Analytical Chemistry lectures

Winter 2022

Acid - Base Equilibria

DR. AMINA AMIMN
A)Acid-base reactions
1.Acid-base reactions in aqueous media
2. Acid-base reactions in non-aqueous media
Chemical composition of aqueous solutions
Water is the most plentiful solvent on earth,is
easily purified,and is not toxic. It is ,therefore,
widely used a medium for chemical analyses.
An aqueous solution consists of basically two
components, the solvent (water) and the solute
dissolved in the water.
Properties of water
Water is “bent” or V-shaped
The O-H bonds of water are covalent.
Water is a polar molecule.
Water can acts as acid or base.
B) Acid-base theories
1) Arrhenius theory
2) Lewis theory
3) Brønsted-lowry theory
 B)Acid-base theories

1B) Arrhenius theory

Acid is the substance which ionizes into H⁺ while
bases give OH⁻.This theory did not discuss the role
of solvent in the ionization process.
2B) Lewis theory
A base is the substance containing an atom with
unshared pair of electron e.g.N,O,S,P.
While an acid is that which accepts to share this
electronic pair.
H⁺ + :OH H:OH
HCl + :NH₃ NH₄⁺Cl⁻
According to Lewis theory, the presence of proton is not
essential for an acid.
a) Compounds containing no OH⁻and react as alkaline e.g.
ammonia
NH₃ + HCl → NH₄⁺Cl⁻
b) Compounds containing no H atoms react as acids e.g.
Boron trichloride in trimethylamine
3B) Brønsted-lowry theory
 Acid is the substance that donates proton (H⁺), while
base is the substance that accept proton (H⁺)
Acid ↔ proton+ conjugate base
HCl ↔ H⁺ +
 CH₃COOH ↔ H⁺ + CH₃COO ⁻
H₂O ↔ H⁺ +OH ⁻
The solvent in this theory is involved in the reaction
as acid or base.
HCl + H₂O ↔ H₃O⁺ + Cl ⁻
NH ₃ +H₂O ↔ NH₄⁺+OH ⁻
Brønsted-lowry theory states that an acid is a proton
donor , and a base is a proton acceptor.
For a molecule to behave as an acid, it must
encounter a proton acceptor (or base).
likewise , a molecule that can accept a proton
behaves as a base if it encounters an acid.
 C) Classification of acids and bases
according to Brønsted –Lowery
theory
A)Acids B) Bases
1 . Neutral molecules (uncharged 1 . Neutral molecules
acids)
e.g.
(uncharged base)
HCl,H₂SO₄,HClO₄,CH₃COOH e.g. NH₃ , R-NH₂ , R₂ NH
2. Charged acids 2. Charged bases
a)Anionic acids e.g.
HSO₄⁻,H₂PO₄⁻
Anionic bases e.g.
b)Cationic acids e.g.NH₄⁺,R-NH₃⁺
CH₃ COO⁻ , Cl⁻
 1C) Conjugate acids and bases
According to Brønsted –Lowery theory, the product
formed when an acid gives up a proton is a potential proton
acceptor and is called the conjugate base of the parent acid.
Example , when the species acid 1 gives up a proton
acid1↔ base1 + proton
We refer to acid1 and base1 as a conjugate acid and base
pair, or just a conjugate pair.
Similarly , every base accepts a proton to produce a
conjugate acid . That is ,
base2 + proton ↔ acid2
 When these two processes are combined , the result is an acid /base,
or neutralization reaction.
acid1 + base2 ⇌base1 + acid2
 For example, in an aqueous solution of ammonia ,water can donate
a proton and acts as an acid to the solute NH₃ :
NH₃ + H₂O ⇌NH₄⁺ + OH ⁻
base1 acid2 conjugate acid1 conjugate base2
 In this reaction , ammonia (base1) reacts with water , which is
labeled acid2 , to give the conjugate acid ammonium ion (acid1) and
hydroxide ion , which is the conjugate base (base2)of the acid water .
 On the other hand, water acts as a proton acceptor,or base,in an
aqueous solution of nitrous acid:

H₂O + HNO ₂ ⇌H₃O⁺ + NO ₂ ⁻

base1 acid2 conjugate acid1 conjugate base2

 2C)Classifying of electrolytes
Electrolytic dissociation theory: when an
electrolytes is dissolved in water it dissociate into
cations (+ ve charge) and anions (- ve charge) .
Electrolytes , which form ions when dissolved in
water (or certain other solvents), produce
solutions that conduct electricity.
1) Strong electrolytes ionize essentially completely
2) Weak electrolytes ionize only partially.
Electrolytes
Strong electrolytes Weak electrolytes
Dissociate completely in Dissociate to a small extent
aqueous solution in aqueous solution.
Conduct current Conduct only a small
current.
efficiently.
 Many inorganic acids,
Inorganic acids such as
including H2CO3,H3BO3 ,
HClO4 , H2SO3
HNO3 ,H2SO4 ,HCl Ammonia and most organic
Alkali and alkaline. bases.
3C)Strengths of acids and bases
Perchloric acid (HClO4) and hydrochloric acid (HCl)
are completely dissociated .
Only ῀ 1% of acetic acid (CH3COOH) is dissociated .
Ammonium ion (NH4⁺ ) is an even weaker acid with
only about 0.01% of this ion being dissociated into
hydronium ions and ammonia molecules.
The weakest acid forms the strongest conjugate base,
thus ammonia has a much strong affinity for protons.
Perchlorate and chloride ions have no affinity for
protons.
Acids

Strong Weak
HCl HOAc
HNO3 HF
HClO4 H2CO3
H2SO4
Bases
Strong NaOH KOH Ba(OH)2
Weak NH3(NH4OH) ( ammonia ammonium
hydroxide)
C6H5NH2 ( aniline)
D)Acid -base equilibrium in aqueous solutions
The dissociation of an acid is expressed by
HA ⇌ H⁺ + A⁻
The dissociation constant of an acid
Ka = ([𝐻⁺ ] [ 𝐴⁻])/([𝐻𝐴 ])

When Ka ˂ 1 , [HA ] ˃ [H⁺ ] [ A⁻] and HA is

not significatly dissociated. Thus,
The smaller the value of Ka, the weaker the acid .
Acid -base equilibrium in aqueous solutions
NH3 (aq) + H2O(l) ⟶ NH4⁺ (aq) + OH⁻ (aq) ----- (1)
In this reaction NH3 acts as base and it’s conjugate acid is
NH4⁺ .
Kb = [NH4 ⁺ ] [OH ⁻ ]/ [NH3]
If we write a reaction for dissociation of acid NH4⁺ we can get
the following equation for Ka :
NH4 + (aq) + H2O(l)⟶ H3O⁺(aq) + NH3(aq) -------- (2)
Ka = [H3O ⁺] [NH3]/ [NH4 ⁺ ]
If we add equation 1 and 2, we will get a new equation:
2H2O(l) ⟶ H3O ⁺(aq) + OH ⁻ (aq)
Kw = [H3O ⁺ ][OH ⁻ ]
Acid -base equilibrium in aqueous solutions

(
Ka × Kb = [H3O⁺] [NH3]/ [NH4⁺]) ([NH4⁺] [OH⁻]/ [NH3])
Ka × Kb = ([H3O⁺] [NH3] / [NH4⁺] )([OH⁻]/[NH4⁺] [NH3])
Ka × Kb = Kw
1D)Relationship between pKa and pKb
pKa + pKb = pKw =14.00
pKa = - log Ka Ka = Kw/ Kb
pKb = - log Kb Kb = Kw/ Ka
pKw = - log Kw Where Kw = 1.0 x 10⁻ ¹⁴
pKa = 14.00 - pKb
pKb = 14.00 - pKa
2D)pH and acidity
2H2O → H3O⁺ + OH⁻
hydronium ion hydroxide ion

pH = -log [H3O⁺]
pOH = -log [OH⁻]
pH Scale
3D)Relationship between pH and pOH
pH + pOH = 14
Therefore , if one of the two values is known it is easily
to calculate the other one.
pH = 14 − pOH
pOH = 14 − pH
:Examples
 Find the pH of a 0.0025 M HCl solution. The HCl is a
strong acid and is 100% ionized in water. The hydronium
ion concentration is 0.0025 M.
pH = - log (0.0025)
= -(-2.60) = 2.60
What is the hydronium ion concentration in a solution
that has a pH of 8.34?
8.34 = - log [H3O+]
- 8.34 = log [H3O+]
[H3O+] = 10-8.34 = 4.57 x 10-9 M
Examples
A solution has a pH of 6.88. What is [H3O⁺]?
[OH⁻]?
A solution has an [OH ⁻] of 1.4 x 10⁻⁷ M. Show that
this solution is slightly basic by calculating its pH.
The ka of HCN is 4.9 x 10⁻ ¹⁰ .calculate the kb for the
CN ⁻ ion .
Calculate the pH of a 4.22 x 10⁻⁴M NaOH solution.