CHAPTER 7

IONIC EQUILIBRIA
7.1 Acids and Bases
 Learning Outcomes

(a) Define acids and bases according to the

Arrhenius, Bronsted-Lowry and Lewis
theories.

(b) Define and identify conjugate acid and

conjugate base according to Bronsted-
Lowry theory.
Definition of acids and bases
There are 3 main definitions for acids and
bases
Arrhenius
Brnsted-Lowry
Lewis
 Arrhenius definition
Acid
a substance that dissociates in aqueous
solution to produces hydrogen ion (H+) or
hydronium (H3O+) ion in aqueous solution.

E.g:
(a) HCl(s) + H2O H3O+(aq) + Cl-(aq)

(b) HCl(aq) H+ (aq) + Cl- (aq)

 Arrhenius definition
Base
- a substance that dissociates in aqueous
solution to produce hydroxide ion (OH-).

E.g:
(a) NH3(s) + H2O(l) NH4+(aq) + OH-(aq)

(b) NaOH(aq) Na+(aq) + OH-(aq)

 Arrhenius definition
If
NH3(aq) + HCl(aq) NH4+(aq) + Cl-(aq)

Can we determine the acid or base in this

equation by using the Arrhenius definition ?
NO
Because Arrhenius definition is limited
we will need a new definition to accommodate
this reaction
 Brnsted-Lowry definition
Acid - proton donor
any substance that can donate a proton (H+)
to another substance (it can be a neutral
compound or an ion)

Base - proton acceptor

any substance that can accept a proton (H+)
from another substance (a base can also be a
neutral compound or an ion)

Video 1
 Brnsted-Lowry definition
NH3(aq) + HCl(aq) NH4+(aq) + Cl-(aq)

According to the Brnsted-Lowry definition,

what is the acid in the above equation?
HCl

According to the Brnsted-Lowry definition,

what is the base in the above equation?
NH3
 Brnsted- Lowry definition
Acid - proton donor
E.g:

1. HNO3(aq) + H2O(l) NO3-(aq) + H3O+(aq)

(acid)

2. NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)

(acid)
 Brnsted-Lowry definition
Base - proton acceptor
E.g:

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

(base)

2. CO32-(aq) + H2O(l) HCO3-(aq) + OH-(aq)

(base)
 HCl(aq) + H2O(l) Cl-(aq) + H3O+(aq)
acid base
Lets label the acid and base.
Who donated the proton?
Lets try!

HCl
Is it an acid or base?
Acid
Who accepted the proton?
H2O
Is it an acid or base?
Base
 Now let us look at NH3 and see why it is a
base.

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

base acid
Lets try!

Did NH3 donate or accept a proton?

Accept
Is it an acid or base?
Base
What is water?
Acid
 Lewis definition
Acid is a substance (atom, ion or molecules) that can
accept a pair of electrons to form a coordinate
covalent bond.
..
H+ H:O:H
..
acid water

An acid - an electron pair acceptor

Base is a substance that can donate a pair of
electrons to form a coordinate covalent bond.

..
:O:H -
..
base

A base - an electron pair donor

 E.g
F H F H
F B + N H F B N H

F H F H
acid base

H .. :O: :O:
O: + C
H C ..
O
..
..

H O: O:
.. H
..
acid ..
base
Carbonic
acid
Example :
i. NH3(aq) + H+(aq) NH4+(aq)
(base) (acid)

ii. NH3(aq) + BF3(aq) H3N BF3

(base) (acid)

iii. Cu2+(aq) + 4NH3(aq) [Cu(NH3)4]2+(aq)

(acid) (base)
 Important points
An acid can have a +, -, or neutral charge
Eg. H3O+, H2SO4, and HCO3-

A base can only have a - charge or neutral

Eg. OH-, CN- or NH3
( lone pair )
 CONCLUSION
ACID
Produce H+ or H3O+ when dissociates in
water
H+ donor
Electron acceptor

BASE
Produce OH- when dissociates in water
H+ acceptor
Electron donor
Conjugate Acids and Bases
The acid-base reaction is reversible.

In the Bronsted-Lowry definition acids and

bases come in conjugate acid-base pairs

Conjugate acid-base pair an acid-base pair

related to each other by the gain or loss of one
H+
 The reactants side are acids and bases.

The products side are also an acid and base

called the conjugate acid and base.

Conjugate acid - a species formed when a

base accepts proton.

Conjugate base a species formed when an

acid donates proton.
 Conjugate Acids and Bases
General reaction between acid and base:

HA + B A- + HB+
acid base conjugate conjugate
base acid

Conjugate Acid - what the base becomes, after it

accepts a proton.
Conjugate Base - what the acid becomes, after it
donates its proton.
Conjugate Acid-Base Pair - The acid and base on
the opposite sides of
the equation.
Example:

HCO3-(aq) + H2O(l) CO32-(aq) + H3O+(aq)

acid base conjugate conjugate
base acid

The bicarbonate ion, HCO3- acts as an acid

(transfer a proton), H2O accepts the proton (as a
Bronsted-Lowry base).
The H3O+, can transfer a proton to carbonate
ion, CO32- to form HCO3- and H2O (reversible
reaction).
 According to the reaction above, the HCO3- and
CO32- are related to one another by the loss or
gain of H+ as are H2O and H3O+.

A pair of compounds or ions that differ by the

presence of one H+ unit is called a conjugate
acid-base pair.

So, CO32- conjugate base to the acid HCO3-

HCO3- conjugate acid of the base CO32-
The stronger the acid, the weaker is its conjugate
base
The stronger the base, the weaker its conjugate
acid
 Bronsted-Lowry Acid/Base Examples
Note: Water can act as acid or base

Acid Base C Acid C Base

HCl + H2O H3O+ + Cl-
H2PO4- + H2O H3O+ + HPO42-
NH4+ + H2O H3O+ + NH3

Base Acid C Acid C Base

:NH3 + H2O NH4+ + OH-
PO43- + H2O HPO42- + OH-
 Exercises
What is the conjugate base for
a) H2SO4 b) HNO3

What is the conjugate acid for

a) CO32- b) CN-

Determine the acid, base, conjugate acid,

and conjugate base for the following
chemical equation:
HI + HCO3- I- + H2CO3
 Exercise

1. Based on Arrhenius theory, identify whether

these compounds are base, acid or salt.
i. HI(aq) ii. N2H4(aq) iii. Ca(NO3)2(aq) iv. Ba(OH)2(aq)

2. Write the conjugate base for the following acids :

i. H2SO4(aq) ii. HS-(aq) iii. NH4+(aq) iv. HClO4(aq)
3. Write the conjugate acid for the following bases :
i. NH3(aq) ii. HCO3-(aq) iii. HPO42-(aq) iv. CN-(aq)

4. Identify the conjugate acid-base pairs for the

following reaction:
i. NH2-(aq) + H2O(l) NH3(aq) + OH-(aq)

ii. NH4+(aq) + CN-(aq) NH3(aq) + HCN(aq)

iii. HClO4(aq) + N2H4(aq) N2H5+(aq) + ClO4-(aq)
5. Identify the Lewis acid and Lewis base for the
following compounds :
i. AlCl3(aq)
ii. Br-(aq)
iii. NH3(aq)
iv. Fe3+(aq)
v. H2S(aq)
vi. BCl3(aq)
 Answers :
Based on Arrhenius theory, these compounds
i. acid ii. base iii. salt iv. base

2. The conjugate base is:

i. HSO4-(aq) ii. S2-(aq) iii. NH3 iv. ClO4-

3. The conjugate acid is:

i. NH4+(aq) ii. H2CO3-(aq) iii. H3PO4(aq) iv. HCN(aq)
4. The conjugate acid-base pairs for the
following reaction:

i. NH2-(aq) + H2O(aq) NH3(aq) + OH-(aq)

base acid conjugate conjugate
acid base
ii. NH4+(aq) + CN-(aq) NH3(aq + HCN(aq)
acid base conjugate conjugate
base acid

iii. HClO4(aq) + N2H4(aq) N2H5+(aq) + ClO4-(aq)

acid base conjugate conjugate
acid base
5. Identify the Lewis acid and Lewis base for the
following compounds :
i. AlCl3(aq) -Lewis acid
ii. Br- (aq) -Lewis base
iii. NH3 (aq) -Lewis base
iv. Fe3+ (aq) -Lewis acid
v. H2S(aq) -Lewis base
vi. BCl3(aq) -Lewis acid
 CHAPTER 7
IONIC EQUILIBRIA
7.1 Theory of Acids and Bases

(c) Define strong acids and bases, weak acid and

base

(d) Define pH and pOH.

Relate pH, pOH and ionic product of water, Kw
at 25C.
 The Strengths of Acids and Bases
The strengths of acids and bases can be
compared in terms of
i. the degree of dissociation ()
ii. the dissociation constant (K)
 Degree of dissociation ()
ability of acids or bases to ionize or dissociate
in aqueous solution.

concentration of acid or base dissociated

=
initial concentration of acid or base

concentration of acid or base dissociated

% dissociation = x 100%
initial concentration of acid or base
 7.1: Strong Acid and Strong Base
Strong acid
Dissociate completely in an aqueous solution to
produce high concentration of H3O+.
100% ionisation
or 100% dissociation @ = 1

100%
Example:
ionisation
HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)
100%
ionisation H O+(aq) + NO3-(aq)
HNO (aq) + H O(l)
3 2 3
 Strong base
strong bases dissociate completely in an aqueous
solution to produce high concentration of OH-.
- 100% ionisation
- or 100% dissociated or =1
100%
ionisation
e.g: NaOH(aq) Na+(aq) + OH-(aq)
 Weak Acid and Weak Base
Weak acid
weak acids dissociate only slightly in an aqueous
solution to produce a low concentration of H3O+.
- % dissociation less than 100% or <<1.

e.g:
CH3COOH(ak) + H2O(l) CH3COO-(aq) + H3O+(aq)
 Weak base
weak bases dissociate only slightly in an
aqueous solution to produce a low
concentration of OH-.
- % dissociation less than 100% or <<1.

e.g:
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
Strong Acid Weak Acid
Strong base

Weak base
 Notes:
Strong acid & strong base are strong electrolyte
(=1).
Weak acid & weak base are weak electrolyte (<<1).
Electrolyte substance that can conduct electricity
in the liquid state or aqueous solution.
The pH Scale

pH concept
 The pH Scale

- method of expressing acidity

- The pH of a solution is defined as the negative

logarithm (log) of the hydrogen ion, H+ or H3O+
concentration.

pH = log H3O+
@ pH = - log [H+]

- If [H+] , pH .
pOH is the negative logarithm (log) of the
hydroxide ion ( OH- )concentration

pOH = log OH

If [OH-] , pOH , pH
 In pure water,

H3O+ = OH = 1 x 10-7M

pH = log H3O+

= log (1 x 10-7 )
= 7
Water and The pH Scale

Kw
 The Water Ionization Constant, Kw

Water molecules auto ionizes, transferring a

proton from one water molecule to another
producing a hydroxonium and hydroxide ion.

2H2O(l) H3O+(aq) + OH(aq)

The equilibrium lies far to the left because OH is

a much stronger base than H2O and H3O+ is a
much stronger acid than water.
The equilibrium constant expression

K = H3O+ (aq)OH(aq)
H2O(l) 2

Because concentration of water is a constant,

K H2O 2 = H3O+OH

or
Kw = H3O+ OH-
Kw is the ionization constant for water at 25C

H2O = (1000/18) mole / L = 55.6 M

In pure water,
H3O+ = OH at 25C.
H3O+ = OH
= 10-7 M

Kw = H3O+ OH
= (1 x 10-7) (1 x 10-7)

Kw = 1 x 10-14 M2

Acid & base

Note: The value of Kw increases with temperature
because the dissociation of water is an
endothermic process. For aqueous solution at
25C,

In neutral solution : H3O+ = OH.

= 1 x 10-7M

In acidic solution: H3O+ > OH

or
H3O+ > 1 x 10-7M and OH < 1 x 10-7M

In basic solution: OH > H3O+

or
OH > 1 x 10-7M and H3O+ < 1 x 10-7M
 At 25C
The water ionization constant expression:
Kw = H3O+ OH = 1 x 10-14

Taking the -ve log of both sides of the

expression:

log (Kw) = log ( H3O+OH )

log(1 x 10-14) = ( log (H3O+ )+( log OH )

14 = pH + pOH
 If,
pH < 7 solution is acidic
pH = 7 solution is neutral
pH > 7 solution is basic

pH scale

0 7 14
acidic neutral basic
[H+]>[OH-] [H+]=[OH-] [H+]<[OH-]
 CHAPTER 7
IONIC EQUILIBRIA
7.1 Acids and Bases
 At the end of this lesson, students should
be able to:
(e) Calculate the pH values of a strong acid and
base.

(f) Relate the strength of a weak acid and weak

base to the respective dissociation
constant, Ka and Kb.

(g) Perform calculations involving pH,

dissociation constant, initial concentration
and the degree of dissociation, .
 pH of the Acid and Base Solution

Strong Acid and Strong Base

A strong acid and a strong base is an acid or a

base that is essentially 100 % dissociated in aq.
solution to produce a high concentration of H3O+
or OH

The degree of dissociation, = 1 or 100%

In strong acids and bases, the [H3O+ ] or [OH-] can
be obtained from the original concentration of the
acid or base used. For example:

HCl H+ + Cl
0.5 M 0.5M

NaOH Na+ + OH
0.1 M 0.1M

H2SO4 2H+ + SO42

0.2M 0.4M

assume that the acid is 100% dissociated

 Calculation of pH values

Calculate the concentration of H+ and determine

pH in
i. a solution in which [OH-] is 2.5 x 10-3 M
ii. a solution in which [OH-] is 1.8 x 10-9 M
 Solution : (Method 1)
Kw = [H+] [OH-]
= 1.0 x 10-14 M2

1.0 10-14
1.0 10 -14
[H ] 4.0 10 M
-12

[OH - ] 2.5 10 -3

pH = - log [H+]
= - log (4.0 x 10-12 M)
= 11.4
 Solution : (Method 2)
[OH-] = 2.5 x 10-3 M
pOH = - log [OH-]
= - log (2.5 x 10-3 M)
= 2.6

From equation; pH + pOH = 14

pH = 14 pOH
= 14 2.6
= 11.4

Thus, [H+] = antilog (-pH)

= 4.0 x 10-12 M
 Example
Calculate the pH of the following solutions:

1. An aqueous solution contains 0.700 g NaOH

in 485 mL water

NaOH is a strong base:

NaOH Na+ + OH

No. of moles = 0.700 g NaOH

40 g NaOH

= 0.0175 moles of NaOH

OH = 0.0175 moles of NaOH
485 x 10-3 L
= 0.0361 M

pOH = log OH
= log 0.0361
= 1.442

pH = 14 pOH
= 14 1.442
= 12.558
 2. A solution of 5 x 10-3 M H2SO4

H2SO4 2H+ + SO42 5 x 10-3

2(5 x 10-3)

pH = log H+
= log (1 x 10-2)
= 2

Extension
 Example
Calculate the pH of 0.15 mol dm-3 of HCl solution.

Solution :
HCl(aq) H+(aq) + Cl-(aq)
[ ]initial 0.15 M 0 0
[ ]final 0 0.15 M 0.15 M

pH = - log [H+]
= - log (0.15 M)
= 0.82
 Exercise
1. What is the pH of a 0.040 M solution of HClO4
?
2. What is the pH of 0.05 M NaOH ?
3. An aqueous solution of HNO3 has a pH of 2.34.
What is the concentration of the acid ?

(Ans : 1.40 , 12.7 , 0.0046 )

 Exercise
1. What is the concentration of a solution of
KOH for which the pH is 11.89?
2. What is the pH of a 0.028 M solution of
NaOH?

Answers:
(7.8 x 10-3, 12.45)
 Exercise
1. Calculate pH for the following solutions:
a) 2.0 x 10-3 M HCl d) 0.025 M KOH
b) 5.0 x 10-4 M HNO3 e) 0.02 M H2SO4
c) 5.4 x 10-3 M NaOH f) 0.005 M Mg(OH)2

2. Calculate the H+ and OH concentration in

solutions with pH:
a) 2.50 b) 8.75 c) 11.73

3. What is the NaOH concentration in a solution

with pH = 10.50.

4. How many grams of NaOH is needed to prepare

250 mL solution with pH = 12.40?
 Answer

1.(a) 2.7 (d) 12.4

(b) 6.82 (e) 1.4
(c) 11.73 (f) 12

2. (a) 3.16 10-3, 3.16 10-12

(b)1.78 10-9 , 5.62 10-6
(c)1.86 10-12 , 5.37 10-3

3. 3.16 10-4
4. 0.25 g
 Weak Acid and Weak Base

- only partially ionize in an aqueous solution

- At equilibrium, an aqueous solution of weak

acid or weak base contains a mixture of non-
ionized acid or base molecule and its
conjugate
- to specify the extent of the dissociation of weak
acid or base is by giving its percent
dissociation which is defined as,

% dissociation = mole/L acid or base dissociated

mole/L acid or base available
 WEAK ACID

Amount of H+ dissociated in a solution of 0.10 M

acetic acid is 1.3 x 10-3 M,

percent dissociation = 1.3 x 10-3 x 100

0.1
= 1.3 %

Consider a general weak acid, HA. The

ionization equation in water is

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

 Given,
c = initial concentration
x = concentration of H3O+ ion dissociated

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

Initial conc C 0 0 0
Change -x 0 +x +x
Eq. conc. cx 0 x x
 The ionization expression is given by:

Ka = H3O+ A
HA

- subscript a indicate an eq. constant for a

weak acid in water

- Ka is called an acid-dissociation constant.

Ka = (x)(x)
(cx)
By assuming only a small amount of acid
dissociates, i.e. Ka <<< 1

HA = cx ~ c

Ka = x2
c
x2 = Ka.c

x = Ka . c

= H3O+
 The approximation ( cx ~ c ) is only valid
if the % is equal or less than 5 % @ Ka
10-4
 Example

Calculate the pH of 0.10 M acetic acid solution ,

given Ka for acetic acid is 1.8 x 10-5 M. The
dissociation of acetic acid in water is given by:

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

[]i 0.10 0 0
x +x +x
[]f 0.10x x x
 Ka = H3O+ CH3COO
CH3COOH

1.8 x 10-5 = (x)(x)

(0.10x)

Assuming x is small, 0.1 x 0.1

x2 = 1.8 x 10-5(0.1)
x = 1.34 x 10-3 M = H3O+
To test the approximation,
3
1.34 10
100%
0.10

= 1.34 % ( < 5 % )

pH = - log H3O+
= - log 1.34 x 10-3
= 2.87
 If the degree of dissociation, is given,

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

(aq)
Initial c 0 0
concen.

Change -c +c +c

Eq.
Concen. c(1-) c c
Ka = H3O+ A
HA

= (c)(c)
c(1)

= c2
1
- Assuming is very small, i.e. <<< 1, so 1
~ 1, the equation above becomes:
Ka = c2 or

= Ka / c
 WEAK BASE
B(aq) + H2O(l) BH+(aq) + OH (aq)

Given, c = Initial concentration

x = concentration of OH ion
dissociated

B(aq) + H2O(l) BH+(aq) + OH(aq)

Initial c 0 0
Concent.
Change -x +x +x
Eq.
Concent. c-x x x
Kb = BH+ OH
B

= (x)(x)
(cx)
Assuming, that only a small amount of acid
dissociates, i.e. Kb <<< 1, therefore:

B = cx ~ c

Kb = x2
c

x = Kb.c = OH
If the degree of dissociation, is given, the same
equation can be derived as the weak acid.

B(aq) + H2O(l) BH+(aq) + OH-(aq)

[]i c 0 0
c +c +c
[ ] eq c(1) c c

Kb = BH+OH
B
= (c)(c)
c(1 )
= c 2
1
 Assuming is very small, i.e. <<< 1,
so 1- 1, the equation above becomes,

Kb = c2

= Kb / c
 Example 1 :
Calculate the pH of a 0.20 M solution of HCN. Ka
for HCN is 4.9 x 10-10.
Solution :
HCN(aq) + H2O(l) H3O+(aq) + CN-(aq)
[ ]initial 0.20 M 0 0
[ ]change -x +x +x
[ ]equilibrium 0.20-x x x
 [H3O ] [CN - ]
At equilibrium, K
a
[HCN]
(x) (x)
Ka = = 4.9 x 10-10 M
(0.20 - x)
Assume that the amount of acid dissociated,
x is small compared with the initial concentration of
acid, c; that is c-x c, therefore

x2 = 4.9 x 10-10 M
(0.20)
x2 = (4.9 x 10-10 M) (0.20 M)
x = 9.9 x 10-6 M
Therefore,
[H+] = 9.9 x 10-6 M

pH = -log [H+]

= 5.00
 Example 2 :
The base-dissociation constant for ammonia, NH3(aq)
is 1.8 x 10-5 M. Calculate the concentration of OH-
ion, pH and % dissociation at equilibrium if the
initial concentration of NH3 is 0.15 M.
Solution :
NH3(aq) + H2O(l) NH4+(aq) + OH-
(aq)

[ ]initial 0.15 M 0 0
[ ]change -x +x +x
[ ]equilibrium 0.15-x x x
 [NH ] [OH-]
K
At equilibrium, 4
b [NH ]
3
Kb =
(x) (x) = 1.8 x 10-5 M
(0.15 - x)
Assume that x is too small compared to the initial
concentration of base, c; that is c-x c, therefore

x2 = 1.8 x 10-5 M
(0.15)
x2 = (1.8 x 10-5 M) (0.15 M)

x = 1.64 x 10-3 M
Therefore, [OH-] = 1.64 x 10-3 M
pOH = -log [OH-]
= 2.79

pH + pOH = 14
pH = 14 2.79
= 11. 21
 1.64 x 10-3 x 100
% dissociation =
0.15
= 1.09 %

1.1 %

) = 0.011
Degree of dissociation (
 Exercise :
1. The Ka for formic acid is 1.8 x 10-4. What is the
pH of a 0.010 M solution of formic acid?
( 2.87)
2. Calculate the percentage of HF molecules
ionized in
(a) a 0.10 M HF solution (7.9 %)
(b) a 0.010 M HF solution (23 % )
given the Ka of HF is 6.8 x 10 -4
 Exercise :
1. A 0.20 M solution of weak acid HX is 9.4%
dissociated. Using this information, calculate
H3O+ , X- and HX concentrations at equilibrium.
Determine also pH and Ka for HX acid.
(1.88 x 10-2 M, 0.1812 M, 1.726, 1.95 x 10-3)

2. Calculate the formate ion concentration and pH of

a solution that is 0.050 M in formic acid.(HCHO2 :
Ka = 1.8 x 10-4).
(CHO2 = 3.0 x10-3 , pH = 2.52 )
 Relationship Between Ka and Kb for an
Acid-base Conjugate Pairs

Consider the acid-base conjugate pair of

ammonium ion, NH4+ and ammonia, NH3.
The dissociation of both species in water is
given by,

NH4+(aq) NH3(aq) + H+(aq)

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

 For ammonium ion,
the expression corresponding to Ka is

Ka = NH3 H3O+
NH4+

For ammonia, the expression corresponding to Kb

is:

Kb = NH4+ OH
NH3
 Therefore, the product of Ka x Kb is

NH3 H+ x NH4+ OH = H+ OH = Kw
NH4+ NH3
 product of the acid dissociation constant for an
acid and the base dissociation constant for its
conjugate base is the ion product constant for
water,
Ka x Kb = Kw

log Ka = pKa , log Kb = pKb and log Kw = pKw,

the equation above can be written as,

pKw = pKa + pKb

= 14
Acid-dissociation constant (Ka) and base-dissociation
constant (Kb)
The value of Ka or Kb can be used to distinguish
the relative acidity strength of weak acid and weak
base.

Ka (pKa ) = [H+] , thus pH (more acidic)

Kb (pKb ) = [OH-] , thus pH (more basic)

 Example :

Acid pKa
CH3COOH 4.74
HCOOH 3.76
Relative acidity, HCOOH > CH3COOH

Base pKb
C6H5NH2 9.37
NH3 4.74
Relative basicity, NH3 > C6H5NH2
 CHAPTER 7
IONIC EQUILIBRIA
7.1 Acids and Bases
 At the end of this lesson, students should be able to:
(h) Explain salt hydrolysis using hydrolysis
equations and classify the salts formed from
the reaction between:

i. Strong acid and strong base

ii. Strong acid and weak base
iii. Weak acid and strong base
 Neutralisation reaction

A salt is an ionic compound that is formed by the

reaction of an acid with a base.

The positive ion of the salt is from the base and

its negative ion is from the acid.

introduction
 Given a general equation:

M(OH) + HX M+ X + H2O
base acid salt

(cation came (anion came

from a base) from an acid)
Salts can be classified as a neutral, acidic or
basic in aqueous solution as they undergo a
process called hydrolysis.
 Salt Hydrolysis

Salt hydrolysis is a chemical reaction

between the anion and/or cation from a salt
with water molecules.

The pH of the solution depends on whether

the cation or anion from the salt is
hydrolysed.
 General equation of neutralization :
HX + MOH MX + H 2O
(acid) (base) (salt) (water)
MX salt dissociation equation:
MX M+ + X-
Cation Hydrolysis: M+(aq) + H2O(c) MOH(aq)+ H+(aq)
Anion Hydrolysis : X-(aq) + H2O(c) HX(aq) + OH-(aq)
 There are 2 types of hydrolysis:

i) Partial hydrolysis
Occurs in a salt solution which comes from a
weak acid and a strong base or a strong acid
and a weak base. In these salt solutions, either
the cations or anions from the salt are
hydrolysed.

ii) Complete hydrolysis

Occur in salt solution which comes from a weak
acid and a weak base. Both cations and anions
from the salt will undergo hydrolysis.
 a) Salt of Strong Acid and Strong Base

Both cations and anions from the salt DO NOT

hydrolyse because both ions are conjugates of a
strong base and strong acid.

The pH of the salt solution = 7 at 25C.

 NaCl, which is formed from hydrochloric
acid (a strong acid) and sodium hydroxide
(a strong base). In water NaCl dissociates
completely into Na+ and Cl-.

Example:

NaCl (s) Na+ (aq) + Cl(aq)

Both the Na+ and Cl- ions are not hydrolysed by

water.
There is no production of extra H+ ions or OH-
ions. Hence solution is neutral.
 b) Salt of Strong Acid and Weak Base
NH4Cl ,which is formed from hydrochloric acid (a
strong acid) and ammonia (a weak base)

EXAMPLE

NH3(aq) + HCl (aq) NH4Cl(aq)

NH4Cl(s) NH4+(aq) + Cl(aq)
 The NH4+ , acts as Bronsted-Lowry acid and
donates a proton to water. On the other hand Cl-
ion does not react with water.

NH4+(aq) + H2O (l) NH3(aq) + H3O+(aq)

Cl-(aq) + H2O (l) HCl (aq) + OH-

this reaction does not take place
known as cationic hydrolysis

Cation from the salt will undergo hydrolysis to

give an acidic solution.
 (c) Salt from a Weak Acid and Strong
Base
1. An example is Na2CO3, which is formed from
carbonic acid (a weak acid) and sodium
hydroxide NaOH (a strong base).

2. Sodium carbonate dissociates completely

into sodium ions and carbonate ions.

Na2CO3 CO32-(aq) + 2Na+(aq)

3. Carbonate ion acts as Bronsted-Lowry base by
accepting a proton from water:
CO32-(aq) + H2O(l) HCO3-(aq) + OH-(aq)

Na+(aq) + H2O(l) NaOH(aq) + H+

this reaction does not take place
known as anionic hydrolysis.

4. Na+ ion does not react with water, because the

NaOH
formed, dissociate completely to Na+ and OH-.
The production of OH- from the hydrolysis of
CO32- ions causes the solution to be basic.
 Example

In these case, the anions which come from a weak

acid will hydrolyse to give a basic solution.

CH3COONa(s) CH3COO(aq) + Na+-(aq)

CH3COO(aq) + H2O(l) CH3COOH(aq) + OH(aq)

Strong acid + strong base neutral salts
Do not hydrolysis

Strong acid + weak base acidic salts

Partial hydrolysis
cation hydrolyzes as an acid.

Weak acid + strong base basic salts

Partial hydrolysis
anion hydrolyzes as a base.
 CHAPTER 7
IONIC EQUILIBRIA
7.1 Acids and Bases
At the end of this lesson, students
should be able to:
(i) Define buffer solution.

(j) Decribe qualitatively how a buffer solution

controls its pH.
At the end of this lesson, students
should be able to:
(k) Derive the Henderson-Hasselbalch
equation.

pH = pKa + log conjugate base

weak acid
pOH = pKb + log conjugate acid
weak base
(l) Calculate the pH of buffer solution.
 Buffer Solution
a solution which has the ability to maintain its pH
when a small amount of strong acid or base is
added to the solution

introduction
 A buffer solution has two requirements,

i) it should have the capacity to control

pH after the addition of a small amount
of strong acid or strong base.

ii) it should control the pH at the desired

value
Two types of buffer solution

a) Acidic Buffer Solution

- Prepared by adding a weak acid to a salt which

contains its conjugate base in some
appropriate amount of water
Example:

CH3COOH and CH3COONa

The reaction which occurs in the buffer solution

CH3COOH(aq) CH3COO(aq) + H+(aq)

CH3COONa (s) CH3COO(aq) + Na+(aq)

The amount of CH3COO- is mainly from the

complete dissociation of CH3COONa because
CH3COOH is a weak acid
Addition of a small amount of strong acid

CH3COO(aq) + H3O+(aq) CH3COOH(aq) + H2O(l)

If a strong base is added to the buffer solution, the

OH- ion will be neutralized by CH3COOH

CH3COOH(aq) + OH(aq) CH3COO(aq)+ H2O(l)

so, the pH of the buffer solution can be maintained

to an appreciable amount
 acid (H+) base (OH-)

H+(added) + CH3COO- OH-(added) + CH3COOH

CH3COO-
CH3COOH CH3COOH CH3COO- + H2O
CH3COO-
CH COOH
CH3COO- 3

CH3COOH (aq) CH3COO- (aq) + H+ (aq)

CH3COONa (aq) CH3COO- (aq) + Na+ (aq)
A buffer system contains ethanoic acid,CH3COOH
and ethanoat ion, CH3COO- from CH3COONa
Calculate the pH of the buffer solution by using
CH3COOH/CH3COONa pair

CH3COOH(aq) CH3COO(aq) + H+(aq)

CH3COONa (s) CH3COO(aq) + Na+(aq)

Ka = CH3COOH3O+
CH3COOH

H3O+ = CH3COOH x Ka
CH3COO

H3O+ = [Link] x Ka
conjugate base
Taking -log at both sides of the equation

- log H3O+ = (- log Ka-log

) [Link]
conjugate base

pH = pKa + log conjugate base

[Link]
 Example:

Calculate the pH of a solution prepared by adding

2.00 g of benzoic acid, C6H5COOH & 2.00 g sodium
benzoate, C6H5COONa in enough water to make
1.00 L solution

(Ka (C6H5COOH) = 6.3 x 10-5 M)

No of moles of C6H5COOH = 2.00/122.1

= 1.64 x 10-2 moles

No of moles of C6H5COONa = 2.00 / 144

= 1.39 x 10-2 moles
C6H5COOH = 1.64 x 10-2 / 1.00
= 1.64 x 10-2 M

C6H5COONa = 1.39 x 10-2 / 1.00

= 1.39 x 10-2 M

pH = pKa + log conjugate base

[Link]

pH = - log 6.3 x 10-5 + log 1.39 x 10-2

1.64 x 10-2

= 4.13
 Example

A buffer solution is prepared by dissolving

0.025 mol CH3COONa in 250 cm3 aqueous
solution of CH3COOH(0.10 mol dm-3).Calculate
the pH of

a)The buffer solution

b)The buffer solution after the addition of 1.0 cm3
H2SO4(0.1 M)
c) The buffer solution after the addition of 1.0 cm3
NaOH(0.1 M)
[Ka CH3COOH = 1.74 x 10-5 moldm-3 ]
 Solution

a) [CH3COOH] = 0.1 mol dm-3 = 0.025 mol

[CH3COO-] = 0.025 mol = 0.10 mol dm-3
0.250

pH = pKa + log [CH3COO-]

[CH3COOH]

= -log (1.74 x 10-5) + log (0.10/0.10)

= 4.76
 b) After adding 1.0 cm3 H2SO4 (0.1 M)

Moles of H2SO4 = MV/1000

= 0.1 x 1 =1.0 x 10-4 mol
1000
In 1 mol of H2SO4,contain 2 mol H+

Mol of acid added = 2( 1x 10-4)

= 2x 10-4

Moles of acid = 0.025 + 2.0 x 10-4

= 0.0252 mol

Moles of base conjugate = 0.025 2x 10-4

= 0.0248 mol
 pH = pKa + log [CH3COO-]
[CH3COOH]

= - log (1.74 x 10-5) + log (0.0248/251 x 10-3)

(0.0252/251x 10-3)
= 4.76 6.95 x 10-3

= 4.75
c) Moles of NaOH added = 0.1 x 1.0 = 1.0 x 10-4 mol
1000

Moles of CH3COO- = 0.025 + 1x 10-4 mol = 0.0251

Moles of CH3COOH = 0.025 - 1x 10-4 mol = 0.0249

pH = -log Ka + log [ CH3COO-]

[CH3COOH]

= -log 1.74 x 10-4 + log ( 0.0251/0.251)

(0.0249/0.251)

= 4.76
 b) Basic Buffer Solution

- Prepared by adding a weak base with its

conjugate acid salt

Example

NH3 and NH4Cl

The reaction, occurring in the buffer solution are

partial dissociation of weak base

NH4Cl NH4+ + Cl-

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

According to Le Chatelier`s Principle, the

presence of a large amount of NH4+ reduces
the dissociation of NH3.

the species present in large amount is

the undissociated NH3 and the NH4+ ion
which come from the complete
dissociation of NH4Cl
 Addition of a small amount of strong acid

H+ (aq) + NH3(aq) NH4+(aq)

Addition a small amount of strong base

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

There will only be a slight change of pH even

when a strong acid or strong base is added to
the solution
Calculating pH of the basic buffer solution

Kb = NH4+ OH
NH3

OH = NH3 x Kb
NH4+
Taking the log of both sides of the equation

logOH = ( - log Kb ) log NH3

NH4+

pOH = pKb + log NH4+

NH3

pOH = pKb + log conjugate acid

[Link]

pH = 14 pOH
 Example:
Calculate the pH of the solution prepared by mixing
500 mL 0.1 M hydrazinium chloride,N2H5Cl with 500
mL 0.2 M hydrazine, N2H4. (Kb = 1.7 x 10-7)

Solution:

No. of moles of N2H5Cl = 500 x 0.1

1000
= 0.05 moles

N2H5Cl = 0.05
(0. 50 + 0.50)
= 0.05 M
No of moles of N2H4 = 500 x 0.2
1000

= 0.1 moles

N2H4 = 0.1
(0.50 + 0.50)

= 0.1 M
 Using the equation,

pOH = pKb + log N2H5Cl

N2H4

pOH = log (1.7 x 10-7 ) + log 0.05

0.1
= 6.469

pH = 14 - pOH
= 14 - 6.469
= 7.531
 Example
A buffer solution is prepared by mixing 400 mL
of 1.50 M NH4Cl solution with 600 mL of 0.10 M
NH3.
i. Calculate the pH of a the buffer solution.
ii. Calculate the pH of the buffer solution after the
addition of
(a) 0.15 M NaOH (b) 0.011 M H
(Assume that the volume of the solution does
not change when HCl and NaOH is added)
Kb for NH3 = 1.8 x 10-5 M
 Solution
i. V = 400 ml + 600 ml
= 1000 ml
=1L

MV 1.50 x 400
mol NH4Cl = 1000 = 1000 = 0.6 mol

mol NH3 = MV = 0.10 x 600 = 0.06 mol

1000 1000

[NH4Cl] = 0.6 mol = 0.6 M

1L
 [conjugate acid]
pOH = pKb + log [weak base]
[NH4 ]
@ pOH = pKb + log
[NH3 ]

= -log(1.8 x10-5)+ log (0.6)

(0.06)
= 5.74

pH = 14 5.74 = 8.26
 ii. (a) pH when 0.15 M NaOH is added
Buffer action :
NH4+(aq) + OH-(aq) NH3(aq) + H2O(l)
[ ]initial 0.60 M 0.15 M 0.06 M
[ ]change -0.15 M -0.15 M +0.15 M
[ ]final 0.45 M 0 0.21 M
[conjugate acid]
pOH = pKb + log [weak base]
-5 (0.45)
= -log(1.8 x 10 )+ log (0.21)

= 5.08

pH = 14 5.08
= 8.92
 ii.(b) pH when 0.011 M HCl is added
Buffer action : NH3(aq) + H+(aq) NH4+(aq)
[ ]initial 0.06 M 0.011 M 0.6 M
[ ]change -0.011 M -0.011 M +0.011 M
[ ]final 0.049 M 0 0.611 M

[conjugate acid]
pOH = pKb + log [weak base]

= -log(1.8 x 10-5)+ log (0.611)

(0.049)
= 5.84

pH = 14 5.84
= 8.16
 Exercise :
1. How many moles of NH4Cl must be added to 2.0 L
of 0.10 M NH4 to form a buffer whose pH is 9.00 ? (
Assume that the addition of NH4Cl does not change
the volume of the solution ) Kb = 1.8 x 10-5 (0.36
mol)
2. Calculate the concentration of sodium benzoate
that must be present in a 0.20 M solution of benzoic
acid ( C6H5CO2H) to produce a pH of 4.00.
(0.13 M)
3. Calculate the pH of a buffer composed of 0.12 M
benzoic acid and 0.20 M sodium benzoate. Ka = 6.3
x 10-5. ( 4.43 )
4. What is the pH of a buffer that is 0.12 M in lactic
acid ( HC3H5O3) and 0.10 M in sodium lactate?
Ka =1.4 x 10-4 (3.77)
 Exercise

A solution is prepared by mixing 100 cm3 aqueous

NH3 (0.1 moldm-3) with 100 cm3 NH4Cl (1.0 mol
dm-3). Calculate the pH of the solution before and
after the addition of 1 cm3 HCl(0.1 mol dm-3).

Kb(NH3) = 1.74 x 10-5 mol dm-3

Answer.
a)8.24
b)8.235
 Exercise
Calculate the pH of a buffer solution consisting
of 0.10 M CH3COOH and 0.25 M CH3COONa.
( Ka for CH3COOH = 1.8 10-5 mol dm-3 )
Calculate the pH when
i ) 10 cm3 of 1.0 M HCl
ii ) 10 cm3 of 1.0 M NaOH
is added to 1.0 dm3 of the buffer solution above.
pH = 5.14
pH = 5.08
pH = 5.20
7.2 ACID-BASE
TITRATIONS
 At the end of this lesson, students
should be able to:
(a) Describe the titration process and
distinguish the end point and
equivalence point.
 ACID-BASE TITRATIONS

Titration is a procedure for

determining the concentration of a
solution using another solution of
known concentration, called
standard solution.
Titration apparatus

titrant

analyte
 Titrant is the solution added from the burette.
The equivalent point is the point at which the
amount of acid and base present exactly
neutralizes one another.
For reactions that have the same stoichiometric
value of acid and base the number of moles of
OH- ions and number of moles of H+ ions are
equal.
E.g: HCl + NaOH NaCl + H2O
(1 mol of acid react with 1 mol of base)
 Indicator is a substance that is generally
added to the solution in the receiving vessel an
which undergoes some sort of colour change
when reaction is over.
The end point of titration is the point when the
indicator changes colour.
 Titration Endpoint

before endpoint endpoint past endpoint

7.2 ACID-BASE
TITRATIONS
 At the end of this lesson students should be
able to:

(b) Sketch and interpret the variation pH

against titre value for titration between :
i. strong acid- strong base
ii. strong acid-weak base
iii. weak acid-strong base
 Strong acid
+
Weak base

Types
Strong acid Weak acid
of
+ +
Strong base Titration Strong base

Weak acid
+
Weak base
 Acid-Base Titration
Titrations involving only strong acids or bases
are straightforward (equivalence pH = 7) .
Titrations involving weak acids or bases are
complicated by hydrolysis of salt formed.
Weak AcidStrong Base pH at equivalence
point will always be >7
Strong AcidWeak Base pH at equivalence
point will always be <7
The Acid-Base Titration Curve
Titrant is a standardized solution with known
concentration added from the burette

Titration curve a graph of pH versus volume

of titrant
- The titration curve serves to profile the
unknown solution

Volumetric stoichiometric calculations where

an amount is calculated using volumes of
substances
 1. STRONG ACID-STRONG BASE
TITRATION

NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq)

The net ionic equation,

H20 H+ (aq) + OH- (aq)
0.10 M NaOH added to 25 mL of 0.10 M HCl
Graph Of pH Vs Volume Graph Of pH Vs Volume
Of Base Of Acid

Video 1
Curve for a strong acid-strong base
titration
 Suitable
indicators for
strong acid-
strong base
titration

Video 2
 2. WEAK ACID-STRONG BASE
TITRATIONS
Neutralization reaction between acetic acid ( weak acid )
and sodium hydroxide (strong base )
CH3COOH(aq) + NaOH(aq) CH3COONa (aq) + H2O(l)

Dissociation of salt:
CH3COONa CH3COO-(aq)+ Na+(aq)

The acetate ion undergoes hydrolysis as follow:

CH3COO- (aq) + H2O (l) CH3COOH (aq) + OH- (aq)

At the equivalence point, only sodium acetate present,

the pH will greater than 7 as a result of the excess OH-
ions formed.
Suitable indicator:
bromophenol blue

Video 4
 Titration of 40.00mL of 0.1000M HF
with 0.1000M NaOH

Curve for a
weak acid-
strong
base
titration
pH = 8.80 at
equivalence point
pKa of HF (hydrolysis of F-)
= 4.89
methyl red
[HF] = [F-]
 3. Strong Acid-Weak Base
Titrations
Titration of HCl, a strong acid with NH3, a weak
base
HCl (aq) + NH3 (aq) NH4Cl (aq)

Dissociation of salt
NH4Cl (aq) NH4+(aq) + Cl-(aq)

At equivalence point (pH < 7):

NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq)

Video 5
pH profile and titration curve of a strong
acid-weak base titration
 Titration of 40.00mL of 0.1000M
NH3 with 0.1000M HCl

pKa of NH4+
= 9.25

Suitable
indicators :
litmus and
methyl red pH = 5.27 at
equivalence
point (hydrolisis
of NH4+)
The Titration
Curve
 The Titration Curve
Types of End Point Equivalence
Titrations (pH Range) Point
Strong Acid
-Strong Base 3 10 7

Weak Acid
-Strong Base 7 11 >7

Strong Acid
-weak Base 37 <7
7.2 ACID-BASE
TITRATIONS
At the end of this lesson students should
be able to:

(c) Identify suitable indicators for acid-

base titrations.
 ACID-BASE INDICATORS
In acid-base titrations, indicators are
substances that have distinctly different
colors in acidic and basic media
An indicator is usually a weak organic
acid or base that has distinctly different
colors in its non-ionized and ionized forms
The end point of a titration occurs when
the indicator changes color.
Video 1
 Not all indicators change color at the same pH
The choice of indicator for a particular titration
depends on the nature of the acid and base
used in titration
By choosing the proper indicator for a titration,
we can use the end point to determine the
equivalence point
There are two types of indicators in acid
base titrations :

a) Weak Acids as Indicator

b) Weak Base as Indicator
 Weak Acids as Indicator

HIn (aq) H+ (aq) + In- (aq)

Colour A Colour B

High concentration of H+ - HIn in non-ionized form

- High intensity of colour A

Low concentration of H+ - HIn in ionized form

- High intensity of colour B

Video 2
Weak Base as Indicator

In solution, the base ionizes to a small extent :

InOH(aq) In+(aq) + OH(aq)

Colour X Colour Y

[H+] is high
- colour of conjugate base (In+) predominates

[OH] is high
- colour of base (InOH) predominates.
 Choosing The Suitable Indicator

Choose an indicator which the end point pH

range lies on the steep part of the titration
curve.

This choice ensures that the pH at the

equivalent point will fall within the range over
which the indicator changes colour.
 Suitable
indicators for
strong acid-
strong base
titration are :
litmus
(red blue),
methyl red
(red yellow ),
phenophthalein,
bromothymol blue
 Some Common Acid-Base Indicators
color
INDICATOR acidic basic pH range
Thymol blue Red Yellow 1.2-2.8
Bromophenol blue Yellow Purple 3.0-4.6
Methyl orange Orange Yellow 3.1-4.4
Methyl red Red Yellow 4.2-6.3
Chlorophenol blue Yellow Red 4.8-6.4
Bromothymol blue Yellow Blue 6.0-7.6
Cresol red Yellow Red 7.2-8.8
Phenolphthalein Colorless Pink 8.3-10.0

The pH range is defined as the range over which the

indicator changes from the acid color to the base color
 The pH
range(end point)
is defined as the
range over
which the
indicator
changes from
the acid color to
the base color
 Exercise :
1. What is the colour of the solution when 3 drops of the
below indicators are added separately to water (pH = 7) ?

Indicator pH range colour change

Phenolphthalein 8.2 10.0 Colourless reddish pink
Methyl orange 3.2 4.2 Red Yellow
Bromothymol
6.0 7.6 Yellow Blue
blue
phenol red 6.8 8.4 Yellow red
 Exercise :
2. The pH range and the colour change for 3 indicator X, Y
and Z is shown in the table below :
Indicator pH range colour change
X 1.2 2.8 Red Yellow
Y 6.0 7.6 Yellow Blue
8.3
Z Colourless Yellow
10.5
What is the colour of the solution when a few drops of
the above indicators are added separately to a buffer
solution whose pH is 6.52 ?
X Y Z
A Orange Green Blue
B Orange Yellow Light blue
C Yellow Green Colourless
D Yellow Orange Colourless
E Yellow Yellow Colourless
 Which indicator(s) would you use for a titration of
HNO2 with KOH ?
Weak acid titrated with strong base.
At equivalence point, will have conjugate base of weak acid.
At equivalence point, pH > 7
Use cresol red or phenolphthalein
 CONCLUSION
Choosing The Suitable Indicator
Choose an indicator which the end point pH range lies on the
steep part of the titration curve.
This choice ensures that the pH at the equivalent point will fall
within the range over which indicator changes colour (Table 6.2)
pH Ranges for Indicator
Types of Titrations End Point pH Range Suitable Indicators
Strong Acid-Strong Base 3 10 Any Indicator
Weak Acid-Strong Base 7 11 Phenolphthalein,
thymol blue
Strong Acid-weak Base 37 Methyl orange, methyl
red
Weak Acid-Weak Base - -
7.3 Solubility equilibria
Learning outcomes:

(a) Define solubility, molar solubility and

solubility product, Ksp.

(b) Calculate Ksp from concentration of

ions and vise versa.
 Solubility
What is the meaning of solubility, s ?
i. The ability of substance to dissolve in a
solvent.
ii. Quantity that dissolves to form a saturated
solution.
s g per 100 mL or g /L
Unit : g mol mol Molarity
Mr L

The greater the solubility, the smaller the

amount of precipitation.
 When a Substance
Dissolve
A slightly soluble salt forms a saturated
solution at room temperature.
In a saturated solution an equilibrium exists
between the solid salt and its dissolved ions.
Example : BaSO4 (s) Ba2+ + SO42- (aq)

13_07

Picture of
BaSO4
dissolving
 Saturated and Unsaturated

A saturated solution contains the maximum

amount of solute that can dissolve.
Undissolved solute remains.

An unsaturated solution does not contain all

the solute that could dissolve
 Each of salt/ionic compound which is slightly
soluble have their own Ksp ( the equilibrium
constant for the equilibrium between an ionic
solid and its saturated solution ).

Solubility the mass of solute that dissolves in

a given quantity of solvent to form a saturated
solution (g L-1 or kg cm-3 or g cm-3).

Molar Solubility the number of moles of a

solute in 1 L of a saturated solution ( mol L-1 ).
 The solubility Product Constant, Ksp

In a saturated solution an equilibrium exists

between the solid salt and its dissolved ions.
For example, the equilibrium :
AgCl (s) Ag+ (aq) + Cl- (aq)

Kc = [ Ag+ ] [Cl- ]
AgCl
The concentration of the solid is constant
and therefore be included with the constant
Kc so that :

Kc [ AgCl] = [Ag+] [ Cl-]

Ksp = [Ag+] [ Cl-]

Ksp = solubility product constant.

 Solubility Product, Ksp

Solubility Product: is the product of the

molar concentrations of the ions involved in
the equilibrium, each raised to the power of
its stoichiometric coefficient in the
equilibrium equation.

MX2(s) M2+(aq) + 2 X(aq)

Ksp = [M2+][X]2
 Example:
Write the expression for the solubility product
of silver chromate, Ag2CrO4

Solution:
First write the balance equation for the
solubility equilibrium,
Ag2CrO4(s) 2Ag+(aq) + CrO42-(aq)

The exponents in the equilibrium constant

expression for Ksp are the coefficient in the
balanced equation. Therefore,
Ksp = [ Ag+ ]2 [ CrO42- ]
 Other example of, Ksp :

MgF2(s) Mg 2+ (aq) + 2F- (aq)

Ksp = [Mg2+] [F-]2

Ag2CO3(s) 2Ag+(aq) + CO32-(aq)

Ksp = [Ag+]2 [CO32-]

Ca3(PO4)2(s) 3Ca2+(aq) + 2PO43-(aq)

Ksp = [Ca2+]3 [PO43-]2
 Exercise :
Write the expression for solubility product, Ksp
and state its unit for the following salt :
1. Mg3(PO4)2 (s) 3Mg2+ (aq) + 2PO43- (aq)

2. Ag2S (s) 2Ag+ (aq) + S2- (aq)

3. ZnCl2 (s) Zn2+ (aq) + 2Cl- (aq)

4. Ag2SO4 (s) 2Ag+ (aq) + SO42- (aq)

5. Fe(OH)3 (s) Fe3+ (aq) + 3OH- (aq)

 Solubility Product
constant (Ksp) of Selected
Ionic Compounds

What do Ksp
values tell us..?
The smaller the
Ksp, the less
soluble the salt!
 Calculating Solubility Product, Ksp
Example 1 :

The solubility of PbI2 is 1.2 x 10-3 mol dm-3.

Calculate its solubility product.
Solution :
assume that solubility = s

PbI2 (s) Pb2+ (aq) + 2I- (aq)

s 2s
Ksp = [Pb2+] [I-]2
given x = 1.2 x 10-3 M
Ksp = (s) (2s)2
= (1.2 x 10-3) (2 x 1.2 x 10-3)2
= 6.91 x 10-9 M3
 Example 2 :
The solubility product, Ksp of CaCO3 at 25oC is 2.8
x 10-9 M2. Calculate the solubility of CaCO3 in g
dm-3 at this temperature.
Solution :
Equilibrium equation :
CaCO3 (s) Ca2+ (aq) + CO32- (aq)
s s

Assume the solubility = x

Ksp = [Ca2+] [CO32-]
= (s) (s)
1.8 x 10-9 = s2
 2.8 x 10-9 s=

s = 5.29 x 10-5

Molar solubility = 5.29 x 10-5 mol dm-3

Molar mass of CaCO3 = 100 g mol-1

Solubility in g dm-3 = (5.29 x 10-5)(100 g mol-1)

= 5.29 x 10-3 g dm-3

 Problem solving 1

Given: AgBr(s) Ag+ + Br

In a saturated solution @ 25oC,

the solubility of [Ag+] = [Br- ]= 5.7 x 107 M.
Determine the Ksp value.

K sp Ag Br
5.7 x 10 3.3 x 10
-7 2 -13
 Problem solving 2
The solubility of Ag2CO3 is 1.26 x 10-4 at 25oC.
Calculate the Ksp for silver carbonate.
Ag2CO3(s) 2 Ag+ + CO32-
Initial 0 0 s use s
Change +2s +s to indicate
Equil 2s s solubility

Ksp = [Ag+]2[CO32-] = (2s)2(s) = 4s3

Ksp = (4)(1.26 x 10-4)3 = 8.00 x 10-12

 Problem solving 3
A saturated solution of silver chromate was
to found contain 0.022 g/L of Ag2CrO4. Find
Ksp

Ag2CrO4 (s) 2Ag+ (aq) + CrO42 (aq)

Ksp = [Ag+]2[CrO42]

So we must find the

concentrations of each
ion and then solve
for Ksp
Ag2CrO4 (s) 2Ag+ + CrO42
Ksp = [Ag+]2[CrO42]

Ag+: 0.022 g Ag2CrO4 X mol

L 332g

mol Ag
1.33 x 104
L
 CrO4 2: 0.022g Ag2CrO4 X mol
L 332 g
2-
mol CrO
6.63 x 105 4
L

K sp 1.33 x 10 6.63 x 10 1.16 x 10
-4 2 -5 -12
 Problem solving 4
Problems working from Ksp values.
Given: Ksp for MgF2 is 6.4 x 109 @ 25 oC
Find: solubility in mol/L and in g/L
MgF2(s) Mg2+ + 2F
s 2s

Ksp = [Mg2+][F]2
Ksp = [s][2s]2 = 4s3
6.4 x 109 = 4s3
s = 1.2 x 10-3 mol L-1
 Problem solving 4(cont.)
Ksp= [x][2x]2 = 4s3
6.4 x 109 = 4s3

-9
1.2 x 10-3 Mg2 MgF2
6.4 x 10
s3
4
-3
now for g/L :
1.2 x 10 mol MgF2 62.3 g
L mol
g MgF2
7.3 x 102
L
 Exercises:
The solubility of calcium sulfate (CaSO4) is found
experimentally to be 0.67 g/L. Calculate the value
of Ksp for calcium sulfate.
2.42 x 10-5 (mol L-1)2
The solubility of lead chromate (PbCrO4) is
4.5 x 105 g/L. Calculate the solubility product of
this compound. 1.94 x 10-14 (mol L-1)2

Calculate the solubility of copper(II) hydroxide,

Fe(OH)2, in g/L.
(Ksp Fe(OH)2 = 4.1 x 10-15) 1.01 x 10-5 mol L-1
 (a) Steps of calculating Ksp from
solubility data

Solubility of compound

Molar solubility of compound

Concentrations of cations and anions

Ksp of compound
 (b) Steps of calculating solubility
from Ksp data

Ksp of compound

Concentrations of cations and anions

Molar solubility of compound

Solubility of compound
 NOTE : s use s to indicate solubility.
Solubility is per mole of salt, not the molarity of
each dissolved ion!
Two ions per formula : s2
Three ions per formula : (2s)2s = 4s3
7.3 Solubility equilibria
 Learning outcomes

At the end of this lesson, students should be able

to:
(c) Predict the possibility of precipitation of
slightly soluble ionic compounds the values of
ion-product, Q to Ksp.
Solubility and Ksp
 Predicting Precipitation
A mixture of two solutions will produce a
precipitation or not depending on the ion product,
Q present.
The solubility equilibrium equation for a slightly
soluble salt, MA :
MA (s) M+ (aq) + A- (aq)
Ksp = [M+] [A-]
If we mix a solution containing M+ ions with
one containing A- ions, the ion product, Q is
given by :
Q = [M+] [A-]
Q has the same form as Ksp but the
concentrations of ions are not equilibrium
concentrations.
 i. Q = Ksp
- the solution is saturated
- equilibrium exist between undissolved
solid salt and its dissolved ions

ii. Q < Ksp

- the solution is unsaturated
- no precipitation of MA
- more salt should be dissolved to
increase the ion concentrations until Q = Ksp

iii. Q > Ksp

- the solution is supersaturated
- MA(s) will precipitate out until the product of
the ionic concentrations is equal to Ksp.
Unsaturated Q < Ksp No precipitate will form
Saturated Q = Ksp No precipitate will form
Supersaturated Q > Ksp Precipitate will occur
 Reaction Quotient (Q):
will a precipitation occur?
Use ion product,Q and compare to Ksp

Q < Ksp reaction proceeds from right to left

Q = Ksp Equilibrium
Q > Ksp reaction proceeds from left to right
 Example 1 :

If 500 mL of 0.014 M CaCl2 is added to 250 mL

of 0.25 M Na2SO4, will a CaSO4 precipitate
form ? ( Ksp for CaSO4 = 2.0 x 10-4 M2)
 Solution :
500 x 10 3
[Ca2+] = 0.014 x = 0.0093 M
750 x 103
2- 250 x 103
[SO4 ] = 0.25 x = 0.083 M
750 x 103

Solubility equilibrium for CaSO4 :

CaSO4 (s) Ca2+ (aq) + SO42- (aq)

Ksp = [Ca2+] [SO42-]

= 2.0 x 10-14 M2
 the ion product,
Q = [Ca2+] [SO42-]
= (0.0093) (0.083)
= 7.72 x 10-4 mol2 dm-6

Q > Ksp(2.0 x 10-4 M2)

Thus, the solution is supersaturated, some

CaSO4 will precipitate.
 Example 2:
50 mL 0.001M NaOH is added to 150 mL 0.01M
MgCl2. Will a precipitate form ?
[Ksp Mg(OH)2 = 2 x 10 11]
Mg(OH)2 (s) Mg2+ (aq) + 2OH (aq)

The total volume after combining the two

solutions is 200mL.
[Mg2+] = 0.01 x 150 7.5 x 10 3 M
200

[OH] = 0.001 x 50 2.5 x 10 4 M

200
 Compare Q and Ksp , [Ksp Mg(OH)2 = 2 x 1011]
Q = [Mg 2+][OH]2
= (7.5 x 10-3) (2.5 x 10-4)2 = 4.69 x 10-10

Therefore:
Q > Ksp

The solution is supersaturated because the

value of Q indicates that the concentrations of
the ions are too large. Thus some of the
Mg(OH)2 will precipitate out of the solution until
the ion product
[Mg2+][OH]2 = 2 x 1011
 Example 3

A solution is 1.5 x 106 M in Ni2+. Na2CO3 is

added to make the solution 6.0 x 104 M in
CO32. Ksp(NiCO3) = 6.6 x 109. Will NiCO3
precipitate?
 We must compare Q to Ksp.
NiCO3 (s) Ni2+ (aq) + CO32 (aq)
Ksp = [Ni2+][CO32]
Q = [Ni2+][CO32]

Q = [1.5 x 106][6.0 x 104] = 9.0 x 1010

Q < Ksp no precipitation
 Exercise :
1. Will a PbSO4 precipitate form when 100 cm3 of
0.003 M Pb(NO3)2 is added to 400 cm3 of 0.04 M
Na2SO4 ? (Ksp for PbSO4 = 1.5 x 10-8 mol2 dm-6)

2. Determine whether a precipitate will formed

when 100 mL of 1.00 x 10-3 M MgCl2 is added to
400 mL of 1.50 x 10-3 M NaOH ? ( Ksp for
Mg(OH)2 = 1.2 x 10-11 mol3 dm-9)
3. (a) The solubility of Ag2SO4 in water at 25OC is
0.506 g for each 100 mL solution. Calculate the
solubility product at this temperature.

(b) If a solution of Na2SO4 is added dropwise to

a 0.01 M Ag2SO4 solution, what is the minimum
concentration of SO42- is necessary to begin
precepitate ?
7.3 Solubility equilibria
 Learning outcomes

At the end of this lesson, students should be able

to:

(d) Define and explain the common ion effect.

(e) Perform calculations related to common ion

effect.
 Common Ion Effect
Common ion an ion that is common to two or
more components in a mixture of a solution of
ions.

Common ion effect the reduction in the

solubility of salt in the presence of a common ion.
 The Common Ion Effect And Solubility
The common ion effect is the reduction in the
solubility in the presence of common ions.

If a soluble chloride salt such as NaCl is

added to this AgCl solution in pure water,

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

NaCl Na+ (aq) + Cl-(aq)

The chloride ion concentration will increase

and shift this equation to the left, thereby
causing some AgCl to precipitate.
 Ag+ , I-
13_07 13_07
Ag+ , I-

Add I-
via NaI
AgI(s) AgI(s)
13_07

AgI(s) Ag+(aq) + I-(aq) Ag+ , I-

add common ion i.e.,

NaI to solution
Direction of Reaction AgI(s)
Reduce solubility i.e., less AgI will dissolve in solution
which means more precipitate forms in solution
 Example :

Consider a saturated solution of silver chloride in

water. The solubility equilibrium is :
AgCl (s) Ag+ (aq) + Cl- (aq)

When NaCl is added to the saturated AgCl

solution ; - the concentration of Cl-(aq) ions
increases. Cl- ion is the common ion.
 According to Le Chateliers principle, the
increase in [Cl-] will cause the position of
equilibrium shift to the left, thereby causing some
AgCl to precipitate.

So, the solubility of AgCl will decrease until the

product once again equal to Ksp.

Conclusion : Addition of common ions will

reduce the solubility of a slightly soluble salt in
its saturated solution.
 Example 1

The solubility of AgCl in pure water is 1.3 x 105

M. What is its solubility in seawater where the
[Cl] = 0.55 M? (Ksp of AgCl = 1.8 x 1010)
 AgCl(s) Ag+ + Cl Ksp= [Ag+][Cl]
I. 0 0.55
C. +s +s
E. +s 0.55 + s
Ksp= [s][0.55 + s] try dropping this s
Ksp = 0.55s - the value of Ksp is very
1.8 x 1010 = 0.55s small
s = 3.3 x 1010 = [Ag+]=[AgCl]

AgCl is much less soluble in seawater

 Example 2
Calculate the solubility of copper(I) iodide, CuI.
(Ksp = 1.1 x 10-12)
a) water b) 0.05 M NaI
 a) CuI (s) Cu+(aq) + I- (aq)
initial 0 0
change +s +s
equilibrium +s +s
-12 + - 2
a) K sp = 1.1 x 10 = [Cu ] [I ] = s
-6
1.05 x 10 = s
 b) CuI (s) Cu+(aq) + I- (aq)
i. 0 0.05
c. +s +s
e. +s 0.05 + s

b) K sp = 1.1 10-12 = [Cu+ ] [I- ]

= s (0.05M + s)
= s (0.05M)
2.0 x 10-11 = s
 Example 2 :
Solubility & Common Ion
Without common ion, solubility is,
s = 1.05 x 10-6 M
but
with common ion, solubility is,
s = 1.0 x 10-11 M
Solubility of AgCl is reduced.
 Example 3

What is the solubility of calcium fluoride in

0.025 M sodium fluoride solution?
Ksp = 6.2 x 10-8 M
 CaF2 (s) Ca2+ (aq) + 2F- (aq)
Initial [ ] 0 0.025M
Changes [ ] +s +2s
Equilibrium [ ] +s 0.025M +2s

K sp = 6.2 10-8 = [Ca +2 ] [F - ]2

2 assume s << 0.25
= s (0.025M + 2s)
6.2 10-8 = s (0.025M) 2
Check assumption
6.2 10 -8

2
= s = 9.92 10 -5
M indeed 9.92 x 10-5 << 0.025
0.025
 Example 4 :
Ksp for AgCl is 1.7 x 10-10 mol2 dm-6. Calculate the
molar solubility of AgCl in
i. Water
ii. In a solution of 0.1 mol dm-3 KCl.
 Solution :
i. Let s be the molar solubility of AgCl in water.

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

s s

Ksp = [Ag+] [Cl-]

1.7 x 10-10 = s2

s = 1.30 x 10-5 mol dm-3

Thus, the solubility of AgCl in water is 1.30 x 10-5 M

ii. Let the solubility of AgCl in 0.10 mol dm-3 KCl
= y mol dm-3.

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

y (y + 0.1)

Ksp = [Ag+] [Cl-]

= (y) (y+0.1)
 Assume y << 0.1, so, (y+0.1) 0.1

1.7 x 10-10 = 0.1y

y = 1.7 x 10-9 mol dm-3

Thus, the solubility of AgCl in 0.1 mol dm-3 KCl is

1.7 x 10-9 M.

the solubility of AgCl decrease in the presence

of Cl- ions (common ion)
Video 1
 Exercise :
1. It was found experimentally that the solubility
of calcium sulphate is 0.67 g L-1. Calculate the
Ksp for calcium sulphate. ( 2.4 x 10-4 )
2. The solubility of silver sulphate is 1.5 x 10-2 mol
L-1. Calculate the solubility product of the salt.
( 1.4 x 10-5 )
3. Will precipitate form if 200 mL of 0.0040 M
BaCl2 are added to 600 mL of 0.0080 M K2SO4 ?
Ksp BaSO4 = 1.1 x 10-10) ( Q> Ksp therefore
BaSO4 will precipitate)