PRECIPITATION REACTIONS Solubility of Salts

When salts are formed and are said to be INSOLUBLE and form when mixing moderately concentrated solutions of the metal ion with chloride ions. They really are usually slightly soluble! Ksp = Equlilibrium solubility product constant

See Table 15.4 on p.753

AgCl(s)

Ag+(aq) + Cl-(aq)

Kc = [Ag+] [Cl-] = 2.79 x 10-10 Remember that solids are NOT included in determining equilbrium constants! Only the concentrations of the aqueous ions matter in determining the equilibrium concentrations. (M) = (mol/L) Therefore, Kc = Ksp = 2.79 x 10-10 You must know the Solubility Rules p.151152

For the following reactants, determine if a precipitate (ppt) will form and what is its formula?
1. 2. 3. 4. 5. 6. NaCl + KBr Na2SO4 + Ba(NO3)2 Pb(NO3)2 + KI LiNO3 + K3PO4 NaOH + CaCl2 (NH4)2CrO4+ MgBr2

For the following reactants, determine if a precipitate (ppt) will form and what is its formula?
1. 2. 3. 4. 5. 6.
No ppt NaCl + KBr Na2SO4 + Ba(NO3)2 ppt = BaSO4 Pb(NO3)2 + KI ppt = PbI2 LiNO3 + K3PO4 No ppt ppt = Ca(OH)2 NaOH + CaCl2 (NH4)2CrO4+ MgBr2 ppt = MgCrO4

Saturated Solutions
If Q<Ksp then the reaction is unsaturated and more will dissolve If Q = Ksp then the reaction is at equilibrium and no more solute will dissolve If Q > Ksp then the reaction is supersaturated and precipitate has formed

If Q>Ksp then a ppt will form

Remember Q = concentration at any given set of conditions PbCl2(s) Pb2+(aq) + 2 Cl-(aq) Ksp = 1.9 x 10-5 (from appendix J) Will a ppt. form if 100. mL of 0.18 M Pb(NO3)2 is added to 100. mL of .25 M HCl?

Use stoichiometry to find the answer. [Pb2+] = (.100 L)(0.18 M) = 0.090 M (.200 L ) [Cl-] = (.100 L) (0.25M) = 0.125 M ( .200L) Q= [Pb2+][Cl-]2 = (.090)(.125)2 = 1.4 x 10-3 ppt will form Q>Ksp

Another Type of Problem

At a temperature other than 25 oC; Consider PbI2 dissolving in water PbI2(s) Pb2+(aq) + 2 I-(aq) Calculate Ksp if [Pb2+] = 0.00130 M

Solution 2. Ksp = [Pb2+] [I-]2 = [Pb2+] {2 [Pb2+]}2 Ksp = 4 [Pb2+]3

Ksp = 4 (1.30 x 10-3)3 = 8.79 x 10-9

Precipitating an Insoluble Salt

Hg2Cl2(s)

Hg22+(aq) + 2 Cl-(aq)

Ksp = 1.1 x 10-18 = [Hg22+] [Cl-]2 If [Hg22+] = 0.010 M, what [Cl-] is required to just begin the precipitation of Hg2Cl2? That is, what is the maximum [Cl-] that can be in solution with 0.010 M Hg22+ without forming Hg2Cl2?

Precipitating an Insoluble Salt

Hg2Cl2(s)

Hg22+(aq) + 2 Cl-(aq)

Ksp = 1.1 x 10-18 = [Hg22+] [Cl-]2 Recognize that Ksp = product of maximum ion concentrations.

Precipitation begins when product ion concentrations EXCEEDS the Ksp.

Precipitating an Insoluble Salt Hg2Cl2(s) Hg22+(aq)

+ 2 Cl-(aq)

Ksp = 1.1 x 10-18 = [Hg22+] [Cl-]2 Solution [Cl-] that can exist when [Hg22+] = 0.010 M,
[Cl ] = K sp 0.010
-8 M

0 = 1.1 x 10

[Cl-] = 1.05 x 10-8 M

If this concentration of Cl- is just exceeded, Hg2Cl2 begins to precipitate.

Hg2Cl2(s)

Hg22+(aq) + 2 Cl-(aq)

Ksp = 1.1 x 10-18 Now raise [Cl-] to 1.0 M. What is the value of [Hg22+] at this point? Solution [Hg22+] = Ksp / [Cl-]2 = Ksp / (1.0)2 = 1.1 x 10-18 M The concentration of Hg22+ has been reduced by 1016 !