are found by
solving two unknowns in two equations. The two equations are in the form of equation
(6) with the two appropriate values for T and Go.

PROCEDURE

1. Prepare standardized 0.01 M NaOH and 0.01 M HCl solutions. Use freshly boiled distilled
water in preparing the NaOH solution, and standardize it against potassium acid
phthalate (KHP) using phenolphthalein end point. The HCl solution may then be
standardized using the standardized NaOH solution.

2. Find the solubility of calcium hydroxide in water at room temperature. (Record the
temperature)

A solution of calcium hydroxide will be stirring at room temperature in the laboratory.
Draw off approximately 40 mL of this solution and record the temperature. Filter the
solution using a long stem funnel. Pipet 10.0 mL of the filtrate into a clean 125-mL
Erlenmeyer flask and add 25.0 mL of distilled water and a few drops of bromothymol
blue indicator. Titrate with standard HCl solution until the yellow endpoint. Repeat two
more times.

3. To prepare 100oC saturated calcium hydroxide solution, bring 100 mL of distilled water
to boil in a 250 mL beaker. After the water has been boiling for several minutes, add
about 2 grams of Ca(OH)2 to the water and keep it near boiling with occasional stirring
until needed.

4. Find the solubility of calcium hydroxide in the hot solution. Bring your hot solution to a
gentle boil for about two minutes. Turn off the burner, measure the temperature and
quickly draw off about 40-50 mL of solution. Quickly filter it using a clean, dry long stem
funnel. Pipet 10.0 mL of the cooled filtrate into each of three clean 125 mL Erlenmeyer
flak and add 25 mL of distilled water and add a few drops of bromothymol blue
indicator. When the solution is cool, titrate with the standard HCl solution until the
yellow end point. Repeat twice more.

CALCULATIONS:

Find the average solubility of calcium hydroxide at each temperature. Use equation (3_
to find the hydroxide ion concentration and then convert this to the molar solubility of
Ca(OH)2. (Should you use 10.0 mL or 35.0 mL for !! ! ?). Solve for Ksp and Go at each
temperature. Determine Ho and So.


QUESTIONS:

1. Look up the 25oC Ksp for calcium hydroxide. How does your room temperature value
compare to the reference (cite your source)? What are the sources of error?

2. Calculate the molar solubility of Ca(OH)2 at 50oC. It is not the average of the 0oC and
100oC solubilities; why not?

3. Why is it necessary to titrate the solution before titrating? How would having a small
amount of Ca(OH)2 in the titration flask affect your results?


REFERENCES:
Euler, W, B.; Kirshchenbaum, L. J.; B. Ruckberg, J. Chem. Educ. 2000, 77, 1039-1040.