CHAPTER 7:

IONIC EQUILIBRIA

7.1 Acids and bases

1
 LEARNING OUTCOMES

a. Define acid and base according to Arrhenius and

Bronsted- Lowry theories.
b. Identify conjugate acid and conjugate base according
to Bronsted- Lowry theory.
c. Relate pH and pOH to the ionic product of water, Kw at
250C
d. Define strong acid and base, weak acid and base, pH,
pOH and pKw
 LEARNING OUTCOMES

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
I. pH,
II. dissociation constant,
III. initial concentration
IV. equilibrium concentration
V. degree of dissociation, α
* perform calculations only on weak monoprotic acids and weak bases
 Theory of Acids and Bases

Arrhenius Theory
Acid is a substance that dissociates in aqueous solution to produce
hydrogen ion (H+) or hydronium (H3O+) ion.

e.g :
HCl(aq) H+(aq) + Cl-(aq)
(acid)
or
HCl(g) + H2O(l) H3O+(aq) + Cl-(aq)
(acid)
Theory of Acids and Bases

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

e.g :
NaOH(aq) Na+(aq) + OH-(aq)
(base)
 Theory
Theory of Acids
of Acids andand Bases
Bases

Bronsted-Lowry Theory

➢ Acid is a substance that can donate a proton (H+) to another substance.

➢ Base is a substance that can accept a proton (H+) from another substance.

e.g :
HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)
(acid) (base)
Theory of Acids and Bases

Conjugate Acid-Base
➢ Conjugate acid - a species formed when a base accepts proton.
➢ Conjugate base - a species formed when an acid donates proton
Example :
HNO2(aq) + H2O(l) H3O+(aq) + NO2-(aq)
(acid) (base) (conjugate acid) (conjugate base)

Conjugate acid-base pair :

HNO2 / NO2- & H2O / H3O+
Acid conjugate base base conjugate acid
 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)
 EXERCISE

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)
 ANSWER

1. 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)
 ANSWER
4. The conjugate acid-base pairs for the following reaction:
i. NH2-(aq) + H2O(aq) NH3(aq) + OH-(aq)

base acid conjugate acid conjugate base

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

Acid base conjugate base conjugate acid

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

Acid base conjugate acid conjugate base

 Strong Acid and Strong Base

Definition strong acid

Strong acid – strong acids dissociate completely in an aqueous solution to
produce high concentration of H3O+.
- 100% ionisation or 100% dissociation
- or α = 1

e.g: HCl(aq) + H2O(l) 100% ionisation H3O+(aq) + Cl-(aq)

HNO3(aq) + H2O(l) 100% ionisation H3O+(aq)+ NO3-(aq)

 Strong Acid and Strong Base

Definition strong base

Strong base – strong bases dissociate completely in an aqueous solution
to produce high concentration of OH-.
- 100% ionisation or 100% dissociation
- or α=1

e.g: NaOH(aq) 100% ionisation Na+(aq) + OH-(aq)

 Weak Acid and Weak Base

Definition weak acid

Weak acid – weak acids dissociate only slightly in an aqueous solution to
produce a low concentration of H3O+
- % dissociation less than 100%
or α<<1.

e.g: CH3COOH(ak) + H2O(l) CH3COO-(aq) + H3O+(aq)

 Weak Acid and Weak Base

Definition weak base

Weak base – weak bases dissociate only slightly in an aqueous solution
to produce a low concentration of OH-.
– % dissociation less than 100%
or α<<1.

e.g: NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)

pH and pOH
The hydrogen ion, H+ concentration / [H+] in a solution is measured using
pH scale method.
pH = - log [H+]
The pH is defined as the negative logarithm (log) of the hydrogen ion, H+ or H3O+
concentration.
If [H+]  , pH  .
For base, concentration of OH- is measured using pOH
pOH = - log [OH-]
The pOH is defined as the negative logarithm (log) of the hydroxide ion.
If [OH-]  , pH .

16
The Strengths of Acids and Bases

The strengths of acids and bases can be compared in terms of

i. the degree of dissociation (α)
ii. the dissociation constant (K)

Degree of dissociation (α)

- ability of acids or bases to ionize or dissociate in aqueous solution.
concentration of acid or base dissociated
α=
initial concentration of acid or base

concentration of acid or base dissociated

% dissociation = x 100%
initial concentration of acid or base
17
Notes:

Strong acid & strong base are strong electrolyte (α=1).

Weak acid & weak base are weak electrolyte (α<<1).

Electrolyte – substance that can conduct electricity in

the liquid state or aqueous solution.

18
The Ionization of Water

Water ionization equation :

H2O(l) H+(aq) + OH-(aq)
[H+ ] [OH- ]
K=c
[H2O]

Since the degree of dissociation of water is extremely small, [H2O] is

assumed as constant.
Kc [H2O] = [H+] [OH-]
Kw = [H+] [OH-]

For pure water at 25oC,

[H+] = [OH-] = 1.0 x 10-7 M

19
The Ionization of Water

[H+] = [OH-] = 1.0 x 10-7 M

Kw = [H+] [OH-]
Kw = (1.0 x 10-7 M)2
= 1.0 x 10-14 M2
Relationship between Kw, pH and pOH at 25oC,

[H+] [OH-] = Kw
-log ([H+] [OH-]) = -log Kw
-log [H+] – log [OH-] = - log (1.0 x 10-14)
pH + pOH = pKw
pH + pOH = 14
20
The Ionization of Water

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-]

21
7.1.5: Calculation of pH values

1. The following examples illustrate calculations involving pH.

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

22
Solution : (Method 1)

Kw = [H+] [OH-]
= 1.0 x 10-14 M2

[H+] = 1.0 x 10-14

= 1.0 x 10-14 = 4.0 x 10-12 M
[OH-] 2.5 x 10-3

pH = - log [H+]
= - log (4.0 x 10-12 M)
= 11.4
23
Solution : (Method 2)

From equation;
[OH-] = 2.5 x 10-3 M
pH + pOH = 14
pOH = - log [OH-]
pH = 14 – pOH
= - log (2.5 x 10-3 M)
= 14 – 2.6
= 2.6
= 11.4

From equation;
pH = - log [H+]
11.4 = - log [H+]
Thus, [H+] = antilog (-pH)
= 4.0 x 10-12 M
24
pH Calculation for Strong Acid and Strong Base

Strong acid and strong base dissociate 100% in aqueous

solution.
Therefore the concentration of H+ and OH- ions can be obtained
directly from their molarities.

25
Example 1 :

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

Thus,
pH = - log [H+]
= - log (0.15 M)
= 0.82
26
 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 ?
4. What is the concentration of a solution of KOH for which the pH is
11.89?
5. What is the pH of a 0.028 M solution of NaOH?

(Ans : 1.40 , 12.7 , 0.00457, 7.75 x 10-3, 12.45)

27
7.1.6: pH Calculation for Weak Acid and Weak Base

A. Weak Acid
General equation for dissociation of weak acid :
HA(aq) + H2O(l) H3O+(aq) + A-(aq)
[ ]initial c 0 0
[ ]change -x +x +x
[ ]equilibrium c-x x x Where, x = cα

@ c(1-α) cα cα
acid-dissociation constant, Ka : [H3O+ ] [A-]
K =
[HA]
a

28
 [H3O+ ] [A-]
K =
[HA]
a

= (x)(x)
c-x
x cα 2

 = c−x @
2

1− α

If x << c, c-x ≈ c, therefore pH of weak acid can be determined

from [H3O+] ( that is the value of the x).

Degree of dissociation , α = x
c
29
B. Weak Base
General equation for dissociation of weak base :
B + H2O BH+ + OH-
[ ]initial c 0 0
[ ]change -x +x +x
[ ]equilibrium c-x x x
@ c(1-α) cα cα

base-dissociation constant, Kb : Kb = [BH+ ] [OH-]

[B]
= x @ cα
2
2

c−x 1− α 30
 If x << c, c-x ≈ c, therefore pH of weak base can be determined
from [OH-] ( that is the value of the x).

 pOH = - log [OH-]

pH = 14 – pOH

31
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)

32
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
33
7.1.7: a) Weak acid
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]
34
 [H3O + ] [CN - ]
K =
a
[HCN]
(x) (x)
Ka = (0.20 - x) = 4.9 x 10-10 M

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
(0.20) = 4.9 x 10 M
-10

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

35
 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 and in (7.9 %)
(b) a 0.010 M HF solution (23 % )
the Ka of HF is 6.8 x 10 -4

36
 ANSWER : QUESTION 1

HCHO2(aq) + H2O (l) H3O+(aq) + CHO2-(aq)

[ ]initial 0.010 M 0 0

[ ]change -x +x +x

[ ]equilibrium 0.010-x x x

at equilibrium, Ka = [H+][CHO2-] = 1.8 x 10-4

[HCHO2]
= (x)(x) = 1.8 x 10-4
0.01-x

37
 ANSWER : QUESTION 1
(x)(x) = 1.8 x 10-4
0.01-x
x2 = 1.8 x 10-4
0.01-x
x2 + 1.8 x 10 -4 x - 1.8x10-6x = 0
Use quadratic equation:
-b b 2 - 4ac
x=
2a
- 1.8 x 10 - 4  (3.24 x 10 − 8) 2 - 4(6.8 x 10 -5 )(1)
x=
2
- 6.8 x 10 - 4  1.6 x 10 - 2
x=
2
38
 ANSWER : QUESTION 1

x = 1.25 x 10 -3 = [H +]

Therefore,
[H+] = 1.25 x 10 -3 M
pH = -log [H+]
= -log [1.25 x 10 -3 ]
= 2.90

39
 ANSWER : QUESTION 2

HF(aq) + H2O (l) H3O+(aq) + F-(aq)

[ ]initial 0.10 M 0 0

[ ]change -x +x +x

[ ]equilibrium 0.10-x x x

at equilibrium, Ka = [H+][F-] = 6.8 x 10-4

[HF-]
= (x)(x) = 6.8 x 10-4
0.10-x
40
 ANSWER : QUESTION 2

Use quadratic equation:

Ka = (x)(x) = 6.8 x 10-4

0.10-x
x2 = (0.10-x)(6.8 x 10-4)

x2 = (6.8 x 10-5) –(6.8 x 10-4)(x)

x2 + (6.8 x 10-4)(x) - (6.8 x 10-5) = 0

41
 ANSWER : QUESTION 1

Use quadratic equation:

- b  b 2 - 4ac
x=
2a
- 6.8 x 10 -4  (6.8 x 10 -4 ) 2 - 4(6.8 x 10 -5 )(1)
x=
2
- 6.8 x 10 -4  1.6 x 10 -2
x=
2

42
 ANSWER : QUESTION 2

x = [H+] = [F-]
= 7.9 x 10-3 M

Percent ionization of HF = concentration ionized x 100%

original concentration
= 7.9 x 10-3 M x 100%
0.10 M
= 7.9%

43
ANSWER : QUESTION 1

solving x by quadratic equation:

x2 = 6.8 x 10-4
0.010 –x
x = [H+] = [F-]
x = 2.3 x 10-3 M
= 0.0023 x 100%
0.010
= 23%

44
B.Weak Base
Example 1 :
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 = 4
at equilibrium, b [NH ]
3
45
 (x) (x)
Kb = (0.15 - x) = 1.8 x 10-5 M
Assume that x is too small compared to the initial concentration of
base, c; that is c-x ≈ c, therefore

x2
(0.15) = 1.8 x 10-5 M
x2 = (1.8 x 10-5 M) (0.15 M)
x = 1.64 x 10-3 M
Therefore,
i. [OH-] = 1.64 x 10-3 M
pOH = -log [OH-]
= 2.79

46
 pH + pOH = 14
pH = 14 – 2.79
= 11. 21

ii. % dissociation = 1.64 x 10-3 x 100

0.15
= 1.09 %
≈ 1.1 %

Degree of dissociation , α = 0.011

47
 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, 1.72, 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 = 2.9 x10-3 , pH = 2.54 )

48
 LEARNING OUTCOMES

h. Explain qualitatively salt hydrolysis using hydrolysis equations of

i. Strong acid and strong base
ii. Strong acid and weak base
iii. Weak acid and strong base
i. Classify the salt formed in (h).
j. Define buffer solution.
k. Explain how buffer solution controls its pH.
l. Write the Henderson-Hasselbalch equation for a given buffer solution.
m. Calculate the pH of buffer solutions using the Henderson-Hasselbalch
equation before and after the addition of strong acid or base.
7.1.8 : Salt Hydrolysis

Salt hydrolysis is the reaction of an anion (-ve ion) or a kation (+ve ion) of a salt (or both)
with water.
General equation of neutralization :
HX + MOH MX + H2O
(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)
50
(i) Salt formed from a Strong Acid and Strong Base

1. An example is 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-:
NaCl (aq) Na+ (aq) + Cl-(aq)

2. 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.

51
(ii) Salt formed from a Strong Acid and Weak Base

1. An example is NH4Cl ,which is formed from hydrochloric acid (a

strong acid) and ammonia (a weak base)
NH3(aq) + HCl(aq) NH4Cl(aq)

2. Ammonium chloride dissociates completely into ammonium ions

and chloride ions:
NH4Cl(s) + aq NH4+(aq) + Cl-(aq)

52
(ii) Salt formed from a Strong Acid and Weak Base

3. The NH+4 , 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) no reaction

4. The production of H3O+(aq) ions from the hydrolysis of the NH4+(aq) ions
causes the solution to be acidic. This is also known as cationic
hydrolysis.

53
(iii) Salt formed 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)

54
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) no reaction

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. This
is also known as anionic hydrolysis.

55
7.1.9: Types of Salt

i. Neutral salt - salt from strong acid-strong base.

- cation of a strong base and anion strong acid do not hydrolyze.
- e.g: NaCl
ii. Acidic salt - salt from strong acid-weak base.
- cation hydrolyzes as an acid.
- e.g: NH4Cl
iii. Basic salt - salt from weak acid-strong base
- anion hydrolyzes as a base.
- e.g: CH3COONa
56
(i) Hydrolysis Salts of Strong Acid-Strong Base

Neutral salt : pH = 7
Example : NaCl
Salt dissociation equation :
NaCl(aq) Na+(aq) + Cl-(aq) (completely dissociated)

Na+(aq) + H2O no reaction

Cl-(aq) + H2O no reaction

Salt from the strong acid-strong base not undergo hydrolysis.

57
(ii) Hydrolysis Salts of Strong Acid-Weak Base

Acidic salt : pH < 7

Example : Ammonium chloride, NH4Cl
Salt dissociation equation :
NH4Cl(aq) NH4+(aq) + Cl-(aq) (completely dissociated)
- only cation will undergo hydrolysis to form H3O+ ion,
therefore, NH4Cl undergoes partial hydrolysis.

Hydrolysis equation for cation :

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

58
(iii) Hydrolysis Salts of Weak Acid-Strong Base

Basic salt : pH > 7

Example : Sodium ethanoate, CH3COONa
Salt dissociation equation :
CH3COONa(aq) CH3COO-(aq) + Na+(aq) (completely dissociated)
- only anion will undergo hydrolysis to form OH- ion,
therefore, CH3COONa undergoes partial hydrolysis.

Hydrolysis equation for cation :

CH3COO-(aq) + H2O(l) CH3COOH(aq) + OH-(aq)
59
7.1.10: Buffer Solutions

Buffer solution is a solution which has the ability to maintain its

pH when a small amount of strong acid or strong base is added
to the solution.

Solution that contains a weak acid and its salt (its conjugate
base) or a weak base and its salt (its conjugate acid).

Two types of buffer solutions :

i. Acidic buffer solution (pH<7)
ii. Basic buffer solution (pH>7)
60
7.1.11. Acidic buffer solution

An acidic buffer solution can be prepared by mixing a weak acid

and its salt (its conjugate base).
Example :
Acetic acid, CH3COOH and sodium ethanoate, CH3COONa
Reaction that occurs in the buffer solution :
CH3COOH(aq) CH3COO-(aq) + H+(aq) (partially dissociated)
CH3COONa(aq) CH3COO-(aq) + Na+(aq) (completely dissociated)
The amount of CH3COO- is mainly from the complete dissociation
of CH3COONa.
61
Actions of acidic buffer solution

When a small amount of acid is added, the H+ ions will be consumed by the
ethanoate ion, CH3COO- to form CH3COOH.
CH3COO-(aq) + H+ (aq)(added) CH3COOH(aq)
As a result, there will be only a small change in pH and [CH3COO-] and [CH3COOH]

When a small amount of base is added to the buffer system, the OH- ions will be
neutralized by the acid, CH3COOH to form CH3COO- and H2O.
CH3COOH(aq) + OH- (aq)(added) CH3COO-(aq) + H2O(l)
As a results, there will be a small change in pH and [CH3COO-] and [CH3COOH]

62
 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
63
 Basic buffer solution

A basic buffer solution can be prepared by mixing a weak base and its salt (its
conjugate acid).
Example :
Ammonia, NH3 and ammonium chloride, NH4Cl
Reaction that occurs in the buffer solution :
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) (partially dissociated)
NH4Cl(aq) NH4+(aq) + Cl-(aq) (completely dissociated)
The amount of NH4+ is mainly from the complete dissociation of NH4Cl.

64
Actions of basic buffer solution

When a small amount of acid is added, the H+ ions will be consumed by

the ammonia, NH3 to form NH4+.
NH3(aq) + H+(aq) (added) NH4+(aq)
As a result, there will be only a small change in pH and [NH3] and [NH4+]

If a small amount of base is added to the buffer system, the OH- ions will
be removed by the ammonium ions, NH4+ to form NH3 and H2O.
NH4+(aq) + OH-(aq) (added) NH3(aq) + H2O(aq)
As a results, there will be a small change in pH and [NH4+] and [NH3] .

65
7.1.12. pH of buffer solution
1) pH of acidic buffer solution
CH3COOH(aq) CH3COO-(aq) + H+(aq)
CH3COONa(aq) CH3COO- (aq) + Na+(aq)
Ka = [CH3COO-] [H+ ]
[CH3COOH]

[H+] = Ka [CH3COOH]
[CH3COO-]
[CH3COOH]
- log [H+] = -log Ka - log
[CH3COO-]

pH = pKa + log [CH3COO ] -OR- pH = pKa + log [conjugate base]

-

[CH3COOH] [weak acid]

(Henderson-Hasselbalch equation)
66
Example 1 :

1. 1.0 litre buffer solution is prepared by mixing 0.10 mole of CH3COOH with
0.10 mole of CH3COONa.
i. Calculate the pH of a the buffer solution.
ii. Calculate the pH of the buffer solution after the addition of
(a) 0.02 mole HCl
(b) 0.02 mol NaOH
(Assume that the volume of the solution does not change when HCl
and NaOH is added)
Ka for CH3COOH = 1.8 x 10-5 M
67
Solution:

V=1L
[CH3COOH] = 0.10 M
[CH3COONa] = 0.10 M
[conjugate base]
pH = pKa + log [weak acid]
[CH3COO-]
pH = pKa + log [CH3COOH]
(0.10)
pH = -log(1.8 x 10-5)+ log (0.10)

pH = 4.74

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ii. (a) pH when 0.02 mol HCl is added

Buffer action : CH3COO-(aq) + H+(aq) CH3COOH(aq)

[ ]initial 0.10 M 0.02 M 0.10 M
[ ]change -0.02 M -0.02 M +0.02 M
[ ]final 0.08 M 0 0.12 M

[CH3COO-] = 0.08 M
[CH3COOH] = 0.12 M

pH = pKa + log [conjugate base]

[weak acid]
(0.08)
pH = -log(1.8 x 10 )+ log (0.12)
-5

pH = 4.57
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ii.(b) pH when 0.02 mol NaOH is added

Buffer action : CH3COOH(aq) + OH-(aq) CH3COO-(aq) + H2O(l)

[ ]initial 0.10 M 0.02 M 0.10 M
[ ]change -0.02 M -0.02 M +0.02 M
[ ]final 0.08 M 0 0.12 M

[CH3COO-] = 0.12 M
[CH3COOH] = 0.08 M

pH = pKa + log [conjugate base]

[weak acid]

pH = -log(1.8 x 10-5)+ log (0.12)

(0.08)
pH = 4.92
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2) pH of basic buffer solution

NH4Cl(aq) NH4+(aq) + Cl-(aq)

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

Kb = [NH4 + ] [OH− ]
[NH3 ]

[OH-] = Kb [NH3 ]
[NH4 + ]
[NH3 ]
- log [OH-] = -log Kb - log
[NH4 + ]

[NH4 + ] [conjugate acid]

pOH = pKb + log -OR- pOH = pKb + log [weak base]
[NH3 ]

(Henderson-Hasselbalch equation)
71
Example 2 :

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

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Solution :

(i) V = 400 ml + 600 ml [conjugate acid]

pOH = pKb + log
= 1000 ml [weak base]

=1L @
[NH4 + ]
pOH = pKb + log [NH3 ]
mol NH4Cl = MV = 1.50 x 400= 0.6 mol
1000 1000 = -log(1.8 x 10-5)+ log (0.6)
(0.06)
mol NH3 = MV = 0.10 x 600 = 0.06 mol
1000 1000 = 5.74
[NH4Cl] = 0.6 mol = 0.6 M
1L pH = 14 – 5.74 = 8.26
0.06 mol
[NH3] = 1L
= 0.06 M

73
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]

= -log(1.8 x 10-5)+ log (0.45)

(0.21)
= 5.08

pH = 14 – 5.08

= 8.92
74
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]
(0.611)
= -log(1.8 x 10-5)+ log (0.049)
= 5.84

pH = 14 – 5.84
= 8.16
75
 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 = 1.8x10-5 )
(0.36 mol)
2. Calculate the concentration of sodium benzoate that must be
present in a 0.20 M solution of benzoic acid ( HC7H5O2 ) to produce
a pH of 4.00. (Ka = 6.28x10-5)(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)
76