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Page I-41 / Determination of Ksp, ∆G˚, ∆H ̊and ∆S˚ for Ca(OH)2 Lab
Determination of Ksp, DG˚, DH˚ and DS˚ for Ca(OH)2 The solubility of hydroxides is easily determined through a titration with a suitable acid (such as HCl). From the molar solubility, the solubility equilibrium constant, Ksp, can be calculated and from this the DG˚ for the dissolution of the material can be determined. Using DG˚ values at two different temperatures and noting that the values of DH˚ and DS˚ are relatively invariant over small temperature ranges, the enthalpy and entropy changes can also be estimated. With knowledge of these constants, DG˚ and Ksp can be calculated at any temperature between 0 ˚C and 100 ˚C. THE REACTION: The solubility of an ionic substance in a solvent can be thought of as a reaction where the solid dissociates into ions in solution. In this experiment, the solubility of calcium hydroxide will be determined, as suggested in the reaction shown below.
Ca(OH)2(s) qe Ca2+(aq) + 2 OH-(aq) 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) Note that the molar solubility of Ca(OH)2 is half of the OH- concentration found by titration. Determination of Ksp, DG˚, DH˚ and DS˚ The concentration of 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 can use:
MHClVHCl = MOH-VOH- where MHCl and MOH- are the molarities and VHCl and VOH- are the volumes of the acid and hydroxide solutions, respectively. The molar solubility of the salt is equal to half of the hydroxide ion concentration The equilibrium constant, Ksp, for Ca(OH)2 is:
Ksp = [Ca2+][OH-]2
Remember that the calcium ion concentration is half the hydroxide ion concentration determined by the titration. The Gibbs Free Energy, DG˚, is related to the equilibrium constant (Ksp) by
DG˚ = -RT ln Ksp
where R is the ideal gas constant (R = 8.3145 J/mol-K) and T is the absolute temperature in Kelvin.
Page I-42 / Determination of Ksp, ∆G˚, ∆H ̊and ∆S˚ for Ca(OH)2 Lab
To find the enthalpy (DH˚) and entropy (DS˚) changes, the following equation is used
DG˚ = DH˚ - TDS˚ where T is the absolute temperature. We assume that DH˚ and DS˚ do not change significantly with temperature which is usually true for this small of a temperature change. Using the free energies (DG˚) found for two different temperatures, DH˚ and DS˚ values are found by solving for two unknowns in two equations. Example: Consider the solubility of Sr(OH)2. Two solutions of Sr(OH)2 are allowed to equilibrate, one at 0 ˚C and the other at 25 ˚C. A 10.00 mL aliquot of each solution is titrated with 0.2000 M HCl. 3.37 mL of the acid are required for the 0 ˚C solution, and 62.90 mL are required for the 25 ˚C solution. At 0 ˚C, the [OH-] is found using:
[OH-] = ([HCl] * VHCl)/VOH- = (0.2000 M * 3.37 mL)/10.00 mL = 0.0674 M Thus, the molar solubility of Sr(OH)2 at 0 ˚C is 0.0674/2 = 0.0337 M. Ksp at 0 ˚C can then be found:
Ksp = [Sr2+][OH-]2 = [0.0337][0.0674]2 = 1.53*10-4 DG˚ can be determined at 0 ˚C (273 K):
DG˚ = -RT ln Ksp = -(8.3145)(273) ln(1.53*10-4) = 19.9 kJ/mol Similarly, the molar solubility at 25 ˚C is found to be 0.6290 M; Ksp is 0.995; and DG˚ is 0.0124 kJ/mole. Now we can determine DH˚ and DS˚ using the values of DG˚ at two temperatures:
DG˚ = 19.9 kJ/mole = DH˚ - (273 * DS˚) DG˚ = 0.0124 kJ/mole = DH˚ - (298 * DS˚)
Subtracting the second equation from the first provides
19.9 kJ/mol - 0.0124 kJ/mol = DH˚ - DH˚ - (273 * DS˚) + (298 * DS˚) 19.9 kJ/mole = 25 DS˚
so DS˚ = 0.80 kJ/mole-K. Using this value of DS˚ at either temperature gives DH˚ = 240 kJ/mole.
Page I-43 / Determination of Ksp, ∆G˚, ∆H ̊and ∆S˚ for Ca(OH)2 Lab
PROCEDURE: 1. Record the concentration of the standardized HCl provided in the laboratory. Obtain about 40 mL of this HCl
solution and place it in a 25 mL buret. 2. 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 until you have at least 30 mL of filtrate (if the filtering is slow, consider starting step 3 below.) Place 10.0 mL of the filtrate into a clean 125 mL Erlenmeyer flask and add 25 mL of distilled water and a few drops of bromothymol blue indicator. Titrate with the standard HCl solution until the yellow endpoint appears (probably no more than 5 mL of HCl will be required to reach the endpoint). Record the volume of HCl used. Repeat this procedure two more times.
3. Prepare a 100 ˚C saturated calcium hydroxide solution by bringing 100 mL of distilled water to a boil in a 250
mL beaker. After the water has been boiling for several minutes, add about 2 g of Ca(OH)2 to the water and keep it near boiling with occasional stirring until needed.
4. 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 the solution using a clean, dry long stem funnel.
5. Place 10.0 mL of the cooled filtrate into each of three clean 125 mL Erlenmeyer flasks and add 25 mL of
distilled water and a few drops of bromothymol blue indicator. When the solution is cool, titrate with the standard HCl solution until the yellow endpoint appears (probably no more than 5 mL of HCl will be required to reach the endpoint). Record the volume of HCl used. Repeat two more times.
6. Dispose of all used and excess chemicals in a waste container. Rinse your buret and all glassware with water
before returning to its original location.
CALCULATIONS: Be sure to look at the example on the previous page for hints on how to get started! 1. Find the average solubility (and parts per thousand) of calcium hydroxide at each temperature by finding
the hydroxide ion concentration and then converting this value to the molar solubility of Ca(OH)2. If one of the three equivalence point volumes differs from the other two, it is acceptable to omit the differing value and use the two values with close precision.
2. Find Ksp at each temperature using the average solubility value. Find DG˚ at each temperature using the two
values of Ksp. 3. Find DH˚ and DS˚ using the values of Ksp and DG˚ at the two temperatures.
Page I-44 / Determination of Ksp, ∆G˚, ∆H ̊and ∆S˚ for Ca(OH)2 Lab
POSTLAB QUESTIONS: 1. Look up the 25 ˚C Ksp for calcium hydroxide in your text or in the Handbook of Chemistry and Physics. How
does your room temperature value compare to the reference? What are the sources of error? Cite your reference for the Ksp value.
2. Calculate the molar solubility of Ca(OH)2 at 50 ˚C using your experimental values of DH˚ and DS˚. (Hint:
First find DG˚ at the new temperature, then determine Ksp and finally solubility.) Is this solubility the average of the 0 ˚C and 100 ˚C solubilities? Why or why not? (Hint: are the equations used to determine solubility linear?)
3. Why is it necessary to filter the solution before titrating? How would having a small amount of Ca(OH)2(s) in
the titration flask affect your results? 4. A 10.00 mL sample of Ba(OH)2 at 0. ˚C is titrated with 0.2500 M HCl, and 4.80 mL of the acid are used to
reach the yellow endpoint.
a. Calculate the concentration of hydroxide in the Ba(OH)2 solution. b. Determine the molar solubility and Ksp of Ba(OH)2. c. Calculate DG˚ for this reaction using the value of Ksp.
5. A second 10.00 mL sample of Ba(OH)2 is obtained at a temperature of 50. ˚C. This solution is titrated with
44.15 mL of 0.2500 M HCl to reach the yellow endpoint.
a. Calculate the concentration of hydroxide in this Ba(OH)2 solution. b. Determine the molar solubility and Ksp.
c. Calculate DG˚ for this reaction using the value of Ksp.
6. Using the values of DG˚ at 0. ˚C and 50. ˚C, calculate DH˚ and DS˚ for this reaction.
