1. 1 PRECIPITATION REACTIONS Solubility of Salts Section 18.4

2. 2 Metal Chloride Salts These products are said to be INSOLUBLE and form when mixing moderately concentrated solutions of the metal ion with chloride ions.

3. 3 Analysis of Silver Group The products are said to be insoluble, they do dissolve to some SLIGHT extent. AgCl(s) = Ag + (aq) + Cl - (aq) When equilibrium has been established, no more AgCl dissolves and the solution is SATURATED.

4. 4 Analysis of Silver Group AgCl(s) = Ag + (aq) + Cl - (aq) When solution is SATURATED, expt. shows that [Ag + ] = 1.67 x 10 -5 M. This is equivalent to the SOLUBILITY of AgCl. What is [Cl - ]? [Cl - ] is equivalent to the AgCl solubility.

5. 5 AgCl(s) = Ag + (aq) + Cl - (aq) Saturated solution has [Ag + ] = [Cl - ] = 1.67 x 10 -5 M Use this to calculate K c K c = [Ag + ] [Cl - ] = (1.67 x 10 -5 )(1.67 x 10 -5 ) = 2.79 x 10 -10

6. 6 K c = [Ag + ] [Cl - ] = 2.79 x 10 -10 Because this is the product of “solubilities”, we call it K sp = solubility product constant See Table 18.2 and Appendix J Solubility Product Constant

7. 7

8. 8 Lead(II) Chloride PbCl 2 (s) = Pb 2+ (aq) + 2 Cl - (aq) K sp = 1.9 x 10 -5

9. 9 Solution Solubility = [Pb 2+ ] = 1.30 x 10 -3 M [I - ] = ? [I - ] = 2 x [Pb 2+ ] = 2.60 x 10 -3 M Solubility of Lead(II) Iodide Consider PbI 2 dissolving in water PbI 2 (s) = Pb 2+ (aq) + 2 I - (aq) Calculate K sp if solubility = 0.00130 M

10. 10 Calculate K sp K sp = [Pb 2+ ] [I - ] 2 = X{2 X} 2 K sp = 4 X 3 = 4[Pb 2+ ] 3 Solubility of Lead(II) Iodide = 4 (solubility) 3 K sp = 4 (1.30 x 10 -3 ) 3 = 8.8 x 10 -9

11. 11 Precipitating an Insoluble Salt Hg 2 Cl 2 (s) = Hg 2 2+ (aq) + 2 Cl - (aq) K sp = 1.1 x 10 -18 = [Hg 2 2+ ] [Cl - ] 2 If [Hg 2 2+ ] = 0.010 M, what [Cl - ] is req’d to just begin the precipitation of Hg 2 Cl 2 ? That is, what is the maximum [Cl - ] that can be in solution with 0.010 M Hg 2 2+ without forming Hg 2 Cl 2 ?

12. 12 Precipitating an Insoluble Salt Hg 2 Cl 2 (s) = Hg 2 2+ (aq) + 2 Cl - (aq) K sp = 1.1 x 10 -18 = [Hg 2 2+ ] [Cl - ] 2 Recognize that. K sp = product of maximum ion concs. Precip. begins when product of ion concs. EXCEEDS the K sp.

13. 13 K sp = 1.1 x 10 -18 = [Hg 2 2+ ] [Cl - ] 2 Solution [Cl - ] that can exist when [Hg 2 2+ ] = 0.010 M, If this conc. of Cl - is just exceeded, Hg 2 Cl 2 begins to precipitate.

14. 14 Hg 2 Cl 2 (s) = Hg 2 2+ (aq) + 2 Cl - (aq) K sp = 1.1 x 10 -18 Now use [Cl - ] = 1.0 M. What is the value of [Hg 2 2+ ] at this point? Solution [Hg 2 2+ ] = K sp / [Cl - ] 2 = K sp / (1.0) 2 = 1.1 x 10 -18 M The concentration of Hg 2 2+ has been reduced by 10 16 !

15. 15 The Common Ion Effect Adding an ion “common” to an equilibrium causes the equilibrium to shift back to reactant.

16. 16 Common Ion Effect PbCl 2 (s) = Pb 2+ (aq) + 2 Cl - (aq) K sp = 1.9 x 10 -5

17. 17 Calculate the solubility of BaSO 4 BaSO 4 (s) = Ba 2+ ( aq ) + SO 4 2- ( aq ) (a)In pure water and (b) in 0.010 M Ba(NO 3 ) 2. K sp for BaSO 4 = 1.1 x 10 -10 The Common Ion Effect

18. 18 K sp for BaSO 4 = 1.1 x 10 -10 BaSO 4 (s) = Ba 2+ (aq) + SO 4 2- (aq) Solution Solubility = [Ba 2+ ] = [SO 4 2- ] = x K sp = [Ba 2+ ] [SO 4 2- ] = x 2 x = (K sp ) 1/2 = 1.1 x 10 -5 M Solubility in pure water = 1.1 x 10 -5 M BaSO 4 in pure water

19. 19 Solution Solubility in pure water = 1.1 x 10 -5 mol/L. Now starting with 0.010 M Ba 2+. Which way will the “common ion” shift the equilibrium? ___ Will solubility of BaSO 4 be less than or greater than in pure water?___ BaSO 4 in in 0.010 M Ba(NO 3 ) 2. BaSO 4 (s) = Ba 2+ (aq) + SO 4 2- (aq)

20. 20 Solution [Ba 2+ ][SO 4 2- ] initial change equilib. The Common Ion Effect + y 0.010 0 + y 0.010 + yy

21. 21 K sp = [Ba 2+ ] [SO 4 2- ] = (0.010 + y) (y) Because y < 1.1 x 10 -5 M (pure), 0.010 + y is about equal to 0.010. Therefore, K sp = 1.1 x 10 -10 = (0.010)(y) y = 1.1 x 10 -8 M = solubility in presence of added Ba 2+ ion. The Common Ion Effect Solution

22. 22 SUMMARY Solubility in pure water = x = 1.1 x 10 -5 M Solubility in presence of added Ba 2+ = 1.1 x 10 -8 M Le Chatelier’s Principle is followed! Add to the right: equilibrium goes to the left The Common Ion Effect BaSO 4 (s) = Ba 2+ (aq) + SO 4 2- (aq)

23. 23 The Common Ion Effect

24. 24 The Common Ion Effect