Ionic Equilibrium

Acid-base equilibrium Solubility equilibrium

Acid – base Equilibrium

The Arrhenius Theory

1. Acid-substances that dissociate in water to produce H+
eg: HA (aq) H2O H+ (aq) + A- (aq)
2. Base-substance that dissociate in water to produce OH-
eg: M(OH) (aq) M+ (aq) + OH- (aq)
H2O

Limitations
a) Cannot account for the basic properties of certain compounds that do not contain
–OH groups/ ions in their molecules such as amines,RNH2,NH3,NA2CO3 and
C2H5ONa2

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

NH3 reacts with HCl by receiving proton or H+ but not by donating OH-
 BRONSTED-LOWRY THEORY
1.Bronsted Acid: Acid substance( molecule or ion) that can donate
a proton, H+ to another substance/to a base
Eg: HCl, HNO3,HF
2. Anionic and cationic salts that have proton that can be transferred/donated such as
NH4 +, HSO4- ,HCO3-

3. Base-substance that can accept a proton from an acid/another substance.

Eg: Negative ion or neutral molecule with a lone pair of electrons which can form a dative
covalent bond with the proton such as H2O,F-, NH3
and OH-
HA + B BH+ + A-
Acid Base Conjugate Conjugate
Acid Base
Proton Proton
Donor Acceptor
- loses - accepts - species - species
Its proton proton formed when formed when
to form to form when a H+ a proton is
base an acid is added to removed from
a base an acid
 Acid-base conjugate pair
1. Species differ by a proton
HA & A-
Acid Conjugate Base
B & BH+
Base Conjugate Acid
2. Water is an amphoteric solvent
Acts as a base
CH3COOH(aq) + H20(l) CH3COO-(aq) + H30+(aq)
Acid Base Conjugate Conjugate
Proton Donor
∼ Proton Acceptor Base Acid
coz has lone hydroxonium ion/
pair of ē oxonium ion/
hydronium ion
Acts as an acid
NH3(aq) + H20(l) NH4+ (aq) + OH-(aq)
Base Acid Conjugate Conjugate
Proton Acceptor Proton Donor Acid Base
ADVANTAGES
- can be used to define acids & bases in gaseous phase.
HCl (g) + NH3 (g) → NH4Cl (g)
acid base
(proton (proton
donor) acceptor)
- Can be used to discuss the strength of an acid or a base.
HA + H2O A– + H3O+
α is increased, eq. position lies to the right, when HA is a stronger acid.
B + H2O BH+ + OH–
B is a stronger base
(α = degree of dissociation)
hexaaquo complexes, [M(H2O)6]n+ which have small highly charged cations (such
as Al3+, Fe2+, Cr3+, Be2+) act as Bronsted–Lowry acids in water.
eg. [Al(H2O)6]3+ + H2O [Al(H2O)5OH]2+ + H3O+
acid base
(proton (proton
donor) acceptor)
 H2O
H2O
H2O
Mn+
Central metal ion
- empty valence
orbitals
H2 O
H2O

H2 O
LIMITATION
Chemical species that do not contain H+ are not defined as acids .eg: BF3

EXERCISE 1
Classify the underlined substances in the following equations as either
acids or base according to Bronsted-Lowry’s definition.
a) HCO3 – + HCl H2CO3 + Cl–
b) NH4+ + NH2– 2NH3
c) CH3CONH2 + H20 CH3CONH3+ + OH–
d) NaH + H20 NaOH + H2

EXERCISE 2
Give the formula of the conjugate acids for the following base.
a) Cl – –
b) C2H5O –
c) NH2OH –
d) C6H5NH2 –
e) HCO3 – –
f) OH – –
 THE BASICITY OF AN ACID
ACID

Monoprotic acid Polyprotic acid/Polybasic acid

- Produces only one single -Donates more than one proton
proton permolecule on permolecule of the acid on dissociation.
dissociation eg: Diprotic acid are – H2SO4,H2CO3
OR Polyprotic acids dissociate in stages

Monobasic acid and have more than one Ka.

- Forms only one conjugate base Eg: H3PO4 H+ + H2PO4 –(K1)
permolecule of the acid H2PO4 - H+ + HPO4 2- (K2)
Eg: HCl , CH3COOH, HNO3 HPO4 2- H+ + PO4 3- (K3)
H3PO4 3H+ + PO4 3-

Ka for H3PO4 = K1 X K2 X K3
= [H+]3 [PO4 2- ]
[H3PO4]
 Lewis Theory
Acid - species( an atom, ion or molecule ) which can form a dative
covalent bond by accepting one pair of electron from a base.
- electron pair acceptor.
- eg : 1. all the positive ions
2. oxidising agents
3. molecules with an incomplete octet of electrons such as
BF3, BeCl2, BCl3, AlCl3
Base – species that has an unshared electron pair which can form a
dative bond with an atom, molecule or ion.
- electron pair donor
- eg:- negative ions
- reducing agents
- molecules with lone pair of electrons such as H2O:, :NH3,
R-CH ..
Neutralisation

The formation of a dative covalent bond between a species that donates an electron pair
(Lewis base) and the species that accepts an electron pair( Lewis Acid)
:

:
: :
H + : O H–
+ O
H H
+
H
H+ + : NH3
N

↓
H H
H

An acid- base reaction( Bronsted- Lowry Theory)

A reaction where an electron pair of a base is accepted by an acid through the formation of
Cl
a dative covalent bond. H
Eg. :NH3 + BCl3 H N B Cl
Lewis Lewis H Cl
base acid
eg:

OH OH –
HO B + H2O HO B OH + H+
OH Lewis OH
Lewis acid base

eg:
2+
H2N :
– :NH
3
:

Cu2+ + 4NH3 Cu
: :
Lewis Lewis H3N NH3
acid base
(Central (liquids) Complex ion
metal ions)
LIMITATION
• HCl(g), Bronsted acid, is not an acid from the point of Lewis
Theory- because it cannot accept an electron pair.
ADVANTAGES
1. Acid-base reaction can be extended to include reactions in
which protons are not involved.
eg. BF3 + NH3 BF3 NH3
Acid Base (No transfer of proton)
2. Lewis bases are also Bronsted – Lowry bases as all electron
pair donors can accept a proton.
3. Lewis acids( eg. Metal ions) need not be Bronsted – Lowry
acids ( proton donors).
So, Lewis Theory broadens the concept of an acid. Lewis
acids includes not only H+ ions but also cations and molecules
with empty valence orbitals that can accept electron pairs
from a Lewis base.
1. Electrolyte- A chemical compound that will conduct electricity in molten
state or in aqueous solution.( because of the presence of free/ mobile ions)
2. Non- electrolyte- A chemical compound that cannot conduct electricity both
in molten state or in aqueous solution.( because they do not have mobile
ions)
Electrolytes

Strong electrolytes Weak Electrolytes

Example
- Mineral acids (HCl, HNO3, H2SO4) - Organic acids (CH3COOH)
- Alkalis ( NaOH, KOH, Ca(OH)2, Ba(OH)2) - Organic bases (amines, NH3 )

- ionic salts.
- Degree of dissociation ~ 100% - Low < 0.1, <0 ( partially ionised)

- Electrical conductivity - Good Poor

- [ions]- high - Low ( most of them remain as
undissociated molecules)
 The strength of acids & bases
Obj. questions Can be compared by

pH Degree of dissociation the dissociation constant

•The [ ] must be the same
•pH = - log [ H+] • Atconstant T,Ka
•α Strength Strength of acid or Kb
•0 7 14
• Degree of dissociation varies with Strength of base
•Acid neutral base
[ ]. • Dissociation constant will
•pH value changes
% dissociation not change with [ ]
with [ ]
• It only depend on the T
* Not a good way
[HA] dissociate x 100%
because [ ] must be • Commonly used to
the same in order to [HA] initial
compare the strength of
compare.
acid/ base
•[]↓,α ↑ [ ]

1.0

1
[ ]
Exercise
1.Arrange the acids in ascending order of the strength of the acid.
Ka/M p Ka
HCOOH 2.09X10-4 3.68
CH3COOH 1.80X10-5 4.75
HCN 4.90X10-10 9.30
H2CO3 7.47X10-7 6.35
Solution: HCN < H2CO3 < CH3COOH < HCOOH

acid strength increase

↑
(Ka or p Ka ↓ )
↑
 Acids

Strong Acids Weak Acids

-Most mineral acids -Organic acids

Eg. : HCl , H2SO4 , HNO3 Eg. : CH3 COOH
HCl + H2O → H3O+ + Cl– CH3 COOH + H2O CH3COO– + H3O+
(almost complete dissociation) (partially dissociates)
α : ̴ 100% < 100%
[H+} :  
pH :  
Ka :  

pKa :  

Way to determine
pH :  determine [H+]  determine [H+] by
–[H+] is obtained directly from [acid] [H+] = √ Ka⋅ C
eg: [H+] = [monoprotic acid] = cα
2[H+] = [dibasic acid] c = concentration of weak acid

eg: H2SO4  2H+ + SO42–  pH = –log [H+]

0.1 M 2 x 0.1 M
 pH = – log [H+]
Calculate the pH of
i) 0.01 mol dm–3 sulphuric acid
ii) 0.01 mol dm–3 CH3COOH (Ka = 1.80 x 10–5 M)
 Bases

Strong Bases Weak Bases

Eg. : NaOH, KOH, Ba(OH)2 Amines, NH3

NaOH → Na+ + OH– NH3 + H2O NH4 + + OH–
α : ̴ 100% ̴ 10%
(almost completely (partially dissociated)
dissociated)
[OH – ] :  
pOH :  
Kb :  
pKb :  

Way to determine
pH :  determine [OH – ]  determine [OH+] by
–[OH – ] is obtained directly from [base] [OH – ] = √ Kb⋅ C
eg: NaOH  Na+ + OH – = cα
0.1 M 0.1 M  pOH = –log [OH – ]
eg: Ba(OH)2  Ba2+ + 2OH–
0.1 M 2 x 0.1 M  pH = 14 – pOH
 pOH = – log [OH] –
 pH = 14 – pOH
 Exercise
1.Calculate the pH of
i. 50 cm3 of 0.5M of Ba(OH)2
ii. 50 cm3 of 0.5M of NH3
(Kb NH3 = 1.75 x 10–5 mol dm–3 )
2.Calculate the pH of
50 cm3 of 0.5M of NH3 + 50 cm3 of 1M of H2SO4

Ostwald Dilution Law

― shows relationship between the concentrations of weak acids / bases and α / Ka; Kb

For weak Acids

HA + H2O H3O+ + A–
Initial
moles in c o o
3
1dm solution
No. of moles
dissociated/ cα cα cα
formed
Eq. moles c - cα cα cα
 [A–] [H3O+]
[HA]

[OH–] [BH+]
[B]
cα ⋅
cα
(1 -2 α )
c cα
1-α

∼
∼

√
Kb
c
[A–] [H3O+] [BH+] [OH–]
[HA] [B]

cα ⋅
cα
c (1 - α )
Ostwald Dilution Law (continued)
cα 2
Ka = 1-α
For weak acids,
α ∼is very small,
∼
∴1 - α 1

∴ Ka = cα 2

√
Ka
α =
c

[H+] = cα

√
Ka For weak bases
=α
c
B + H2 O BH + + OH–
= √ Ka C Initial moles in
1dm3 solution c o
o
∴ [H+] = √ Ka ⋅ C
No. of moles
dissociated/formed cα cα
cα
Eq. moles c - cα cα cα