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
ions (H+) or hydronium ions (H3O+) hydroxide ions (OH-) in water
in water solution. 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+
to a base ion from an acid.

▪ Acid is a proton (H+) ▪ Base is a proton (H+)

donor. ▪ Loss of proton acceptor ▪ 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 Substance that can donate a
of nonbonding electrons pair of nonbonding electrons
 ▪ An acid is an electron ▪ A base is an electron
pair acceptor. pair donor.
▪ Positive ions usually act as ▪ Negative ions usually act
Lewis acid as Lewis bases
Example:
▪ All cations are Lewis acids since OH-, CN-, CH3COO-, NH3, H2O,
they are able to accept electrons. CO
▪ Example: Cu2+, Fe2+, Fe3+

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 Common ionised in aqueous solution. Common
strong acids: 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

MONORPOTI Substances that are able Substances that are able

C (x = 1) to donate only one (1) to accept only one (1)
proton proton

HCl , HNO3 , CH3COOH NaOH , KOH , NH3

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

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

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

Species formed when H+ is removed the acid or base, the stronger the
from an acid conjugate
Acid = loss H Base = Add H

▪ The stronger the acid or base, the

weaker the conjugate. ▪ The weaker
.

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 pKwis 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

b) [H+] = 1.0x10-3

c) [OH-] = 2.9x10-4

d) [OH-] = 1.5x10-5
To write &
balance the chemical
equation !!!!!!
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 SOLUTION Determine the pH of 1.0 M solution of
CH3COOH. Given its Ka = 1.8x10-5
Change (C) -x x x
Equilibrium 1.0-x x x
(E)

K
a
=

1.8 x 10-5 x = [H3O+]

pH = -log [H3O+]
= - log (4.24 x 10-3)
x2 = 1.8 x 10-5 1.0 – x ≈ 1.0 (5% RULE)
= 2.37
x = 4.24 x 10-3 This approximation is valid if [x] / [initial] < 0.05 ▪
Ka or Kb < 10-4
SUMMARY : pH CALCULATION (WEAK ACID / BASE)

H3O+(aq) I C 0 0 C -x +x +x Ka = x2/ C
EC-xxx x
WEAK pH = - log x
BOH (aq)+ H2O (l) ⇋ H3O+(aq)
WEAK
+ OH-(aq) I C 0 0 C -x +x +x Kb= x2/ C
HA (aq)+ H2O (l) ⇋ A-(aq)+
EC-xxx
 pOH = - log 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.

 DEFINITION
HYDROLYSIS
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 SALTSOLUTION

▪ 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 SALTSOLUTION

▪ 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 SOLUTION Determine the pH of 0.42 M ammonium
chloride (NH4Cl). Given Kbfor NH3 is 1.8
x 10-5.
 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 SALTSOLUTION
 ▪ 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
 Determine the pH of a 0.15 M solution of CH
EXAMPLE 3COONa. Given Ka
for CH3COOH is 1.8 x 10-5

SOLUTION

BASIC 🡪 KbThe
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.)
Kbx
 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.
aqueous solution
▪ HF in an
+
HA (weak acid) B (conjugate base) 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.
SOLUTIONAssumption:

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 Kbfor NH3is 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

1) Define
REVISION
 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 Kbvalue 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 Kafor
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+ CH3NH2d) 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,NH3in 1L solution. Given Kafor NH4+is
5.6 x 10-10.
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