Solubility and Complex Ion

Equilibria
Chapter 16

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SOLUBILITY PRODUCT

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 AgCl(s) ⇄ Ag+(aq) + Cl¯(aq)

Ksp = 1.6x10-10 = [Ag+(aq)][Cl¯(aq)]

This is the reaction for dissolving solid silver chloride in

water. The equilibrium constant for reactions of this
type are called solubility products – Ksp.

Can use the Ksp to calculate solubility.

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 AgCl(s) ⇄ Ag+(aq) + Cl¯(aq)
at equilibrium x x
Ksp = 1.6x10-10 = [Ag+(aq)][Cl¯(aq)] = x2

x  1.6  1010  1.3  105 M

So a saturated solution of AgCl is 1.3x10-5M

Ksp of CaF2 is 4.0x10-11

Ca 22(s)
K sp [CaF ⇄Ca
][ F ]2 +2(aq) x ) 2  4.0  1011
( x )(+22F¯(aq)
at equilibrium x 2x
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Your turn to try one: what is the molar solubility of iron(II) sulfide?

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 What is the molar solubility of
lead(II) bromide? Ksp = 4.6x10-6

1.0.0021M
2.0.013M
3.0.017M
4.0.010M
5.I’m lost

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 Predicting if a precipitate will form:
The Ksp for PbF2 is 4x10-8. If you add a
50mL of a 1.0mM solution of Ba(NO3)2 to
50mL of a 0.10M solution of KF, will a
precipitate form?
1.Write the reaction.
PbF2(s) ⇄ Pb+2(aq) + 2F¯(aq)
2.Write Q and calculate its value:
Q = [Pb+2(aq)][F¯(aq)]2=(.001/2)(0.10/2)2) =
1.25x10-6
3.Compare Q to K, and determine which
direction the reaction will proceed.
Q>K, so the reaction proceeds left. 7
 Will a precipitate form if 0.10L of 8.0x10-3M lead(II)
nitrate is added to 0.40L of 5.0x10-3M sodium
sulfate?
1. Determine what will precipitate
From table of Ksp values, find Ksp of lead(II) sulfate = 1.3x10-8
2. Determine the concentration of relevant ions
MiVi=MfVf, final V = 0.50L, so Mf=Mi(Vi/Vf)
[Pb2+]= 0.008M(0.1/0.5)=1.6x10-3M
[SO4-2] = 0.005M(0.4/0.5) = 0.004M
3. Calculate Q, and compare it to Ksp
Q = [Pb2+][SO4-2] = [1.6x10-3][0.004] = 6.4x10-6
So Q > Ksp=1.3x10-8
Since Q > K, precipitate will form.
Will a precipitate form when 150mL of 0.010M Sr(NO3)2 is
added to 450mL of 0.016M K2CrO4? 8
Which is less soluble:

1.Sr3(PO4)2 Ksp = 1x10-31

2.AgI Ksp = 1.5x10-16

Sr3(PO4)2(s) ⇄ 3Sr+2(aq) + 2PO4-3(aq)

3x 2x
Ksp(Sr3(PO4)2) = (3x)3(2x)2 = 1x10-31, x = 3x10-7M

AgI(s) ⇄ Ag+(aq) + I¯(aq)

x x
Ksp(AgI) = x2 = 1.5x10-6, x = 1.2x10-8M

Sr3(PO4)2 is more soluble than AgI! 9

It is true that solubility decreases in the series
• PbSO4 Ksp = 1.3x10-8
• AgCl Ksp = 1.6x10-10
• BaCrO4 Ksp = 8.5x10-11

But is the same thing true for this series?

• AgI Ksp = 1.5x10 -16 • 1.2x10 -8
M
• Zn(OH)2 Ksp = 4.5x10 -17 • 2.2x10 -6
M
• 1.0x10-4M
• Sr3(AsO4)2 Ksp = 4.3x10 -19

1. Yes
2. No
3. lost
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Things that can alter solubility
1. Common ion
2. pH
3. Complex ions

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 COMMON ION EFFECT
Consider the solubility of lead(II) carbonate, Ksp = 4.6x10-6

PbBr2(s) ⇄ Pb+2(aq) + 2Br¯(aq)

Ksp = [Pb+2(aq)][Br¯(aq)]2 = (x)(2x)2 = 4.6x10-6 x = 0.01M

What is the solubility of PbBr2 in the presence of 0.10M KBr(aq)?

Ksp = [Pb+2(aq)][Br¯(aq)]2 = (x)(2x+0.10)2 = (x)(0.10)2 = 4.6x10-6

Approximation that 2X << 0.10,
Solving, x = 4.6x10-4M

In the presence of a common ion, the solubility is greatly reduced!

Le Chatelier’s principle!
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 pH EFFECTS
Consider the solubility of magnesium fluoride, Ksp = 6.8x10-6

MgCO3(s) ⇄ Mg+2(aq) + CO3-2(aq)

Ksp = [Mg+2(aq)][ CO3-2(aq)] = (x)(x) = 6.4x10-9 x = 1.2x10-3M

However, it is freely soluble in 1.0M HCl(aq). WHY?

Acid alters the concentration of CO3-2(aq) by driving the

equilibrium towards protonated species.

The solubility of any insoluble salt containing a basic anion will be

affected by pH: F¯, CO3-2, S-2, OH¯, PO4-3, SO4-2

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 Complex Ions
Metal ions can act as Lewis acids, reacting with Lewis Bases:

Formation Constant

Be2+(aq) + F–(aq) ⇄ BeF+(aq) K1 = 7.9 x 104

BeF+(aq) + F–(aq) ⇄ BeF2(aq) K2 = 5.8 x 103

BeF2(aq) + F–(aq) ⇄ BeF3– (aq) K3 = 6.1 x 102

BeF3– (aq) + F–(aq) ⇄ BeF42– (aq) K4 = 2.7 x 101

The BeF42– (aq) is called a complex ion.

The Lewis base is called the ligand. 14
 Complex Ions
Metal ions can act as Lewis acids, reacting with Lewis Bases:

Formation Constant
Ag+ + NH3 ⇄ AgNH3+ Kf1 = 2.1 x 103
AgNH3+ + NH3 ⇄ Ag(NH3)2+ Kf2 = 8.2 x 103

Because these equilibria lie to the right, they reduce the

concentration of free metal ion, and can increase the
solubility of insoluble salts.

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 Complex Ions
Metal ions can act as Lewis acids, reacting with Lewis Bases:

Formation Constant
Ag+ + NH3 ⇄ AgNH3+ Kf1 = 2.1 x 103
AgNH3+ + NH3 ⇄ Ag(NH3)2+ Kf2 = 8.2 x 103

AgI(s) ⇄ Ag+(aq) + I¯(aq) Ksp = 1.5x10-16, solubility 1.2x10-8M

In presence of 1M NH3(aq):
AgI(s) + 2NH3(aq) ⇄ Ag(NH3)2+(aq) + I¯(aq) K = Kf1xKf2xKsp=2.6x10-9

[ Ag ( NH 3 ) 2 ][ I  ] ( x )( x )
K 2
 x  2.6  109  5.1  105
[ NH 3 ] 12
Note approximation: [NH3] = 1-2x, but x is very small. 16
 Complex Ions
Bottom lines:
• Nomenclature: complex ion, ligand
• Lewis acid/base reaction
• Idea of formation constant
• General effect of increasing solubility of ‘insoluble’ ions

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