Ionic Equilibrium 1

Solubility
The maximum amount of solute which dissolves in a definite volume of solvent at constant temperature is called its
solubility.

Solubility Product
Solubility Product : The equilibrium between a solid ionic salt and its saturated aqueous solution is described by
the solubility product expression.
When we place some solid AgI(s) in water, a very small amount dissolves, and the following equilibrium exists when
the solution has becomes saturated
AgI(s) Ag+ (aq) + I– (aq)
(in a saturated solution of AgI)

First we mix AgI(s)

in pure water, a very
After filtering inso lub le solid
small amount of AgI fi
we get saturated solution of AgI
dissolves

This is a heterogeneous equilibrium because it involves a solid reactant (AgI) in equilibrium with ions in aqueous
solution.
We write the equilibrium law as follows, omitting the solid from the mass action expression.
Ksp = [Ag+ ] [I–] .....(1)
The equilibrium constant, Ksp is called the solubility product constant.
It is important that you understand the distinction between solubility and solubility product. The solubility of a salt
is the amount of the salt that dissolve in a given amount of solvent to give a saturated solution. The solubility product
is the product of the molar concentration of the ions in the saturated solution raised to appropriate powers.
The solubility of salt changes with temperature, so a value of Ksp applies only at temperature at which it was
determined.
The term on the right in equation (1), the product of the molar concentration of the dissolved ions of the solute
is called the ion product of AgI.
The ions product aqcuires a constant value, Ksp, in a saturated solution only terms is the product equal to the
solubility product constant.
Ksp can be determined from molar solubilities. How much of the salt is required to give a saturated solution in a
specified amount of solution. The molar concentration of the salt in its saturated solution is called molar solubility, it equal
the no. of moles of salt dissolves in one litre of saturated solution. The molar solubility can be used to calculate the Ksp
value the assumption that all of the salt that dissolve 100% dissociate into the ions implied in the salt formula.
AgI(s) Ag+ (aq.) + I–(aq.)
Let the solubility be s s s
Ksp = [Ag+] [I–] = [s] [s] = s2

Ex.: For a general partially soluble electrolyte AxBy(s) xAy+ + yBx–

Let the solubility be s in xs ys
2 Ionic Equilibrium

Ksp = [Ay+]x [Bx–]y = [xs]x [ys]y

Ksp = xx . y.y (s)x + y

##1. The solubility of AgCl in water is 1.435 × 10–3 g/L at 25°C. Calculate Ksp for AgCl, at this temperature.

Sol. First of all we write the chemical equation for the equilibrium from which we construct the equilibrium expression
for Ksp
AgCl(s) Ag+ (aq) + Cl– (aq)
Ksp = [Ag+ ] [Cl–]
To calculate Ksp, we need the concentration of ions expressed in moles per liter.
The first step will be to convert 1.435 × 10–3 g of AgCl to moles, which will give us the molar solubility of the
salt – the number of moles of AgCl dissolve per liter.
From the molar solubility of the salt we will calculate the molarities of the ions in the solution.
We also see the composition of the solvent into which the salt will be placed. Does it contains any of the ion
involved in the equilibrium ?
If it doesn’t the initial concentration will be equal to zero. However, if the solvent contains a solute that is a source
of one of the ions in the equilibrium. We will use its concentration as the initial concentration of that ion.
When the salt dissolves the concentration of the ions increases, and will have values determined by the
stoichiometry of the salt. We will obtain these from the molar solubility.
Equilibrium values are obtained by initial concentration and change in concentration at equilibrium.
We substitute then into the ions product equation to calculate Ksp.
First we calculate the no. of moles of AgCl dissolve in per liter

Solubility of AgCl = 1435

. · 10-3 molesper Liter = 10-5 M
1435
.

AgCl(s) Ag+ (aq) + Cl– (aq)

Initial conc. 0 0
Conc. at Eq.
when AgCl diss. 10–5 10–5
We now substitute the equilibrium ion concentration into Ksp
Ksp = [Ag+] [Cl–] = [10–5] [10–5] = 10–10 M2
The Ksp of AgCl is thus calculate to be 10–10 at 25°C.
##2. The molar solubility of silver chromate, Ag2CrO4, in water is 6.7 × 10–5 mol L–1 at 25°C. What is Ksp for Ag2CrO4 ?

Sol. We begin with the equilibrium equation and Ksp expression.

Ag2CrO4(s) 2Ag+(aq) + CrO42– (aq) Ksp = [Ag+]2 [CrO42–]
The solute is pure water, so neither Ag+ nor CrO42– is present before the salt dissolves. The initial concentration
of Ag+ and CrO42– are therefore zero. When one liter of pure water dissolves 6.7 × 10–5 mol of Ag2CrO4, we can
see by the coefficients in the equilibrium equation that 100% dissociation would produce 6.7 × 10–5 mol of CrO42–
and 2 × (6.7 × 10–5 mol).

Ag2CrO4(s) 2Ag+(aq) + CrO42– (aq)

Initial conc.(M) 0 0
–5
Conc.(M) at eq. when 2 × (6.7 × 10 ) 6.7 × 10–5
Ag2CrO4 diss.
 Ionic Equilibrium 3

Substitute the equilibrium concentrations into the mass action expression for Ksp gives
Ksp = [2 × (6.7 × 10–5)]2 (6.7 × 10–5) = 1.1 × 10–12
So the Ksp of Ag2CrO4 at 25°C is calculated to be 1.1 × 10–12.

##3. Exactly 1.00 L of a saturated aqueous solution of CaF2 was carefully evaporated at 298 K, and a residue of 0.017
g of CaF2 was obtained. Calculate the Ksp of CaF2 at 298 K.

Sol.

We take given saturated solution of CaF2 is taken in test tube, an after

carefully evaporated a residue of 0.017 g of CaF2 was obtained. means
0.017 g of CaF2 is dissolves in one litre solution .

0.017 = 2179
. · 10-4 moles / L
Solubility of CaF2 = 78
CaF2(s) Ca2+(aq) + 2F– (aq)
Conc.(M) at eq. when 2.179 × 10–4 2 × 2.179 × 10–4
CaF2 diss. in saturated
Ksp = [Ca2+] [F–]2
= (2.179 × 10–4) (2 × 2.179 × 10–4 )2 = 4.14 × 10–11

##4. The molar solubility of PbCl2 in a 0.10 M NaCl solution is 1.7 × 10–3 mol L–1 at 25°C. Calculate the Ksp for PbCl2.

Sol. Again, we start by writing the equation for the equilibrium and the Ksp expression.
PbCl2(s) Pb2+(aq) + 2Cl–(aq) Ksp = [Pb2+] [Cl–]2
In this problem, the PbCl2 is being dissolved not in pure water, but in 0.10 M NaCl, which contains 0.10 M Cl–,
(It also contains 0.10 M Na+, but that’s not important here because Na+ doesn’t affect the equilibrium and so doesn’t
appear in the Ksp expression.) The initial concentration of Pb2+ is zero because none is in solution to
begin with. The initial concentration of Cl–, however is 0.10 M. When the PbCl2 dissolves in the NaCl solution, the
Pb2+ concentration increases by 1.7 × 10–3 M and the Cl– concentration increases by 2 × (1.7 × 10–3 M).
PbCl2(s) Pb2+(aq) + 2Cl–(aq)
Initial conc.(M) 0 0.10 (due to 0.10 M NaCl)
–3
Conc.(M) at eq. when 1.7 × 10 2 × (1.7 × 10–3 ) + 0.1 ~ 0.10
PbCl2 diss.
Substituting the equilibrium concentrations into the Ksp expression gives
Ksp = (1.7 × 10–3) (0.10)2 = 1.7 × 10–5

##5. What is the molar solubility of AgCl in pure water at 25°C ?

Sol. To solve this problem, we need three things :

4 Ionic Equilibrium
1. The equilibrium chemical equation for a saturated solution of AgCl
2. The Ksp equation, which we figure out from the equilibrium equation.
3. The value of Ksp for AgCl
The relevant equations are
AgCl(s) Ag+ (aq) + Cl– (aq) Ksp = [Ag+] [Cl–] = 1.8 × 10–10
First, we see that the solvent is pure water, so neither Ag+ nor Cl– ion is present
in solution at the start; their initial concentrations are zero.

Let s is the molar solubility of the salt – the number of moles of AgCl that
dissolves in 1 L. Because 1 mol of AgCl yields 1 mol Ag+ and 1 mol Cl– , the
concentration of each of these ions increases by s.
AgCl(s) Ag+ (aq) + Cl– (aq)
Initial conc. 0 0
Conc. at Eq.
when AgCl diss. s s
We now substitute the equilibrium ion concentration into Ksp
Ksp = [Ag+] [Cl–] = [s] [s] = s2 = 1.8 × 10–10
s = 1.3 × 10–5
The molar solubility of AgCl in water at 25°C is 1.3 × 10–5 moles /Liter.

##6. What is the molar solubility of CaF2 in a 0.01 M NaF solution.

Sol. Ksp expression

CaF2(s) Ca+2 (aq) + 2F– (aq) Ksp = 3.4 × 10–11
That we are adding the CaF2 to a solvent into which it dissolves. This time, however, the solvent isn’t water; it’s
a solution of NaF, which contains one of the ions of the salt CaF2. Therefore, our initial concentrations will not both
be zero. The solvent doesn’t contain any compound, so the initial concentration of CaF2 is equal to zero, but the
solvent does contain 0.01 M NaF, which is completely dissociated and yields 0.01 M Na+ and 0.01 M F–. The initial
concentration of F– is therefore 0.01 M. These are the values we place in the initial row.
Next, let s be the molar solubility of CaF2 where s mol of CaF2 dissolves per liter, the concentration of Ca2+ is s
and that of F– be 2s + 0.01.
CaF2(s) Ca+2 (aq) + 2F– (aq)
Initial conc. 0 0.01
Conc. at Eq.
when CaF2 diss. s 2s + 0.01
2+ – 2 2 –11
Ksp = [Ca ] [F ] = s (2s + 0.01) = 3.4 × 10 .
Neglecting s2 and s3 terms, (s being very small),
we get s = 3.4 × 10–7 moles per liter

Precipitate will form Ion product > Ksp (supersaturated)

RSIon product = K (saturated)

TIon product < K
sp
No precipitate will form ( unsaturated)
sp

##7. Equal volume of 0.02 M CaCl2 and 0.04 M Na2SO4 are mixed will a ppt. appear. (Ksp for CaSO4 = 2.4 × 10–5)
 Ionic Equilibrium 5
Sol. To answer this question, we will calculate the ion product for CaSO4 using the concentration of the ions in the
solution to be prepared. Only if the calculated ions product is larger than Ksp will a precipitate be expected. To
perform the calculation correctly, we need the correct form of the ion product. We can obtain this by writing the
solubility equilibrium and the Ksp expression that applies to a saturated solution.
CaSO4(s) Ca+2 (aq) + SO42– (aq) Ksp = 2.4 × 10–5

In the original solution the 0.02 M CaCl2 contain 0.02 M Ca+2 and the 0.04 M Na2SO4 contain
0.04 M SO42–
What are the concentrations of these ion after dilution to determine these we use the equation that apply to all
delute problems involving molarity.
MiVi = MfVf

M i Vi
Solving for Mf gives Mf = Vf
The initial volumes of both solutions are V mL and when the two solutions are combined the final total volume is
2V mL. Therefore,
When equal volume of
V · 0.02 = 0.01 M
[Ca+2]final = 2V 0.02 M Ca2+ and 0.04
M SO42– are mixed then
V · 0.04 = 0.02 M ions concentrated
[SO42–]final = 2V products
We now substitute these values in the equilibrium equation [Ca+2] [SO42–] > Ksp
hence ppt forms.
Ksp = [Ca+2] [SO42–] = (0.01) (0.02) = 2 × 10–4 > 2.4 × 10–5
Hence ppt. of CaSO4 forms.

##8. What is the molar solubility of Mg(OH)2(s) in a buffer solution having [OH–] = 1.0 × 10–5 M, that is, pH = 9.00 ?
Mg(OH)2(s) Mg2+(aq) + 2OH–(aq) Ksp = 1.8 × 10–11

Sol. First, note that because the solution is a buffer, any OH– coming from the
dissolution of Mg(OH)2(s) is neutralized by the acidic component of the buffer.
Therefore, the pH will remain at 9.00 and the [OH – ] at
1.0 × 10–5 M. We will use the Ksp expression and [OH–] = 1.0 × 10–5 M to
calculate [Mg2+] in the solution.
Ksp = [Mg2+] [OH–]2 = 1.8 × 10–11
Ksp = [Mg2+] × (1.0 × 10–5)2 = 1.8 × 10–11

. · 10-11 = 018
18
[Mg2+] = . M
. · 10-10
10

For every mole of Mg2+(aq) appearing in solution, 1 mol of Mg(OH)2(s) must have
dissolved. Thus the molar solubility of Mg(OH)2 and the equilibrium concentration
of Mg2+ are the same, meaning that the molar solubility of Mg(OH)2 at pH 9.00
is 0.18 mol Mg(OH)2 / L.

##9. Ksp for SrF2 = 2.8 × 10–9 at 298 K. How much NaF should be added to 100 ml of solution having 0.016 M in Sr+2
ions to reduce its concentration to 2.5 × 10–3 M.
6 Ionic Equilibrium

Sol. We are adding a molar NaF in 100 mL of 0.016M Sr2+ solution;

Finally molar concentration of [Sr2+] = 2.5 × 10–3 M
ppt. of SrF2 forms because [Sr2+] ion concentration is reduces
Sr2+(aq.) + 2F– ¾ ® SrF2(s)
Initially conc. 0.016 M a
At equilibrium 2.5 × 10–5 a – 2 {0.016 – (2.5 × 10–5)}
We know, Initial [Sr2+] = 16 × 10–3 M
Left [Sr2+] = 2.5 × 10–3 M
\ [Sr ] precipitated = (16 – 2.5) × 10–3 = 13.5 × 10–3 M
2+

\ [F–] needed for this precipitation = 2 × 13.5 × 10–3 M = 27.0 × 10–3 M (‡ Sr2+ + 2F– ¾ ® SrF2)
Also [Sr2+] [F–]2 = KspSrF = 2.8 × 10–9
2

2.8 · 10-9
\ [F–]2 =
2.5 · 10-3
\ [F–] = 1.058 × 10–3 M i.e., the concentration of F– which will also appear in solution state.
– –3
Thus, [F ] needed = [27.0 + 1.058] × 10 M = 28.058 × 10–3 M
\ NaF needed for 1 litre = 28.058 × 10–3 × 42 g
-3
\ NaF needed for 100 mL = 28.058 · 10 · 42 g = 0.1178 g
10

##10. What [Ba2+] is necessary to start the precipitation of BaSO4 in a solution that is 0.0015 M in Na2SO4 ? Assume
that the Ba2+ comes from addition of a solid soluble ionic compound such as BaCl2. For BaSO4, Ksp = 1.1 × 10–10.

Sol. We how that Na2SO4 is a soluble ionic compound and that the molarity of SO42– is equal to the molarity of the
Na2SO4 solution. We are given Ksp for BaSO4, so we solve for [Ba2+].
Because Na2SO4 is a soluble ionic compound, we know that [SO42–] = 0.0015 M. We can use Ksp for BaSO4 to
calculate the [Ba2+]
[Ba2+] [ SO42– ] = 1.1 × 10–10
. · 10-10 = 11
11 . · 10-10 = 7.3 · 10-8 M
[Ba2+] = 2-
[SO4 15. · 10-3
Addition of enough BaCl2 to give a barium ion concentration of 7.3 × 10–8 M just satisfies Ksp for BaSO4; that is,
Qsp = Ksp. Ever so slightly more BaCl2 would be required for Qsp to exceed Ksp and for precipitation of BaSO4 to
occur. Therefore
[Ba2+] > 7.3 × 10–8 M (to initiate precipitation of BaSO4)

##11. A saturate solution of CaF2 is found to contains 4 × 10–4 M fluoride ion. Calculate the Ksp of CaF2. Neglect
hydrolysis.
Sol. Given saturated solution of CaF2 have [F–] = 4 × 10–4
Equilibrium state between solid CaF2(s) and its saturate solution
CaF2(s) Ca2+(aq.) + 2F–(aq.)
Let the solubility be s s 2s
Given [F–] ion concentration in the saturated solution is
2s = 4 × 10–4, s = 2 × 10–2
Ksp = [Ca2+] [F–]2 = (2.0 × 10–4) (4.0 × 10–4)2 = 32 × 10–12