ACIDS AND BASES

CHE 434
PROCESS CHEMISTRY

Arrhenius Theory
Acid = substance that ionize in
water to produce hydrogen ion (H +).

HCl H+ + Cl Base =substance that ionize in

water to produce hydroxide ion
(OH-)

NaOH Na+ + OH-

Brnsted-Lowry Theory
Concept: acid-base reactions involve the transfer
of H+ ions from one substance to another
Acid =substance capable of donating a proton
(H+).
Base = substance that can accept a proton (H +)
Base
acceptor.
(B)
For example:

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

Acid
(B)

For example:
Acid
(B)

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

Base (B)

 Water can act both as Brnsted acid

and Brnsted base.
Water is an amphiprotic.
Amphiprotic = a substance that can act
both as Brnsted acid and Brnsted
base.

Proton Transfer Equilibria in

Water
Proton transfer between acids
and bases is FAST IN BOTH
DIRECTIONS.
So, previous equations give:
HF (g) + H2O (l) H3O+ (aq) + F- (aq)
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

Conjugate Acids and

Conjugate Bases

When a species donates a proton (so it

acts a Brnsted acid), it becomes the
conjugate base.
When a species accepts a proton (so it
acts a Brnsted base), it becomes the
conjugate acid.

The Strength of Brnsted-Lowry

Acids and Bases

The stronger the

acid, the weaker
is its conjugate
base.
The stronger the
base, the weaker
is its conjugate
acid.

 Strong acid completely transfer its

proton to water, no undissociated
molecules
Weak acid partially dissociates in aq
solution exist as acid molecules +
constituent ions.
Negligible acidity (CH4) contains
hydrogen but has no acidic behaviour
in water.

The strength of a Brnsted acid is

measured by its acidity constant
(Ka).
The strength of a Brnsted base is
measured by its basicity constant
(Kb).

Acidity constant
constant), Ka:

HX (aq) + H2O (l)

Ka

(or

acid

ionization

H3O+ (aq) + X- (aq)

H O X

HX
The larger the value Ka, the stronger the
acid

 If Ka is very small (Ka <<1) , [HX] is

large with respect to [X-],
So,
1. PROTON RETENTION by the acid is
favoured.
2. Very small fraction of acid is
DEPROTONATED.

Basicity constant (or base ionization

constant), Kb:

B (aq) + H2O (l)

BH+ (aq) + OH- (aq)

BH OH

Kb

 If Kb is very small (Kb <<1) , [B] is large

with respect to [BH+],
So,
1. Very small fraction of base is
PROTONATED.

Autopyrolysis (or
Autoionization)
Since water is amphiprotic, a proton
transfer equilibrium exists with an
absence of added acids or bases.

 Autopyrolysis constant:

K c H 3O OH

In pure water at 25oC,

K w H 3O OH

1.0 10

14

pK= -log K
pKa + pKb = pKw
pH/OH= -log[H3O+]/[OH-]
pH + pOH = 14.00

Strong and Weak Acids and

Bases
An acid or base is classified as either
weak or strong depending on the size
of its acidity constant.
Strong acid: The proton transfer
equilibrium lies strongly in favour of
donation of a proton to water. pKa <
0, Ka > 1

 Weak acid: The proton transfer

equilibrium lies in favour of ionized
acid.
pKa > 0, Ka < 1

 Strong base: species that is mostly

protonated in water.
pKb < 0, Kb >
1

Weak base: species that is only

partially protonated in water.
pKb > 0, Kb < 1

Percent Ionization
Measure the strength of an acid,
strong acid has greater percent
ionization.

Example: 0.035M solution of HNO2

contains 3.7 x 10-3 M H+(aq).

 The conjugate base of any strong

acid is a weak base.
The conjugate base of any weak acid
is a strong base.
The conjugate acid of any strong
base is a weak acid.
The conjugate acid of any weak base
is a strong acid.

Polyprotic Acids
Polyprotic acid = a species that loses
protons in succession, and
successive deprotonations are
progressively less favourable.
This is because the additional
electrostatic work must be done to
remove the positively charged
proton.

Characteristic of BrnstedLowry Acid

Acidic proton is the donatable proton.

There are 3 types of acidic proton:
1. Aqua Acid = the acidic proton is on a
water molecule coordinated to a central
metal ion.
For example:

[Fe(H2O)6]3+(aq) + H2O(l) Fe(H2O)5(OH)]2+

(aq)
+ H3O+(aq)

2.Hydroxoacid = the acidic proton is

on a hydroxyl group without a
neighbouring oxo group (=O)
For example: Te(OH)6

3. Oxoacid = the acidic proton is on

a hydroxyl group with an oxo
group (=O) attached to the same
atom.
For example: H2SO4

 The successive stages in the

deprotonation of an aqua acid:
AQUA ACID
OXOACID

HYDROXOACID

The strength of aqua acids increase

with increasing positive charge of the
central metal ion and with decreasing
ionic radius.

Lewis Theory

A more general definition

Acid electron-pair acceptor
Base electron-pair donor.
Example: BF3 (acid)and NH3 (base)

 A Brnsted-Lowry base is a Lewis

base, but Lewis base can donate its
electron pair to other than H+