CHEMISTRY FORM 6

PHYSICAL
CHEMISTRY
CHAPTER 10 : ACID
BASE EQUILIBRIA

Acid / Base Theory

Arrhenius
Theory

Bronsted
Lowry
Theory

Lewis
Theory

7.1 Theory of Acid and Base

7.1.1 The Arrhenius Theory
Acid are substance that dissociate in water to produce
hydrogen ions, H+ (aq)
HA (aq) H+ (aq) + A- (aq)
Base are substance that dissociate in water to yield hydroxide
ions, OH- (aq)
MOH (aq) M+ (aq) + OH- (aq)
Disadvantage many organic compounds like amine RNH 2 and
ammonia contain no OH- (aq) ions but show basic properties in
water. So strictly speaking, ammonia is not Arrhenius base.
To solve it, chemist suggested that aqueous solution of
ammonia contain contains the compound call ammonium
hydroxide, NH4OH. This explanation is not acceptable as
theres no evidence supporting the existence of this
compound in solution.

7.1.2 The Bronsted Lowry Theory

A Bronsted-Lowry acid is substance (molecule or ion) that
donate protons
to a base (proton donor)
accept protonsfrom
A Bronsted-Lowry base is substance that
acid (proton acceptor).
Thus for a reversible reaction, acid-base reaction involve proton
transfer
HA + BHB + A Base is usually negative ion or neutral molecule with a lone pair
electron that can formed dative bond with proton. When an
acid loses proton to a base, itself will formed base. The base
formed as a result of donating proton is called as conjugate
base. Similarly a base in accepting proton forms an acid, so this
acid is known as conjugate acid.
HCl (aq) + NH3 (aq)
Cl- (aq)
+ NH4+ (aq)
Acid base
conjugate
conjugate
base
acid

NH3 (g) + H2O (l)

Bronsted
Lowry base

H2CO3 (aq) + H2O (l)

Bronsted
Lowry acid

Bronsted
Lowry acid

H 2O

Bronsted
Lowry base

(l) + HSO4- (aq)

Bronsted
Lowry base

Bronsted
Lowry acid

CH3COO- (aq) + H2O (l)

Bronsted
Lowry base

Bronsted
Lowry acid

NH4+ (aq) + OH- (aq)

Conjugate
acid

Conjugate
base

HCO3- (aq) + H3O+ (aq)

Conjugate
base

Conjugate
acid

H3O+ (aq) + SO42- (aq)

Conjugate
acid

Conjugate
base

CH3COOH (aq) + OH- (aq)

Conjugate
acid

Conjugate
base

7.1.3
Lewis Theory
Lewis acid a substance which can form a dative covalent
receiving lone pair electron from Lewis base
bond by .
Lewis base a substance which form dative covalent bond by
donating lone pair electron to Lewis acid
..
Neutralisation occur when Lewis base donate a lone pair
electron to form dative bond with Lewis acid.
For example the reaction between boron trifluoride and
F
F
H
ammonia
H
F

B
F

N
H

Similarly, the reaction between boric acid, [B(OH)3 and

H3BO3] and water

In this case, boric acid is classified as acid, not because it

O on water donate the lone pair electron to B
produce H+ but ..
One of the most important applications of the Lewis acid
base theory is in describing the formation of complex ions.
Ligand act as Lewis base which donate lone pair electron to
central metal ion, which act as a Lewis acid

Cu2+ (aq) + 4 NH3 (aq)

[ Cu (NH3)4 ]2+ (aq)

Al3+ (aq) + 4 OH- (aq)

[ Al (OH)4 ]- (aq)

Lewis acid
Positive metal (normally from dblock)
Molecules with incomplete octet

Lewis base
Negative ion (ligand)
Molecules with extra lone pair
electron

(central atom)
Example

Example

Zinc (II) ion, Zn2+ ; Lead (II) ion, Pb2+

Water (H2O) ; cyanide ion (CN-)

Chromium (III) ion, Cr3+

Oxalate ion, (C2O42-)

Exercise 1 : Identify Bronsted-Lowry acid / base ;

conjugate acid / base
a)
NH3 + H2O
NH4+ + OH
b) H2O
+ HCO3
CO32- + H3O+
c)
H2NCONH2 + H2O
H3N+CONH2 + OH
d) H2NCONH2 + NH3
H2NCONH- + NH4+
No

Bronsted Lowry
acid

Bronsted Lowry
base

Conjugate acid

H2 O

NH3

NH4+

OH

HCO3-

H2 O

H3O+

CO32-

H2O

H3N+CONH2

OH

H2NCONH2

H2NCONH2
NH3

NH4+

Conjugate base

H2NCONH-

Exercise 2 : Write the formula of the conjugate acid for each

of the following bases
a) Ammonia ; NH3

b) Carbonate ion ; CO32-

NH4+

c) Hydroxylamine ; NH2OH
NH3OH

d) Pyridine ; C6H5N
C6H5NH+

HCO3-

Exercise 3 : Identify the Lewis acid and Lewis base in the following reaction
a)Cl2
+
AlCl3 Cl+ + AlCl4

b)

Lewis
base
SO3
+

Lewis
acid
CaO

CaSO4

Lewis
Lewis
acid
base

c)H3BO3 +
H2O B(OH)4- +
H+
Lewis
Lewis

acid
base

d) CH3COCl + FeCl3 CH3CO+

+ FeCl4Lewis
Lewis

acid
base

e) CH3COO
CH3COOH + HF2Lewis+ 2 HF Lewis

base

f) Cu2+ Lewis
+
4 NH3
acid

acid
[Cu(NH3)4]2+
Lewis
base

7.2 The Strengths of Acid and Base

Strong acid : .
Acid which dissociate completely in water
Equation
HX + H2O H3O+ + XWeak acid :
Acid which dissociate partially in water
Equation
HA + H2O H3O+ + AStrong base : Base

which dissociate completely in water

Equation
MOH M+ + OHWeak base : Base
...
which dissociate partially in water
Equation
NH3 + H2O NH4+ + OH The strength of acid and base can be compared in terms of
degree of dissociation
(varies with concentration)
the dissociation constant (does not vary with concentration)

7.2.1
The degree of dissociation of acids and dissociation
constant (Ka) and p Ka
completely
When a strong acid dissolve in water, it will
dissociate according to the equation
HCl (g) + H2O (l)
H3O+ (aq) + Cl- (aq)
Initial
c 0 0
At the end 0
c c
As HCl will be completely dissociate in water, the concentration of

0
HCl will be
and this will cause the value of K C to become

Consider the dissociation of a weak monoprotic acid, HA in water is

HA (aq) + H2O (l) H3O+ (aq) + A- (aq)

Initial
c
0
0
At equil.
c (1 )
c c
In the dissociation of weak acid, since the dissociation of acid are
so small, it does not affect much the water. In another word, [H 2O]
.
[H 3O ][A ]
Ka
Equilibrium constant is re-expressed as

HA

CH3COOH + H2O CH3COO- + H3O+

HOBr + H2O OBr- + H3O+

[H 3O ][BrO ]
Ka
[HOBr]

[H 3O ][CH 3COO ]
Ka
[CH 3COOH]
C6H5COOH + H2O C6H5COO- + H3O+

[H 3O ][C 6 H 5COO ]
Ka
[C 6 H 5COOH]

HSO4- + H2O SO42- + H3O+

[H 3O ][SO 4 ]
Ka
[HSO 4 ]

Acid which dissociate more than 1 mole of H+

As for polyprotic acid (....)
;
it goes through stages of dissociation. Each stage of dissociation it has its
own Ka value.
Consider carbonic acid, H2CO3 ; dissociate in 2 distinct stages in water
Stage 1 : H2CO3 + H2O HCO3- + H3O+
Stage 2 : HCO3- + H2O CO32- + H3O+

[H 3O ][HCO 3 ]
K a1
[H 2 CO 3 ]

Ka2

Overall : H2CO3 + 2 H2O CO32- +

2 H 3O +

Ka = Ka1 x Ka2 [H 3O ][HCO 3 ] [H 3O ][CO 3

[H 2 CO 3 ]
[HCO 3 ]

[H 3O ][CO 3 ]

[HCO 3 ]
2

2
] = [H 3O ] [CO 3 ]
[H 2 CO 3 ]

Since the value of Ka is usually small, pKa is often used to compare

the strength of acid where pKa = - log Ka. So,
smaller the pKa ; stronger the acid that is.

Example : The table below shows the Ka values of some acids.

Calculate the pKa of each acid and arrange in ascending order of
their acid strength
Acids

Ka (mol dm-3)

pKa

Ethanoic acid, CH3COOH

1.80 x 10-5

4.74

Chloric (I) acid, HOCl

3.71 x 10-8

7.43

Benzoic acid, C6H5COOH

6.31 x 10-5

4.20

Methanoic acid, HCOOH

2.09 x 10-4

3.68

Increasing order of acid strength :

CH3COOH < C6H5COOH < HCOOH

7.2.2 The degree of dissociation of base and dissociation

constant (Kb) and pKb

In the dissociation of base, it is similar in the way of dissociation

of acid
Consider a weak base, B, which undergoes partial dissociation in
water
B- (aq) + H2O (l)
HB (aq) + OH- (aq)

The equilibrium constant is called the base dissociation constant,

[OH ][HB]
Kb, and is given by
Kb
[B ]

The value of Kb measures the strength of base. Higher the value

of Kb, stronger the base ; greater the extent of its dissociation in
water. Since the value of Kb is usually small, pKb is often used to
compare
where pKb = - log Kb. So, the
smaller the strength of base stronger
the value of pKb ; .. the base that is.

Example : The table below shows the Kb values of some bases.

Calculate the pKb of each base and arrange in ascending order of

Kb (mol dm-3)

pKb

Ammonia, NH3

1.78 x 10-5

4.75

Methylamine, CH3NH2

4.37 x 10-4

3.36

Trimethylamine, (CH3)3N

6.31 x 10-5

4.20

Phenylamine, C6H5NH2

4.17 x 10-10

9.38

Base

Increasing order of basic strength :

C6H5NH2 < NH3 < (CH3)3N < CH3NH2

7.3

Ostwald dilution Law, Ka and Kb

Consider a weak acid, HA, with concentration, C mol dm-3 and the
degree of dissociation, .
In aqueous solution, HA undergoes partial ionisation ;
HA (aq) + H2O (l) H3O+ (aq) + A- (aq)
Initial
At eq

Since

c
c (1 )

0
c

--

[H 3O ][A ]
K a so replacing all the value into equation
[HA]

(c)(c)
and since is usually small ; (1 ) 1
Ka
c(1 )

Ka = c2 and
Since c = [H3O+]

pKa = - log Ka
so

= [H3O+] / c

and [H 3O ] c ; so [H 3O ] K a c and pH lg [H 3O ]

Same thing occur for calculation involving Kb and the

concentration of [OH-]. Consider the reaction below, where
B (aq) + H2O (l) HB (aq) + OH (aq)

Initial
c
1
At equilibrium c(1 )

0
--

0
c

[OH ][HB]
Since K b
so replacing all the value into equation
[B ]

(c)(c)
Kb
and since is usually small ; (1 ) 1
c(1 )

Kb = c2 and
Since c = [OH-]

pKb = - log Kb
so = [OH-] / c

and [OH ] c ; so [OH ] K b c and pOH lg [OH ]

Example 11 : Calculate (a) the concentration of H + ions in 0.120 mol dm-3 solution of ethanoic
acid (b) the degree of dissociation of ethanoic acid [K a = 1.80 x 10-5 mol dm-3]

a) [H+] = Ka x c
= (1.80 x 10-5 x 0.120
= 1.47 x 10-3 mol dm-3

b) [H+] = c
= 1.47 x 10-3 / 0.120
= 0.0122

Example 12 : Calculate the concentration of H+ ions in a 0.20 mol dm-3 HCN solution. the
value of pKa of HCN is 9.3.

a) Ka

= 10-pKa
= 10-9.3
= 5.01 x 10-10 mol dm-3

[H+] = Ka x c
= (5.01 x 10-10 x 0.20
= 1.0 x 10-5 mol dm-3

Example 13 : The concentration of OH- in an aqueous solution of ammonia of concentration

0.150 mol dm-3 is 1.64 x 10-3. Calculate (a) degree of dissociation (b) the base dissociation
constant of aqueous NH3.

a) [H+] = c
= 1.64 x 10-3 / 0.150
= 0.0109

b) Ka = c 2
= 0.150 x 0.01092
= 1.79 x 10-5 mol dm-3

Example 14 : A solution of nitric (III) acid, HNO2, is 1.5% ionised. Calculate (a) its
concentration in mol dm-3. (b) hydrogen ion concentration, [H+] of the solution. [Given Ka of
HNO2 = 5.01 x 10-4 mol dm-3]

a) Since it is 1.5% ionised,

= 0.015
Ka = c 2
c = 5.01 x 10-4 / 0.0152
= 2.23 mol dm-3

b) Since it is 1.5% ionised,

= 0.015
[H3O+] = c
= 2.23 x 0.015
= 0.0334 mol dm-3

Example 15 : An aqueous solution of 1.00 x 10-2 mol dm-3 dimethylamine produce OH- ions of
concentration 4.37 x 10-7 mol dm-3. Calculate (a) the dissociation constant of base and (b)
degree of dissociation of base

a) Kb = [OH-]2 / c
= (4.37 x 10-7)2 / 0.0100
= 1.91 x 10-11 mol dm-3

b)

= [OH-] / c
= (4.37 x 10-7) / 0.0100
= 4.37 x 10-5

10.4.4
Relative acidity of Oxoacids
An oxoacid is acid in which the ionisable hydrogen atom is bonded
to O atom.
When an oxoacid dissociates to give one or more protons, it forms
the corresponding oxoanion which is a conjugate base.
Oxoacid

Oxoanion

The strength of an oxoacid increase if

a) In oxidation number of the central atom increased.

Oxoacid

HClO

HClO2

HClO3

HClO4

Oxidation
number

+1

+3

+5

+7

Ka (mol dm-3)

2.8 x 10-8

1.0 x 10-2

~ 103

~ 107

Increase acid strength

b)

with an increase of electronegativity of the central atom.

Oxoacid

HIO

HBrO

HClO

Electronegativity of halogen
atom
Ka (mol dm-3)

I = 2.5

Br = 2.8

Cl = 3.0

2.4 x 10-11

2.6 x 10-9

2.8 x 10-8

Increase acid strength

i)

These trend in acid strength can be explain in terms of molecular

structure of oxoacid
Consider the dissociation of an oxoacid H O X in water :
H O X (aq)
+ H2O (l) H3O+ (aq) + OX- (aq)
When an oxoacid dissociate, the H+ ion dissociate from O that is
bond with X. Thus, higher the oxidation number of X, greater the
tendency of X to draw electrons away from the oxygen atom
bonded to H and the easier it will be for H to dissociate, thus
increasing Ka

ii) The

more electronegative X is, the greater will be the tendency of

X to draw electron away from O thus weakening the O H bond.

7.5
The Dissociation of Water : Ionic Product of Water
Pure water is a very weak electrolyte since the degree of
dissociation of pure water is very small.
H2O (l) H+ (aq) + OH- (aq)
H = + 57.3 kJ/mol
The Kc for this reaction ; Kc = [H+] [OH-] / [H2O] or
Kc [H2O] = [H+] [OH-]
Since the dissociation of water is so small that makes it
almost constant, so Kw = Kc [water]. Kw here is called as ionic
product of water.
At 25oC (298 K), the dissociation constant for water is 1.0 x
10-14 mol2 dm-6. If [H+] = [OH-] for neutral solution, [H+] =
1.0 x 10-7 mol dm-3
[OH-] =
Same as Kc, Kw gives different values at different
temperatures. Since the reaction is an endothermic process,
equilibrium will shift to the right position upon increasing the
temperature and make the value of Kw become large.

Temp (oC)
Kw(mol2 dm-6)
pKw

10

20

30

50

1.14 x 10-15 1.86 x 10-15 2.93 x 10-15 6.81 x 10-15 1.47 x 10-14 5.48 x 10-14
14.9

14.7

14.5

14.2

13.8

Kw can also be expressed in terms of pKw = - log Kw = -log (1.0 x 10-14) = 14

13.3

7.5.1

Relationship between Ka , Kb , and Kw.

Consider the chemical equilibrium between ethanoic acid and its

conjugate base
CH3COOH (aq) + H2O (l)
CH3COO- (aq) + H3O+ (aq)

[H 3O ][CH 3COO ]
Ka
[CH 3COOH]
CH3COO- (aq) + H2O (l)

CH3COOH (aq) + OH- (aq)

[CH 3COOH][OH ]
Kb
[CH 3COO ]

[
CH
COOH
][
OH
]
[
H
O
][
CH
COO
]
3
3
3
Hence, Ka x Kb =

[CH 3COO ]
[CH 3COOH ]

= [H3O+][OH-]
= Kw

Similarly, for ammonia and its conjugate acid :

NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

[OH ][ NH 4 ]
Kb
[ NH 3 ]
NH4+ (aq) + H2O (l) NH3 (aq) + H3O+ (aq)

[H 3O ][ NH 3 ]
Ka

[ NH 4 ]
Hence Ka x Kb

[H 3O ][ NH 3 ]
[OH ][ NH 4 ]

[ NH 4 ]
[ NH 3 ]

= [H3O+][OH-]
= Kw

7.6
The pH Scale
The pH of a solution is used to denote hydrogen ion concentration in
the solution. It is the negative logarithm to the base ten of the
hydrogen ion concentration in mol dm-3.
pH = lg [H+] or lg [H3O+]
If concentration of OH- is considered, pOH
= lg [OH-]
At 25oC, Kw = 1.0 x 10-14 mol2 dm-6 , pKw = 14 = pH + pOH
[H+]
mol dm-3

10-1

10-2

10-3

10-4

10-5

10-6

10-7

10-8

10-9

pH

Strengt
h

Strong acid

Weak acid

Ne
utral

10-10 10-11 10-12 10-13 10-14

10

Weak base

11

12

13

14

Strong base

pH value usually lie within the range of 0 14. However, it is

possible, in theory, for a very strong acid solution to have a pH
less than 0 or more than 14.

a) 0.01 mol dm-3 of hydrochloric acid, HCl

a) Since HCl, conc of H+ = 0.01

pH = - lg [H+]
= - lg 0.01
=2
c) 0.010 mol dm-3 of ethanoic acid,
CH3COOH (Ka = 1.8 x 10-5 mol dm-3)

[H+] = Ka x c
= (1.8 x 10-5 x 0.010
= 4.24 x 10-4 mol dm-3
pH = - lg 4.24 x 10-4
= 3.37
e) 0.01 mol dm-3 of sodium hydroxide,
NaOH

Since NaOH, conc of OH- = 0.01

pOH = - lg [OH-]
= - lg 0.01
=2
pH = 14 pOH = 14 2
= 12

b) 0.01 mol dm-3 of sulphuric acid, H2SO4

Since 1 mol H2SO4 = 2 mol H+

[H+] = 2 x 0.01 = 0.02
pH = - lg 0.02
= 1.7
d) 2.0 x 10-8 of hydrochloric acid

since conc of acid is less than1 x 10-7,

water diss, conc of H+ = OH- = 1 x 10-7
So, conc of H+ = 1 x 10-7 + 2.0 x 10-8
= 1.2 x 10-7 mol dm-3
pH = - lg 1.2 x 10-7 mol dm-3
= 6.92
f) 8 x 10-3 mol dm-3 of magnesium hydroxide,
Mg(OH)2

Since 1 mol Mg(OH)2 = 2 mol OHconc of OH- = 1.6 x 10-2

pOH = - lg [OH-]
= - lg 0.016 = 1.80
pH = 14 pOH = 14 1.80
= 12.2

g) 0.01 mol dm-3 of ammonia, NH3 (pKb =

4.7)
-4.7

pKb = -lg [Kb] ; Kb = 10

Kb = 2.0 x 10-5 mol dm-3
[OH-] = Kb x c
= (2.0 x 10-5 x 0.01
= 4.47 x 10-4 mol dm-3
pOH = - lg 4.47 x 10-4
= 3.35
pH = 14 3.35 = 10.65

h) 4.0 x 10-8 mol dm-3 potassium hydroxide,

KOH

since conc of base is less than1 x 10-7,

water diss, conc of H+ = OH- = 1 x 10-7
So, conc of OH- = 1 x 10-7 + 4.0 x 10-8
= 1.4 x 10-7 mol dm-3
pOH = - lg 1.4 x 10-7 mol dm-3
= 6.85
pH = 14 6.85 = 7.15

i) A 0.100 mol dm-3 of an alkaline solution produced by a weak base has a pH of 9.10. Calculate
a) the concentration of OHb) degree of dissociation.

pOH = 14 pH
= 14 9.10 = 4.90
[OH-] = 10-4.90
= 1.26 x 10-5 mol dm-3

[OH-] = c
= [OH-] / c
= 1.26 x 10-5 / 0.100
= 1.26 x 10-4

j) At 298 K, 0.200 mol dm-3 of nitrous acid, HNO2 is 1.5% dissociated. Calculate
a) the value of pKa (b) the degree of dissociation for 0.500 mol dm-3 and its pH.

a) Since it is 1.5% ionised,

= 0.015
Ka = c 2
Ka = 0.200 x 0.0152
= 4.50 x 10-5 mol dm-3
pKa = 4.35

b) Ka = c 2
4.50 x 10-5 = 0.500 x 2
= 9.49 x 10-3
[H+] = c = 0.500 x 9.49 x 10-3
= 4.74 x 10-3 mol dm-3
pH = 2.32

k) A solution was prepared by mixing 0.15 mol dm-3 of ethanoic acid and 0.010 mol of
hydrochloric acid and making up the solution 1.00 dm3 with distilled water. [Ka of CH3COOH =
1.80 x 10-5 mol dm-3]. Calculate a) [CH3COO-] at equilibrium b) pH of the mixture solution

a)

CH3COOH + H2O
CH3COO- + H3O+
Initial :
0.15
0
0
At equilibrium : 0.15 (1-x)
0.15 x
0.15 x
since the conc of H3O+ = 0.010 + 0.15 x 0.010 (as x is very small)
Ka = [CH3COO-][H3O+] / [CH3COOH]
1.80 x 10-5 = [CH3COO-] (0.010) / 0.15
[CH3COO-] = 0.15 x 1.80 x 10-5 / 0.010
= 2.7 x 10-4 mol dm-3
[H3O+] = 2.7 x 10-4 + 0.010 = 0.01027 mol dm-3
pH = 1.99 2

7.7
Acid Base Indicator
~ is a water soluble dye that change colour according to
the concentration of hydrogen ions in the solution to
which indicator is added.
Example, litmus paper is a weak organic acid which is
represented using formula HIn.
HIn (aq) + H2O (l)H3O+ (aq) + In- (aq)
red
blue
If the solution is acidic (high in H3O+) ; equilibrium will
shift to the left to form more red colour molecules
If the solution is basic, (less in H3O+) ; equilibrium will
shift to the right and make the solution look more blue.
The equilibrium constant for the equation above is
called indicator dissociation constant, KIn

HIn (aq) + H2O (l)

K HIn

[H 3O ][In ]

[HIn]

rearrange

H3O+ (aq) + In- (aq)

taking lg to the equation , lg [H 3O ] lg K HIn

thus, pH pK HIn

[HIn]
[In ]
[HIn]
lg
[In ]

[H 3O ] K HIn

[HIn] colour of acid indicator

lg
[In ] colour of conjugate base

[ HIn]
If
[ In ] > 10, colour of acid indicator will be seen

[ HIn]
-1
If
< 10 , colour of conjugate base will be seen
[ In ]

To the reason above, the detectable colour range of

indicator is pKHIn 1.

If [HIn] = [In-] , the intermediate colour of the indicator is

seen.

Colour change
Acid base

Approximate
pH range

pKHIn

Methyl orange

Red-orange Yellow

3.1 4.4

3.7

Bromophenol blue

Yellow-blue Violet

3.0 4.6

3.8

Methyl red

Red Yellow

4.2 6.1

5.0

Bromothymol blue

Yellow Blue

6.0 7.6

7.1

Phenol red

Yellow Red

6.4 8.2

7.8

Colourless Pink

8.3 9.8

9.3

Indicator

Phenolphetalein

7.7.1 The End-Point of a Titration

The equivalence point refers to the point at which there are
equal amounts (in moles) of H3O+ (aq) and OH- (aq) in the
titration flask. Equivalence point can be tell by noting the
colour change of the acid base indicator. The point in a
titration at which the indicator changes colour is called endpoint.

At end-point of the titration,

All the acid has been neutralised by alkali
The solution in the conical flask contain salt and water only
The colour of the indicator will be midway between the
colour of acid and its conjugate base

Titration of Strong Acid Strong Base (HCl NaOH)

The change of pH that occur during titration of hydrochloric acid and
sodium hydroxide is followed by using a pH meter. Alkali solution is
added slowly to 25 mL HCl 0.100 M in a beaker and the pH changes
occur for each mL of alkali solution added is recorded
1. At the beginning, pH value is low (strong acid)
2. Before the equivalence point / end point, each mL of NaOH added will
cause the pH value raise until when it reaches around 24 mL where it
reaches around pH 7.
3. Equivalence point / end point occur at 25 mL of NaOH 0.100 M. If one
drop of NaOH is added to this mixture now, the pH will change sharply
from 3.5 to 10.0. The pH at the equivalence point is the pH of the
resultant salt. Thus the pH at equivalence point is 7.0, which is the pH
of sodium chloride solution.
4. After the equivalence point / end point, the pH raise slowly for each mL
of NaOH added.
The choice of indicator for strong acid strong base titration is
somewhere from pH range 3.5 to 10.0. Thus, methyl orange,
Bromothymol blue and phenolphthalein can be used as indicator.

Titration Curve of Strong Acid Strong Base (HCl NaOH)

14
12
10
Phenolphthalein
Equivalence point

8
7

End point

Bromothymol blue

6
4

Methyl orange

2
0

10

15

20

25

30

35

Titration of Strong Acid Weak Base (HCl NH 3)

The pH obtained when 0.10 mol dm-3 ammonia solution (weak base) is
added to 25.0 cm3 of 0.10 mol dm-3 hydrochloric acid is shown in graph
below

1. At the beginning, pH value is low (strong acid)

2. Before the equivalence point / end point, each cm3 of NH3 added will
cause the pH value raise until when it reaches around 24 cm3 where it
reaches pH = 5.3
3. At equivalence point (pH = 5..3), it is less than 7 because the salt of
ammonium chloride will undergoes hydrolysis. The ammonium ions react
with water to produce hydroxonium ion.
NH4+ (aq) + H2O (l)

NH3 (aq) + H3O+ (aq)

This will result the solution being acidic.

4. After equivalence point, another drop of ammonium solution added to
the mixture will cause the pH to raise gradually to 7
5. Therefore, methyl orange (pH range of 3.1 4.4) is a suitable indicator
because it changes colour within the pH range of 3 to 7, the vertical
portion of graph.

Titration Curve of Strong Acid Weak Base (HCl NH 3)

14
12
10
Phenolphthalein
8
7

Bromothymol blue

End point

Equivalence point

Methyl orange

2
0

10

15

20

25

30

35

Titration of Weak Acid Strong Base (NaOH CH 3COOH)

The pH curve obtained when 25.0 cm3 of 0.100 mol dm-3 of ethanoic
acid, CH3COOH is titrated against a 0.100 mol dm-3 of sodium hydroxide,
NaOH is shown in figure below

1. At the beginning, pH value is rather high (weak acid)

2. Before the equivalence point / end point, each cm3 of NaOH added will
cause the pH value raise until when it reaches around 24 cm3 where it
reaches pH = 6.5
3. The equivalence point (pH = 9), it is more than 7 because the salt of
sodium ethanoate is formed. The ethanoate ions react with water to
produce hydroxide ion.
CH3COO- (aq) + H2O (l)

CH3COOH(aq) + OH- (aq)

This will result the solution being basic.

4. After equivalence point, another drop of sodium hydroxide added to the
mixture will cause the pH to raise gradually to 10.5
5. Therefore, phenolphthalein (pH range of 8.0 9.8) is a suitable indicator
because it changes colour within the pH range of 6.510.5, the vertical
portion of graph

Titration Curve of Weak Acid Strong Base (CH3COOH NaOH)

14
12
10
Phenolphthalein
8

Equivalence point

End point

Bromothymol blue

6
4

Methyl orange

2
0

10

15

20

25

30

35

Titration of weak acid and weak base (CH3COOH NH3)

There is no sharp rise in pH at equivalence point. Instead, the pH

increases gradually upon increasing of base. Therefore, theres no
suitable indicator for this titration.
14
12
10

Phenolphthalein

Bromothymol blue

7
6

Methyl orange

4
2
0

10

15

20

25

30

35

Titration of polyprotic acids and strong base

When a weak polyprotic acid, like phosphoric (V) acid, is titrated with
NaOH, the titration curve obtained shows separate equivalence points for
each displaceable proton.

H3PO4 (aq) + NaOH (aq) NaH2PO4 (aq) + H2O

NaH2PO4 (aq) + NaOH (aq) NaHPO4 (aq) + H2O (2)

NaHPO4 (aq) + NaOH (aq) Na3PO4 (aq) + H2O (3)

(1)

1. From the equation 1 3 above, there should be 3 level of equivalence

point. The first equivalence point occurs at pH 3.6, which is
correspondent to the equation (1). At this point, methyl orange is the
most suitable indicator.
2. As for the second equivalence point, it occurs at pH 9.0, which is
correspondent to the (2). Phenolphthalein, at this moment, is the most
suitable indicator.
3. The third equivalence point should be around 75.0 cm3, according to eq.
(3). However this is realised in this titration as no sharp increase in pH
about 13 (pH for Na3PO4) as this is the pH of NaOH used in this titration

Titration Curve of Polyproctic Acid Strong Base (H3PO4 NaOH)

14
12
10
Phenolphthalein
8
7

Bromothymol blue

6
4

Methyl orange

2
0

10

20

30

40

50

60

70

Titration involving Sodium Carbonate and Hydrochloric Acid

the pH curve obtained when 25.0 cm3 of 0.100 mol dm-3 of sodium
carbonate is titrate with 0.100 mol dm-3 of hydrochloric acid.

1. The first corresponding equivalence point occur at pH = 9. This is due to

the formation of acid salt, NaHCO3 as
Na2CO3 (aq) + HCl (aq) NaHCO3 (aq) + NaCl (aq)
Phenolphthalein is the most suitable indicator for this equivalence point.
2. The second equivalence point occur at pH = 4 at 50.0 cm3 HCl added. This
corresponds to the formation of carbonic acid.
NaHCO3 (aq) + HCl (aq) NaCl (aq) + CO2 (g) + H2O (l)
Or

HCO3- (aq) + H+ (aq) H2O (l) + CO2 (g)

Methyl orange is the most suitable indicator for this equivalence point

Titration Curve of Polyproctic Base Strong Acid (HCl Na 2CO3)

14
12
10
Phenolphthalein
8
7

Bromothymol blue

6
4

Methyl orange

2
0

10

20

30

40

50

60

70

1. When 25.0 cm3 of 0.100 dm-3 HCl (aq) is titrated with 0.100 mol dm-3 NaOH (aq), the pH of
the solution increased. Calculate the pH of the solution after the following volume of NaOH
have been added
a) 24.90 cm3
b) 25.10 cm3

a) NaOH + HCl NaCl + H2O

Mol H+ = MV / 1000
= (0.100)(25.0)/1000
= 0.0025 mol
Mol OH- = MV / 1000
= (0.100)(24.90)/1000
= 0.00249 mol (lim)
Mol of excess H+ = 0.0025-0.00249
= 0.00001 mol
Conc. of H+ = mol x 1000 / Vtot
[H+]= 0.00001 x 1000/(24.9+25.0)
= 2.00 x 10-4 mol dm-3
pH = - lg 2.00 x 10-4 mol dm-3
= 3.70

a) NaOH + HCl NaCl + H2O

Mol H+ = MV / 1000
= (0.100)(25.0)/1000
= 0.0025 mol (lim)
Mol OH- = MV / 1000
= (0.100)(25.10)/1000
= 0.00251 mol
Mol excess OH- = 0.00251-0.0025
= 0.00001 mol
Conc. of OH- = mol x 1000 / Vtot
[OH-]= 0.00001x 1000/(25.1+25.0)
= 1.996 x 10-4 mol dm-3
pOH = - lg 1.996 x 10-4 mol dm-3
= 3.70
pH = 14 3.70
= 10.3

2. When 15.0 cm3 of 0.200 dm-3 H2SO4 (aq) is titrated with 0.100 mol dm-3 NaOH (aq), the
pH of the solution increased. Calculate the pH of the solution after the following volume of
NaOH have been added
a) 55.0 cm3
b) 65.0 cm3

2 NaOH + H2SO4 Na2SO4 + 2 H2O

Mol of H2SO4 = MV / 1000
= (0.200)(15.0)/1000
= 0.0030 mol
Since 1 mol of H2SO4 = 2 mol H+
Mol of H+ = 0.0030 x 2 = 0.0060 mol
Mol OH- = MV / 1000
= (0.100)(55.0)/1000
= 0.0055 mol (lim)
Mol of excess H+ = 0.006 - 0.0055
= 0.0005 mol
Conc. of H+ = mol x 1000 / Vtot
[H+]= 0.0005 x 1000/(15.0 + 55.0)
= 7.14 x 10-3 mol dm-3
pH = - lg 7.14 x 10-3 mol dm-3
= 2.15

2 NaOH + H2SO4 Na2SO4 + 2 H2O

Mol of H2SO4 = MV / 1000
= (0.200)(15.0)/1000
= 0.0030 mol
Mol of H+ = 0.0030 x 2
= 0.0060 mol (lim)
Mol OH- = MV / 1000
= (0.100)(65.0)/1000
= 0.0065 mol
Mol of excess OH- = 0.0065 - 0.0060
= 0.0005 mol
Conc. of OH- = mol x 1000 / Vtot
[OH-]= 0.0005 x 1000/(15.0 + 65.0)
= 6.25 x 10-3 mol dm-3
pOH = - lg 6.25 x 10-3 mol dm-3
= 2.20
pH = 14 2.20
= 11.80

1. 25.0 cm3 of a solution containing sodium carbonate, Na2CO3 and sodium bicarbonate,
NaHCO3 required 17.5 cm3 of 0.100 mol dm-3 hydrochloric acid for neutralisation with
phenolphthalein as indicator and 41.3 cm3 of the same acid with methyl orange indicator.
Calculate the
(a) concentration of Na2CO3 in mol dm-3
(b) concentration of sodium bicarbonate in
mol dm-3

With phenolphthalein as indicator :

End point for the reactions are for
Na2CO3 + HCl NaHCO3 + NaCl

M Na 2CO3 VNa 2CO3

M HCl VHCl

M Na 2CO3 (25.0)

(0.100)(17.50) 1
MNa2CO3 = 0.0700 mol dm-3

With methyl orange as indicator :

End point for the reactions are for
NaHCO3 + HCl NaCl + H2O + CO2
Since NaHCO3 come from 2 sources
Na2CO3 NaHCO3 NaCl
or directly
NaHCO3 (from mixture) NaCl
VHCl for Na2CO3 = 17.5 + 17.5 = 35.0
VHCl for NaHCO3 mixture = 41.3 35
M NaHCO3 VNaHCO3= 6.3
1 cm3

M HCl VHCl
1

M NaHCO3 (25.0)
(0.100)(6.30)

1
1

MNaHCO3 = 0.0252 mol dm-3

10.8 Buffer solution

where pH do not change much when a little
A buffer solution is a solution .
acid or base is added
There are 2 types of buffer solutions.
An acidic buffer that keeps the pH below 7
An alkaline buffer that keeps the pH above 7
Acidic buffer solutions consist of a weak acid and salt of the weak acid.
The salt contributes the conjugate base of the weak acid. Example:
An aqueous solution which contain equal amounts in moles of ethanoic
acid (CH3COOH) and salt, sodium ethanoate (CH3COONa). The salt
supplies the conjugate base, CH3COO- (aq) of weak ethanoic acid. This
buffer solution pH 5

An aqueous solution which contains a mixture of sodium dihydrogen

phosphate, NaH2PO4, which act as the weak acid and disodium hydrogen
phosphate, Na2HPO4 act as the salt. The salt supplies conjugate base,
HPO4- (aq) of weak acid.

Alkali buffer solutions consist of weak base and salt of the weak base.
The salt contributes the conjugate acid of the weak base. Example :
An aqueous solution which contain equal amounts in moles of ammonia
solution (NH3) and salt, ammonium chloride (NH4Cl). The salt supplies the

10.8.1
The Action of Acidic Buffer solution
An acidic buffer solution has a pH around 4 7. To see how an
acidic buffer solution works, consider a mixture of sodium
ethanoate and ethanoic acid.
CH3COONa (aq)
CH3COO- (aq) + Na+ (aq) . fully
dissociates
CH3COOH (aq) CH3COO- (aq) + H+ (aq) partially dissociates

The mixtures contain a high concentration of conjugate base,

CH3COO- (aq) yet the concentration of H+ (aq) is low
If

small amount of acid is added to the buffer solution, the large

number of ethanoate ion will react with the H+ contribute from
the acid added. Therefore, adding H+ will not effect much the
system thus the pH remain virtually constants
If a small amount of alkali is added to the buffer solution, the
hydrogen ion from weak acid will react with OH- from the base.
Removing hydrogen ion will cause the equilibrium of ethanoic
acid shift to the right. So, the H+ lost will be compensated and
the pH of the buffer solution will remain constant.

10.8.2
The Action of Alkali Buffer Solution
An alkali buffer solution has a pH around 7 10. To see how an
alkali buffer solution works, consider a mixture of ammonia
solution and ammonium chloride
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq) partially dissociates
NH4Cl (aq) NH4+ (aq) + Cl- (aq)

... completely dissociates

The mixtures contain a high concentration of conjugate acid, NH4+

(aq) yet the concentration of OH- is low.
If a small amount of acid is added to the buffer solution, it will
neutralised the OH- from the ammonia solution. Here, the
equilibrium will shift to the right to produce more OH- so the
hydroxide ion lost will be compensated and the pH remains
approximately constant.
If a small amount of base is added, the NH4+ from the salt will
react with the OH- supplied, to form ammonia solution. Again,
this will keep the pH of alkaline solution remain constant.

The pH value of an acidic solution can be calculated from the acid

dissociation constant, Ka and also the concentration of acid and salt.
H3O+ (aq) + A- (aq) NH3 (aq) + H2O (l)

HA (aq) + H2O (l)

and

salt : MA M+ (aq) + A- (aq)

Ka

[H 3O ][A ]
[HA]

[ H 3O ] K a

[HA]
[A ]

NH4+ (aq) + OH- (aq)

and salt : NH4Cl NH4+ + Cl-

[ NH 4 ][OH ]
Kb
[ NH 3 ]
[OH ] K b

[ NH 3 ]
[ NH 4 ]

When lg the equation :

When lg the equation :

[HA]
lg [H 3O ] lg K a lg
[A ]

[ NH 3 ]
lg [OH ] lg K b lg
[ NH 4 ]

Since [A-] contributed by salt while

[HA] contributed by weak acid

pH pK a lg

[acid]
[salt ]

Since [NH4+] contributed by salt while

[NH3] contributed by weak base

[base]
pOH pK b lg
[salt ]

Example : Calculate the pH of a buffer solution prepared by dissolving 32.8 g of

sodium ethanoate, NaCH3COO in 1.00 dm3 of 0.100 mol dm-3 ethanoic acid,
CH3COOH. [Ka = 1.75 x 10-5 mol dm-3]

[acid ]
pH pK a lg
pH = 5.36
[ salt ]
(0.100)
5
pH lg(1.75 10 ) lg 32.8
( 82 )

Example : Calculate the pH of a buffer solution prepared by adding 10.7 g of

ammonium chloride to 500 cm3 of 0.500 mol dm-3 ammonia solution
(Kb = 1.80 x 10-5 mol dm-3)
pOH = 4.65
pH = 14 pOH
= 9.35
b

[base]
pOH pK lg
[ salt ]
5

pOH lg(1.80 10 ) lg

(0.500)
(

10.7
53.5
0.5 dm 3

10.8.4
Buffer Capacity
~ amount of acid / base that can be absorbed by the buffer
solution without a significant change of pH. Larger the capacity,
greater the amount of acid / base must be added in order to
produce a significant change.
Buffer capacity depends on the concentration of the weak acid
(HA) and its conjugate base (A-) present.
The pH range in which a buffer effectively neutralise added acids
and bases and
[ salt ]
If the ratio
= 1.0,
[acid
] then pH = pKa ;
[ salt ]
if the ratio [ acid
= 0.1,
] then pH = pKa + 1 ;
[ salt ]
if the ratio [ acid
= 10,
] then pH = pKa 1.

Where maximum buffer

capacity is achieved

So the significant concentration of both acid and salt present

[ salt ]
should be in between 10-1 < [acid ]< 10

Titration Curve of Weak Acid Strong Base (CH3COOH NaOH)

14
12
10
8

Equivalence point

End point

7
6
ne
buffer zo

4
pH = pKa
2
0

10

15

V
20

25

30

35

Titration Curve of Strong Acid Weak Base (HCl NH 3)

14
12
10
14-pH
pOH =
pKb 8
7
6

ne

End point

buffer zo

Equivalence point

4
2
0

10

15

V
20

25

30

35

Example : 25.0 cm3 of 0.100 mol dm-3 ethanoic acid was titrated with
0.100 mol dm-3 sodium hydroxide solution
a) Write an equation for the reaction above.
b) Sketch a pH curve for the reaction and indicate in your graph the region
where the mixture can function as a buffer.
c) What is the pH of the solution when it has maximum buffer capacity.
a) CH3COOH + NaOH CH3COONa + H2O

10.8.5
Preparing a buffer solution of specified pH
Acidic buffer solution can be prepared by adding
Weak acid to
salt of the weak acid while basic buffer

Weak base
salt
of weak base
solution can be prepared by adding ..to

The following steps are used to prepare buffer solutions of a

specified pH
1 Choose a weak acid / base whose pKa / pKb value is close to
the desire pH of buffer solution
2 Choose a suitable salt of the weak acid / base
3 Calculate the required amount of mixture by adjusting
[acid] / [salt] or [base] / [salt] ratio

Example : Explain how a buffer solution with a pH 5.40 can be prepared from
ethanoic acid and sodium ethanoate [ pKa of CH3COOH = 4.76]

[salt ]
pH pK a lg
[acid ]

Mol of salt = 4.365

Mass of salt use = mol x RMM
= 4.365 x [12(2) +1(3) + 16(2) + 23
= 358 g

[salt ]
5.40 4.76 lg
[acid]
Buffer Solution with pH 5.40 is prepared
[salt ]
[salt ]
lg
0.64
4.365 by dissolving 358 g of CH COONa into 1.0
3
[acid]
[acid]
dm3 of CH3COOH 1.00 mol dm-3
Example : Explain how a buffer solution with a pH 10.2 can be prepared from
ammonia aqueous solution and ammonium chloride, NH 4Cl [ Kb of NH3 = 1.78 x 10-5
mol dm-3] pOH 14 pH
Mol of salt = 0.112 mol
14 10.2 3.8
Mass of salt use = mol x RMM
[salt ]
= 0.112 x [14(1) + 1(4) + 35.5(1)
pOH pK b lg
[base]
= 5.99 g
[salt ]
5
3.8 lg(1.78 10 ) lg
Buffer solution with pH 10.2 can be
[base]
prepared by dissolving 5.99 g of NH4Cl
[salt ]
[salt ]
lg
0.95
0.112
into 1.0 dm3 of NH3 1.00 mol dm-3
[base]
[base]

Example : calculate the mass of sodium ethanoate solution that has to be added to
1.00 dm3 of 0.100 mol dm-3 ethanoic acid to prepare a buffer solution of pH 4.50 [ K a
of CH3COOH = 1.74 x 10-5 mol dm-3]

[salt ]
pH pK a lg
[acid ]

Since conc of acid = 0.100

[salt] = 0.5495 x 0.100
Mol = MV = 0.05495 x 1 = 0.05495 mol
[
salt
]
Mass of salt use = mol x RMM
4.50 lg 1.74 10 5 lg
[acid]
= 0.05495 x [12(2) +1(3) + 16(2) + 23
[salt ]
[salt ]
= 4.51 g
lg
0.26
0.5495
[acid]
[acid]

10.8.6
Application of Buffer Solution
Chemical Analysis Some titration, for example EDTA
titrations, have to be carried out in the solutions in which
the pH is maintained at a constant value
Research in bacteriology buffer solution is needed to
maintain the pH of culture media so that the bacteria can
propagate under the right pH condition.
Fermentation processes buffer system are essential in
biological reactions that are catalysed by enzymes. Enzymes
have very narrow and specific pH limit at which it work the
best. Hence fermentation processes that utilised yeast as the
fermenting organism must take place in buffer solution.
Otherwise, small changes in pH will cause the death of yeast
and stop the fermentation.

Industrial processes buffer solution play an

important role in many industrial processes.
They are used in the manufacture of dyes and
photographic material
The importance of buffers in biological
systems. Buffer solutions are very important in
biological systems. Blood, for example, is a
buffer solution that can soak up the acids and
bases produced in biological reactions. The pH
of human blood is carefully controlled at a
value very close to 7.4 by conjugate acidbase
pairs, primarily H2CO3 and its conjugate base
HCO3-. The oxygen-carrying ability of blood
depends on control of the pH to within 0.1 pH
unit.

11.0 Solubility Equilibrium

of
~ equilibrium betweenSalt
..............
undissociated
Oppositely
solute (in solid)
and its charged
.................................... ions in
the solution.

When increasing quantities of a sparingly soluble

ionic solid are added to water, a saturated solution is
eventually formed.

The dissolving and precipitating of ionic compounds

are phenomena that occur both within us and around
us. Examples:
1. The dissolving of tooth enamel in acidic solutions
causes tooth decay.
2. The precipitation of certain salts in our kidney
produces kidney stones.
3. The precipitation of CaCO3 from groundwater is
responsible for the formation of stalactites and
stalagmites within limestone caves.

11.1 Solubility product

When a sparingly soluble salt can no more dissolve in

saturated
solvent,
a ..................... solution is formed

For example, when dissolving silver chloride, AgCl (s) ;

AgCl
(s) Ag+ (aq) + Cl.............................................................
(aq)

The product of the concentrations of Ag+ (aq) + Cl(aq) ions in a saturated solution of silver chloride is
solubility
called asproduct
..............................of silver chloride. Based
on the equation
K x [AgCl] = [Ag+][ Cl- ]

Since the concentration of a pure solid is constant, the

+
simplifies=to[Ag
become
Kabove
x [constant]
][ Cl- ]
Ksp = [Ag+][ Cl- ]
Another example is lead (II) hydroxide, which is a
base. It is sparingly soluble in water. In aqueous
solution, lead (II) hydroxide
dissociate according to the
Pb2+ (aq) + 2 OH- (aq)
equation ,

So, the Ksp of lead (II) hydroxide is written as

Ksp = [Pb2+][OH-]2
In general, AxBy x Ay+ (aq) + y Bx- (aq)
Ksp = [Ay+]x [Bx-]y

Compound

Dissociation equation

Solubility product, Ksp

Unit

HgCl

HgCl Hg+ + Cl-

Ksp =[Hg+][Cl-]

PbBr2

PbBr2 Pb2+ + 2 Br-

Ksp =[Pb2+][Br-]2 mol3 dm-9

Ag2CrO4
BaSO4
Fe2(CO3)3
Ca3(PO4)2

mol2 dm-6

mol3 dm-9
Ag2CrO4 2 Ag+ + CrO42- Ksp
=[Ag+]2[CrO42-]
Ksp =[Ba2+][SO42-] mol2 dm-6
BaSO4 Ba2+ + SO42Fe2(CO3)3 2Fe3+ + 3CO32-Ksp
mol5 dm-15
=[Fe3+]2[CO32-]3
Ca3(PO4)2 3 Ca2+ + 2PO43-Ksp=[Ca2+]3[PO43-]2 mol5 dm-15

11.2
Definition : Solubility & Solubility Product
11.2.1
Solubility

Solubility is the quantity of solute that dissolved in unit

volume of saturated solution at a given temperature. Thus
solubility is often measured in g dm-3 or mol dm-3.

RMM
g dm-3
mol dm-3

RMM x

11.2.2
Solubility Product, Ksp

The solubility product, Ksp, of a sparingly soluble

electrolyte is the product of the concentrations of the ions
in a saturated solution at a given temperature. The
concentration of ions are raised to appropriate powers
depending on the stoichiometry of the equation.
Therefore, there is no fixed units for Ksp.

Ksp measures the extent a sparingly soluble salt can

more solubl
dissolve in water. The higher the Ksp value, the ..................
the salt.

Example 1 : Calculation of Ksp from

Solubility values. Given the solubility of
AgI is 6.24 x 10-8 mol dm-3, calculate its
Ksp
Agl (s) Ag+ (aq) + I- (aq)
x
x
x
Ksp = [Ag+][I-]
= (x)(x) = (6.24 x 10-8)2
= 3.89 x 10-15 mol2 dm-6
Given the solubility of Pbl2 is 1.21 x 10-3
mol dm-3, calculate its Ksp.

PbI2 Pb2+ + 2 Ix
x
2x
Ksp = [Pb2+][I-]2
= (x)(2x)2 = 4x3
= 4 (1.21 x 10-3)3
= 7.09 x 10-9 mol3 dm-9

Example 2 : Calculation of Solubility

given Ksp. Calculate the solubility of
CaCO3 given that its solubility product,
Ksp, is 4.72 x 10-15 mol2 dm-6.
CaCO3 (s) Ca2+(aq)+ CO32-(aq)
x

x
x
Ksp = [Ca2+][CO32-]
4.72 x 10-15 = (x)(x)
= 6.87 x 10-8 mol dm-3
Calculate the solubility of Ag2CrO4, given
that its solubility product, Ksp, is 2.4 x 10-12
mol3 dm-9.

Ag2CrO4 2 Ag+ + CrO42x

2x x
Ksp = [Ag+]2 [CrO42-]
= (2x)2 (x) = 4x3
2.4 x 10-12 = 4 (x)3
x = 8.4 x 10-5 mol dm-3

Given the solubility of Fe(OH)3 is 3.49 x

10-5 mol dm-3 calculate its Ksp

Fe(OH)3 Fe3+ + 3 OHx

x
3x
Ksp = [Fe3+][OH-]3
= (x)(3x)3 = 27x4
= 27 (3.49 x 10-5)4
= 4.01 x 10-17 mol4 dm-12

Calculate the solubility of Al(OH)3, given

that its solubility product, Ksp, is 1.9 x 10-33
mol4 dm-12.

Al(OH)3 Al3+ + 3 OHx

x
3x
Ksp = [Al3+] [OH-]3
= (x) (3x)3 = 27x4
1.9 x 10-33 = 27 (x)4
x = 2.9 x 10-9 mol dm-3

Be sure not to confuse solubility with solubility

product (Ksp).

The solubility of a salt is the amount present in a unit

amount of a saturated solution expressed in mol dm3 or g dm-3.

The solubility product is an equilibrium constant. K sp

values are always small, usually < 10-4.

Generally, a low vaiue of Ksp means that:

i) The concentration of the ions is low at equilibrium.
ii) The substance is not very soluble

There is a connection between them - if either is

known, the other can be calculated.

Example 3: The Ksp values for the silver haiides are

given below.
Salt

AgCl

AgBr

AgI

Ksp / mol2 dm-6

1.8 x 10-10

3.3 x 10-13

1.5 x 10-16

Arrange these salts in increasing order of solubility.

AgI < AgBr
<
AgCl
Note : Direct comparisons of solubility on the basis
of Ksp values can only be made for salts having the
same ion ratio. For example, the ion ratio for silver
haiides is 1:1, the ion ratio for lead halides is 1:2.

11.3
Solubility and the Common Ion Effect

The solubility of a substance is affected not only by

temperature but also by the presence of other solutes.

Example:
The value for Ksp for manganese(ll)
hydroxide, Mn(OH)2, is 1.6 x 10-13 mol3 dm-9. Calculate the
solubility of Mn(OH)2 in
b) In 0.020 mol dm-3 NaOH
a) In water
In base, OH- is contributed
In water, Mn(OH)2 dissociate
mainly by NaOH,
according to the equation
so [OH-] = 0.020
2+
Mn(OH)2 Mn + 2 OH
Mn(OH)2 Mn2+ + 2 OHKsp = [Mn2+][OH-]2
Ksp = [Mn2+][OH-]2
= (x)(2x)2 = 4x3
-13
2
1.6
x
10
=
(x)(0.020)
1.6 x 10-13 = 4x3
-10
-3
x
=
4.0
x
10
mol
dm
x = 3.4 x 10-5 mol dm-3
Conclusion: In the presence of a common ion, OH- in this case, the solubility
of the Mn(OH)2 ...........................
decreased in NaOH solution.
Mn(OH)2 (s) Mn2+ (aq) + 2 OH- (aq)
This is in accordance with Le Chatelier's principle. As [OH-] increases, the

left, forming more Mn(OH)2

11.4
Applications of Solubility Product
1.
To Determine the Solubility of Sparingly Soluble Saits
2.
Predicting Precipitation

At a particular temperature, Ksp value indicates the

maximum product of ion concentrations in solution at
equilibrium.
MX (s)
M+ (aq) + X- (aq)
Ionic product, Q = [M+] [X-]

If ionic product Q = Ksp

The system is at equilibrium and the solution is
saturated, formation of precipitate is observed.
If ionic product [M+] [X-] < Ksp

The system is not at equilibrium and the solution is not

saturated (ie. more solid can dissolve until equilibrium
is achieved), so no precipitate formed
If ionic product [M+] [X-] > Ksp

The system is not at equilibrium and the solution is

supersaturated. The concentrations of the ions in
solution are too high and thus the salt will

Example 1: Will a precipitate form when 50 cm3 of 0.050 mol

dm-3 AgNO3 is added to 50 cm3 of 0.10 mol dm-3 KBrO3?
[Ksp AgBrO3 = 6.0 x 10-5 mol2 dm-6]
Mol
[AgNO3] = mol x 1000 / V
AgNO3 = MV / 1000
= (0.050)(50) / 1000
= (2.5 x 10-3)(1000)/(50+50)

= 2.5 x 10-3 mol

= 0.025 mol dm-3

Mol KBrO3 = MV / 1000

[KBrO3] = mol x 1000 / V
-3
=
(0.10)(50)
/
1000
=
(5.0
x
10
)(1000)/(50+50)

= 5.0 x 10-3 mol

= 0.050 mol dm-3
Since AgBrO3 Ag+ + BrO3Q = [Ag+][BrO3-]
= (0.025)(0.050)
= 1.25 x 10-3 mol2 dm-6
Since Q > Ksp ; so precipitate of
AgBrO3 will form.

Example 2: Will a precipitate of BaF2 form if 150 cm3 of

0.050 mol dm-3 of Ba(NO3)2 is mixed with 50 cm3 of 0.0050 mol
dm-3 of KF? [Ksp BaF2 = 1.7 x 10-6 mol3 dm-9]
Mol Ba(NO3)2 = MV / 1000
= (0.050)(150) / 1000
= 7.5 x 10-3 mol
Mol KF
= MV / 1000
= (0.0050)(50)/1000
= 2.5 x 10-4 mol

[Ba(NO3)2] = mol x 1000 / V

= (7.5 x 10-3)(1000)/(150+50)
= 0.0375 mol dm-3
[KF]
= mol x 1000 / V
= (2.5 x 10-4)(1000)/(150+50)
= 0.00125 mol dm-3

Since BaF2 Ba2+ + 2 FQ = [Ba2+][F-]2

= (0.0375)(0.00125)2
= 5.86 x 10-8 mol3 dm-9
Since Q < Ksp ; so no precipitate of
BaF2 will form.

There are limitations of solubility products. For example,

Ksp is not applicable when there is the formation
Insoluble
/ soluble complex salt
of .........................................................
Example 3: PbCl2 in dilute HCI:

PbCI2 (s) Pb2+ (aq) + 2Cl- (aq)

(1)

HCI (aq) H+ (aq) + Cl- (aq)

decrease
In the presence of dilute HCI, solubility of
presence of chloride ion
PbCI2 ....................... due to the ..........................................
left
which shifts the position of equilibrium (1) to ........
When PbCl2 in concentrated HCI:
PbCI2 (s) Pb2+ (aq) + 2CI- (aq)

(2)

Pb2+ (aq) + 4CI- (aq) PbCl42- (aq)

The formation of the

complex ion shifts the position of
right
equilibrium 1 to the ......... Thus PbCI2(s) dissolves readily
in concentrated HCI.

1 When NaOH is added to a 0.10 mol dm-3 magnesium

nitrate solution, at what pH will magnesium hydroxide
begin to precipitate?(Ksp of Mg(OH)2 =1.2 x 10-11 mol3 dm[Mg9)2+] before Mg(OH)2 precipitated = 0.10 mol dm-3.
Mg(OH)2 Mg2+ + 2 OHQ = [Mg2+][OH-]2 = 1.2 x 10-11
Q = 0.10 (x)2 = 1.2 x 10-11
x = [OH-] = 1.1 x 10-5 mol dm-3
pOH = -lg (1.1 x 10-5) = 4.96
pH = 14 4.96
= 9.0
2. The solubility product of lead (II) iodide is 1.4 x 10-8 mol3
dm-9.
2+
a.
the
mass
PbICalculate
(aq)
+ 2ofI- lead(II)
(aq)Ksp iodide
= [Pb2+that
] [I-]2will dissolve in
2 (s) Pb
3 of water.
500Kcm=
(x)(2x)2
1.4 x 10-8 = 4x3
sp
x = 1.5 x10-3 mol dm-3
Mol of PbI2 in 500 cm3 water = (1.5 x 10-3) x 500 /
1000
=
0.00075 mol
Mass = mol x RMM ; Mass = 0.0075 x (207) +

b. When 500 cm3 0.10 mol dm-3 potassium iodide solution is

added to lead(II) iodide, what happens to the solubility of
lead(II) iodide?

Solubility of PbI2 decrease.

c. What is this effect called?
Common ion effect
d. Calculate the mass of PbI2 that will dissolve in 500 cm3
0.10 mol dm-3 potassium iodide solution.
PbI2 (s) Pb2+ (aq) + 2 I- (aq)Ksp = [Pb2+] [I-]2
1.4 x 10-8 = [x] (0.10)2
x = 1.4 x 10-6 mol dm-3
Mol of PbI2 that dissolves in 500 cm3 KI solution
mol = 1.4 x 10-6 x 500 / 1000
mol = 7.0 x 10-7 mol
Mass = (7.0 x 10-7) x [207 + 2(127)]
= 3.2 x 10-4 g

11.5 Systematic Qualitative Analysis

The principles of solubility equilbria can be applied in

many areas of qualitative analysis, for example, in the
precipitation of metal hydroxides.
Hydroxide

Ksp value

Hydroxide

Ksp value

Fe(OH)3

2.0 x 10-39

Co(OH)2

6.3 x 10-15

AI(OH)3

1.0 x 10-33

Mn(OH)2

2.0 x 10-13

Cr(OH)3

1.0 x 10-33

Mg(OH)2

1.1 x 10-11

Zn(OH)2

2.0 x 10-17

Ca(OH)2

5.5 x 10-6

Fe(OH)2

7.9 x 10-16

Ba(OH)2

5.0 x 10-3

The .............................. the Ksp values, the more soluble

the hydroxide is.
In systematic qualitative analysis, the precipitation of the
different hydroxides can be controlled by using either
NaOH (aq) or NH3 (aq) or NH4CI / NH3 (aq).

MOH (s) M+ (aq) + OH- (aq)

Ksp = [M+] [OH-]