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+) acceptor.
For example:
Base
(B)

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 (or acid ionization
constant), Ka:

HX (aq) + H2O (l) H3O+ (aq) + X- (aq)

Ka
H O X
3

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)

Kb
BH OH

B
 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 Brnsted-Lowry 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 HYDROXOACID OXOACID

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+