Overview of the Chapter

Chapter 17:
The goal of this chapter is to understand the equilibria that
Solubility & Complex exist between ionic solids and their ions in solution, and
factors that affect that equilibrium.
Ion Equilibria
write (heterogeneous) equilibrium equations & K expressions
calculate and interpret Ksp
Ksp is the solubility product constant
using Ksp, calculate solubility of salts
mol/L (molar solubility), and g/L
factors that affect solubility
common ion effect
pH
formation of complex ions
calculations to determine whether precipitation of a solid
will occur when 2 solutions are combined

Solubility Equilibria
equilibrium between a solid and its ions in solution
ex. for calcium phosphate
Ca3(PO4)2 (s) 3 Ca2+ (aq) + 2 PO43 (aq)
this is a heterogeneous equilibrium
equilibrium constant: Ksp solubility product constant
for calcium phosphate: Ksp = [Ca2+]3[PO43]2

we can now refine our understanding of solubility

rules from Chapter 4
solids that we classified as insoluble typically
have small Ksps and low molar solubilities
slightly soluble or sparingly soluble
 Some Solution Terminology
the solubility equilibrium can also be referred to as
the dissolutionprecipitation equilibrium
dissolution
Ca3(PO4)2 (s) 3 Ca2+ (aq) + 2 PO43 (aq)
precipitation
soln may be saturated, unsaturated, or supersaturated
unsaturated soln: more solid can dissolve
reaction continues in forward direction
toward equilibrium (Q < Ksp)
supersaturated soln: ion [ ]s are too high; solid will
precipitate out of the solution
reaction continues in reverse direction toward
equilibrium (Q > Ksp)
saturated soln: solution is at equilibrium (Q = Ksp)
Ion Concentrations in a Saturated Solution
consider 2 different preparations of a saturated soln
of CaF2
examine the relationships between [Ca2+], [F], Ksp
CaF2 (s) Ca2+ (aq) + 2 F (aq)
Ksp = [Ca2+][F]2
preparation 1: put solid CaF2 in a flask; add water;
wait until equilibrium is established
at equilibrium: [Ca2+] = 2.0 x 104 M
[F] = 4.0 x 104 M
Calculate Ksp.
note: with this preparation, [F] = 2[Ca2+]
Why?

Ion Concentrations in a Saturated Solution example:

examine the relationships between [Ca2+], [F], KSP A saturated solution of silver chromate is prepared
CaF2 (s) Ca2+ (aq) + 2 F (aq) by dissolving solid Ag2CrO4 in water, and allowing the
Ksp = [Ca2+][F]2 solution to reach equilibrium.
preparation 2: a soln with containing Ca2+ is mixed The saturated solution has [Ag+] = 1.3 x 104 M.
with a solution containing F; after some time, Determine [CrO42] and Ksp.
equilibrium is established
Ag2CrO4 (s) 2 Ag+ (aq) + CrO42 (aq)
at equilibrium: [Ca2+] = 0.038 M
Ksp = 3.2 x 1011 initial [ ] --- 0 0
Determine equilibrium [F]. [] --- + 2x +x
equil [ ] --- 2x M xM
note: with this preparation, [F] 2[Ca2+]
Why not?
 Using Ksp to Determine Solubility Comparing Solubilities of Salts
example: salts with greater solubility have higher [ions] in
Calculate the solubility (in mol/L and g/L) of nickel (II) saturated solution
sulfide in water at 25C. For NiS, Ksp = 3.0 x 1019. solubility is related to equilibrium position

define: x = mol of solid that dissolve per L of soln the farther to the right the equilibrium
x is the molar solubility of the salt; units mol/L position, the greater the solubility
be careful about comparing Ksps directly to
NiS (s) Ni2+ (aq) + S2 (aq) determine relative solubilities of 2 salts . . .
initial [ ] --- 0 0 must consider the salt stoichiometry and
[] --- +x +x relationship between Ksp & x
equil [ ] --- xM xM

Comparing Solubilities of Salts Factors that Affect Solubility

the common ion effect
Which has greater solubility in water at 25C? The molar solubility of MgF2 in water at 25C is
PbCl2 or PbF2 2.6 x 104 mol/L.
for PbCl2 Ksp = 1.6 x 105
for PbF2 Ksp = 4.0 x 108 Determine the molar solubility of MgF2 in 0.10 M
NaF (aq). For MgF2, Ksp = 7.4 x 1011.
MgF2 (s) Mg2+ (aq) + 2 F (aq)
initial [ ] --- 0 0.10
Which has greater solubility in water at 25C?
PbCl2 or CaSO4 [] --- +x + 2x
for PbCl2 Ksp = 1.6 x 105 equil [ ] --- xM (0.10 + 2x) M
for CaSO4 Ksp = 6.1 x 105 solve x; x = molar solubility = 7.4 x 109 mol/L
the presence of a common ion (here F) reduces the
solubility of a salt

example:
Determine the solubility of lead (II) hydroxide in a
solution with pH = 10.00. For Pb(OH)2,
Ksp = 1.2 x 1015.
soln with pH = 10.00 has [OH] = 1.0 x 104 M
example: CaCO3 (s) Ca2+ (aq) + CO32 (aq)
calcium carbonate will be more soluble in acidic soln
because the following reaction results in decreased
[CO32]:
CO32 (aq) + H+ (aq) HCO3 (aq)
some common examples of basic anions:
CO32, OH, PO43, SO42, C2O42, CN, F, S2
remember that the following anions are neutral:
Cl, Br, I, NO3, ClO4
the solubility of salts with these anions is not
affected by lowering the pH of the solution
Factors that Affect Solubility
pH of solution
In general, for an ionic compound with a basic anion,
solubility will increase as the pH of the solution decreases.
H+ present reacts with the basic anion
[anion] decreases
Le Chateliers principle predicts that equilibrium
will shift to the right (in the direction of greater
dissolution of solid).
Factors that Affect Solubility
complex ion formation
The solubility of an ionic compound may increase
dramatically if a solution containing a Lewis base is
added.
added Lewis base may react with a metal
cation to form a Lewis acid-base adduct
called a complex ion
formation of complex ion is an equilibrium
with equilibrium constant, Kf formation
constant
example:
AgCl has very limited solubility in water and acidic
solution, but will dissolve in NH3(aq):

AgCl (s) Ag+ (aq) + Cl (aq) Ksp = 1.6 x 1010

Ag+ (aq) + 2 NH3 (aq) [Ag(NH3)2]+ (aq) Kf = 1.7 x 107
AgCl (s) + 2 NH3 (aq) [Ag(NH3)2]+ (aq) + Cl (aq) KC = 0.0028

Ag+ ions in solution react with NH3 to form the

complex ion [Ag(NH3)2]+
as the complex ion forms, [Ag+] in soln decreases
as [Ag+] decreases, the solubility equilibrium
position to shifts to the right more AgCl dissolves

another example of complex ion

formation and effect on solubility:

NH3 (aq) added to a solution

of CuSO4 (aq)

initially a precipitate of
Cu(OH)2 (s) forms as solution
becomes basic

then the dissolution of Zn(OH)2 (s) ! Zn2+ (aq) + 2 OH- (aq); Ksp = 2.1 x 10-16
Cu(OH)2 is observed after Zn2+ (aq) + 4 OH- (aq) ! Zn(OH)42-(aq); Kf = 2.8 x 1015
further addition of NH3 (aq) as Zn(OH)2 (s) + 2 OH- (aq) ! Zn(OH)42- (aq); KC = 0.59
Cu(NH3)22+ forms
Calculation of Solubility After Complex Ion Formation
example (see example 17.11 in text):
Calculate the molar solubility of AgBr in 2.25 M
Na2S2O3 (aq).
For AgBr, Ksp = 5.0 x 1013; for the complex ion
[Ag(S2O3)2]3, Kf = 2.9 x 1013.
Precipitation of Ionic Solids
For an ionic solid, MX the solubility equilibrium is
given by:
MX (s) Mn+ (aq) + Xn (aq)
When 2 solutions are combined one soln
containing Mn+, and one soln containing Xn will a
precipitate of MX form?
Is the system at equilibrium? If not, in what
direction does the reaction proceed to reach
equilibrium?
Q vs K calculation
Calculation of Solubility After Complex Ion Formation
example (see example 17.11 in text):
Calculate the molar solubility of CuI in 0.88 M KCN
(aq).
For CuI, Ksp = 1.1 x 1012; for the complex ion
[Cu(CN)2], Kf = 1.0 x 1016.
Precipitation of Ionic Solids
determine concentrations of ions after solutions are
combined:
mol ion
[ion] =
total soln volume
calculate the ion product, Q
compare Q to Ksp:
if Q = Ksp, the solution is saturated;
solution is at equilibrium
if Q > Ksp, the solution is supersaturated;
precipitation of solid will occur
if Q < Ksp, the solution is unsaturated;
precipitation will not occur -
more solid will dissolve
example:
250.0 mL of 0.0062 M AgNO3 (aq) and 250.0 mL of
0.00014 M Na2CO3 are combined. Will a precipitate
of Ag2CO3 form? For Ag2CO3, Ksp = 8.1 x 1012.
Ag2CO3 (s) 2 Ag+ (aq) + CO32 (aq)
Q = [Ag+]2[CO32]
example:
Determine the minimum concentration of carbonate
ion required to cause the precipitation of silver
carbonate from a 5.8 x 104 M solution of AgNO3.
For Ag2CO3, Ksp = 8.1 x 1012.
Ag2CO3 (s) 2 Ag+ (aq) + CO32 (aq)
Ksp = [Ag+]2[CO32]
solve for [CO32] present in a saturated solution of
Ag2CO3;
[CO32] at equilibrium OR when Q = Ksp
any greater [CO32] will result in Q > Ksp and
precipitation of solid