sku 3023

Week 8-9
13/4 26/4
SOLUBILITY EQUILIBRIA

MS AINI & PM DR ISMAIL

SKU3023

SEM 2 2014/2015

Subtopics & Learning Objectives

Subtopics

Learning
Objectives

1. The commonion effect

To understand the
common-ion
effect

4. Ksp and
Solubility

To understand the
concepts of Ksp
and solubility

2. The buffers
solution

To understand the
concept of
buffered solution

5. Factors
Affecting
Solubility

To know the factors

that affecting
solubility.

3. Addition of
Strong Acids
or Bases to
Buffers

To know the
calculations of
buffers solutions

MS AINI & PM DR ISMAIL

SKU3023

Learning
Objectives

Subtopics

6. Q and Ksp

SEM 2 2014/2015

To determine
whether a solution
will form
precipitate.

The Common-Ion Effect

Previously, we examined the equilibrium concentrations
of ions in solutions containing a weak acid or a weak
base.
Now, we consider solutions that contain not only a
weak acid, but also a soluble salt of that acid.
What happens when NaC2H3O2 is added to a solution of
HC2H3O2?

The Common-Ion Effect

Sodium Acetate, is a soluble ionic compound and is therefore
a strong electrolyte. It dissociates completely in aqueous
solution to form Na+ and C2H3O2- ions:
NaC2H3O2 (aq)

Na+ (aq) + C2H3O2- (aq)

In contrast, Acid Acetate is a weak electrolyte that ionizes as

follows:
HC2H3O2 (aq) H+ (aq) + C2H3O2- (aq)
The addition of C2H3O2- from Sodium Acetate, causes this
equilibrium to shift to the left, thereby decreasing the
equilibrium concentration of H+ (aq).

Exercise
What
is the pH of a solution made by adding of 0.30 mol of

acetic acid (pH =2.64) and 0.30 mol of sodium acetate to

enough water to make 1.0 L of solution? (Ka = 1.8 x 10-5)
Ion from
salt

HC2H3O2 (aq)

H+ (aq)

C2H3O2- (aq)

Initial

0.30 M

0.30 M

Change

-XM

+XM

+XM

Equilibri
um

(0.30 X) M

XM

(0.30 + X) M

Ka = = 1.8 x 10-5 =
Ka = 1.8 x 10-5 =

Assume X is small & can be

ignored (0.30 X 0.30)

X = 1.8 x 10-5 = [H+]

Checking assumption:

pH = - log [H+] = - log (1.8 x 10-5 ) = 4.74

< 5% assumption justified

The Common-Ion Effect

The ionization of a weak base is also decreased by the
addition of a common ion.
For example, the addition of NH4+ (as from the strong
electrolyte NH4Cl) into NH3 (weak base) causes the base
dissociation equilibrium of NH3 to shift to left,
decreasing the equilibrium concentration of OH- and
lowering the pH:
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)
Addition of NH4+ from NH4Cl shifts
equilibrium to the left, reducing [OH-]

BUFFERS
Buffers or Buffered Solutions are solutions which
contain a weak conjugate acid-base pair.
e.g. (HC2H3O2 + NaC2H3O2) & (NH3 + NH4Cl)
Buffers resists changes in pH upon addition of small
amounts of strong acid or strong base.
This is because it contains both an acidic species to
neutralize OH- ions and a basic species to neutralize
H+ ions.
These requirements are fulfilled by a weak acid-base
conjugate pair such as HC2H3O2-C2H3O2- or NH4+-NH3.
Human blood is the example of buffers which has pH
buffered at about 7.4

BUFFERS
Consider
a buffers composed of HX and X- ; the acid
dissociation equilibrium in this buffers involves both the acid
and its conjugate base:
HX (aq)

H+ (aq)

X- (aq)

The corresponding acid-dissociation-constant expression is:

Ka =
Solving this expression for [H+], we have:
[H+] = Ka

We see from this expression that [H+] (thus the pH), is

determined by value of Ka and the ratio of the
concentration of the conjugate acid-base pair, [HX] / [X].

BUFFERS
If a small amount of hydroxide is added to an equimolar
solution of HF and NaF, for example, the HF reacts with the
OH to make F and water.
The reaction causes [HF] to
decrease and [F-] to
increase.
As long as the change in the
ratio [HF] / [F-] is small the
change in pH will be small.

BUFFERS
If a small amount of hydrogen ion is added to an
equimolar solution of HF and NaF, for example, the F
reacts to form HF and water.
The reaction causes [F-] to
decrease and [HF] to
increase.
As long as the change in the
ratio [HF] / [F-] is small the
change in pH will be small.

Buffer Calculations
Considering
the expression of Ka and [H+] derived earlier;

[H+] = Ka
Taking the - log of both sides of the equation, we have:
- log [H+] = - log (Ka ) = - log Ka log
Because - log [H+] = pH and - log Ka = pKa, we have:
pH = pKa log = pKa + log
In general, (Henderson-Hasselbalch equation)
pH = pKa + log

Exercise
What
is the pH of a buffer that is 0.12 M in lactic acid

(HC3H5O3) and 0.10 M in sodium lactate? For lactic acid,

Ka = 1.4 x 10-4.
Initial

HC3H5O3 (aq)

H+ (aq) + C3H5O3- (aq)

0.12 M

0.10 M

Change

-XM

+XM

+XM

Equilibrium

(0.12 X) M

XM

(0.10 + X)
M

Ka = = 1.4 x 10-4 =
[C3H5O3-] = [base] = 0.10 ; [HC3H5O3] = [acid] = 0.12
pH = pKa + log = -log (1.4 x 10-4) + log (0.10/0.12)
= 3.85 + (-0.08) = 3.77

Addition of Strong Acids

or Bases to Buffers

To calculate how the pH of the buffer responds to the addition of

a strong acid or a strong base, we follow the following strategies:
1. Consider the acid-base neutralization reaction, and determine
its effect on [HX] and [X-].
2. Use Ka and the new [HX] and [X-] to calculate [H+].

Exercise
A
buffer is made by adding 0.300 mol HC2H3O2 and 0.300
mol NaC2H3O2 to enough water to make 1.00 L of solution.
The pH of the buffer is 4.74.
a) Calculate the pH of this solution after 0.020 mol of NaOH is added.
b) Calculate the pH of this solution after 0.020 mol of HCl is added.

Before the reaction, since mol HC2H3O2 = mol C2H3O2

pH = pKa + log = log (1.8 10-5) + log
Since log = 0
pH = pKa = log (1.8 10-5) = 4.74

a) Calculate the pH of this solution after 0.020 mol of NaOH is added.

The 0.020 mol NaOH will react (completely) with 0.020 mol
of the acetic acid:
HC2H3O2(aq) + OH-(aq)

Before rxn
After rxn
the

C2H3O2-(aq) + H2O(l)

HC2H3O2

C2H3O2

OH

0.300 mol
0.280 mol

0.300 mol
0.320 mol

0.020 mol
0.000 mol

new pH = pKa + log = 4.74 + log

= 4.74 + 0.06 = 4.80

b) Calculate the pH of this solution after 0.020 mol of HCl is added.

The 0.020 mol HCl will react (completely) with 0.020 mol
of the acetic acid:
C2H3O2- (aq) + H+(aq)

Before rxn
After rxn
the

HC2H3O2 (aq)

HC2H3O2

C2H3O2

H+

0.300 mol
0.320 mol

0.300 mol
0.280 mol

0.020 mol
0.000 mol

new pH = pKa + log = 4.74 + log

= 4.74 + (- 0.06) = 4.68

Ksp and Solubility

Consider the equilibrium that exists in a saturated solution
of BaSO4 in water:
BaSO4(s) Ba2+(aq) + SO42-(aq)
The equilibrium constant expression for this equilibrium is:
Ksp = [Ba2+] [SO42-]
Where the equilibrium constant, ksp, is called the solubility
product.
If the reaction is; MX2 (s) M2+ (aq) + 2X- (aq), its Ksp is:

K sp [M 2 ] [X ]2

Solubility Products
Ksp is not the same as solubility.
Solubility is generally expressed as the mass of solute
dissolved in 1 L (g/L) or 100 mL (g/mL) of solution, or in
mol/L (M).

Solubility indicates the amount of salt that dissociates to

form a saturated solution.
In essence, it indicates the equilibrium position for a given
set of conditions. You can have different solubilities with the
same Ksp.

Calculate solubility given Ksp

Write the dissociation equation
Use the equation to consider the amount of ions given
that s (s for solubility) of the solid dissociates
Write the Ksp expression and substitute your s values
and solve
Pay attention to freaky powers and roots!

Exercise

Copper(II) iodate has a Ksp of 1.4 X 10-7 at 20oC.

What is the molar solubility of the salt?
Cu(IO3)2(s)
-s

Cu2+

+ 2 IO3-

+s

+2s

Ksp = [Cu+2] [IO3-]2 = (s) (2s)2 = 4s3

Ksp = 1.4 X 10-7 = 4s3
s = 3.3 X 10-3 M

Exercise
In a saturated solution of silver carbonate, what is the
molar solubility of the salt? Ksp = 8.1 X 10-12
Ag2CO3(s)
-s

2 Ag+

+ CO3-2

+2s

+s

Ksp = [Ag+]2 [CO3-2] = (2s)2 (s) = 4s3

Ksp = 8.1 X 10-12 = 4s3
s = 1.3 X 10-4 M

Comparing Solubilities
The relative solubilities can be deduced by comparing
values of Ksp. But be careful!
These comparisons can only be made for salts having the
same ION:ION ratio
Which salt is more soluble?
Ag2S ; Ksp = 1.0 X 10-49 ; Ag2S 2 Ag+ + SNi(CN)2 ; Ksp = 3.0 X 10-23 ; Ni(CN)2 Ni+2 + 2 CN Since both make 3 ions (4s3) the larger Ksp is the
more soluble salt - Ni(CN)2!

Exercise
Which salt is more soluble?
PbCl2 Ksp = 1.6 X 10-5
PbBr2 Ksp = 4.6 X 10-6
PbI2

Ksp = 1.4 X 10-8

Factors Affecting Solubility

The Common-Ion Effect
If one of the ions in a solution equilibrium is already
dissolved in the solution, the equilibrium shifts to the
left and the solubility of the salt decreases.

BaSO4(s) Ba2+(aq) + SO42-(aq)

Addition of Ba2+ and SO42- shifts
equilibrium, reducing solubility

Exercise
Calculate
the molar solubility of CaF2 in a solution of 0.010

M in Ca(NO)2. Ksp for CaF2 is 3.9 x 10-11.

CaF2 (s)

Ca2+

+ 2 F-

Initial

0.010 M

Change

XM

+XM

+2XM

Equilibrium

(0.010 + X) M

2XM

Th

co
Ksp = [Ca2+] [F-]2 = 3.9 x 10-11 = (0.010 + X) (2X)2
m
Assuming 0.010 + X 0.010
m
2
= (0.010)(2X)
on
-io
2
-10
n
X = = 9.8 x 10
=
Ca 2
X = = 3.1 x 10-5 M
+
The very small value of x validates the simplyfying assumption.
From the calculation; 3.1 x 10-5 mol of solid CaF2 dissolves per liter of the
0.010 M Ca(NO)2 solution added.

Factors Affecting Solubility

pH

If a substance has a basic anion, it is more

soluble in an acidic solution.

Substances with acidic cations are more

soluble in basic solutions.

For example, a saturated solution of Mg(OH)2,

have a basic anion. If an acid is being added to
the solution, solid of Mg(OH)2 will dissolves until
it reach new equilibrium.
Mg(OH)2 (s) Mg2+ (aq) + OH- (aq)
2 H+ (aq) + Mg(OH)2 (s) Mg2+ (aq) + H2O(l)

Factors Affecting Solubility

Complex Ions
Metal ions can act as Lewis acids and form complex ions
with Lewis bases in the solvent.
The formation of these complex ions increases the
solubility of these salts.

Factors Affecting Solubility

Complex Ions e.g. formation of Ag(NH3)2

Factors Affecting Solubility

Amphoterism
Amphoteric metal
oxides and hydroxides
are soluble in strong
acid or base, because
they can act either as
acids or bases.
Examples of such
cations are Al3+, Zn2+,
and Sn2+.

Will a Precipitate Form?

In a solution,
If Q = Ksp, the system is at equilibrium and the
solution is saturated.
If Q < Ksp, more solid will dissolve until Q = Ksp.
If Q > Ksp, the salt will precipitate until Q = Ksp.

Determine if a precipitate will form

Substitute molarities into Q
Compare Q to Ksp
If precipitation occurs, consider the
stoichiometry and limiting reactant

Exercise
Determining Precipitation Conditions
A solution is prepared by adding 750.0 mL of 4.00 X 10-3
M Ce(NO3)3 to 300.0 mL of 2.00 X 10-2 M KIO3. Will
Ce(IO3)3 (Ksp = 1.9 X 10-10) precipitate from this solution?
Ce(IO3)3 (s) Ce3+ (aq) + IO3- (aq)
Q = [Ce3+ ] [IO3-] = (4.00 X 10-3)(2.00 X 10-2) = 8.0 X 10-5
Q > Ksp
Yes! Precipitate will form.
There are 0.003 mol of Ce3+ ions and 0.006 mol of IO3- ions in the
solutions. Hence, only maximum of 0.003 mol of Ce(IO3)3 precipitate
can formed.

Exercise
A solution is prepared by mixing 150.0 mL of 1.00 X 10-2 M
Mg(NO3)2 and 250.0 mL of 1.00 X 10-1 M NaF. Calculate
the concentrations of Mg2+ and F- at equilibrium with solid
MgF2 (Ksp = 6.4 X 10-9).
Answer : [Mg2+] = 2.1 X 10-6 M ; [F-] = 5.50 X 10-2 M