UNIT 4

Part 1

1
2
 Properties
ACIDS

Sour

Burning or tingling sensation on the skin

Litmus paper Blue → red.

BASES

Bitter

Slippery

Litmus paper Red → blue.

3
 Common Inorganic Acids and
Bases
• ACIDS:
HCl, HBr, HI, HNO3, HNO2, H2SO4,
H3PO4

• BASES:
NaOH, KOH, Ca(OH)2, Mg(OH)2

4
5
Theory of Electrolytic Dissociation
(Svante Arrhenius, ca. 1884)

Electrolytes are substances whose

aqueous solutions conduct electricity.
Solutions of non-electrolytes do not
conduct electricity.
Electrolytes dissolved in water dissociate
into ions. It is these ions which are
responsible for conducting the electrical
current.
6
 Electrolytes

Ionic compounds (salts)

Acids

Non-Electrolytes

Covalent compounds
(Excepting acids)

7
 ELECTROLYTES
NaCl(s) ⇋ Na+(aq) + Cl–(aq)

8
NON-ELECTROLYTES

Glucose

Sucrose

9
 Electrolytes
Electrolytes can be either weak or strong.

A STRONG ELECTROLYTE IS A WEAK ELECTROLYTE IS

COMPLETELY DISSOCIATED PARTIALLY DISSOCIATED

10
 Arrhenius Acids and Bases
+
Acid: An electrolyte whose cation is H
–
Base: An electrolyte whose anion is OH
Acids → H +
Aqueous solution
Bases → OH –

HCl(aq) → H (aq) + Cl (aq)

+ –
Acid
NaOH(aq) → Na (aq) + OH (aq) Base
+ –

11
Svante August Arrhenius
1859 - 1927 12
Svante August Arrhenius
1859 -1927 13
Brønsted-Lowry Theory (1923)

Acid → H +
PROTON DONOR

Base ← H + PROTON ACCEPTOR

14
 Brønsted-Lowry Theory
BASE CONJUGATE BASE

+ –
HA(aq) + H2O (l) ⇋ H3O (aq) + A (aq)
ACID CONJUGATE ACID

H+

15
16
The Hydronium Ion
H + H2O → H3O
+ +

17
18
Acid – Base Conjugate Pairs
Members of an acid-base conjugate pair
differ from one another by one proton.
–
HCl / Cl
–
HCN / CN

NH4+ / NH3

CH3COOH / CH3COO –
19
Brønsted-Lowry Acid-Base Reaction in
Aqueous Solution

20
Brønsted-Lowry Acid-Base Reaction in
Aqueous Solution

21
Brønsted-Lowry Acid-Base Reaction in the
Gas Phase
BASE CONJUGATE BASE

NH3(g) + HCl(g) → NH4+

+ Cl –

ACID CONJUGATE ACID

H+ NH4Cl(s)
22
 PROTON ACCEPTOR

PROTON DONOR

23
Thomas Martin Lowry Johannes Nicolaus Brønsted
1874 - 1936 1879 - 1947

24
 Lewis Theory

Acid ←
ELECTRON-PAIR
ACCEPTOR

Base → ELECTRON-PAIR
DONOR

25
 Lewis Acid-Base Reaction

ELECTRON-PAIR
DONOR
(Lewis Base) LEWIS ADDUCT

NH3(g) + BF3(g) → NH3BF3 (g)

ELECTRON-PAIR
ACCEPTOR
(Lewis Acid)

26
ELECTRON-PAIR
DONOR LEWIS ADDUCT

ELECTRON-PAIR
ACCEPTOR

27
Gilbert Newton Lewis
1875 - 1946
28
 The Auto-Ionization of Water

BASE ACID CONJUGATE BASE

+ –
H2O (l) + H2O (l) ⇋ H3O (aq) + OH (aq)
CONJUGATE ACID
H+

H+
A substance that can behave either as an
acid or as a base is said to be amphoteric 29
The Auto-Ionization of Water
Arrhenius Formalism

+ –
H2O (l) ⇋ H (aq) + OH (aq)

30
 The Ion Product of Water
+ -
[H 3 O ][ OH ]
K= 2
[H 2 O]
In pure water, at 25 oC,
At 25 oC, Kw = 1.0 x 10-14
[H+] = [OH–] = 1.0 x 10-7 mol/L

+ +
K w = [H 3 O ][ OH ] = [H ][ OH ] - -

(Where, K [H 2 O] = K w )
2

31
Acidic, Basic and Neutral Solutions

Neutral solution: [H+] = [OH-]

Acidic solution: [H+] > [OH-]

Basic solution: +
[H ] < -
[OH ]

32
 Exercise 1

a) Calculate the hydrogen ion

concentration in a 0.10 M HCl
o
solution, at 25 C.
b) What is its pH?

33
 Exercise 2

a) Calculate the hydrogen ion

concentration in a 0.10 M NaOH
o
solution, at 25 C.
b) What is its pH?

34
 The pH Scale

pH = - log [H+]

The pH of pure water, at 25 oC, is

+ -7
pH = - log [H ] = - log (1.0 x 10 ) = +7.00

35
 The “p” Function
The “p” function can be extended to any
quantity Y, so that:

pY = - log Y
Thus, for pure water, at 25 oC,

pOH = +7 and pKw = +14.00

36
 o
In any aqueous solution, at 25 C,
+ –
[H ][OH ] = Kw = 1.0 x 10-14

pH + pOH = pKw = +14.00

37
38
The pH of some
common fluids.

39
40
41
 Weak Acids and Bases
A weak acid (or a weak base) is one which
is incompletely dissociated. Incomplete
dissociation is usually taken to mean less
than 10% dissociation at all reasonable
analytical concentrations.
The analytical concentration, C, is the
amount of substance dissolved per litre of
solution and is independent of any
subsequent equilibrium.
42
Strong Acid HA Weak Acid HB

43
 Weak Acids
+ –
HA(aq) + H2O (l) ⇋ H3O (aq) + A (aq)
+ –
HA(aq) ⇋ H (aq) + A (aq) Arrhenius

The equilibrium expression for the dissociation

of an acid in water is

K=
[H O ][A ]
3
+ −

[HA ][H 2 O ]
44
 Ka
The acid dissociation constant, Ka, is
given by

Ka =
[H 3O ][A ] [H ][A ]
+ −
=
+ −

[HA] [HA]
Where, Ka = K [H2O]

45
46
 Exercise 3
Consider a 0.20 M acetic acid (CH3COOH)
solution, at 25 oC. [ Ka = 1.8 ×10–5 ]

a) List the major species in the solution.

b) Calculate their respective concentrations.
a) What is the pH of this solution?

47
Strong Acid

Weak Acid

48
 Weak Bases
+ –
B(aq) + H2O (l) ⇋ BH (aq) + OH (aq)
The equilibrium expression for the dissociation
of a base in water is

K=
[BH ][OH ]
+ −

[B][H 2 O ]
49
 Kb
The base constant, Kb, is given by

Kb =
[BH ][OH ]
+ −

[B]
Where, Kb = K [H2O]

50
51
 Exercise 4

Calculate the pH of a 1.00 M ethylamine

o
(CH3CH2NH2) solution, at 25 C.
[ Kb = 5.6 ×10–4 ]

52
 Exercise 5

How many millilitres of glacial acetic

acid (CH3COOH) are required to
prepare 500.0 mL of an aqueous
solution having a pH of 2.4, at 25 oC.
[ ρ = 1.049 g/cm3, Ka = 1.8 ×10–5 ]

53
Glacial Acetic Acid Crystalline Acetic Acid
54
 Degree of Dissociation of a Weak
Electrolyte
For the process
+ –
HA(aq) ⇋ H (aq) + A (aq)
the degree of dissociation, α, is given by:
C HA − [ HA ]
α=
C HA
Where, CHA is the analytical concentration
of HA. 55
The degree of dissociation of a weak acid
decreases when its analytical concentration
is increased. (Wilhelm Ostwald, 1853-1932).

CHA ↑ ⇔ [H ] ↑ ⇔ α ↓
+

56
57
 Exercise 6

In a 0.100 M solution of hydrofluoric

acid, HF, the percent dissociation is
8.1%. Calculate Ka.

58
Friedrich Wilhelm Ostwald
1853 - 1932
59
60
 Polyprotic Acids
Acids containing more than one acidic
hydrogen are termed polyprotic.

E.g., H2SO4, H2CO3 (diprotic)

H3PO4 (triprotic)

61
Polyprotic acids have several stages of
dissociation, i.e., for any diprotic acid,
H2A,

– +
H2A ⇋ HA + H Ka1
– 2– +
HA ⇋ A + H Ka2

62
63
 Exercise 7

Calculate the pH of a 1.0 M sulphuric

o
acid (H2SO4) solution, at 25 C.
Ka1 >> 1
Ka2 = 1.2 ×10–2

64
 Exercise 8
–2
Calculate the pH of a 1.0 ×10 M
sulphuric acid (H2SO4) solution, at
o
25 C.
Ka1 >> 1
Ka2 = 1.2 ×10–2

65
 Exercise 9

Calculate the pH of a 5.0 M phosphoric

acid (H3PO4) solution and the
equilibrium concentrations of all the
other species in the solution (H3PO4,
– 2– 3– o
H2PO4 , HPO4 , and PO4 ), at 25 C.
[Ka1 = 7.5 ×10–3 Ka2 = 6.2 ×10–8
Ka3 = 4.8 ×10–13 ]

66
End of Unit 4
Part 1

67