CHEM 301 LECTURE

Unit 9. SOL UBILITY EQUILIBRIA SOLUBILITY EQUIL IBRIUM a heterogeneous equilibrium the solid (precipitate) is in equilibrium with the ions in the solution (aqueous) Solubility Product Constant AgCl (s) Ag2 CrO 4 (s) SrCrO 4 (s) Ag
+ (aq)

+ Cl
+ (aq)

(aq)

Ksp = [Ag ][ Cl ] = 1.6 x 10

-2 (aq)

-10

2Ag Sr
+2

+ CrO 4
-2

Ksp = 1 x 10

-12 -5

(aq)

+ CrO 4

(aq)

Ksp = 3.6 x 10

Ksp and Equilibrium Concentrations Example1 : If the concentration of CrO 4 in a certain solution in equilibrium with SrCrO 4 is 2.0 x 10 M, calculate +2 the concentration of Sr in the aqueous part. -2 Answer: 1.8 x 10 M
-2 -3

Example2 : Calcium phosphate is a water-insoluble mineral used as a fertilizer. Calculate the [PO 4 ] in equilibrium +2 -6 -26 with the solid if [Ca ] = 5.0 x 10 . (Ksp = 1.2 x 10 ) -6 Answer: 9.8 x 10 M

-3

Ksp and Precipitate Formation To predict precipitate formation, solve for the ion product, Q If Q < Ksp - unsaturated solution (no ppt) Q = Ksp - saturated solution (solubility limit) Q > Ksp - supersaturated solution (ppt will form) Example3 : As K2 CrO 4 is added to a solution in which [Sr ] = 1.0 x 10 M. (a) if the [CrO 4 ] added is 3.0 x10 M, will a precipitate form? Answer: No, Q = 3.0 x 10 M < Ksp
-5 -2 -2 +2 -3

(b) at what [CrO 4 ] will a precipitate start to form? Answer: [CrO 4 ] > 3.6 x 10 M
-2 -2

-2

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CHEM 301 LECTURE

Example4 : When 0.200 L of 0.0060 M Sr(NO 3 )2 is mixed with 0.100 L of 0.015 M K 2 CrO 4 , will a precipitate form? Answer: No, Q = 2.0 x 10 < Ksp
-5

Example5 : If 200 mL of a 0.2 M NaOH is added to a 1 L solution of 0.1 M CaCl 2 , will a precipitate form? Ca(OH)2 Ksp = 8 x 10
-6

Answer: Yes, Q = 7 x 10 > Ksp

-5

Fractional Precipitation Example6 : In a solution containing [Cl ] = 0.020 M and [Br ] = 0.020 M, (a) as AgNO 3 is added, which will precipitate first? AgCl Ksp = 1.6 x 10
-10 -13 -

AgBr Ksp = 7.7 x 10 Answer: AgBr

(b) what [Ag ] is needed to precipitate AgBr without pr ecipitating AgCl? Answer: 3.9 x 10
-11

M < [Ag ] < 8.0 x 10 M

-9

(c) what is the [Br ] when AgCl starts to precipitate? Answer: [Br ] = 9.6 x 10 M
-5

(d) what is the percentage of Br remaining? Answer: 0.48 %

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CHEM 301 LECTURE

Example7 : As AgNO 3 is added to a solution containing [Cl ]= 0.10 M and [CrO 4 ] = 0.10 M, (a) which will precipitate first? AgCl Ksp = 1.6 x 10
-10 -12

-2

Ag2 CrO 4 Ksp = 1.2 x 10 Answer: AgCl

(b) what is the [Cl ] when Ag2 CrO 4 starts to precipitate? Answer: [Cl ] = 4.6 x 10 M
-5

(c) what percentage of Cl remain when Ag2 CrO 4 starts to precipitate?

Ksp and Solubility molar solubility (s): the concentration in M of a saturated solution solubility: the maximum amount of solute that can be dissolved in a given solvent at a specific temperature (g/L) solubility = molar solubility X MW AgCl (s) Cu(OH)2 (s) Ag
+ (aq)

+ Cl
+2 (aq)

(aq)

Ksp = (s)(s) = s
-

Cu

+ 2OH (aq)

Ksp = (s)(2s) = 4s

formula AgCl CdSO 4 Cu(OH)2 Ag2 CrO 4 Al(OH)3 Fe2 S3

Ksp 2 s 2 s 3 4s 3 4s 4 27s 5 108s

-51

Example8 : Calculate the solubility of Ag2 S (MW=247.8 g/mol) if its Ksp = 6.0 x 10 3 -51 Answer: 4s = 6.0 x 10 -17 s = 1.1 x 10 M -15 solubility = 2.7 x 10 g/L

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CHEM 301 LECTURE

Example9 : What is the solubility of Fe(OH) 3 (MW = 106.9 g/mol) if its Ksp = 1.1 x 10 ? 4 -36 Answer: 27s = 1.1 x 10 -10 s = 4.5 x 10 M -8 solubility = 4.8 x 10 g/L

-36

Example10 : What is the Ksp of CdS (MW=144.4 g/mol) if its solubility is 4.1 x 10 -14 Answer: s = 2.8 x 10 M 2 -28 Ksp = s = 8.1 x 10

-12

g/L?

Factors that Affect Solubility Common Ion Effect: decreases solubility Example11 : (a) Calculate the molar solubility of AgCl in water. (Ksp =1.6 x 10 ) -5 Answer: 1.3 x 10 M
-10

(b) Calculate the molar solubility of AgCl in 6.5 x 10 M AgNO 3 solution. -8 Answer: 2.5 x 10 M

-3

Example12 : Calculate the molar solubility of CaCO 3 in 0.10 M Na2 CO 3 solution. (Ksp =4.9 x 10 ) -8 Answer: 4.9 x 10 M

-9

Complex Ion Formation: increases solubility Effect of pH: basic oxides more soluble in acidic solution, acidic oxides more soluble in basic solution

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