CHM271

CHAPTER 3
IONIC EQUILIBRIUM

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 CHAPTER 3 : IONIC EQUILIBRIUM
3.1 Definitions of acid and base by Arrhenius, Bronsted-Lowry and
Lewis
3.1.1 Types of acid & bases
3.1.2 Acid-Base conjugate pairs
3.2 Calculation of pH and pOH (monoprotic, diprotic & triprotic acid
and base)
3.2.1 Definitions of pH, pOH, Kw, pKw, Ka, Kb, pKa and pKb
3.2.2 Strong acid and bases
3.2.3 Equilibria in solutions of weak acids and bases
3.2.4 Degree of dissociation (percent ionization)
 CHAPTER 3 : IONIC EQUILIBRIUM
3.3 Hydrolysis reaction
3.3.1 Methods producing salt
3.3.2 Acidic, basic and neutral salt solutions
3.3.3 Salt hydrolysis. Calculation of pH/pOH values
3.4 Buffer system
3.4.1 Acidic buffer
3.4.2 Basic buffer
3.4.3 Simple calculation of pH/pOH of buffer solution
 ARRHENIUS THEORY
ACID BASE
Substance that produce hydrogen Substance that produce hydroxide
ions (H+) or hydronium ions (H3O+) ions (OH-) in water solution.
in water solution.

2-
2

Limited apply only to water/aqueous solutions

 It shows that all ACIDS contain hydrogen but not all substance containing
hydrogen are ACIDS.
 Disadvantage of Arrhenius theory is that many organic compound do not
contain OH- such as amines and ammonia show BASIC properties in water.
 BRONSTED-LOWRY THEORY
ACID BASE
Substance that can donate an H+ ion Substance that can accept an H+ ion
to a base from an acid.
 Acid is a proton (H+) donor.  Base is a proton (H+) acceptor
 Loss of proton  Gain proton

 Unlike Arrhenius theory which

consider liquids and aqueous
phase, Bronsted Lowry theory can
also be used to define ACIDS and
BASES in the gaseous phase.
 Eventhough, there are no H3O+ or
OH- produce
 LEWIS THEORY
ACID BASE
Substance, that can accept a pair of Substance that can donate a pair
nonbonding electrons of nonbonding electrons
 An acid is an electron pair  A base is an electron pair
acceptor. donor.
 Positive ions usually act as Lewis  Negative ions usually act as
acid Lewis bases
 All cations are Lewis acids since Example:
they are able to accept electrons. OH-, CN-, CH3COO-, NH3, H2O,
 Example: Cu2+, Fe2+, Fe3+ CO

The important of Lewis theory is that

its broaden the scope of ACID-BASE
reaction by including the reactions
which not involved proton.
 TYPES OF ACID & BASE
STRONG WEAK
Acids / bases that are completely Acids/bases that are only partially
ionised in aqueous solution ionised in aqueous solution.
Common strong acids: Common weak acids
HNO3, HCl, HBr, H2SO4 CH3COOH, HCOOH, HF, HCN
Common strong Base Common weak Base
LiOH, NaOH, KOH NH3, NH4OH
 TYPES OF ACID & BASE (B–L)
ACID, HxA BASE, B(OH)x
MONORPOTIC Substances that are able to Substances that are able to
(x = 1) donate only one (1) proton accept only one (1) proton

HCl , HNO3 , CH3COOH NaOH , KOH , NH3

DIPROTIC Substances that are able to Substances that are able to
(x = 2) donate two (2) protons accept two (2) protons

H2SO4 , H2CO3 Ba(OH)2 , Ca(OH)2

TRIPROTIC Substances that are able to Substances that are able to
(x = 3) donate three (3) protons accept three (3) protons

H3PO4 , H3AsO4 Al(OH)3

 CONJUGATE PAIR (B-L)
Acid + Base → Conjugate Base + Conjugate Acid

Conjugate acid (contain more H)

Species formed when H+ is added to a base

Conjugate base (contain less H)

Acid = loss H
Species formed when H+ is removed from an acid Base = Add H

 The stronger the acid or base, the weaker the conjugate.

.  The weaker the acid or base, the stronger the conjugate
EXAMPLE
 PRACTICE

For the following, identify the conjugate acid and the conjugate base.

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

b)HCOOH(aq) + H2O(l)⇋ HCOO-(aq)+H3O+(aq)

c)HCN(aq) + H2O (l) ⇋ CN-(aq) + H3O+(aq)

 THE IONIC PRODUCT FOR WATER, Kw

 Water molecules can function as both acids and bases.

 One water molecule (acting as a base) can accept a hydrogen ion from
a second one (acting as an acid).

Fully written

Simplified form
 However, the hydroxonium ion is a very strong acid, and the hydroxide
ion is a very strong base.
 As fast as they are formed, they react to produce water again
 THE IONIC PRODUCT FOR WATER, Kw
Kw = [H3O+][OH-] = [H+][OH-]
Kw : equilibrium constant for water (unitless)
[H+]/[H3O+] : molar concentration of hydrogen (M)
[OH-] : molar concentration of hydroxide (M)

 In pure water at 25°C, the concentration of H+ and OH- are 1.0 × 10-7 M.
Kw = [H+][OH-]
= (1.0 × 10-7) (1.0 × 10-7)
= 1.0 × 10-14

 Kw and pKw is exactly the same

pKw = - log Kw
= - log (1.0 × 10-14)
= 14
 pH & pOH – A MEASURE OF ACIDITY
 pH = negative log of the hydrogen concentration.

pH = - log [H+]
@
pH = - log [H3O+]
[H+] > [OH-] [H+] = [OH-] [H+] < [OH-]

 pOH = negative log of the hydroxide concentration.

pOH = - log [OH-]

 Relation between pKW, pH & pOH

pKw = pH + pOH = 14
- log Kw = - log [H+] + - log [OH- = 14
 pH & pOH – A MEASURE OF ACIDITY

 The higher the pH, the less acidic the solution

 The lower the pH, the more acidic the solution

 The higher the pOH, the less basic the solution

 The lower the pOH, the more basic the solution

 SUMMARY : pH CALCULATION (STRONG ACID / BASE)

pKw = Kw =
 PRACTICE
1. Determine the pH of the given [H+] and [OH-];
a) [H+] = 3.2x10-4 To write &
balance the
chemical
equation !!!!!!
b) [H+] = 1.0x10-3

c) [OH-] = 2.9x10-4

d) [OH-] = 1.5x10-5
 PRACTICE
2. The pH of a solution was 5.8. Determine the [H+] ion concentration of
the solution.

3. Determine the pH of a 0.122 M solution of HCl.

4. Determine the pH of a 0.1 M solution for the following strong bases:

i. MOH

ii. M(OH)2
 ACID DISSOCIATION CONSTANT, Ka
 Ka = quantitative measure of acid strength for weak acid

 General form of B-L acid ionisation;

 If Ka is large = stronger acid

 If Ka is small = weaker acid
 lower the value for the constant, the more the equilibrium lies to the left.
 BASE DISSOCIATION CONSTANT, Kb
 Kb = quantitative measure of acid strength for weak base

 General form of B-L acid ionisation;

 If Kb is large = stronger base

 If Kb is small = weaker base
 lower the value for the constant, the more the equilibrium lies to the left.
 pKa / pKb

pKa = - log Ka

pKb = - log Kb

 The lower the value for pKa / pKb = the stronger the acid/base
 The higher the value for pKa / pKb = the weaker the acid/base
 pH CALCULATION (WEAK ACID / BASE)

EXAMPLE Determine the pH of 1.0 M solution of CH3COOH.

Given its Ka = 1.8x10-5
SOLUTION
CH3COOH (aq) + H2O (l)⇋CH3COO-(aq) + H3O+(aq)
Initial (I) 1.0 0 0
Change (C) -x x x
Equilibrium (E) 1.0-x x x
Ka = 1.8 x 10-5 x = [H3O+]
pH = -log [H3O+]
= - log (4.24 x 10-3)
= 2.37
1.0 – x ≈ 1.0
x2 = 1.8 x 10-5 (5% RULE)
This approximation is valid if [x] / [initial] < 0.05
x = 4.24 x 10-3
 Ka or Kb < 10-4
SUMMARY : pH CALCULATION (WEAK ACID / BASE)

HA (aq) + H2O (l) ⇋ A-(aq) + H3O+(aq)

Ka = x2 / C
WEAK I C 0 0
x
C -x +x +x
pH = - log x
E C-x x x

BOH (aq) + H2O (l) ⇋ H3O+(aq) + OH- (aq) Kb= x2 / C

WEAK I C 0 0
C -x +x +x pOH = - log x
E C-x x x pH = 14 - pOH
 PRACTICE

1) Determine the pH of a 0.55 M solution of ammonia.

Given that Kb= 1.86 x 10-5 for ammonia.
Ans : 11.5

2) A 0.233 M solution of a formic acid, HCOOH has a pH of 4.22. Determine

the value of Ka.
Ans : 1.56 x 10-8

3) A 1.02 M NH3 solution has a pH of 9.56. Determine the value of Kb.

Ans : 1.29 x 10-9
 DEGREE & PERCENTAGE IONIZATION, ∝
DEGREE OF IONIZATION
The quantity of acid molecules dissociate into hydrogen ion, H+ which
determine the acid strength.
 Usually quantified as percent ionization.

 Measuring the strength of acid;

 The stronger the acid, the greater the percent ionization.

 HYDROLYSIS
DEFINITION Reaction of an anion or a cation of a salt, or both
with water.
 Affects the pH of a solution
 Hydrolysis of cation (A+) = Acidic salt
 Hydrolysis of anion (B-) = Basic salt
 Only strong conjugate acid/base can form hydrolysis reaction.
 Formation of H3O+ or OH- ion from hydrolysis reaction clarify the
acidity/basicity of salt
 NEUTRAL SALT SOLUTION

 Form from strong acid & strong base

 When the salt form, it dissolves in water & dissociates completely;

 They do not undergo hydrolysis / do not react with water

 Thus, their solution are assumed to be neutral.

 ACIDIC SALT SOLUTION
 Derived from a strong acid & weak base.

 When the salt form, it dissociates in water to form NH4+ and Cl- ions.

 Cl- is weak conjugate base of a strong acid ; do not react with water.

 NH4+ is strong conjugate acid of a weak base ; has an ability to

transfer a proton to water during hydrolysis reaction.

 As the reaction produces H3O+, the solution will be acidic solution.

 pH CALCULATION FOR ACIDIC SALT SOLUTION
EXAMPLE Determine the pH of 0.42 M ammonium chloride (NH4Cl).
Given Kb for NH3 is 1.8 x 10-5.

SOLUTION

ACIDIC  Ka
The concentration of the ions are also equal to 0.42 M after dissociation.

NH4+(aq) + H2O (l) ⇋ NH3(aq) + H3O+ (aq)

Initial (I) 0.42 0 0
Change (C)
-x x x
Equilibrium (E)
0.42-x x x
SOLUTION (CONT.)
Ka x = [H3O+]
= 1.53 x 10-5 M

pH = -log [H3O+]
= - log (1.53 x 10-5)
= 4.81
Ka

5.6 × 10-10

x2 = 2.35 x 10-10
x = 1.53 x 10-5 M
 BASIC SALT SOLUTION

 Derived from a strong base & weak acid

 When the salt form, it dissociates in water to form CH3COO- and Na+
ions.

 Na+ is weak conjugate acid of a strong base ; do not react with water.
 CH3COO- is strong conjugate base of a weak base ; has a tendency
to hydrolyze and accept a proton from water.

 Because the reaction produces OH-, the solution will be basic solution.
 pH CALCULATION FOR BASIC SALT SOLUTION
EXAMPLE Determine the pH of a 0.15 M solution of CH3COONa.
Given Ka for CH3COOH is 1.8 x 10-5

SOLUTION

BASIC  Kb
The concentration of the ions are also equal to 0.15 M after dissociation.
CH3COO-(aq) + H2O (l) ⇋ CH3COOH (aq) + OH-(aq)
Initial (I) 0.15 0 0
Change (C) -x x x
Equilibrium (E)
0.15-x x x
SOLUTION (CONT.)
Kb x

pOH

Kb

5.6 × 10-10 pH = 14 – 5.04

= 8.96
x2 = 8.4 x 10-11
x = 9.2 x 10-6 M
 BUFFER SOLUTION
DEFINITION
Solution of a weak acid / base and its salt containing its conjugate base /
conjugate acid which resists changes in pH when small quantities an acid
or an alkali are added to it
 Necessary to keep the correct pH for
enzymes in many organisms to work.
 2 types :
 Acidic : weak acid + conjugate base (salt)
 Basic : weak base + conjugate acid (salt)
 pH of the buffer solution can be changed by
changing the ratio of acid/base to salt.
 Must contain relatively large concentration of
acid or base to react with any OH- or H+
added to it.
 ACIDIC BUFFER SOLUTION
Weak acid and a salt containing its conjugate base
 Eg; CH3COOH & CH3COONa / HF & NaF.
 pH less than 7.
B+ (conjugate base)
 HF in an aqueous solution HA (weak acid)

Acidic buffer

 Then add and dissolve sodium fluoride into the solution and mix the two

 Since Na+ is the conjugate of a strong base, it will have no effect on the pH
or reactivity of the buffer.
 Addition of NaF to the solution increase the concentration of F-.
 The presence of significant amounts of HF, and F-, allows the solution to
function as a buffer.
 HOW DO BUFFER SOLUTIONS WORK?

If acid is added:

 The buffer solution must remove most of the new hydrogen ions
otherwise the pH would drop markedly.
 Hydrogen ions combine with the F- to make HF. since the HF is a weak
acid, most of the new hydrogen ions are removed in this way.
 Since most of the new hydrogen ions are removed, the pH won't change
very much - but because of the equilibria involved, it will fall a little bit.
 HOW DO BUFFER SOLUTIONS WORK?

If base is added

 HF, will neutralize added amounts of base, OH-

 slightly increasing the concentration of F- in the solution and decreasing
the amount of HF slightly.
 Again, since most of the OH- is neutralized, little pH change will occur.
 BASIC BUFFER SOLUTIONS
Weak base and a salt containing its conjugate acid
 Eg; NH3 & NH4Cl /
 pH more than 7.
 NH3 in an aqueous solution BOH (weak base) B+ (conjugate acid)

Basic buffer

 Then add and dissolve NH4Cl into the solution and mix the two

 Since Cl- is the conjugate of a strong acid, it will have no effect on the pH
or reactivity of the buffer.
 Addition of NH4Cl to the solution increase the concentration of NH4+.
 The presence of significant amounts of NH3, and NH4 +, allows the
solution to function as a buffer.
 HOW DO BUFFER SOLUTIONS WORK?

• If acid is added:

 Hydrogen ion is going to collide with is an ammonia molecule to form

ammonium ions.
 Most, but not all, of the hydrogen ions will be removed
 HOW DO BUFFER SOLUTIONS WORK?

If base is added

 Hydroxide ions from the alkali are removed by a simple reaction with
ammonium ions.
 Most (but not all) of the the hydroxide ions are removed from the solution.
HOW DO BUFFER SOLUTIONS WORK?
 HENDERSON-HASSELBALCH EQUATION

Calculation of pH and pOH for buffer solution

@
EXAMPLE
A solution contains 0.15 M HCOOH and 0.12 M NaHCOO.
Determine the pH of the solution? Given Ka for HCOOH is 1.8 x 10-4.

SOLUTION
Assumption:
1. Assume that the HCOO- concentration is the same as
the concentration of the HCOONa
2. Concentration of the acid at equilibrium is the same as
the concentration of the acid we used
pH = pKa + log [NaHCOO] / [HCOOH]
= - log (1.8 x 10-4) + log (0.12 / 0.15)
= 3.65
EXAMPLE
Determine the pH of a buffer solution containing 0.1 M NH3 and
0.05 M NH4Cl. Given Kb for NH3 is 1.8 x 10-5.

SOLUTION

pOH = pKb + log [NH4Cl] / [NH3]

= - log (1.8 x 10-5) + log (0.05 / 0.1)
= 4.44

pH = 14 – 4.44
= 9.56
 REVISION

1) Define
i. An acid and base according to Lewis theory.
ii. Conjugate acid according to Bronsted-Lowry theory.

2) The dissociation constant of a base, BOH at 25°C is 1.5 x 10-10.

If the concentration of BOH is 0.015 M, determine
i. The degree of dissociation
ii. The concentration of hydroxide ion in the solution.

3) Write the ionization equation of ammonia in water and determine the

pH value of a 0.10 M ammonia solution. Given Kb value of ammonia is
1.8 x 10-5.
 REVISION
4. Calculate the pH of a 0.200 M solution of NH4CI. Given Kb value of
ammonia is 1.8 x 10-5 and Kw=1.0x10-14.

5. Determine the pH value of a 0.25 M sodium acetate, CH3COONa.

Given Ka for CH3COOH is 1.8 x 10-5.

6. Determine each of the following acid-base reactions produce

acidic, basic or neutral salt. Write the hydrolysis reaction where
applicable.
a) HNO3 + CH3NH2 d) HBr + Ba(OH)2
b) HF + KOH e) H2SO4 + NH3
c) H2CO3 + NaOH f) HClO4 +NaOH
7. Determine the pH of a buffer solution containing 0.60mol solution
of ammonium nitrate, NH4NO3 and 0.40 mol of ammonia,NH3 in 1L
solution. Given Ka for NH4+ is 5.6 x 10-10.
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