Thermodynamic Analysis of Aqueous Equilibria

Purpose: To determine ΔH and ΔS of different aqueous equilibria by applying

principles of thermodynamics.
Procedure:
1) Take an Erlenmeyer flask with 100mL distilled water and insulate it from
surroundings at a specific temperature.
2) Add 1g AgCl to the distilled water.
3) Note the molarity of anions and cations.
4) Calculate the Ksp.
5) Repeat the same steps at different temperatures varying from 25˚C to 90˚C
for equilibria 1-4.

Results: Concentratio Conc. Of Ksp lnKsp 1/T in K^-1

XTemp. n of Cation anion (M)
(˚C) (M)
25 1.00E-07 1.00E-07 2.01E-07 -15.42 0.003356
30 1.21E-07 1.21E-07 1.46E-14 -31.85495058 0.003298697
50 2.40E-07 2.40E-07 5.77E-14 -30.48358785 0.003094538
80 5.81E-07 5.81E-07 3.37E-13 -28.71840757 0.002831658

Temp. Concentratio Conc. Of Ksp lnKsp 1/T in K^-1

(˚C) n of Cation anion (M)
(M)
25 1.00E-07 1.00E-07 2.01E-07 -15.42 0.003356
30 1.92E-05 1.92E-05 3.68E-10 -21.7222425 0.003298697
50 7.42E-05 7.42E-05 5.50E-09 -19.01857127 0.003094538
80 4.23E-04 4.23E-04 1.79E-07 -15.53722261 0.002831658
Temp. Concentratio Conc. Of Ksp lnKsp 1/T in K^-1
(˚C) n of Cation anion (M)
(M)
25 1.00E-07 1.00E-07 2.01E-07 -15.42 0.003356
30 0.0317 0.0158 1.59E-05 -11.05062254 0.003298697
50 0.0366 0.0183 2.45E-05 -10.6162683 0.003094538
80 0.0442 0.0221 4.32E-05 -10.05023865 0.002831658

Temp. Concentratio Conc. Of Ksp lnKsp 1/T in K^-1

(˚C) n of Cation anion (M)
(M)
25 1.00E-07 1.00E-07 2.01E-07 -15.42 0.003356
30 3.21E-07 2.14E-07 3.61E-25 -56.28112718 0.003298697
50 2.42E-07 4.28E-07 4.25E-25 -55.01332186 0.003094538
80 4.86E-07 3.26E-07 2.08E-25 -53.24173684 0.002831658

1/T in K^-1 v/s lnKsp

0
lnKsp

0
-23.00 -22.00 -21.00 -20.00 -19.00 -18.00 -17.00 -16.00 -15.00
1/T in K^-1

1/T in K^-1 v/s lnKsp

0
lnKsp

0
0
-16 -15 -14 -13 -12 -11 -10 -9
1/T in K^-1
 1/T in K^-1 v/s lnKsp
0
lnKsp

0
-60.00 -55.00 -50.00 -45.00 -40.00 -35.00 -30.00 -25.00 -20.00 -15.00 -10.00
1/T in K^-1 v/s lnKsp

Discussion: X Hf (Kj/mol) Sf(J/mol)

H2O (l) -285.8 70
H+ (aq) 0 0
OH-(aq) -230 -10.8
(-230+0)-(-285.8) (-10.8+0)-(70)
55.8 -80.8

Hf (Kj/mol) Sf(J/mol)
AgCl (l) -127 96.3
Ag+(aq0 105.6 72.7
Cl-(aq) -167.2 56.5
(-167.2+105.6)-(-127) (56.5+72.7)-(96.3)
65.4 32.9

Hf (Kj/mol) Sf(J/mol)
Ag2SO4 (l) -717.2 199.8
Ag+ (aq) 105.6 72.7
SO4(2-)(aq) -909.3 20.1
(-909.3+(2*105.6))-(-717.2) (20.1+(2*72.7))-(199.8)
19.1 -34.3
 Hf (Kj/mol) Sf(J/mol)
Ca3(PO4)2 (s) -4120.82 235.98
Ca (2+) (aq) -542.83 -53.14
PO4(3-) (aq) -1277.38 -221.75
((2*-1277.38) +(3*-542.83)) -(- ((2*-221.75) +(3*-53.14))-
4120.82) (235.98)
-62.43 838.9

Conclusion: The theoretical and experimental are not really the same. There is some difference in
both these values.

Post Lab Questions:

1) The solubility of NaNO3 in water increases as temperature increases. What can we say about
∆H and ∆S from this information only?

Both delta H and delta S increases

2) What is the molar solubility of Pb(IO3)2 in water at 25 0 C? The Ksp of Pb(IO3)2 is 2.5 x 10-13.

Solubility of Pb (IO3)2 is 0.25

3) In these experiments, how can you verify the solution analyzed was saturated?

is a saturated We can know if the solution analyzed was saturated by the presence of excess solute
which can no longer dissolve is an evidence that a solution is saturated. Here, not all AgCl(s) added
dissolved. Therefore, its solution. Saturation can be confirmed by adding more AgCl(s) and seeing if
ion concentrations change.

4) In the virtual world here, we neglect other subsequent equilibria that can influence solubility.
What other equilibria could be important to consider in the real world for the solubility of Ca3(PO4)2
and Ag2SO4

In real world lab factors like temperature and the rate of stirring can influence the solubility.