4.

Acid-Base
Equilibria
 Properties of Acids
1. They taste sour.

2. They can conduct electricity.

l Can be strong or weak electrolytes in
aqueous solution

3. React with metals to form H2 gas.

4. Change the color of indicators

¡ - (for example: blue litmus turns to red).

5. React with bases (metallic hydroxides) to form

water and a salt.
 Properties of Acids
6. They have a pH of less than 7 (more on
this concept of pH in a later lesson).

7. They react with carbonates and

bicarbonates to produce a salt, water, and
carbon dioxide gas.

8. How do you know if a chemical is an acid?

Ø It usually starts with Hydrogen.

Ø HCl, H2SO4, HNO3, etc. (but not

water!)
 Properties of Bases (metallic hydroxides)
• React with acids to form water and a salt.

• Taste bitter.

• Feel slippery (don’t try this either).

• Can be strong or weak electrolytes in aqueous

solution

• Change the color of indicators (red litmus turns

blue).
 Examples of Bases
(metallic hydroxides)

Ø Sodium hydroxide, NaOH (lye for

drain cleaner; soap)

Ø Potassium hydroxide, KOH

(alkaline batteries)

Ø Magnesium hydroxide, Mg(OH)2

(Milk of Magnesia)

Ø Calcium hydroxide, Ca(OH)2

(lime; masonry)
4.1.1 : 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 in
aqueous solution.

7
e.g :
HCl(aq) H+(aq) + Cl-(aq)
(acid)
or
HCl(g) + H2O(l) H3O+(aq) + Cl-(aq)
(acid)
8
Base is a substance that dissociates in
aqueous solution to produce hydroxide
ion (OH-).
e.g :
NaOH(aq) Na+(aq) + OH-(aq)
(base)

9
 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)

10
 Lewis Theory
Acid is a substance (atom, ion or
molecules) that can accept a pair of electrons
to form a coordinate covalent bond.
Base is a substance that can donate a pair
of electrons to form a coordinate covalent
bond.

11
example :
i. NH3(aq) + H+(aq) NH4+(aq)
(base) (acid)

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

(base) (acid)
12
iii. Cu2+(aq) + 4NH3(aq) Cu(NH3)4]2+(aq)

(acid) (base)

iv. H+(aq) + OH-(aq) H2O(l)

(acid) (base)

13
 Table 6.1 : Examples of Lewis acids and bases
Lewis acid Lewis base

(a) Positive ions (a) Negative ions

e.g : H+ , Fe2+ , Al3+ e.g : OH- , CN- , Cl-

(b) Molecules with an (b) Molecules with lone pair

incomplete octet of of electrons.
electrons. e.g : H2O , NH3 , ROH
e.g : BF3 , BeCl2 , BCl3

14
7.1.2: Conjugate Acid-Base

Conjugate acid - a species formed when a base

accepts proton.
Conjugate base – a species formed when an
acid donates proton.

15
.

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

16
 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)

17
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)

18
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)
19
How Do We Measure pH?
ØForless accurate
measurements, one can
use

l Litmus paper
§“Red” paper turns
blue above ~pH =
8
§“Blue” paper turns
red below ~pH = 5
l An indicator
Indicators
 How Do We Measure pH?

For more accurate

measurements,
one uses a pH
meter, which
measures the
voltage in the
solution.
7.1.4: 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.
23
 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 ­.

24
The Ionization of Water

Water ionization equation :

H2O(l) H+(aq) + OH-(aq)

K c
[H ] [OH-]
[H2O]

25
Since the degree of dissociation of water is
extremely small,the equilibrium lies to the left,
[H2O] is assumed as constant.
Kc [H2O] = [H+] [OH-]
Kw = [H+] [OH-]
=ionization constant of water
For pure water at 25oC,
[H+] = [OH-] = 1.0 x 10-7 M

26
 [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 27
 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-]
[H+]> 1X10-7 = 1X 10-7 [OH-] > 1X 10-7
[OH-] < 1X10-7 [H+] < 1X 10-7

28
7.1.5: Calculation of pH values
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

29
Solution : (Method 1)

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

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

pH = - log [H+]
= - log (4.0 x 10-12 M)
= 11.4

30
Solution : (Method 2)

[OH-] = 2.5 x 10-3 M

pOH = - log [OH-]
= - log (2.5 x 10-3 M) From equation;
= 2.6 pH + pOH = 14
pH = 14 – pOH
= 14 – 2.6
From equation; = 11.4
pH = - log [H+]
11.4 = - log [H+]
Thus, [H+] = antilog (-pH)
= 4.0 x 10-12 M
31
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)

32
7.1.3: Strong Acid and Strong Base
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)

33
 Strong base – strong bases dissociate
completely in an aqueous solution to produce high
concentration of OH-.
- 100% ionisation or 100% dissociated
- or α=1
e.g: NaOH(aq) 100% ionisation Na+(aq) + OH-(aq)

34
Acid and Base Strength

§Strongacids are
completely dissociated in
water.
l Their conjugate
bases are quite
weak.

§Weak acids only

dissociate partially in
water.
l Their conjugate
bases are weak
bases.
Acid and Base Strength

§Substances with
negligible acidity do not
dissociate in water.
l Their conjugate bases
are exceedingly
strong.
pH Scale
 pH scale
Scale from 1-14

Indicates the H+
concentration of a
solution in Moles/L
pH = -log [H+]

These are the

pH values for
several
common
substances.
 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.

40
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

41
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.
42
EXERCISE: Classifying Acid and Base Strength
from the Chemical Formula

PROBLEM:
Classify each of the following compounds as a strong acid,
weak acid, strong base, or weak base.
(a) KOH (b) (CH3)2CHCOOH
(c) H2SeO4 (d) (CH3)2CHNH2

PLAN:
We examine the formula and classify each acid or base,
using the text descriptions. Particular points to note for
acids are the numbers of O atoms relative to ionizable H
atoms and the presence of the –COOH group. For bases,
note the nature of the cation or the presence of an N atom
that has a lone pair.
SOLUTIO
N:
(a)Strong base: KOH is one of the group 1A(1)
hydroxides.
(b) Weak acid: (CH3)2CHCOOH is a carboxylic acid, as
indicated by the –COOH group. The –COOH proton is the
only ionizable proton in this compound.

(c) Strong acid: He2SO4 is an oxoacid in which the number

of atoms exceeds the number of ionizable protons by
two.
(d) Weak base: (CH3)2CHNH2 has a lone pair of electrons
on the N and is an amine.
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)

45
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 )

46
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

concentrationof acidor basedissociate

d
% dissociati
on x100%
initialconcentrat
ionof acidor base

47
 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 α<<1.
e.g: CH3COOH(ak) + H2O(l) CH3COO-(aq) + H3O+(aq)

48
 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)

49
7.1.6: pH Calculation for Weak Acid and Weak Base

A. Weak Acid
General equation for dissociation of weak acid :
HA + H2O H3O+ + A-
[ ]initial c 0 0
[ ]change -x +x +x
[ ]equilibrium c-x x x
@ c(1-α) cα cα
acid-dissociation constant, Ka :
[H3 O ] [A- ]
K
a
[HA]
50
 cα2

= cx x @
2

Ka
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).
Ka = x2 /c
x = ( Ka. c )1/2

Degree of dissociation , α = x
c

51
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]
x2 cα 2

c x @
= 1 α
52
 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
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)

53
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

54
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

at equilibrium, [H3O ] [CN- ]

K
a
[HCN]
55
 Ka = (x) (x) = 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
(0.20)
= 4.9 x 10 -10 M

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
56
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 % )
the Ka of HF is 6.8 x 10 -4

57
 Solution 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

58
Assume that the amount of acid dissociated, x is small compared to
the initial concentration of acid, c; that is c-x ≈ c, therefore

(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)(0.01)
x = 1.34 x 10 -3 = [H +]

Therefore,
[H+] = 1.34 x 10 -3 M

pH = -log [H+] = -log [1.34 x 10 -3 ]

= 2.87 59
Solution 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

0.01-x
60
Use quadratic equation:

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

0.01-x
x2 = (0.01-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

61
Use quadratic equation:

-b b2 - 4ac
x
2a
- 6.8x10-4 (6.8x10-4 ) 2 - 4(6.8x10-5 )(1)
x
2
- 6.8x10-4 1.6 x 10-2
x
2

62
 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%
63
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%

64
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- ]
at equilibrium, K 4
b [NH ]
3 65
 (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
66
 pH + pOH = 14

pH = 14 – 2.79

= 11. 21

1.64 x 10 - 3 x 100
ii. % dissociation = 0.15

= 1.09 %

≈ 1.1 %

Degree of dissociation (α) = 0.011

67
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, 0.742, 1.86 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 = 9.0 x10-5 , pH = 1.00 )

68
7.1.10: Buffer Solutions

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

pH(or slightly change) 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)
69
Buffering Capacity
§ Buffering capacity is the amount of acid or base that can
be added to a buffer without destroying its effectiveness.

§ The buffering capacity increases with increasing absolute

concentration of the buffer components.

§ As the [base]:[acid] ratio approaches 1, the ability of the

buffer to neutralize both added acid and base improves.

§ Buffers that need to work mainly with added acid generally

have [base] > [acid].

§ Buffers that need to work mainly with added base

generally have [acid] > [base]
Buffering Effectiveness
1. A good buffer should be able to neutralize
moderate amounts of added acid or base.

2. However, there is a limit to how much can be

added before the pH changes significantly.

3. The buffering capacity is the amount of acid or

base a buffer can neutralize.
4. The buffering range is the pH range the buffer
can be effective

5. The effectiveness of a buffer depends on two

factors
1. the relative amounts of acid and base
2. the absolute concentrations of acid and base
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.

73
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]
74
 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
75
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.

76
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.
NH3+(aq) + OH-(aq) (added) NH3(aq) + H2O(aq)
As a results, there will be a small change in pH and [NH4+] and
[NH3] .

77
7.1.12. pH of buffer solution
pH of acidic buffer solution

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

CH3COONa(aq) CH3COO- (aq) + Na+(aq)
[CH COO - ] [H ]
Ka = 3
[CH3 COOH]
Ka [CH3 COOH]
[H+] = [CH3 COO- ]
[CH3 COOH]
- log [H+] = -log Ka - log [CH3 COO- ]

[CH3 COO- ] [conjugate base]

pH = pKa + log -OR- pH = pKa + log [weak acid]
[CH3 COOH]
(Henderson-Hasselbalch equation)
78
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

79
Solution:

• V=1L
[CH3COOH] = 0.10 M

[CH3COONa] = 0.10 M

pH = pKa + log [conjugate base]

[weak acid]

[CH3 COO- ]
pH = pKa + log [CH COOH]
3
(0.10)
pH = -log(1.8 x 10-5)+ log (0.10)

pH = 4.74

80
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
[conjugate base]
pH = pKa + log [weak acid]
(0.08)
pH = -log(1.8 x 10 )+ log (0.12)
-5

pH = 4.57
81
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
[conjugate base]
pH = pKa + log [weak acid]
(0.12)
pH = -log(1.8 x 10-5)+ log (0.08)

pH = 4.92

82
pH of basic buffer solution
NH4Cl(aq) NH4+(aq) + Cl-(aq)
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
[NH 4 ] [OH ]
Kb =
[NH3 ]

Kb [NH3 ]
[OH-] = [NH 4 ]
[NH 3 ]
- log [OH-] = -log Kb - log [NH 4 ]

[NH 4 ]
pOH = pKb + log -OR- pOH = pKb + log [conjugate acid]
[NH3 ] [weak base]

(Henderson-Hasselbalch equation)

83
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
Solution :
i. V = 400 ml + 600 ml
= 1000 ml
=1L 84
 MV 1.50 x 400
mol NH4Cl = 1000 = 1000 = 0.6 mol

mol NH3 = MV = 0.10 x 600 = 0.06 mol

1000 1000
0.6 mol
[NH4Cl] = 1 L = 0.6 M

[NH3] = 0.06 mol = 0.06 M

1L

pOH = pKb + log [conjugate acid]

[weak base]
[NH 4 ]
@ pOH = pKb + log
[NH3 ]

= -log(1.8 x 10-5)+ log (0.6)

(0.06)
= 5.74
pH = 14 – 5.74 = 8.26
85
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
86
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

pOH = pKb + log [conjugate acid]

[weak base]

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

(0.049)
= 5.84

pH = 14 – 5.84
= 8.16
87
Exercise :

1. How many moles of NH4Cl must be added to 2.0 L of 0.10 M NH3 to

form a buffer whose pH is 9.00 ? ( Assume that the addition of
NH4Cl does not change the volume of the solution ) (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.(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)

88
Chemistry In Action: Maintaining the pH of Blood
 Acid – base properties of salt
q A salt is an ionic compound formed by the reaction between
an acid and a base.

q A general equation for the formation of salt as below:

M(OH) + HX M+X- + H2O

base acid salt

q The anion of the salt is the conjugate base of an acid.

q The cation of the salt is the conjugate acid of a base.

q Salt are strong electrolytes – completely dissociate into ions

in water.

q Salt hydrolysis :
§ the reaction of an anion or a cation of a salt, or both, with
water.
§Usually affects the pH of a solution.
üSalts that produce neutral solutions:

NaNO3 (s) Na+(aq) + NO3- (aq)

Salts containing an alkali metal ion or alkaline earth metal

ion (Be2+) and the conjugate base of a strong acid (e.g Cl-,
Br- and NO3-) do not undergo hydrolysis.
üSalts that produce basic solutions:

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

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

üSalt that produce acidic solutions:

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

NH4+ (aq) + H2O NH3 (aq) + H3O+(aq)
üSalts in which both the cation and anion hydrolyze

Ka > Kb solution is acidic

Ka = Kb solution is neutral
Ka< Kb solution is basic

üFor example:
NH4CN + H2O NH4+ + CN-
NH4+ + H2O NH3 + H3O+ Ka = 5.6 x 10-10
CN- + H2O HCN + OH- Kb = 2.0 x 10-5

Kb > Ka, thus the solution is basic

4.2.1 : Acid- Base Titration

Titration is a procedure for determining the concentration of a

solution using another solution of known concentration called
standard solution.

Titration Curve is a graph of pH versus volume of titrant

96
Titration apparatus

titrant

analyte

97
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. (number of
moles of OH- ions and number of moles of H+ ions are equal)
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.

98
Types of Acid-Base Titrations

3 types of acid-base titration :

(A) Strong Acid-Strong Base Titration

(B) Strong Acid-Weak Base Titration
(C) Weak Acid-Strong Base Titration

99
 7.2.2: pH Calculation for Acid-Base Titration
(A)Strong Acid-Strong Base Titration
Example :
A 25.00 mL sample of 0.10 M HCl is titrated with 0.1 M NaOH. Calculate
the pH of the solution
i. before the addition of NaOH
ii. after the addition of 10.0 mL of NaOH
iii. after the addition of 24.9 mL of NaOH
iv. at the equivalence point
v. after the addition 25.1 mL of NaOH
vi. after the addition of 35.0 mL of NaOH
Sketch the titration curve and determine the appropriate indicator
for this titration. 100
Solution :
i. pH before the addition of 0.10 M NaOH

Dissociation equation of HCl :

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

[ ]initial 0.10 M 0 0
[ ]final 0 0.10 M 0.10 M

pH = -log[H+]
= -log(0.1)
= 1.0

101
ii. pH after the addition of 10.0 mL of 0.10 M NaOH

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

ninitial 2.5 x 10-3 1.0 x 10-3 0
nfinal 1.5 x 10-3 0 1.0 x 10-3
1.5 x 10 - 3 mol 1.0 x 10 - 3 mol
[ ]final 35.0 x 10 - 3 L 35.0 x 10 - 3 L

= 0.043 M = 0.029 M

The pH solution is calculated from the amount of HCl left after

partial neutralization.

pH = -log [H+]
= -log (0.043)
= 1.37 102
iii. pH after the addition of 24.9 mL of 0.10 M NaOH

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

ninitial 2.5 x 10-3 2.49 x 10-3 0
nfinal 0.01 x 10-3 0 2.49 x 10-3
0.01 x 10 - 3 mol 2.49 x 10 - 3 mol
[ ]final 49.9 x 10 - 3 L 49.9 x 10 - 3 L

= 2.0 x 10-4 M = 0.0499 M

The pH solution is calculated from the amount of HCl left after

partial neutralization.
pH = -log [H+]
= -log (2.0 x 10-4)
= 3.7
103
iv. at the equivalence point
At the equivalence point, moles of H+ = moles of OH-
MNaOH VNaOH nNaOH 1
MHCl VHCl
= n = 1
HCl

MNaOH.VNaOH = MHCl.VHCl

= 25.0 mL

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

ninitial 2.5 x 10-3 2.5 x 10-3 0
nfinal 0 0 2.5 x 10-3
2.5 x 10 - 3 mol
[ ]final 0 50.0 x 10 - 3 L
= 0.05 M

104
The calculation involves a complete neutralization reaction.
NaCl Na+(aq) + Cl-(aq)
(does not undergo hydrolysis)

The pH solution is calculated from the dissociation of water.

Kw = [H+] [OH-]

where : [H+] = [OH-]

[H+] = 1.0 x 10 - 14 M2
= 1.0 x 10-7 M
pH = - log (1.0 x 10-7)
=7
105
v. pH after the addition of 25.1 mL of 0.10 M NaOH

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

ninitial 2.5 x 10-3 2.51 x 10-3 0
nfinal 0 0.01 x 10-3 2.51 x 10-3
[ ]final used limiting reagent
0.01 x 10 - 3 mol 2.5 x 10-3 mol
50.1 x 10 - 3 L
50.1 x 10-3 L
= 1.996 x 10-4 M = 0.05 M
The pH solution is determined from the amount of NaOH left.
pOH = -log [OH-]
= -log (1.996 x 10-4)
= 3.70
pH = 14 – 3.70
= 10.3

106
vi. pH after the addition of 35.0 mL of 0.10 M NaOH

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

ninitial 2.5 x 10-3 3.5 x 10-3 0
nfinal 0 1.0 x 10-3 2.5 x 10-3
1.0 x 10 - 3 mol 2.5 x 10 - 3 mol
[ ]final 60.0 x 10 - 3 L 60.0 x 10 - 3 L

= 0.0167 M = 0.0417 M
The pH solution is determined from the amount of NaOH left.
pOH = -log [OH-]
= -log (0.0167)
= 1.78

pH = 14 – 1.78
= 12.2
107
 7.2.3: i)The titration curve for strong acid-strong base titration

NaOH (mL) 0 10 24.9 25 25.1 35

pH 1.0 1.37 3.7 7 10.3 12.2

pH
14
12
10
8
Eq.
point 6
4
2
0 VNaOH (mL)

0 10 20 25 30 40 50 108
7.2.3: i)The titration curve for strong acid-strong base titration

NaOH 0.1 M (mL) 0 10 24.9 25 25.1 35

pH 1.0 1.37 3.7 7 10.3 12.2

pH
14
12
10
8
Eq.
point 6

4
2
0 VNaOH (mL)

0 10 20 25 30 40 50 109
 Weak Acid-Strong Base Titrations

Consider the neutralization reaction between CH3COOH (a weak acid) and

NaOH (a strong base):

CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)

The equation can be simplified to:

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

Acetate ion undergoes hydrolysis as follow:
CH3COO- (aq) + H2O (l) OH- (aq) + CH3COOH (aq)

At equivalence point, when only sodium acetate present, the pH

will be greater than 7 as a result of the excess OH- ions formed.
After addition of 10mL of 0.10M NaOH to 25mL of 0.10M CH3COOH

CH3COOH + NaOH CH3COONa + H2O

Initial 0.10 x 25 0.10 x 10 0

(mol) 1000 1000
= 2.5x 10-3 = 1.0 x 10-3
Change -1.0 x 10-3 -1.0 x 10-3 +1.0 x 10-3
(mol)
Final 1.5 x 10-3 0 1.0 x 10-3
(mol)

At this stage, we have a buffer system made up of CH3COONa and CH3COOH

The total volume of the solution is 35mL.

[CH3COOH] = 1.5x10-3 mol = 0.0429 M

35x 10-3 L

[CH3COO-] = 1.0x10-3 mol = 0.0286 M

35x 10-3 L

pH = pKa + log [CH3COO-]

[CH3COOH]
= -log (1.8 x 10-5) + log 0.0286
0.0429
= 4.57
After addition of 25mL of 0.10M NaOH to 25mL of 0.10M CH3COOH

CH3COOH + NaOH CH3COONa + H2O

Initial 0.10 x 25 0
(mol) = 2.5x 10-3 1000
= 2.5 x 10-3
Change -2.5 x 10-3 -2.5 x 10-3 +2.5 x 10-3
(mol)
Final 0 0 2.5 x 10-3
(mol)

The total volume is 50 mL

 So, the [salt]:

[CH3COONa] = 2.5 x 10-5 mol = 0.050M

50 x 10-3 L

pH at equivalence point = 8.72

After addition of 35mL of 0.10M NaOH to 25mL of 0.10M CH3COOH

CH3COOH + NaOH CH3COONa + H2O

Initial (mol) 2.5x 10-3 3.5 x 10-3 0

Change -2.5 x 10- -2.5 x 10-3 +2.5 x 10-
(mol) 3 3

Final (mol) 0 1.0 x 10-3 2.5 x 10-3

Since OH- is much stronger base than CH3COO-, neglect CH3COO-

Total volume is 60 mL

[OH-] = 1.0x10-3 mol = 0.0167 M

60x 10-3 L

pOH = -log 0.0167

= 1.78

pH = 14 – 1.78
= 12.22
 Strong Acid-Weak Base Titrations

Consider the titration of HCl, a strong acid and NH3, a weak base:

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

Or simply

H+ (aq) + NH3 (aq) NH4Cl (aq)

The pH at equivalence point is less than 7 due to hydrolysis of

NH4+ ion:

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

 Acid-Base Indicators
§ Usually a weak organic acid or base that has distinctly different
colors in its non-ionized and ionized forms.

§ Let consider a weak monoprotic acid, HIn.

§ To be an effective indicator, HIn and its conjugate base In-,

must have distinctly different colours

§ In solution, the acid ionizes to a small extent:

n Hln (aq) H+(aq) + ln-(aq)

n Kin = [H+][In-]
n [Hln]
§ If the indicator is in a sufficiently acidic medium, the equilibrium
shifts to the left and the predominant color of the indicator is that
of non-ionized form (HIn).

n [Hln] > 10 Color of acid (Hln) predominates

n [In-]

§ In basic medium, the equilibrium shift to the right and the color of
solution will be due mainly to the conjugate base (In-).

n [HIn] < 0.1 Color of conjugate base (In-) predominates

n [In-]

§ In the middle of color change of the indicator, HIn and In- are
present in equal amounts, [Hln] = [In-], so
§ Kin = [H+]
§ Or pKin = pH
 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

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

Phenolphthalei
8.2 – 10.0 Colourless reddish pink
n
Methyl orange 3.2 – 4.2 Red Yellow
Bromothymol
6.0 – 7.6 Yellow Blue
blue
phenol red 6.8 – 8.4 Yellow red

123
Exercise :
2. The pH range and the colour change for 3 indicator X, Y and Z
is shown in the table below :
pH
Indicator colour change
range
1.2 –
X Red Yellow
2.8
6.0 –
Y Yellow Blue
7.6
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
124