Chemistry Malaysian Matriculation Full Notes Amp Slides For Semester 1 and 2 PDF

WELCOME TO SKO16
CHEMISTRY
CHEMISTRY
CHEMISTRY
CHEMISTRY SK016
Chapter Topics Hours
1.0 Matter 7
2.0 Atomic Structure 7
3.0 Periodic Table 4
4.0 Chemical Bonding 2
5.0 State of Matter 7
6.0 Chemical Equilibrium 5
7.0 Ionic Equilibria 12
Total 54
08/16/11 matter 2
CHEMISTRY SK026
Chapter Topic Hours
8.0 Thermochemistry 4
9.0 Electrochemistry 6
10.0 Reaction Kinetics 7
11.0 Intro To Organic Chemistry 4
12.0 Hydrocarbons 8
13.0 Aromatic Compounds 3
14.0 Haloalkanes (Alkyl halides) 4
15.0 Hydroxy compounds 3
08/16/11 matter 3
CHEMISTRY SK026
Chapter Topic Hour
16.0 Carbonyl 4
17.0 Carboxylic acids & Derivatives 4
18.0 Amines 5
19.0 Amino acids and Proteins 2
20.0 Polymers 1
08/16/11 matter 4
ASSESSMENT
1. COURSEWORK (20%)
 Continuous evaluation (tutorial/test/quiz) - 10%
 Practical work - 10%
2. MID-SEMESTER EXAMINATION - 10%
3. FINAL EXAMINATION (70%)

 Paper 1 (30 multiple choice questions)- 30%
 Paper 2 (Part A-
structured) (Part
B-long structured) -100%
08/16/11 matter 5
REFERENCE BOOKS
 CHEMISTRY ,9th Ed. – Raymond Chang, McGraw-Hill
 CHEMISTRY –The Molecular Nature of Matter and

Change, 3rd Ed.– Martin Silberberg, McGraw Hill
 CHEMISTRY – The Central Science, 9th Ed. Theodore

L.Brown, H.Eugene LeMay,Jr, Bruce E Bursten,
Pearson Education
 GENERAL CHEMISTRY – Principle & Structure, 6th Ed.

James E Brady, John Wiley and Sons.
08/16/11 matter 6
 GENERAL CHEMISTRY – Principle and Modern
Applications, 8th Ed. Ralph H. Petrucci, William
S. Harwood, Prentice-Hall
 ORGANIC CHEMISTRY, 7th Ed – T.W.Graham

Solomon,Craig B.Fryhle, John Wiley and Sons
 ORGANIC CHEMISTRY, 4th Ed – L.G. Wade, Jr,

Prentice Hall
 ORGANIC CHEMISTRY, 6th Ed – John

McMurry, Thompson – Brooks/Cole
08/16/11 matter 7
Chapter 1 : MATTER
1.1 Atoms and Molecules
1.2 Mole Concept
1.3 Stoichiometry
08/16/11 matter 8
08/16/11 matter 9
Learning Outcome
At the end of this topic, students should be
able to:
(a) Describe proton, electron and neutron in

terms of the relative mass and relative
charge.
(b) Define proton number, Z, nucleon
number, A and isotope.
(c) Write isotope notation.
08/16/11 matter 10
Introduction
 Matter
 Anything that occupies space and has
mass.
e.g: air, water, animals, trees, atoms, etc
 Matter may consists of atoms, molecules or

ions.
08/16/11 matter 11
Classifying Matter
08/16/11 matter 12
 A substance is a form of matter that has
a definite or constant composition and
distinct properties.
Example: H2O, NH3, O2
 A mixture is a combination of two or

more substances in which the
substances retain their identity.
Example : air, milk, cement
08/16/11 matter 13
An element is a substance that cannot be
separated into simpler substances by
chemical means.
Example : Na, K, Al,Fe
A compound is a substance composed of

atoms of two or more elements chemically
united in fixed proportion.
Example : CO2, H2O, CuO
Three States of Matter
SOLID LIQUID GAS
08/16/11 matter 15
a) Atoms
 An atom is the smallest unit of a chemical
element/compound.
 In an atom, there are 3 subatomic particles:
- Proton (p)
- Neutron (n)
- Electron (e)
08/16/11 matter 16
Modern Model of the Atom
 Electrons move around the region of the atom.
08/16/11 matter 17
 All neutral atoms can be identified by the
number of protons and neutrons they
contain.
 Proton number (Z)  is the number of

protons in the nucleus of the atom of an
element (which is equal to the number of
electrons). Protons number is also known as
atomic number.
 Nucleon number (A)  is the total number

of protons and neutrons present in the
nucleus of the atom of an element. Also
known as mass number.
Subatomic Particles
Particle Mass Charge Charge
(gram) (Coulomb) (units)

Electron (e) 9.1 x 10-28 -1.6 x 10-19 -1
Proton (p) 1.67 x 10-24 +1.6 x 10-19 +1
Neutron (n) 1.67 x 10-24 0 0
08/16/11 matter 19
Isotope
 Isotopes are two or more atoms of the same
element that have the same proton number in
their nucleus but different nucleon number.
08/16/11 matter 20
Examples:
1 2 3
1 H H (D)
1 H (T)
1
235 238
92 U 92 U
Isotope Notation
An atom can be represented by an isotope
notation ( atomic symbol )
X= Element symbol
Z = Proton number of X (p)
A= Nucleon number of X
= p+n
08/16/11 matter 22
Nucleon number of
mercury, A = 202 Total charge on
the ion
The number of neutrons

Proton number
=A–Z
of mercury,
= 202 – 80
Z = 80
= 122
08/16/11 matter 23
 In a neutral atom:
 number of protons equals number of
electrons
 In a positive ion:
 number of protons is more than number of
electrons
 In a negative ion:
 number of protons is less than number of
electrons
Exercise 1
Give the number of protons, neutrons, electrons
and charge in each of the following species:
Symbol Number of : Charge

Proton Neutron Electron
200
80 Hg
63
29 Cu
17
8 O 2
59
27 Co 3 
08/16/11 matter 25
Exercise 2
Write the appropriate notation for each of the
following nuclide :
Species Number of : Notation

Proton Neutron Electron for nuclide
A 2 2 2
B 1 2 0
C 1 1 1
D 7 7 10
08/16/11 matter 26
b) Molecules
A molecule consists of a small number of
atoms joined together by bonds.
08/16/11 matter 27
A diatomic molecule
 Contains only two atoms
Ex : H2, N2, O2, Br2, HCl, CO
A polyatomic molecule
 Contains more than two atoms
Ex : O3, H2O, NH3, CH4
08/16/11 matter 28
Learning Outcomes
At the end of this topic, student should be able
to :
(a) Define relative atomic mass, Ar and
relative molecular mass, Mr based on
the C-12 scale.
(b) Calculate the average atomic mass of an

element given the relative abundance of
isotopes or a mass spectrum.
08/16/11 matter 29
Relative Mass
i. Relative Atomic Mass, Ar

A mass of one atom of an element
compared to 1/12 mass of one atom of 12C
with the mass 12.000 amu
Mass of one atom of element

Re lative atomic mass, A r 
1 X Mass of one atom of 12 C
12
08/16/11 matter 30
 Mass of an atom is often expressed in atomic
mass unit, amu (or u).
 Atomic mass unit, amu is defined to be one

twelfth of the mass of 12C atom
 Mass of a 12C atom is given a value of exactly 12

amu
1 u = 1.660538710-24 g
 The relative isotopic mass is the mass of an

atom, scaled with 12C.
08/16/11 31
Example 1
Determine the relative atomic mass of an
element Y if the ratio of the atomic mass of Y to
carbon-12 atom is 0.45
ANSWER:
08/16/11 matter 32
ii) Relative Molecular Mass, Mr
A mass of one molecule of a
compound compared to 1/12 mass of one
atom of 12C with the mass 12.000amu
Relative molecular mass, Mr

Mass of one molecule

1 x Mass of one atom of 12
C
12
08/16/11 matter 33
The relative molecular mass of a
compound is the summation of the
relative atomic masses of all atoms in
a molecular formula.
Example 2
Calculate the relative molecular mass of

C5H5N,
Ar C = 12.01
Ar H = 1.01
Ar N = 14.01
08/16/11 matter 35
MASS SPECTROMETER
 An atom is very light and its mass cannot be
measured directly
 A mass spectrometer is an instrument used to
measure the precise masses and relative
quantity of atoms and molecules
08/16/11 36
08/16/11 matter 37
Mass Spectrum of Monoatomic Elements
 Modern mass
spectrum converts
the abundance into
percent abundance
08/16/11 38
Mass Spectrum of Magnesium
 The mass spectrum of Mg
Relative abundance
shows that Mg consists of 3

isotopes: 24Mg, 25Mg and
63 26Mg.
 The height of each line is

8.1 9.1 proportional to the abundance
of each isotope.
24 25 26 m/e
24Mg is the most abundant of
(amu) 
the 3 isotopes
08/16/11 matter 39
Learning Outcomes
At the end of this topic, student should be able

to :
(a) Calculate the average atomic mass of an

element given the relative abundances of
isotopes or a mass spectrum.
08/16/11 matter 40
How to calculate the relative atomic
mass, Ar from mass spectrum?
 Ar is calculated using data from the mass
spectrum.
 The average of atomic masses of the entire
element’s isotope as found in a particular
environment is the relative atomic mass, Ar of
the atom.
(isotopicmass abundance
)
Averageatomicmass
abundance
08/16/11 matter 41
Example 1:
Calculate the relative atomic mass of neon
from the mass spectrum.
08/16/11 42
Solution:
Average atomic  (% abundance  isotopic mass)

=
 % abundanc e
mass of Ne
= (90.5  20 u)  (0.3  21 u)  (9.2  22 u)
(90.5  0.3  9.2)
= 20.2 u
Relative atomic mass Ne = 20.2

Example 2:
Copper occurs naturally as mixture of

69.09% of 63Cu and 30.91% of 65Cu. The
isotopic masses of 63Cu and 65Cu are 62.93
u and 64.93 u respectively. Calculate the
relative atomic mass of copper.
08/16/11 44
Solution:
Average atomic 
=
(%abundance isotopicmass)
mass of Cu % abundance
(69.09  62.93 u)  (30.91 64.93 u)
= (69.09  30.91)
= 63.55 u
Relative atomic mass Cu = 63.55

Example 3:
Naturally occurring iridium, Ir is composed

of two isotopes, 191Ir and 193Ir in the ratio of
5:8. The relative isotopic mass of 191Ir and
193Ir are 191.021 u and 193.025 u
respectively. Calculate the relative atomic

mass of Iridium
08/16/11 46
Solution:
Average atomic =  abundance  isotopic mass 

mass of Ir  abundance
(5  191 .021 u)  (8  193 .025 u)

= (5  8 )
= 192.254 u
Relative atomic mass Ir = 192.254

08/16/11 47
Mass Spectrum of Molecular
Elements
A sample of chlorine which contains 2 isotopes
with nucleon number 35 and 37 is analyzed
in a mass spectrometer. How many peaks
would be expected in the mass spectrum of
chlorine?
35Cl-35Cl
35Cl-37Cl MASS SPECTROMETER
37Cl-37Cl
_ _
+
Cl2
35Cl-35Cl+
35Cl-37Cl+
Cl2 + e  Cl2+ + 2e
37Cl-37Cl+
Cl2 + e  2Cl+ + 2e
35Cl+
37Cl+
Mass Spectrum of Diatomic
Elements
Exercise:
How many peaks would be expected in a mass
spectrum of X2 which consists of 3 isotopes?
MATTER
1.2 Mole Concept
Learning Outcome
able to:
a) Define mole in terms of mass of

carbon-12 and Avogadro’s constant, NA
Avogadro’s Number, NA
 Atoms and molecules are so small – impossible

to count
 A unit called mole (abbreviated mol) is devised

to count chemical substances by weighing
them
 A mole is the amount of matter that contains

as many objects as the number of atoms in
exactly 12.00 g of carbon-12 isotope
 The number of atoms in 12 g of 12C is called

Avogadro’s number, NA = 6.02 x 1023
Example:
1 mol of Cu contains 6.02  1023 Cu atoms
1 mol of O2 contains 6.02  1023 O2 molecules

O atoms
2  6.02  1023
1 mol of NH3 contains 6.02  1023 NH3 molecules
6.02  10N
23 atoms
3  6.02  10H
23 atoms
1 mol of CuCl2 contains 6.02  1023 Cu2+ ions
23- ions
2  6.02  10Cl
Mole and Mass
Example:
Relative atomic mass for carbon, C = 12.01
Mass of 1 C atom = 12.01 amu
Mass of 1 mol C atoms = 12.01 g
Mass of 1 mol C atoms consists of 6.02 x 1023 C atoms

= 12.01 g
12.01 g
 Mass of 1 C atom =
6.02 x 10 23
= 1.995 x 10-23 g
12.01 amu = 1.995 x 10-23 g
1.995 x 10 23 g
1 amu =
12.01 amu
= 1.66 x 10-23 g
Example:
From the periodic table, Ar of nitrogen, N is 14.01

The mass of 1 N atom = 14.01 amu
The mass of 1 mol of N atoms = 14.01 g
The molar mass of N atom = 14.01 g mol1
The molar mass of nitrogen gas = 28.02 g mol1
 The nucleon number of N = 14
Mr of CH4 is 16.05
The mass of 1 CH4 molecule = 16.05 amu
The mass of 1 mol of CH4 molecules = 16.05 g
The molar mass of CH4 molecule = 16.05 g mol1
Learning Outcome
able to:
(a) Interconvert between moles, mass,
number of particles, molar volume of gas
at STP and room temperature.
(b) Define the terms empirical & molecular
formulae
(c) Determine empirical and molecular
formulae from mass composition or
combustion data.
08/16/11 MATTER 61
Example 1:
Calculate the number of moles of molecules for
3.011 x 1023 molecules of oxygen gas.
Solution:
6.02 x 1023 molecules of O2  1 mol of O2 molecules
3.01110 23 molecules  1 mol

3.011 x 1023 molecules of O2 
6.02  10 23 molecules
= 0.5000 mol of O2 molecules

Example 2:
Calculate the number of moles of atoms for
1.204 x 1023 molecules of nitrogen gas.
Solution:
6.02 x 1023 molecules of N2 1mol of N2 molecules
 2 mol of N atoms
23
1.204 x 1023 molecules of N2  1. 204  10 molecules  2 mol
6.02 10 23 molecules
= 0.4000 mol of N atoms

Example 3:
Calculate the mass of 0.25 mol of chlorine gas.
Solution:
1 mol Cl2  2  35.45 g
0.25 mol Cl2  2  35.45 g  0.25 mol

1 mol
 18 g
or
mass = mol x molar mass
= 0.25 mol x (2 x 35.45 g mol-1)
= 18 g
Example 4:
Calculate the mass of 7.528 x 1023 molecules of
methane, CH4
Solution:
6.02 x 1023 CH4 molecules  (12.01 + 4(1.01)) g
23
7.528 x 1023 CH4 molecules  16 . 05 g  7.528  10
6.02  10 23
= 20.06 g
Molar Volume of Gases
 Avogadro (1811) stated that equal volumes of gases
at the same temperature and pressure contain
equal number of molecules
 Molar volume is a volume occupied by 1 mol of gas
 At standard temperature and pressure (STP), the
molar volume of an ideal gas is 22.4 L mol 1
Standard Temperature and Pressure
273.15 K 1 atm 760 mmHg
0 C 101325 N m-2
101325 Pa
Standard Molar Volume
08/16/11 MATTER 67
 At room conditions (1 atm, 25 C), the molar
volume of a gas = 24 L mol-1
Example 1:
Calculate the volume occupied by 1.60 mol of
Cl2 gas at STP.
Solution:
At STP,
1 mol Cl2 occupies22.4 L
1.60 mol Cl2 occupies 1.60 mol  22.4 L

1 mol
= 35.8 L
08/16/11 MATTER 69
Example 2:
Calculate the volume occupied by 19.61 g of

N2 at STP
Solution:
1 mol of N2 occupies 22.4 L
 19.61 
  mol  22.4 L
19.61 g  2(14.01) 
of N2 occupies
2(14.01) g mol 1 1 mol
= 15.7 L
08/16/11 MATTER 70
Example 3:
0.50 mol methane, CH4 gas is kept in a cylinder at
STP. Calculate:
(a) The mass of the gas
(b) The volume of the cylinder
(c) The number of hydrogen atoms in the cylinder
Solution:
(a) Mass of 1 mol CH4 16.05
= g
Mass of 0.50 mol CH4 16=.05 g  0.50 mol

1 mol
= 8.0 g
08/16/11 MATTER 71
(b) At STP; 1 mol CH4 gas occupies 22.4 L
0.50 mol CH4 gas occupies 22.4 L  0.50 mol

1 mol
= 11 L
(c) 1 mol of CH4 molecules  4 mol of H atoms
0.50 mol of CH4 molecules  2 mol of H atoms
1 mol of H atoms 
6.02 x 1023 atoms
2 mol of H atoms 
2 x 6.02 x 1023 atoms
 1.2 x 1024 atoms
08/16/11 MATTER 72
Exercise
A sample of CO2 has a volume of 56 cm3 at STP.
Calculate:
a) The number of moles of gas molecules

(0.0025 mol)
a) The number of CO2 molecules

(1.506 x 1021 molecules)
a) The number of oxygen atoms in the sample

(3.011x1021atoms)
Notes: 1 dm3 = 1000 cm3

08/16/11 1 dm3 =1L MATTER 73
Empirical And Molecular Formulae
- Empirical formula => chemical formula

that shows the simplest ratio of all
elements in a molecule.
- Molecular formula => formula that show

the actual number of atoms of each
element in a molecule.
08/16/11 MATTER 74
- The relationship between empirical formula
and molecular formula is :
Molecular formula = n ( empirical formula )
08/16/11 MATTER 75
Example:
A sample of hydrocarbon contains 85.7%

carbon and 14.3% hydrogen by mass. Its
molar mass is 56. Determine the empirical
formula and molecular formula of the
compound.
08/16/11 MATTER 76
Solution:
C H
Mass 85.7 14.3
85.7 14.3
Number
of moles 12.01 1.01
= 7.1357 = 14.1584
Simplest ratio 1 1.984

2
Empirical formula = CH2

56
n
14.03
 3.99
4
Molecular formula  n(CH2 )

 Molecular formula  C 4H8
Exercise:
A combustion of 0.202 g of an organic sample

that contains carbon, hydrogen and oxygen
produce 0.361g carbon dioxide and 0.147 g water.
If the relative molecular mass of the sample is
148, what is the molecular formula of the sample?
Answer : C6H12O4
08/16/11 MATTER 79
Learning Outcome
able to:
(a) Define and perform calculation for each of
the following concentration measurements :
i) molarity (M)
ii) molality(m)
iii) mole fraction, X
iv) percentage by mass, % w/w
v) percentage by volume, %v/v
08/16/11 MATTER 80
Concentration of Solutions
 A solution is a homogeneous mixture of
two or more substances:
solvent + solute(s)
e.g: sugar + water – solution

sugar – solute
water – solvent
08/16/11 MATTER 81
08/16/11 MATTER 82
Concentration of a solution can be expressed
in various ways :
a) molarity
b) molality
c) mole fraction
d) percentage by mass
e) percentage by volume
08/16/11 MATTER 83
a) Molarity
 Molarity is the number of moles of

solute in 1 litre of solution
moles of solute (mol)

molarity, M 
volume of solution (L)
 Units of molarity: mol L-1

mol dm-3
M
08/16/11 MATTER 84
Example 1:
Determine the molarity of a solution
containing 29.22 g of sodium chloride, NaCl
in a 2.00 L solution.
Solution:
nNaCl
MNaCl 
Vsolution
 29.22 
 mol 
  (22.99  35.45) 
2.00 L
= 0.250 mol L-1

Example 2:
How many grams of calcium chloride, CaCl2
should be used to prepare 250.00 mL
solution with a concentration of 0.500 M
Solution:
nCaCl  M CaCl x Vsolution
2 2
= 0.500 mol L1  250.00  103 L
mass of CaCl2  nCaCl x molar mass

2
= (0.500  250.00  103) mol

 (40.08 + 2(35.45)) g mol1
= 13.9 g
b) Molality
 Molality is the number of moles of

solute dissolved in 1 kg of solvent
moles of solute (mol)

molality, m 
mass of solvent (kg)
 Units of molality:mol kg-1

molal
m
08/16/11 MATTER 89
Example:
What is the molality of a solution
prepared by dissolving 32.0 g of CaCl2 in
271 g of water?
Solution:
32.0 g
nCaCl 2 
40.08  2(35.45) g mol-1
 32.0 mol 
 
Molality of CaCl2   110.98 3 
271 10 kg
 1.06 mol kg1

Exercise:
Calculate the molality of a solution
prepared by dissolving 24.52 g of sulphuric
acid in 200.00 mL of distilled water.
(Density of water = 1 g mL-1)
Ans = 1.250 mol kg-1

c) Mole Fraction (X)
Mole fraction is the ratio of number of

moles of one component to the total
number of moles of all component present.
For a solution containing A, B and C:

nA
Mol fraction of A, X A 
nA  nB  nC
nA

nT
08/16/11 MATTER 93
 Mol fraction is always smaller than 1
 The total mol fraction in a mixture

(solution) is equal to one.
XA + XB + XC + X….. = 1
 Mole fraction has no unit (dimensionless)

since it is a ratio of two similar quantities.
08/16/11 MATTER 94
Example:
A sample of ethanol, C2H5OH contains
200.0 g of ethanol and 150.0 g of water.
Calculate the mole fraction of
(a) ethanol
(b) water
in the solution.
Solution:
nethanol 200.0 g
=
(2(12.01)  5(1.01)  16.00) g mol1
nwater 150.0 g
=
1
(2(1.01)  16.00) g mol
 200.0 mol 
 
Xethanol =
 45.07 
 200.0 mol    150.0 mol 
   
 45.07   18.02 
= 0.3477
Xwater = 1  0.3477
= 0.6523
d) Percentage by Mass (%w/w)
Percentage by mass is defined as the

percentage of the mass of solute per mass
of solution.
mass of solute
%ww  x100
mass of solution
Note:
Mass of solution = mass of solute + mass of solvent
08/16/11 MATTER 98
Example:
A sample of 0.892 g of potassium
chloride, KCl is dissolved in 54.362 g of
water. What is the percent by mass of
KCl in the solution?
Solution:
0.892 g
% mass   100%
0.892 g  54.362 g
= 1.61%
Exercise:
A solution is made by dissolving 4.2 g of
sodium chloride, NaCl in 100.00 mL of
water. Calculate the mass percent of
sodium chloride in the solution.
Answer = 4.0%
e) Percentage by Volume (%V / V)
Percentage by volume is defined as the
percentage of volume of solute in milliliter per
volume of solution in milliliter.
volume of solute
%v  x 100
v volume of solution
Note:
mass of solution
Density of solution 
volume of solution
08/16/11 MATTER 101
Example 1:
25 mL of benzene is mixed with 125 mL
of acetone. Calculate the volume percent
of benzene solution.
Solution:
25 mL
% volume   100%
25 mL  125 mL
= 17%
Example 2:
A sample of 250.00 mL ethanol is labeled
as 35.5% (v/v) ethanol. How many
milliliters of ethanol does the solution
contain?
Solution:
Vethanol
% volume of ethanol   100 %
Vsolution
35.5%  250.00 mL
Vethanol 
100%
= 88.8 mL
Example 3:
A 6.25 m of sodium hydroxide, NaOH
solution has has a density of 1.33 g mL-1
at 20 ºC. Calculate the concentration
NaOH in:
(a) molarity
(b) mole fraction
(c) percent by mass
Solution:
nNaOH
(a) M =
Vsolution
6.25 m of NaOH
 there is 6.25 mol of NaOH in 1 kg of water
for a solution consists of 6.25 mol of NaOH and 1

kg of water;
mass solution
Vsolution =
solution
masssolution = massNaOH + masswater
massNaOH = nNaOH  molar mass of NaOH
= 6.25 mol  (22.99 + 16.00 + 1.01) g mol1
= 250 g
masssolution = 250 g + 1000 g
= 1250 g
1250 g
Vsolution = 1
1.33 g mL
6.25 mol
MNaOH =
 1250 3 
  10 L 
 1.33 
= 6.65 mol L1

nNaOH
(b) XNaOH =
nNaOH  n water
1 kg of water contains 6.25 mol of NaOH
mass water
nwater =
molar mass of water
1000 g
= 1
(2(1.01)  16.00) g mol
6.25 mol
XNaOH =
 1000 
 6 .25 mol  mol 
 18.02 
= 0.101
massNaOH
(c) %(w/w) of NaOH =  100%
massNaOH  mass water
250 g
=  100%
250 g  1000 g
= 20.0%
Exercise:
An 8.00%(w/w) aqueous solution of
ammonia has a density of 0.9651 g mL-1.
Calculate the
(a) molality
(b) molarity
(c) mole fraction
of the NH3 solution
Answer: a) 5.10 mol kg-1

b) 4.53 mol L-1
c) 0.0842
MATTER
1.3 Stoichiometry
Learning Outcome
At the end of the lesson, students should be able
to:
a) Determine the oxidation number of an
element in a chemical formula.
b) Write and balance :

i) Chemical equation by inspection method
ii) redox equation by ion-electron method
Balancing Chemical Equation
 A chemical equation shows a chemical

reaction using symbols for the reactants and
products.
 The formulae of the reactants are written on

the left side of the equation while the
products are on the right.
08/16/11 MATTER 114

Example:
xA + yB zC + wD
Reactants Products
08/16/11 MATTER 115

 A chemical equation must have an equal number
of atoms of each element on each side of the
arrow
 The number x, y, z and w, showing the relative

number of molecules reacting, are called the
stoichiometric coefficients.
 A balanced equation should contain the smallest

possible whole-number coefficients
 The methods to balance an equation:

a) Inspection method
b) Ion-electron method
08/16/11 MATTER 116

Inspection Method
1. Write down the unbalanced equation. Write the

correct formulae for the reactants and products.
1. Balance the metallic atom, followed by non-
metallic atoms.
1. Balance the hydrogen and oxygen atoms.
1. Check to ensure that the total number of atoms of
each element is the same on both sides of equation.
08/16/11 MATTER 117

Example:
Balance the chemical equation by applying the
inspection method.
NH3 + CuO → Cu + N2 + H2O
08/16/11 MATTER 118

Exercise
Balance the chemical equation below by applying
inspection method.
1. Fe(OH)3 + H2SO4 → Fe2(SO4)3 + H2O
2. C6H6 + O2 → CO2 + H2O
3. N2H4 + H2O2 → HNO3 + H2O
4. ClO2 + H2O → HClO3 + HCl
08/16/11 MATTER 119

Redox Reaction
 Mainly for redox (reduction-oxidation)

reaction
08/16/11 MATTER 120

 Oxidation is defined as a process of electron loss.
 The substance undergoes oxidation
 loses one or more electrons.
 increase in oxidation number
 act as an reducing agent (electron donor)
Half equation representing oxidation:
Mg  Mg2+ 2e
Fe2+  Fe3+ + e
2Cl-  Cl2 + 2e
08/16/11 MATTER 121

 Reduction is defined as a process of electron gain.
 The substance undergoes reduction
 gains one or more electrons.
 decrease in oxidation number
 act as an oxidizing agent (electron acceptor)
Half equation representing reduction:
Br2 + 2e → Br-
Sn4+ + 2e → Sn2+
Al3+ + 3e → Al
Oxidation numbers of any atoms can be
determined by applying the following rules:
1. For monoatomic ions,

oxidation number = the charge on the ion
e.g: ion oxidation number
Na+ +1
Cl- -1
Al3+ +3
S2- -2
08/16/11 MATTER 123

2. For free elements, e.g: Na, Fe, O2, Br2, P4, S8
oxidation number on each atom = 0
1. For most cases, oxidation number for

O = -2
H = +1
Halogens = -1
08/16/11 MATTER 124

Exception:
1. H bonded to metal (e.g: NaH, MgH2) oxidation number
for H = -1
1. Halogen bonded to oxygen (e.g: Cl2O7) oxidation
number for halogen = +ve
1. In a neutral compound (e.g: H2O, KMnO4) the total of
oxidation number of every atoms that made up the
molecule = 0
1. In a polyatomic ion (e.g: MnO4-, NO3-) the total
oxidation number of every atoms that made up the
molecule = net charge on the ion
08/16/11 MATTER 125

Exercise
1. Assign the oxidation number of Mn in the following
chemical compounds.
i. MnO2 ii. MnO4-
1. Assign the oxidation number of Cl in the following
chemical compounds.
i. KClO3 ii. Cl2O72-
1. Assign the oxidation number of following:
i. Cr in K2Cr2O7
ii. U in UO22+
iii. C in C2O42-
08/16/11 MATTER 126

Balancing Redox Reaction
 Redox reaction may occur in acidic and basic

solutions.
 Follow the steps systematically so that

equations become easier to balance.
08/16/11 MATTER 127

Balancing Redox Reaction In Acidic
Solution
Fe2+ + MnO4- → Fe3+ + Mn2+
1. Separate the equation into two half-

reactions: reduction reaction and oxidation
reaction
i. Fe2+ → Fe3+
ii. MnO4- → Mn2+
08/16/11 MATTER 128

1. Balance atoms other than O and H in each
half-reaction separately
i. Fe2+ → Fe3+
ii. MnO4- → Mn2+
08/16/11 MATTER 129

3. Add H2O to balance the O atoms
Add H+ to balance the H atoms
i. Fe2+ → Fe3+
ii. MnO4- + → Mn2+ +
8H+ 4H2O
4. Add electrons to balance the

charges
i. Fe2+ → Fe3+ +
ii. MnO4- + 8H+ + 1 e → Mn2+ + 4H2O
5e
130
08/16/11 MATTER
3.Multiply each half-reaction by an integer, so that
number of electron lost in one half-reaction equals
the number gained in the other.
i. 5 x (Fe2+ → Fe3+ + 1e)

5Fe2+ → 5Fe3+ + 5e
ii. MnO4- + 8H+ + 5e → Mn2+ + 4H2O
08/16/11 MATTER 131

1. Add the two half-reactions and simplify where
possible by canceling the species appearing on both
sides of the equation.
i. 5Fe2+ → 5Fe3+ + 5e
ii. MnO4- + 8H+ + 5e → Mn2+ + 4H2O
___________________________________
5Fe2+ + MnO4- + 8H+ → 5Fe3+ + Mn2+ + 4H2O
___________________________________
5. Check the equation to make sure that there
are the same number of atoms of each kind
and the same total charge on both sides.
5Fe2+ + MnO4- + 8H+ → 5Fe3+ + Mn2+ + 4H2O

Total charge reactant Total charge product
= 5(+2) + (-1) + 8(+1) = 5(+3) + (+2) + 4(0)
= + 10 - 1 + 8 = + 15 + (+2)
= +17 = +17
Exercise: In Acidic Solution
C2O42- + MnO4- + H+ → CO2 + Mn2+ + H2O
Solution :
08/16/11 MATTER 134

Balancing Redox Reaction In Basic Solution
1. Firstly balance the equation as in acidic

solution.
1. Then, add OH- to both sides of the equation so
that it can be combined with H+ to form H2O.
1. The number of OH- added is equal to the
number of H+ in the equation.
08/16/11 MATTER 135

Example: In Basic Solution
Cr(OH)3 + IO3- + OH- → CrO32- + I- + H2O
08/16/11 MATTER 136

Exercise:
1. H2O2 + MnO4- + H+  O2 + Mn2+ + H2O

(acidic medium)
2. Zn + SO42- + H2O  Zn2+ + SO2 + 4OH-
(basic medium)
3. MnO4- + C2O42- + H+  Mn2+ + CO2 + H2O
(acidic medium)
4. Cl2  ClO3- + Cl- (basic medium)
08/16/11 MATTER 137

Stoichiometry
 Stoichiometry is the quantitative study of

reactants and products in a chemical
reaction.
 A chemical equation can be interpreted in

terms of molecules, moles, mass or even
volume.
08/16/11 MATTER 138

C3H8 + 5O2  3CO2 + 4H2O
 1 molecule of C3H8 reacts with 5 molecules of O2

to produce 3 molecules of CO2 and 4 molecules of
H2O
 6.02 x 1023 molecules of C3H8 reacts with 5(6.02 x

1023) molecules of O2 to produce 3(6.02 x 1023)
molecules of CO2 and 4(6.02 x 1023) molecules of
H2O
C3H8 + 5O2  3CO2 + 4H2O
 1 mol of C3H8 reacts with 5 moles of O2 to

produce 3 moles of CO2 and 4 moles of H2O
 44.09 g of C3H8 reacts with 160.00 g of O2 to

produce 132.03 g of CO2 and 72.06 g of H2O
 5 moles of C3H8 reacts with 25 moles of O2 to

produce 15 moles of CO2 and 20 moles of H2O
 At room condition, 25 ºC and 1 atm pressure;
22.4 dm3 of C3H8 reacts with 5(22.4 dm3) of O2
to produce 3(22.4 dm3) of CO2
Example 1:
How many grams of water are produced in the
oxidation of 0.125 mol of glucose?
C6H12O6(s) + O2(g)  CO2(g) + H2O(l)

Solution:
From the balanced equation;
1 mol C6H12O6 produce 6 mol H2O
0.125 mol C6H12O6 produce H2O

0.125 mol  6 mol
1 mol
mass of H2O = (0.125 x 6) mol
x (2.02 + 16.00) g mol-1
= 13.5 g
Example 2:
Ethene, C2H4 burns in excess oxygen to form
carbon dioxide gas and water vapour.
(a) Write a balance equation of the
reaction
(b) If 20.0 dm3 of carbon dioxide gas is
produced in the reaction at STP, how
many grams of ethene are used?
Solution:
(a) C2H4 + O2  CO2 + H2O
(b) 22.4 dm3 is the volume of 1 mol CO2
20.0 dm3 is the volume of 3 CO2

20.0 dm  1 mol
3
2 mol CO2 produced by 1 mol C2H422.4 dm
mol CO2 produced by

C2H4  20.0 
 mol   1 mol
20.0  22.4 
22.4 2 mol
 20.0 
 
massethane   22.4  mol x [2(12.01)  4(1.01)] g mol-1
2
= 12.5 g
Learning Outcome

able to:
a) Define the limiting reactant and
percentage yield
b) Perfome stoichiometric calculations
using mole concept including limiting
reactant and percentage yield.
Limiting Reactant/Reagent
 Limiting reactant is the reactant that is

completely consumed in a reaction and limits
the amount of product formed
 Excess reactant is the reactant present in

quantity greater than necessary to react with
the quantity of limiting reactant
08/16/11 MATTER 148

Example:
3H2 + N2  2NH3
If 6 moles of hydrogen is mixed with 6 moles of nitrogen,
how many moles of ammonia will be produced?
Solution:
3 mol H2 reacts with 1 mol N2
6 mol H2 reacts with
6 mol  1 mol
3 mol
= 2 mol N2
N2 is the excess reactant
H2 is the limiting reactant
 limits the amount of products formed
3 mol H2 produce 2 mol NH3
6 mol H2 produce 6 mol  2 mol

3 mol
= 4 mol NH3
or
1 mol N2 react with 3 mol H2
6 mol N2 react with 6 mol  3 mol

molNH3
1 mol
= 18 mol H2
H2 is not enough
 limiting reactant
 H2 limits the amount of products formed
3 mol H2 produce 2 mol NH3
6 mol N2 produce 6 mol  2 molmol NH3

3 mol
= 4 mol NH3
Exercise:
Consider the reaction:
2 Al(s) + 3Cl2(g)  2 AlCl3(s)
A mixture of 2.75 moles of Al and 5.00 moles of Cl2 are

allowed to react.
(a) What is the limiting reactant?
(b) How many moles of AlCl3 are formed?
(c) How many moles of the reactant remain at
the end of the reaction?
08/16/11 MATTER 154

PERCENTAGE YIELD
 The amount of product predicted by a balanced

equation is the theoretical yield
 The theoretical yield is never obtain because:
1. The reaction may undergo side reaction
2. Many reaction are reversible
3. There may be impurities in the reactants
08/16/11 MATTER 155

4. The product formed may react further to
form other product
5. It may be difficult to recover all of the
product from the reaction medium
 The amount product actually obtained in a

reaction is the actual yield
08/16/11 MATTER 156

Percentage yield is the percent of the actual
yield of a product to its theoretical yield
actual yield
% yield  x 100
theoretica l yield
08/16/11 MATTER 157

Example 1:
Benzene, C6H6 and bromine undergo reaction as follows:
C6H6 + Br2  C6H5Br + HBr
In an experiment, 15.0 g of benzene are mixed with excess

bromine
(a) Calculate the mass of bromobenzene, C6H5Br that
would be produced in the reaction.
(b) What is the percent yield if only 28.5 g of
bromobenzene obtain from the experiment?
CHAPTER 2
ATOMIC STRUCTURE
2.1 Bohr’s Atomic Model
Learning Outcomes
At the end of this topic students should be able
to:-
a) Describe the Bohr’s atomic model.
b) Explain the existence of electron energy
levels in an atom.
c) Calculate the energy
1 of electron at− 18
its level
E n= − R H 2
, R H = 2.18x10 J
(orbit) using. n
Learning Outcomes
d) Describe the formation of line spectrum of
hydrogen atom.
e) Calculate the energy change of an electron
1 1 − 18
duringE =transition.
RH 2
− 2 where RH = 2.18× 10 J
n1 n2
f) Calculate the photon of energy emitted by an

E= h where = c /
electron that produces a particular
wavelength during transition.
Learning Outcomes
g) Perform calculation involving the Rydberg
equation for Lyman, Balmer, Paschen,
1
Brackett 1 Pfund
and 1 series: 7 −1
= RH 2
− 2
where R H = 1.097× 10 m
n1 n2
n1 n2
g) Calculate the ionisation energy of hydrogen

atom from the Lyman series.
Learning Outcomes
i) State the weaknesses of Bohr’s atomic
model.
j) State the dual nature of electron using de
Broglie’s postulate and Heisenberg’s
uncertainty principle.
Bohr’s Atomic Model
In 1913, a young
Dutch physicist, Niels
Böhr proposed a
theory of atom that
shook the scientific
world.
The atomic model he
described had
electrons circling a
central nucleus that
contains positively
change proton.
Böhr also proposed
that these orbits can
only occur at
specifically
“permitted” levels
according to the
energy levels of the
electron and explain
successfully the lines
in the hydrogen
spectrum.
First Postulates
Electron moves in
circular orbits about
the nucleus.
While moving in the
orbit, the electron
does not radiate or
absorb any energy.
[orbit = energy level=shell]
Orbit is a pathway where the electron is move

around the nucleus.
Orbit
Second Postulate
The moving electron
has a specific amount
of energy; its energy
is quantised.
The energy of an electron in its level is given by:
1
En= − RH 2
n
RH (Rydberg constant) = 2.18 x 10-18J.
n (principal quantum number) = 1, 2, 3 …. ∞ (integer)
Note:
n identifies the orbit of electron
Energy is zero if electron is located infinitely far from
nucleus
Third postulate
At ordinary conditions,
the electron is at the
ground state (lowest
level).
If energy is supplied,
electron absorbed the
energy and is promoted
from a lower energy
level to a higher ones.
(Electron is excited)
Fourth Postulate
Electron at its excited states is unstable.
It will fall back to lower energy level and
released a specific amount of energy in the
form of light (photon).
The energy of the photon equals the energy
difference between levels.
Electron is excited from lower to higher
energy level.
A specific amount of energy is absorbed
∆E = hν = E3-E1
n =1 n=2 n=3 n=4
Electron falls from higher to lower energy level .

A photon is emitted.
∆E = hν = E1-E3
Radiant energy emitted when the electron
moves from higher-energy state to lower-energy
state is given by:
E= Ef − E i
Where:
1 1
Ef = − RH 2
E i= − R H 2
nf ni
 1    1   1 1 
∆E = −R H  2  −  − R H  2   Thus, ∆E = R H  2 − 2 
n 
n  n   i n f 
 f    i 
The amount of energy released by the
electron is called a photon of energy.
A photon of energy is emitted in the form of
radiation with appropriate frequency and
wavelength.
E = hv
Where : h (Planck's constant) = 6.63 x 10-34 J s

v = frequency (s-1)
c
=
v
Where : c (speed of light) = 3.00 x 108 ms-1
hc
Thus : ∆E =
λ
Rydberg Equation
Wavelength emitted by the transition of
electron between two energy levels is
calculated using Rydberg equation:
1 1 1 7 −1
= RH 2
− 2 where R H = 1.097× 10 m
n1 n2
n1 n2
Example 1
Calculate the wavelength, in nanometers of the
spectrum of hydrogen corresponding to n = 2
and n = 4 in the Rydberg equation.
Exercises:
1. Calculate the energy of hydrogen electron in the:
(a) 1st orbit
(b) 3rd orbit
(c) 8th orbit
1. Calculate the energy change (J), that occurs when an

electron falls from n = 5 to n = 3 energy level in a
hydrogen atom.
2. Calculate the frequency and wavelength (nm) of the

radiation emitted in question 2.
Emission Spectra
Emission Spectra
Continuous Line
Spectra Spectra
Continuous Spectrum
A spectrum consists of radiation distributed over
all wavelength without any blank spot.
Example : electromagnetic spectrum, rainbow
It is produced by white light (sunlight or
incandescent lamp) that passed through a
prism
Formation of Continuous Spectrum
Regions of the Electromagnetic Spectrum
Line Spectrum (atomic spectrum)
A spectrum consists of discontinuous & discrete
lines with specific wavelength.
It is composed when the light from a gas
discharge tube containing a particular element
is passed through a prism.
Formation of Atomic / Line
Spectrum
The emitted light (photons) is then separated
into its components by a prism.
Each component is focused at a definite
position, according to its wavelength and forms
as an image on the photographic plate.
The images are called spectral lines.

Spectrum
Spectrum
Example : The line emission spectrum of
hydrogen atom
Line spectrum are composed a few
wavelengths giving a series of discrete line
separated by blank areas
It means each line corresponds to a specific
wavelength or frequency.
Formation of Line Spectrum
When electron absorbed radiant energy, they
will move from lower energy level to higher
energy level (excited state).
This excited electron is unstable and it will fall
back to lower energy level.
During the transition, electron will release
energy in the form of light with specific
wavelength and can detected as a line
spectrum.
Differences Between Line &
Continuous Spectra
Continuous Spectrum Line Spectrum
A spectrum that A spectrum that contain
contains all only specific
wavelength without wavelengths.
any blank spots. A spectrum of discrete
Example: Rainbow. lines with certain
wavelengths.
Example: Emission
spectrum an element.
(Lyman Series)
n=∞
n=5
n=4
Energy n=3
n=2
n=1
Emission of photon
Line E
spectrum λ
Lyman Series
(Balmer Series)
n=∞
n=5
n=4
Energy n=3
n=2
n=1
Emission of photon
Line E
spectrum λ
Lyman Series Balmer Series
Energy Level in Hydrogen Atom
Example
Complete the following table
Spectrum
Series nf ni
region
Lyman 1 2,3,4,… ultraviolet
Balmer 2 3,4,5,… Visible/uv
Paschen 3 4,5,6,… Infrared
Brackett 4 5,6,7,… Infrared
Pfund 5 6,7,8,… Infrared

Example
The following diagram is the line spectrum of
hydrogen atom. Line A is the first line of the
Lyman series.
A B C D E E
Line λ
spectrum v
Specify the increasing order of the radiant energy,

frequency and wavelength of the emitted photon.
Which of the line that corresponds to
i) the shortest wavelength?
ii) the lowest frequency?
Example
The line spectrum of Balmer is given as below:
W Y
Describe the transitions of electrons that lead to the lines

W, and Y, respectively.
Solution
For W: transition of electron is from n =4 to n = 2

For Y: electron shifts from n = 7 to n = 2
Example
E D C B A
Line
spectrum Paschen series
(a) Which of the line in the Paschen series

corresponds to the longest wavelength of
photon?
(b) Describe the transition that gives rise to the line.

Solution
Line A.
The electron moves from n=4 to
n=3.
Example
With refer to the second line in the Balmer series of the
hydrogen spectrum, Calculate;
a)the wavelength in nm
b)the frequency
c)the energy
Example
Refer to last line of hydrogen spectrum in Lyman
series, Calculate:
a) Wavelength
b) Frequency
c) Wave number; where wave number = 1
For Lyman series; n1 = 1 & n2 = ∞

Ans:
i. 9.116 x10-8 m
ii. 3.29 x1015 s-1
iii. 1.0970 X 107 m-1
Ionization Energy
Defination : Ionization energy is the minimum
energy required to remove an electron in its
ground state from an atom (or an ion) in
gaseous state.
M (g) → M+ (g) + e ∆H = +ve
Ionization Energy
The hydrogen atom is ionised when electron is
removed from its ground state (n = 1) to n = ∞.
At n = ∞, the potential energy of electron is

zero, here the nucleus attractive force has no
effect on the electron (electron is free from
nucleus)
Example
n1 = 1, n2 = ∞
∆E = RH (1/n12 – 1/n22)
= 2.18 x 10-18 (1/12 – 1/∞2)
= 2.18 x 10-18 (1 – 0)
= 2.18 x 10-18 J
Ionisation energy
= 2.18 x 10-18 x 6.02 x 1023 J mol-1
= 1.312 x 106 J mol-1
= 1312 kJ mol-1
Example
Calculate the energy to ionized :
(a) a hydrogen atom.
(b) 1 mol of hydrogen atom.
Solution
(a)
1 1
E= − R H 2
− 2
n1 n2
− 18 1 1
= − 2.18× 10 2
− 2
1 ∞
− 18
= 2.18× 10 J
Solution
(b) 1 H atoms need 2.18 x 1018 J
1 mol H atom
= 2.18 x 1018 x 6.02 x 1023
= 1.31 x 106 J
The energy to ionized 1 mol of hydrogen atom is

1.31 X 106 J
Example
10.97 10.66 10.52 10.27 9.74 8.22
The Lyman series of the spectrum of hydrogen is

shown above. Calculate the ionisation energy of
hydrogen from the spectrum.
Solution
∆E = h X c/λ = h x c x wave no.
= (6.626x10-34 Js)(3x108 ms-1)(10.97x106 m-1)
= 218.06 x 10-20 J
= 2.18 x 10-18J
Ionisation energy
= (2.18 x 10-18) (6.02x1023 J mol-1)
= 1.312 x 106 J mol-1
= 1312 kJ mol-1
The weaknesses of Bohr’s Theory
It can only explain the hydrogen spectrum or
any spectrum of ions contain one electron.
example: He+, Li2+.Therefore, it did not account
for the emission spectrum of atom containing
more than 1 electron.
Electron are wavelike, we can’t define the
precise location of a wave because a wave
extends in space.
de Broglie’s Postulate
In 1924 Louis de Broglie proposed that not only
light but all matter has a dual nature and
possesses both wave and particle properties.
Electron is both particle and wave.
Tiny particle such as electron does have wave

properties.
De Broglie deduced that the particle and wave

properties are related by the expression:
Example
Electron has dual nature properties. Why don't we
see the wave properties of a Baseball?
de Broglie’s Postulate
h
=
mµ
h = Planck constant (J s)
m = particle mass (kg)
µ = velocity (m/s)
λ = wavelength of a matter wave
Heisenberg’s Uncertainty Principle
It is impossible to know simultaneously both the
momentum p (defined as mass times velocity) and the
position of a particle with certain.
Stated mathematically,
h
x p≥
4π
where ∆x = uncertainty in measuring the position
∆p = uncertainty in measuring the momentum
= ∆mv
h = Planck constant
2.2 Quantum Mechanical Model
Learning Outcomes
At the end of this topic students should be able
to:-
Define the term orbital.
State the four quantum numbers in an orbitals.
sketch the 3-D shape of s, p and d orbitals.
Atomic Orbital
Definition
An orbital is a three-
dimensional region in
space around the
nucleus where there
is a high probability of
finding an electron.
Quantum Numbers
Each of the electrons in an atom is described and
characterised by a set of four quantum
numbers, namely
principal quantum number, n
angular momentum quantum number, l
magnetic quantum number, m
electron spin quantum number, s.

Principal Quantum Number, n
n determines the energy level (electron shell)
and size of an orbital.
The principal quantum number n, may have +ve
value starting from n =1, 2, 3, …, ∞.
As n increase :
i) the orbital become larger
ii) electron has higher energy

Principal Quantum Number, n
n 1 2 3 4
Orbital size
Energy
increases
Angular Momentum Quantum
Number, l
Alternative name:
- Subsidiary Quantum Number
- Azimuthal Quantum Number
- Orbital Quantum Number
The value of l indicates the shape of the
atomic orbital.
The allowed values of l are 0, 1, 2,…, ( n - 1)

Number, l
Letters are assigned to different numerical
values of
Value of l Symbol Orbital shape

0 s spherical
1 p dumbbell
2 d cloverleaf
3 f
Number, l
value is depend on n. (i.e., 0 ≤ l < n).
If n = 1, l = 0 (s-orbital) One subshell
(s orbital)
If n = 2, l = 0 (s-orbital)
two subshells
= 1 (p-orbital) (s and p orbitals)
If n = 3, l = 0 (s-orbital)
three subshells
= 1 (p-orbital)
(s, p, and dorbitals)
= 2 (d-orbital)
Magnetic Quantum Number, m
Describe the orientation of orbitals in space.
Possible values of m depend on the value of l.
For a given l, m can be : -l, …, 0, …, +l
Example:
If l = 0, m = 0 » 1 orientation of s orbital
If l = 1, m = -1,0,+1 » 3 orientation of p orbital
(px, py, pz)
If l = 2, m = -2,-1, 0,+1,+2 » 5 orientation of d orbital
(
dxy,dxz,dyz,dx2-y2,dz2)
Electron Spin Quantum Number, s
The value of s represent the
direction of an electron rotation
on its own axis.
either clockwise or
anticlockwise
It has 2 value : +½ and -½

Shape of Atomic Orbital
s orbitals
Spherical shape with the nucleus at the centre.
When l = 0 , m = 0 , only 1 orientation of s

orbital.
The larger value of n, the size of s orbital gets

larger.
Shape of s orbital with different n
Z Z Z
Y Y Y
X X X
1s 2s 3s
Shape of Atomic Orbitals
p orbitals
Can be represent as a pair of dumb-bell shaped
When l = 1, m = -1, 0, +1
3 orientation of p-orbitals px, py, and pz.
As n increases, the p orbitals get larger.

Shape of p orbital
px
py pz
Shape of Atomic Orbitals
d orbitals
All the d orbitals do not look alike.
When l = 2 , m = -2, -1, 0, +1, +2.
There are five orientation of d orbitals.

Shape of d orbital
dx2-y2 dz2 dxy
dxz dyz
Set of Four Quantum Numbers
4 quantum number n,l,m and s enable us to
label completely an electron in any orbital of an
atom. Example:
4 quantum numbers of 2s orbital electron are
n = 2 , l = 0 , m = 0 and s = +½ and -½
Can be simplified as (2,0,0,+½)

n, l , m, s or (2,0,0,-½)
n, l , m, s
Exercise
Orbital
Shell n l m No. of orbitals
notation
1 1 0 1s 0 1
0 2s 0 1
2 2
1 2p -1,0,+1 3
Exercise
Predict the following quantum numbers whether
they are allowed or not
(a) (1,0,0,-½)
(b) (2,0,1,1)
(c) (0,1,1,+½)
(d) (4,1,0,-½)
2.3 Electronic Configuration
Learning Outcomes
At the end of this topic students should be able to:-
State and apply Aufbau principle, Hund's rule and
Pauli exclusion principle in filling of electrons in
orbitals of an atom.
Write the electronic configuration of atoms and

monoatomic ions.
(a) Orbital diagram
(b) spdf notation

Learning Outcomes
Explain the anomalous electronic configurations
of chromium and copper.
Introduction
The electronic configuration of an atom show
how electron are filled in the orbital.
Electronic configuration describes the
arrangement of electron in an atom.
Electronic Configuration
Method 1: Orbital diagram
Example: 8O
Box
1s 2s 2p
Method 2: s,p,d,f notation
Example: 8O Number of electrons
in the subshells
1s 2 2s 2 2p4
Principal quantum Azimuthal quantum

number, n number, l
To enable us to do electronic configuration, we
have to obey the following rules:
a) The Aufbau Principle
b) The Pauli Exclusion Principle
c) The Hund rule

Aufbau Principle
State that electrons are filled in the orbitals in
order of increasing energy.
Electrons should occupy the orbital with the
lowest energy first before enters the one with
higher energy.
Relative Energy Level
of Atomic Orbitals
4d
n=5 5s
4p
n=4 3d
4s
energy
Energy
n=3 3p
3s Orbital energy levels
in a many-electron atom
n=2 2p
2s
n=1
1s
Order of orbitals (filling) in multi-electron atom
Order of orbitals (filling) in multi-electron atom
The order of filling orbitals is:

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s
Start with the 1s orbital and move downward,
following the arrows. Example:
(a) 4Be (b) 10Ne
Electronic configuration 4Be : 1s2 2s2

Electronic configuration 10Ne : 1s2 2s2 2p6
Pauli Exclusion Principle
No two electrons in an atom can have the same
four quantum numbers (n, l, m, s).
Eg : Li (3 electrons)
Hund’s Rule
States that when electrons are added to the
orbital of equivalent energy (degenerate
orbitals), each orbital are filled singly with
electron of the same spin first before it is paired.
The electron in half-filled orbitals have the same
spins, that is, parallel spins.
Example
1) Carbon (6 electron)
1s 2s 2p
2) Oxygen (8 electron)
1s 2s 2p
Exercise
Write the electronic configuration of the following
atom or ion:
(a)C
(b)Ne
(c)Al
(d)Al3+
(e)Cl
(f) Cl-
The Anomalous Electronic
Configurations of Cr and Cu
Cr and Cu have electron configurations which are
inconsistent with the Aufbau principle. The
anomalous are explained on the basis that a
filled or half-filled orbital is more stable.
Expected (Aufbau
Element Observed/actual
Principle)
1s22s22p63s23p6 4s2
Cr (Z=24) 1s22s22p63s23p6 4s1 3d5
3d4
1s22s22p63s23p6 3d9 1s22s22p63s23p6 3d10
Cu (Z=29)
4s2 4s1
Orbital diagram
24Cr : 18[Ar]
3d 4s
3d orbital with a half filled orbital arrangement are more

stable.
24Cr : 18[Ar]
Actual
3d 4s
Ar : 1s 2 2s2 2p6 3s2 3p6

18
*Half filled orbital arrangement increase stability of Cr atom
Copper expected orbital notation (Aufbau Principle)
Cu : 18[Ar]
3d 4s
3d orbital with fully filled orbital arrangement is more stable.
Copper actual orbital notation
Cu : 18[Ar]
3d 4s
Ar : 1s 2 2s2 2p6 3s2 3p6

18
3.0 PERIODIC TABLE
1
LEARNING OUTCOMES
• At the end of the lesson the students should be

able to :
• (i) Indicate period, group and block (s, p, d, f).
• (ii) Specify the position of metals, metalloids
and non-metals in the periodic table.
• (iii) Deduce the position of elements in the
periodic table from its electronic
configuration.
2
3.1 Classification of elements
• The periodic table is a table that arranges
all the known elements in order of
increasing proton number.
• This order generally coincides with

increasing atomic mass.
3
• A vertical column of elements is called a
group and a horizontal row is known as a
period.
• Elements in the same group have the

same number of valence electrons.
Group number = number of valence electrons

(if the element is in block s and d)
Group number = number of valence electrons + 10

(if the element is in block p)
4
Transition metals
For example, oxygen and sulphur are both found in group

16 which means that they both have 6 valence electrons. 5
GROUP
• Main Groups in Periodic Table
– Group 1 : alkali metals (except H)
– Group 2 : alkaline earth metals
– Group 3-11 : transition metals
– Group 17 : halogens
– Group 18 : inert/ noble gases
– Group 12 : Zn, Cd, Hg
6
• The periods in the Periodic Table are
numbered from 1 to 7
• For example, hydrogen and helium are
in Row 1 or Period 1 because their
principal quantum number, n, of the
main electron shell is 1. (H:1s1 ;He: 1s2)
Period number = Principle quantum number
7
Blocks
• All the elements in the Periodic Table can
be classified into 4 main blocks according
to their valence electrons configuration.
• These main blocks are s, p, d and f block.
8
s- block
• Group 1 and 2
• The filling of valence electrons involve the s
orbital
• Configuration of the valence electrons :
ns1 to ns2
• Eg:
Na : 1s2 2s2 2p6 3s1
11
Ca : 1s2 2s2 2p6 3s2 3p6 4s2
20
9
p-block
• Group 13 to 18
• The filling of valence electrons involve s and
p orbital.
• The configuration of valence electrons:
ns2 np1 to ns2 np6
• Eg.
Al : 1s 2 2s2 2p6 3s2 3p1
13
Te : 1s 2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2
52
5p4 10
d-block
• Groups 3 to 12
• The filling of valence electrons involve s and d
orbitals.
• Group 3 to 11 known as Transition metal.
• Configuration of valence electron :
• Eg. (n-1) d1 ns2 to (n-1) d10 ns2
2 2 6 2 6 3 2 or
23V : 1s 2s 2p 3s 3p 3d 4s
[Ar] 3d3 4s2
where [Ar] = 18 electrons
11
f-block
• Involve the elements in the series of
lanthanides (Ce to Lu) and actinides (Th
to Lr).
• The filling of valence electrons happen in

the subshell of 4f and 5f.
12
elements block period group Numbe
r of
K : 1s 2 2s2
s 4 1 velenc
1
19
2p6 3s2 3p6 e

Mg
12 4s :
1 1s 2 s 3 2 electro
2
2s 2 2p62 3s22 n
15 : 1s 2s
P p 3 15 5
2p6 3s2 3p3
Bv : 1s 2 2s2 p 4 17 7
35
2p6 3s2 3p6
Ni2 : 1s
10 2 2s52 d 4 10 10
4s
28 3d 4p
2p6 3s2 3p6
4sZr :
2 3d 8 2 2s2
1s d 5 4 4
40
2p6 3s2 3p6
4s2 3d10 4p6
5s2 3d2
Example
• Classify the following elements into its

appropriate group, period and block.
A ……1s2 2s2 2p6 3s2 3p6
B …….1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p5
C …….1s2 2s2 2p6 3s2 3p6 4s2
D …….1s2 2s2 2p6 3s2 3p6 3d3 4s2
E …….1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6
15
Element Group Period Class/block
A 18 3 Inert gas / block p
Block p
B 17 4
Block s
C 2 4
Transition element/
D block d
5 4
Inert gas / block p
E
18 4
16
3.2 Periodicity
4.2.1 Periodic trends in the size of atom

(atomic radii)
• The size /radius of atom is difficult to be
defined exactly because the electron cloud
has no clear boundary.
• Therefore, the atomic radius is taken as

half of the distance between the nuclei of
two adjacent identical atom.
17
Radius, r = a/2 (Å)
Size  volume
V = 4/3 πr3 , V  r
a
• Down the group, atomic radii increases.
 Across period, atomic radii decreases.
• Across the period of d-block (transition elements)

the change in atomic radii is small as valence
electrons are filled in the 3d degenerate orbitals.
18
Two factors that influence the changes of
atomic radii in the Periodic Table are:
i. Effective nuclear charge

experienced by the valence
electrons
ii. The principal quantum number, n, of

the valence electrons
19
i. Effective nuclear charge (Zeff )
• Electrons around the nucleus experience
different nucleus attraction.
• Those electrons closer to the nucleus

experience a greater attraction than
those that are farther away.
• The actual nuclear charge experienced by

an electron is called the effective nuclear
charge, Zeff
20
• Effective nuclear charge increase, nucleus
attraction stronger, atomic radii decrease
• Across the period, the effective nuclear

charge increases as proton number
increase.
• As a result, the attraction between the

nucleus and valence electrons become
stronger, causing the atomic radius to
decrease. 21
ii. The principal quantum number of the
valence electrons
• As we move down a group, the number of
shells increases, more inner electrons are
present to shield the valence electrons
from the nucleus.
• The valence electrons are farther from the

nucleus.
• Thus, the attraction between the nucleus

and valence electrons decreases, therefore,
the atomic radius increase.
22
• Down a group, the atomic radius increases
because of the increasing principal quantum
number (n) of the valence electron.
23
Across
period 3
Across
Period 2
24
The graph shows that :
•Atomic radius decreases when :
* Across a period (from left to right)

* Moving up a group in the periodic table.
•Atomic radius increases when

* Going down the group
• The greater the nucleus attraction, the

smaller the atomic radius.
25
Example
Arrange the following atoms in order of increasing radius P,Si,N.
Solution
• N and P are in the same group and N is above
P.
• Atomic radius increases as we go down the
group.
• Therefore, the radius of N is smaller than that Group Group
of P 14 15
• Both Si and P are in the third period and Si is N
to the left of P.
• Atomic radius decreases as we move from Si P
left to right.
• Therefore, the radius of P is smaller than Si.
• Thus the order of increasing radius :
N<P<Si
26
3.2.2 Trends in the ionic radii
• When electrons are added to an atom, the
mutual repulsions between them increase.
• This enlarge the domain of electron cloud.
• Therefore, negative ions (anions) are

larger than the atoms from which they are
formed.
27
• When electrons are removed from the
valence shell, the electron-electron
repulsions decrease but the nuclear
charge remains the same.
• So the remaining electrons are to be

pulled closer together around the nucleus.
• Therefore, cations are smaller than the

atoms from which they are formed.
28
29
Isoelectronic species
• Isoelectronic species are groups of atoms and

ions which have the same electronic configuration.
Within isoelectronic species:

a) the more positive the charge, the smaller the
species
E.g :
• Na+, Mg2+, Al3+and Si4+ ions are isoelectronic
(10 e) with the electron configurations as
1s2 2s2 2p6.
30
Isoelectronic species with electronic configuration
1s2 2s2 2p6 (10 electrons)
species Number of
Na+ 11
proton
Mg2+ 12
Al3+ 13
Si4+ 14
•When proton number increase, effective nuclear
charge increase.
•The attraction between nucleus and remaining
electron increase.
•Therefore, the ionic radii decrease.
•The ionic radii of Na+ > Mg2+ > Al3+ > Si4+
Isoelectronic species with electronic
1s2 2s2 2p6 3s2 3p6 (18 electrons)
species Number of
P3- 15
proton
S2- 16
Cl- 17
•When proton number increase, effective nuclear
charge increase.
•The attraction between nucleus and remaining
electron increase.
•Therefore, the ionic radii decrease.
•The ionic radii of Cl- < S2- < P3-
Exercise
Na+,Si4+ ,Mg2+, N3- ,O2- ,Al3+ and F- are

isoelectronic with the electronic configuration as
1s2 2s2 2p6. Arrange in an descending order
the size of those isoelectronic species.
Answer :
N3- > O2- > F- > Na+ > Mg2+ > Al3+> Si4+
33
34
3.2.3 Trends in the ionization
energies
• The ionization energy (IE) is the minimum
energy required to remove an electron from a
gaseous atom in its ground state.
 The first ionization energy (IE ) is the
1
minimum energy required to remove the first
electron from the atom in its ground state.
E.g:
energy + X(g) → X+(g) + e- ΔH = IE1
35
i) Ionization energy across a period :
 The effective nuclear charge increases, the

atomic size decreases.
 Electrons are held tightly to the nucleus

thus it is difficult to remove the first electron.
 Therefore the first ionisation energy is high.
It can be said that the first ionization energy

increases from left to right.
However, there are some irregularities in the trend.

36
‫٭‬Be ■N
♦B ▲O
■
▲
‫٭‬
♦
37
Anomalous cases in Period 2
a) Between group 2 and 13
• B : 1s 2 2s2 2p1 in group 13 has a lower IE

5 1
than 4Be: 1s2 2s2 in group 2.
• Be loses a 2s electron while B loses a 2p

electron.
• Less energy is needed to remove an electron

from partially-filled 2p orbital in B than to
remove an electron from fully/completely filled
2s orbital in Be.
38
b) Between group 15 and 16
• O (group16) has lower IE1 than N (group 15)
• 7N :1s2 2s2 2p3 (the half-filled 2p orbital )
O :1s 2 2s2 2p4( the partially-filled 2p orbital)

8
• When N loses an electron it must come from the

half-filled 2p orbital which is more stable than
that of electron of the partially-filled orbital in O.
• As a result, the first ionization energy of N is
higher than of O.
39
ii) Ionization energy going down the group
• Going down the group, the atomic size
increases as the energy level, n increases.
• Therefore the outer electrons are farther

from the nucleus and are held less tightly
(weaker attraction) by the nucleus.
• Thus, it is easy to remove the first electron.
• Hence the Ionization Energy decreases

down the group.
40
• Second ionization energy (IE2) is the minimum
energy required to remove an electron from a
positive gaseous ion.
X+(g) → X2+(g) + e-
• When an electron is removed from a neutral
atom, the mutual repulsion among the remaining
electrons decrease.
• Since the nuclear charge remain constant, the

electron are held tightly to the nucleus.
• Therefore more energy is needed to remove

another electron from the positively charged ion.
41
• Thus, ionization energies always increase in the
following order :
IE1< IE2< IE3< IE4<…..
• Although the removal of a subsequent electron

from an atom requires an increment amount of
energy but it may not be consistence.
• We can determine the electronic configuration of

the valence electron for an element by using the
ionization energy.
42
Example 1
• 4Be
• The ionization energies (kJmol-1) of Beryllium
are shown below.
IE1 IE2 IE3 IE4

899 1757 14850 21005
43
• The ratio between the ionization energies are:
IE 2 1757
  1.95
IE 1 899
IE 3 14850
  8.45
IE 2 1757
IE 4 21005
  1.41
IE 3 14850
44
• A sharp increase in ionization energy
occurs when an inner-orbital electron is
removed.
• The sharp increase is in IE3. It means the

3rd electron occupies the inner shell.
• Therefore, there are 2 valence electrons.

Hence, Be is in group 2 with valence
configuration ns2.
45
Example 2
• Five successive ionization energies (kJmol-1)

of atom M is shown below:
IE1 IE2 IE3 IE4 IE5

800 1580 3230 4360 16000
• Determine
i) the electron configuration of the valence
electron.
ii) the group number in the periodic table.
46
• The sharp increase is in IE5, this means
the 5th electron occupies the inner shell.
• Therefore, there are 4 valence electrons.
• Hence, the valence electronic

configuration for M is ns2 np2 in group 14
of the periodic table.
47
Trends in the electronegativity
• Electronegativity is the relative tendency of

an atom to attract electrons to itself when
bonded with another atom.
• Electronegativity increases up a group and

across a period. This follows the trends for
ionization energy and electron affinity.
48
a) Across period
• The nuclear charge increase
• The atomic size decrease
• Hence, the nucleus attraction stronger
• Therefore, the electronegativity
increase
49
b) Down a group
• The principle quantum number increase

• The atomic size increase
• Hence, weaker nuclear attraction
• Therefore electronegativity decrease
50
Trends in the melting or boiling point
• The melting or boiling point depends on

the types of intermolecular forces that exist
between the molecules.
51
Across the period
• Melting and boiling point of the 3rd period

elements
Element Na Mg Al Si P S Cl Ar
Melting 98 650 660 1410 44 120 -101 -189
point
(oC)
Boiling 890 1120 2450 2360 280 445 -34 -186
point
(oC)
52
• The variation of melting and boiling point of
elements in the 3rd period can be discussed
as:
(a) Metallic structure (Na to Al)
(b) Gigantic covalent structure (Si)
(c) Simple molecular structure (P to Ar)
53
a)Metallic structure (Na to Al)
Metal has positive metal ions attracted to the

electrons sea which form the metallic bonding.
Strength of metallic bonding is proportional to the

number of valence electrons.
e e e e
The more valence Na+ Na+ Na+ Na+
electrons, the stronger e e e e
Na+ Na+ Na+ Na+
the metallic bond and e e e e
the higher the melting Na+ Na+ Na+ Na+
/ boiling point
54
b) Gigantic covalent structure (Si)
• Silicon has a gigantic covalent structure.
• Melting and boiling point of Si is very high

because high energy is needed to break the
infinity amount of the strong covalent bond.
55
c) Simple molecular structure ( P to Ar)
• The non-metal that exist as molecules of P4, S8,
Cl2 and Ar (monoatom).
• The covalent bond between the atoms is very
strong but the intermolecular force (Van der
Waals), is very weak.
• The strength of Van der Waals force is
proportional to molecular size (relative molecular
weight)
– Molecular size: Ar < Cl2 < P4 < S8
– therefore
melting / boiling point : Ar < Cl < P < S 56
Melting and boiling points down the group
Group 1
• The size increase, the attraction between
nucleus and electron sea become weaker.
• Therefore, less energy is needed to
overcome the attraction.
• Thus, melting and boiling point
decrease.
57
Group 17
• The size of molecules increase, the
intermolecular forces (Van der Waals) become
stronger.
• Therefore, more energy is needed to overcome

the attraction
- Thus, melting and boiling point increase.
58
Metallic character
• Metallic properties are:

- shiny with various colours and most are silvery.
- malleable and ductile
- good thermal and electric conductor
• Generally, metallic character :

- Increases down a group
- Decreases across the period
59
• The easier to the electrons to be removed
from an atom, the more metallic the
element.
• Therefore metallic character increases down

a group and decreases across a period.
Metalloids
metal nonmetal
(semimetal)
60
Acid-base behavior of oxides of Period 3
For Period 3:
Na Mg Al Si P S Cl
• When react with oxygen :

(a) Na & Mg form basic oxide
(b) Al form amphoteric (both acidic and

basic) oxide.
(c) Si, P, S & Cl form acidic oxide
61
• Na reacts with oxygen to form a basic oxide.
4Na (s) + O2 (g)→2Na2O (s)
• The oxide will produce base solution when react
with water.
Na2O (s) + H2O (l) → 2NaOH (aq)
• Mg burns in oxygen to form a basic oxide, MgO.

2Mg (s) + O2 (g) →2MgO (s)
MgO (s) + 2HCl (aq) →MgCl2 (aq) + H2O (l)
base acid
62
• Al forms amphoteric oxide, can react either
with an acid or a base.
Al2O3(s) + 6HCl(aq) → 2AlCl3(aq) + 3 H2O (l)
base acid
Al2O3(s) + 2NaOH(aq) + 3H2O(l) → 2NaAl(OH)4 (aq)

acid base sodium aluminate
63
Si, P, S & Cl burn in oxygen to form acidic oxide.
Si :
Si (s) + O2 (g) → SiO2 (s)
SiO2 (s) + NaOH (aq) → Na2SiO3(aq)+H2O (l)
acid base
64
P:
P4 (s) + 3O2 (g) → P4O6 (s)
P4O6 (s) + 6H2O (l) → 4H3PO3 (aq)

phosphorus acid
65
S:
S (s) + O2 (g) →SO2 (g)
SO2 (g) + H2O (l) → H2SO3 (aq)
sulfurous acid
Cl :
Cl2O7 (g) + H2O (l) → 2HClO4 (aq)
hypochloric acid
66
CHAPTER 4
CHEMICAL BONDING
 Chemical bond is the force that
holds two atoms together in a
molecule or compound
 Valence electrons play an

important role in the formation of
chemical bonds
CHAPTER 4
CHEMICAL BONDING
4.1 Lewis Structure
4.2 Molecular Shape and Polarity
4.3 Orbital Overlap and Hybridization
4.4 Intermolecular Forces
4.5 Metallic Bond
4.1 Lewis Structure
4.1.1 Lewis Symbol
A Lewis symbol consists of:

 the symbol of an element
 dots or cross is used to represent the

valence electrons in an atom of the
element.
Example
The Lewis symbol of atom
Group 1 2 13 14 15 16 17 18
Valence 1 2 3 4 5 6 7 8
electron
Lewis dot
symbol
 Elements in the same group have the
same valence electronic configurations
 similar Lewis symbols.
4.1.2 Octet Rule
 Octet rule states that atoms tend to form
bonds to obtain 8 electrons in the valence
shell
 Atoms combine to achieve stablility
 to have the same electronic
configuration as a noble gas
 Atoms achieve noble gas configuration
through:
i) transferring electrons
ii) sharing electron
 Bond formation involve transferring or
sharing of only valence electrons
Electronic Configuration of Cations and
Anions
1)Noble gas configuration

Group 1, 2 and 13 elements donate valence
electrons to form cations with noble gas
configurations
Example:
Na : 1s22s22p63s1
Na+ : 1s22s22p6 (isoelectronic with Ne)
Ca : 1s22s22p63s23p64s2
Ca2+ : 1s22s22p63s23p6 (isoelectronic with Ar)
 Group 15, 16 and 17 elements accept
electrons to form anions with noble gas
configurations
Example:
O : 1s22s22p4
O2 : 1s22s22p6
(isoelectronic with neon)
Cl : 1s22s22p63s23p5
Cl : 1s22s22p63s23p6
(isoelectronic with Ar)
2) Pseudonoble gas configuration
 d block elements donate electrons from

4s orbitals to form cations with
pseudonoble gas configuration.
Example:
Zn : 1s22s22p63s23p64s23d10
Zn2+ : 1s22s22p63s23p63d10
(pseudonoble gas configuration )
3) Stability of the half-filled orbitals
 d block element can also donate electrons to
achieve the stability of half-filled orbitals
Example:
Mn : 1s22s22p63s23p64s23d5
Mn2+ : 1s22s22p63s23p63d5
(stability of half-filled 3d orbital )
Fe : 1s22s22p63s23p64s23d6
Fe3+ : 1s22s22p63s23p63d5
(stability of half-filled 3d orbital)
4.1.3 Formation of the bonds
using Lewis Symbols
i.Ionic (electrovalent) bond

ii.Covalent bond
iii.Dative (coordinate) bond
4.1.3.1 Ionic bond (Electrovalent
bond)
 Ionic bond (electrovalent bond) is
an electrostatic attraction between
positively and negatively charged
ions.
 Ionic compounds are formed when
electrons are transferred between

atoms (metal to nonmetal) to give
electrically charged particles that
attract each other .
Example 1: NaCl
Sodium, an electropositive metal, tends to

remove its valence electron to obtain noble gas
electronic configuration (Ne)
Chlorine, an electronegative element, tend to

accept electron from Na to obtain noble gas
electronic configuration (Ar)
 The electrostatic forces between Na+ and
Cl- produce ionic bond
 These two processes occur simultaneously
+
Example 2: CaCl2
Ca: 1s2 2s2 2p6 3s2 3p6 4s2

(Has two electrons in its outer shell)
Cl: 1s2 2s2 2p6 3s2 3p5

(Has seven outer electrons)
Calcium Chloride
If Ca atom transfer 2 electrons, one to each
chlorine atom, it become a Ca2+ ion with the stable
configuration of noble gas.
At the same time each chlorine atom to achieve

noble gas configuration gained one electron
becomes a Cl- ion to achieve noble gas
configuration.
The electrostatic attraction formed ionic bond

between the ions.
Ionic bond
(Formed by transfer of electrons)
Calcium Chloride
+ + 2
Example 3: LiF
+
Lewis structure and formation of ionic compounds
1) CaCl2
+ + 2
2) MgO
+
3) CaBr2
+ +
 Ionic bond is very strong, therefore ionic
compounds:
1. Have very high melting and boiling
points
2. Hard and brittle
3. Can conduct electricity when they

are in molten form or aqueous
solution because of the mobile ions
Exercises:
By using Lewis structure, show how the

ionic bond is formed in the compounds
below.
( a ) KF
( b ) BaO
( c ) Na2O
4.1.3.2 Covalent Bond
Definition of covalent bond
i. Chemical bond in which two or more
electrons are shared by two atoms.
ii. The electrostatic force between the electrons
being shared the nuclei of the atoms.
Why should two atoms share electrons?
To gain stability by having noble gas

configuration (octet)
Example
F + F F F
7e- 7e- 8e- 8e-
Lewis structure of F2
single covalent bond lone pairs F F lone pairs
single covalent bond

lone pairs F F lone pairs
9.4
Covalent compounds:
 Compounds may have these covalent

bonds:
i. Single bond
ii. Double bond
iii. Triple bond.
Lewis structure of water
H + O+ H H O H
2e- 8e- 2e-
or
single covalent bonds
H O H
Double bond – two atoms share
two pairs of electrons
O C O or O C O
8e- 8e- 8e-
double bonds double bonds
Triple
+
bond – two atoms share
three pairs of electrons
N N or N N
8e- 8e-
triple bond
triple bond
4.1.3.3 Coordinate Covalent Bond
(Dative Bond)
 Dative bond is a bond in which the pair of

shared electrons is supplied by one of
the two bonded atoms
 Involve overlapping of a full orbital and

an empty orbital
Requirement for dative bonds:
i. Donor atoms should have at
least
one lone pair electrons
ii. The atoms that accepts these
electrons should have empty
orbitals.
i.Single bond
i.Double bond
i.Triple bond
Steps in Writing Lewis Structures
1. Count total number of valence e- of atoms involved.
2. Add 1 for each negative charge. Subtract 1 for each
positive charge.
3. Draw skeletal structure of the compound. Put least
electronegative element in the center.
4. Complete an octet for all atoms except hydrogen
5. If structure contains too many electrons, form double
and triple bonds on central atom as needed.
Example
Draw the Lewis structure for each of the
following compounds:
i. HF
ii. CH4
iii. CHCl3
iv. NH3
v. H2O
Total no. of valence
electrons
H: 1e
F: 7e
Total : 8e
Number of electrons
C : 4e
4H: 4e
Total : 8e
Center atom: N
 Count electrons:
C : 4e
H : 1e
3Cl: 21e
Total: 26 e
Count number of
electrons
N : 5e
3H : 3e
Total : 8e
4.1.5 Bond Length
Compare the bond length between single,
double and triple bond
Bond length :
The distance between nuclei of the atoms involves in the
bond
C C C C C C
1.54 Å 1.34 Å 1.20 Å
As the number of bonds between the carbon increase,

the bond length decreases because C are held more
closely and tightly together
As the number of bonds between two atoms increases,
the bond grows shorter and stronger
The sum of formal charge on
each atom should equal:
i.zero for a molecule
ii.the charge on the ion for a
polyatomic ion
Formal charge is used to find

the most stable Lewis
structure
EXAMPLE
1) Draw all the possible Lewis structure

of COCl2.
2) Predict the most plausible structure.
SOLUTION
1) 2)
The most plausible structure is (2)
Formal charge is determined before

completing a Lewis structure to predict
the most stable structure because
formal charge closest to zero.
EXERCISE 1
 Draw the possible Lewis

structures for HNO2.
 Determine the most plausible
Lewis structures for HNO2.

EXERCISE 2
 Suggest the possible Lewis

structure for H2SO4. Explain
your answer.
EXERCISE 3
1) HCN
1) CO2
1) SCN
 Three conditions:
1) Incomplete octet
2) Expanded octet
3) Odd no. electron

 Occurs when central atom has less
than 8 electrons.
 Elements that can form incomplete
octet are:
Boron,B , Beryllium, Be &
Aluminium, Al
 This is due to elements being
relatively small in size but having high
nuclear charge.
 Occurs when central atom has more
than 8 electrons.
 Formed by non-metals that have d
orbitals
OR
 Non-metals of the 3rd, 4th, 5th….rows
in the periodic table
 Nitrogen may form compounds
that contain odd number
electrons.
Example:
Nitric oxide, NO
Nitrogen dioxide, NO2
 The use of two or more Lewis
structures to represent a particular
molecule.
 Requirement:
Molecules/ions must have multiple

bonds and lone pairs electrons at
the terminal atoms.
RESONANCE STRUCTURE FOR NO3-
EXERCISE:
Write Lewis structures of the
following compounds/ ions:
CCl4 CO32- HCN PCl3 HNO3
PO43- C2H4 C2H2 CH2Cl2 ICl
NH4+ NF3 H2S N2H4 PH3
CS2 NO2- XeF4 NH3 HCOOH
SO42- ICl4- SF6 O3 NO2
4.2 MOLECULAR SHAPE
AND POLARITY
LEARNING OUTCOMES
At the end of the lesson, students should
be able to;
1. Explain valence shell electron repulsion theory.
(VSEPR)
2. Draw the basic molecular shapes : linear, trigonal
planar, tetrahedral, trigonal bipyramidal and
octahedral.
3. Predict and explain the shapes of molecule and
bond angles in a given species.
4. Explain bond polarity and dipole moment.
5. Deduce the polarity of molecules based on the
shapes and the resultant dipole moment
63
4.2 MOLECULAR SHAPE
AND POLARITY
i. VSEPR theory
ii. 5 basic shapes
iii. polarity
64
Molecular shape: Introduction
shows the 3-dimensional arrangement of

atoms in a molecule
Predicted by using Valence Shell
Electron Pair Repulsion (VSEPR) theory
65
4.2.1 VSEPR
The Valence-Shell Electron Repulsion

theory states that:
The valence electron pairs around

the central atom are oriented as far
apart as possible to minimize the
repulsion between them.
66
The repulsion may occur either between:
a) bonding pair & another bonding pair
b) bonding pair & lone pairs or
c) between lone pair & another lone

pairs
67
The strength of repulsion:
The order of repulsive force is:
Lone pair- > Lone pair-bonding > Bonding pair-bonding
lone pair pair repulsion
pair repulsion
repulsion
Decrease of the repulsion force
Note:
The electron pairs repulsion will determine the
orientation of atoms in space
68
4.2.2 Shape of a molecule
 Basic shapes are based on the repulsion
between the bonding pairs.
 Tips to determine the molecular shape :

Step 1
Draw Lewis structure of the molecule
Step 2
Consider the number of bonding pairs
Step 3
Place bonding pairs as far as possible to
69 minimize repulsion.
A. Molecules with 2 bonding pairs
 shape
Example: BeCl2
Lewis structure
Be : 2e 180°
2Cl :14e
Total : 16 e
.. ..
:Cl Be Cl: .. Linear
..
70
B. Molecules with 3 bonding-pairs
 Example: BCl3
 Repulsive forces
Lewis structure between pairs are the
B: 3e
same
3Cl : 21e
Total: 24e
120°
:
Cl
..
..
.. ..
: Cl
.. B Cl :
..
Trigonal planar
71
C. Molecules with 4 bonding pairs
 Example: CH4  Equal repulsion
Lewis structure between bonding pairs
– equal angle
H
H C H 109.5°
Tetrahedral
72
D. Molecules with 5 bonding pairs
 Example: PCl5
 Lewis structure  Shape:
90°
:
Cl
..
..
..
.. Cl :
Cl
: P ..
.. 120°
..
Cl :
..
Cl
..
..
:
Trigonal bipyramidal
73
E. Molecules with 6 bonding pairs
 Example: SF6
Lewis structure
Octahedral
S : 6e
6F : 42e
90o
Total : 48e
90o
F
F
F S F
F
F
74
2 electron pairs in the valence shell
of central atom:
Class of Number Number Shape

molecules of bonding of lone
pairs pairs
AB2 2 0 180°
Linear
75
of central atom:
pairs pairs
AB3 3 0
120°
76
trigonal planar
of central atom:
pairs pairs
AB4 4 0
109.5o
77
Tetrahedral
of central atom:

pairs pairs
AB5 5 0
90°
120°
78
Trigonal pyramidal
of central atom:

pairs pairs
AB6 6 0
90°
90°
79
Octahedral
4.2.3 Effect of lone pairs on
molecular shape
The geometries of molecules and

polyatomic ions,
ions with one or more lone
pairs around the central atom can be
predicted using VSEPR.
The molecular geometry is determined

by the repulsions of electron pairs in
the valence shell of the central atoms.
atoms
80
 Repulsion between electron
pairs decreases in the order of:
Lone pair- > Lone pair- > Bonding pair-

lone pair bonding bonding pair
repulsion repulsion
pair repulsion
Stronger to weaker repulsion
81
 Electrons in a bond are held by the
attractive forces exerted by the nuclei of
the two bonded atoms therefore, they take
less space of repulsion.
 Lone- pair electrons in a molecule occupy

more space; therefore they experience
greater repulsion from neighboring lone
pairs and bonding pairs
82
Number of electron pair : 3
Example : SO2
 Class of molecules : AB2E

 Molecular shape : Bent / V-shaped
83
Example : NH3

 Molecular shape : Trigonal pyramidal
84
Example : H2O
 Class of molecules : AB2E2

 Molecular shape : Bent / V-shaped
85
Example : SF4

 Molecular shape : Distorted tetrahedron /
seesaw
86
Example : ClF3
 Molecular shape : T-shaped
87
Example : I3-
 Molecular shape : Linear
88
Example : BrF5
 Molecular shape : Square pyramidal
89
Example : XeF4
 Molecular shape : Square planar
90
Shape of molecules which the central
atom has one or more lone pairs

pairs pairs
AB2E 2 1
Bent / V-shaped
91
Bond angle : < 120o
of central atom:

pairs pairs
AB3E 3 1
Trigonal pyramidal
92
Bond angle : < 109.5o
of central atom:
pairs pairs
AB2E2 2 2
Bent / V-shaped
Bond angle : < 109.5o
93
of central atom:
pairs pairs
AB4E 4 1
Distorted tetrahedral
(see-saw)
94 Bond angle : < 90o
of central atom:

pairs pairs
AB3E2 3 2
T-shaped
95
Bond angle : < 90o
of central atom:

pairs pairs
AB2E3 2 3
Linear
96
Bond angle : 180o
of central atom:
pairs pairs
AB5E 5 1
Square pyramidal
97 Bond angle :90o and
180o
of central atom:

pairs pairs
AB4E2 4 2
Square planar
98
Bond angle : 90o
99
COMPARISON OF BOND ANGLE
IN CH4, NH3 AND H2O
109.5o 107.3o 104.5o
100
a) CH4
 Has 4 bonding pairs electrons.
 The repulsion between the bonding pairs

electrons are equal.
equal
 The bond angles are all 109.5o
101
b) NH3
 has 3 bonding pairs electron and 1 lone pair

electron.
 according to VSEPR, lone pair - bonding pair >

bonding pair - bonding pair repulsion.
repulsion
 Lone- pair repels the bonding-pair more strongly,

strongly
the three NH bonding-pair are pushed closer
together, thus HNH angle in ammonia become
smaller, 107.3o.
102
c) H2O
 Has 2 bonding pairs electrons and 2 lone pair

electrons.
 According to VSEPR, lone pair – lone pair >
lone pair – bonding pair > bonding pair –
bonding pair repulsion.
repulsion
 Lone-pair tend to be as far from each other as
possible.
 Therefore, the two OH bonding-pairs are
pushed toward each other.
 Thus, the HOH angle is 104.5o.
103
4.2.4 POLAR AND NONPOLAR
MOLECULES
 A quantitative measure of the polarity of a bond is

its dipole moment ( µ ).
µ
µ = Qr
µ
Where : µ = dipole moment
Q = the product of the charge from
electronegativity
r = distance between the charges.
Dipole moments are usually expressed in debye units(D)

104
E.g : Polarity of HF
 Hydrogen fluoride is a covalent molecule with

a polar bond.
 F atom is more electronegative than H atom,

so the electron density will shift from H to
F.
 The symbol of the shifted electron can be

represented by a crossed arrow to indicate
the direction of the shift.
H F
105
The consequent charge separation can be
represented by :
δ + : partial positive charge

δ - : partial negative charge
106
 Diatomic molecules containing atoms of
different elements (e.g. : HCl, NO and CO)
have dipole moments and are called polar
molecules.
 Diatomic molecules containing atoms of the

same element (e.g. : H2, N2 and Cl2) do not
have dipole moments and are called nonpolar
molecules.
107
For polyatomic molecules, the polarity of the
bond and the molecular geometry determine
whether there is a dipole moment.
Even if polar bond are present, the molecules

will not necessarily have a dipole moment.
108
Example
Predict the polarity of the following molecules:

– Carbon dioxide, CO2
– Carbon tetrachloride, CCl4
– Chloromethane, CH3Cl
– Ammonia, NH3
109
(a) Carbon dioxide, CO2
- molecular geometry : linear

- oxygen is more electronegative than carbon,
- Dipole moment can cancell each other
- has no net dipole moment (µ = 0)
- therefore CCl4 is a nonpolar molecule.
110
(b) Carbon tetrachloride, CCl4
- molecular geometry : tetrahedral

- Chlorine is more electronegative than carbon,
- Dipole moment can cancell each other
- has no net dipole moment (µ = 0)
- therefore CCl4 is a nonpolar molecule.
111
( c) Chloromethane, CH3Cl

- Cl is more electronegative than C, C is more
electronegative than H
- Dipole moment cannot cancell each other
- has a net dipole moment (µ ≠ 0)
- therefore CH3Cl is a polar molecule.
112
(d ) Ammonia, NH3

- N is more electronegative than H,
- Dipole moment cannot cancell each other
- has a net dipole moment (µ ≠ 0)
- therefore NH3 is a polar molecule.
113
Factors that affected the
polarity of molecules
molecular geometry
electronegativity of the bonded atoms.
114
BOND
NON-POLAR
POLAR
NON-POLAR
MOLECULES
NON-POLAR POLAR
MOLECULES MOLECULES
Symetrical molecules Non-symetrical molecules

- basic molecular shape with the - basic molecules with different
same terminal atom terminal atom
- molecules with lone pairs linear - molecules with lone pairs except
(from trigonal bipyramidal) and linear and square planar
square planar with the same
terminal atom
115
Exercises :
Predict the polarity of the following molecules:
 SO2 ; HBr ; SO3 ; CH2Cl2 ; ClF3 ; CF4 ; H2O ;

XeF4 ; NF3 ; Cis-C2H2Cl2 ; trans-C2H2Cl2
116
4.3 ORBITAL OVERLAP AND
HYBRIDIZATION
1. Formation Covalent Bond

2. Formation Hybrid orbitals
3. Orbital Overlapping
117
Objectives
At the end of this subtopic, students should be

able to:
1. Draw and describe the formation of sigma(
and pi() bonds from overlapping of orbitals.
2. Draw and explain the formation of hybrid
orbitals of a central atom: sp, sp2, sp3, sp3d, sp3d2
using appropriate examples.
3. Draw orbitals overlap and label sigma( and
pi() bonds of a molecule.
118
4.3.1 Valence Bond theory
• explains the formation of covalent bonds
and the molecular geometry outlined by
the VSEPR.
• States that a covalent bond is formed
when the neighboring atomic orbitals
overlap.
• Overlapping may occur between:
a) orbitals with unpaired electrons
b) an orbital with paired electrons and
another empty orbitals (dative bond)
119
Example:
The s-orbital of the

H H
Hydrogen atom
Change in electron
density as two hydrogen
atoms approach each
other.
High electron density as

the orbitals overlap
(covalent bond formed)
120
10.3
FORMATION OF COVALENT BOND
• Valence bond theory - Covalent bond is formed

when two neighbouring atomic half-filled orbitals
overlap.
• Two types of covalent bonds are

a) sigma bond (σ)
b) pi bond ()
121
a)  bond
• formed when orbitals overlap along its

internuclear axis (end to end overlapping)
Example:
i. overlapping s orbitals
H + H H H
 bond
122
ii. Overlapping of s and p orbitals
Px orbital
H + x H x
 bond
123
• iii. Overlapping of p orbitals
x
+ x
x
 bond
124
b) bond
• Formed when two p-orbitals of the same
orientation overlap sideways
y y y y
125
 bond
y y y y
 bond
126
Formation of bonds in a molecule
• Covalent bonds may form by:
a) overlapping of pure orbitals
b) overlapping of hybrid orbitals
127
Overlapping of pure orbitals
• Example :
i. O2
ii. N2
128
O2
Consider the ground state configuration:
Two unpaired electrons to be used in
bonding.
O : 1s2 2s2 2p4
y y
1s 2s 2p 
Overlapping occurs between

the p-orbitals of each atom O O x
σ
129 
y y

O O x
σ
130
N2
131
4.3.2 Formation Hybrid orbitals
• Overlapping of hybrid orbitals and the pure orbitals
occur when different type of atoms are involved in
the bonding.
• Hybridization of orbitals:
mixing of two or more atomic orbitals to form a new
set of hybrid orbitals
• The purpose of hybridisation is to produce new

orbitals which have equivalent energy
• Number of hybrid orbitals is equal to number of

pure atomic orbitals used in the hybridization
process.
132
Hybridization
• Hybrid orbitals have different shapes
from original atomic orbitals
• Types of hybridisation reflects the
shape/geometry of a molecule
• Only the central atoms will be involved
in hybridisation
133
10.4
Hybridization of orbitals
i. sp
ii. sp2
iii. sp3
iv. sp3d
v. sp3d2
134
sp3 hybridization
• one s orbital and three p orbitals are mixed to

form four sp3 hybrid orbitals
• the geometry of the four hybrid orbitals is
tetrahedral with the angle of 109.5o .
135
sp3 hybrid
• Mixing of s and three p orbitals
sp3
sp3
sp3
sp 3
136
Example:
1) CH4
• Lewis structure :
• Valence orbital diagram ;
H:
C ground state :
C excited :
C hybrid :
• Orbital Overlap :
• Molecular Geometry :
137
Example : Methane, CH4
Ground state : C : 1s2 2s2 2p2 Lewis Structure
H
H C H
1s 2s 2p
H
Excitation: to have 4
unpaired electrons H
Excited state : sp3

1s 2s 2p
C sp3
sp3 H
H sp3
sp3 hybrid H
shape: tetrahedral
138
Fig. 10.8
sp3-Hybridized C atom in CH4
sp3
1s sp3 sp3 1s
sp3
1s
139
Example 2 :
NH3
Lewis structure :
Valence orbital diagram ;
H:
N ground state :
N excited :
N hybrid :
Orbital Overlap :
Molecular Geometry :
140
Fig. 10.9
sp3
1s sp3 sp3
1s
sp3
1s
141
Example:
3) H2O
• Valence orbital diagram;

O ground state :
O hybrid :
• Orbitals overlap:
142
sp 2 hybridization
• one s orbital and two p orbitals are
mixed to form three sp2 hybrid
orbitals
• the geometry of the three hybrid
orbitals is trigonal planar with the
angle of 120o .
143
Fig. 10.12
s sp2
px py sp2 sp2
one
144
s orbital + two p orbitals three sp2 orbitals
• simplified drawing of sp2 orbitals:
Shown together
(large lobes only)
145
Example:
1) BF3
F:
B ground state :
B excited :
B hybrid :
• Orbital overlap:
146
Example: BF3
Pure p orbital


sp2 sp2
F : 1s22s22p5
sp2

Shape : trigonal planar
147
Example:
2) C2H4
C ground state :
C excited :
C hybrid :
148
Fig. 10.16a-c
 bonds
 bond
149
150
10.5
sp hybridization
• one s orbital and one p orbital are
mixed to form two sp hybrid orbitals
• the geometry of the two hybrid
orbitals is linear with the angle of
180o
151
Types of hybrid orbitals
Formation of sp Hybrid Orbitals
sp sp Produces linear shape
152
10.4
Example:
1) BeCl2
Cl :
Be ground state :
Be excited :
Be hybrid :
153
Fig. 10.11
154
Example:
2) C2H2
C ground state :
C excited :
C hybrid :
155
Fig. 10.19a-c
156
Example:
3) CO2
O:
C ground state :
C excited :
C hybrid :
157
3
sp d hybridization
• one s orbital, three p orbitals and
one d orbital are mixed to form five
sp3d hybrid orbitals.
• the geometry of the five hybrid
orbitals is trigonal bipyramidal with
the angle of 120o and 90o
158
• simplified drawing of sp3d orbitals:
159
Example:
1) PCl5
Cl :
P ground state :
P excited :
P hybrid :
160
Example:
2) ClF3
F:
Cl ground state :
Cl excited :
Cl hybrid :
161
3
sp d 2 hybridization
• one s orbital, three p orbitals and
two d orbitals are mixed to form six
sp3d2 hybrid orbitals
• the geometry of the six hybrid orbitals
is octahedral with the angle of 90o
162
• Simplified drawing of sp3d2 orbitals:
163
Example:
1) SF6
F:
S ground state :
S excited :
S hybrid :
164
Example:
2) ICl5
Cl :
I ground state :
I excited :
I hybrid :
165
How do I predict the hybridization of the central atom?
Count the number of lone pairs AND the number

of atoms bonded to the central atom
No of Lone Pairs
+
No of Bonded Atoms Hybridization Examples
2 sp BeCl2
3 sp2 BF3
4 sp3 CH4, NH3, H2O
5 sp3d PCl5
166 6 sp3d2 SF6

10.4
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or
display.
167
Exercise:
• For each of the following, draw the orbital
overlap to show the formation of covalent
bond
a) XeF2
b) O3
c) ICl4
d) OF2
168
4.4 Intermolecular forces
LEARNING OUTCOMES
At the end of the lesson, students should be able
to;
1. Describe intermolecular forces
i. van der Waals forces :
- dipole-dipole interactions or permanent
dipole
- London forces or dispersion forces
ii. Hydrogen bonding
2. Explain factors that influence the strength of van der Waals
forces
3. Explain the effects of hydrogen bonding on
i. boiling point
ii. Solubility
iii. Density of water compared to ice
1. Explain the relationship between :
i. intermolecular forces and vapour pressure
ii. Vapour pressure and boiling point
4.4 Intermolecular forces
4.4.1 Types of intermolecular
forces
4.4.2The effect of
intermolecular forces
on the physical
properties.
171
Intermolecular Forces
 Intermolecular forces are the

attractive forces between
molecules
172
Effects of intermolecular
forces on physical properties
 Have effects on these physical
properties:
a) boiling point
b) melting point
c) solubility
d) density
e) electrical conductivity
173
Intermolecular Forces
Van der Waal Hydrogen

Forces Bond
Between Between
covalent covalent
molecules
molecules with H
covalently
bonded to
F, O or N
174
4.4.1.1 van der Waal Forces
 Forces that act between covalent
molecules
 Three types of interaction:
i. Dipole-dipole attractive
forces
- act between polar molecules
ii. London Dispersion forces
- act between non-polar
molecules 175
Dipole-dipole forces
(permanent dipole forces)
 Exist in polar covalent compounds
 Polar molecules have permanent dipole due
to the uneven electron distributions
Example:
- +
-
+ 
H Cl H Cl
Chlorine is more Dipole-dipole forces; the

electronegative, partially positive end attracts
thus it has higher the partially negative end
electron density
176
4.4.1.2. London Dispersion Forces
 attractive forces that exist between

non-polar molecules
 result from the temporary
(instantaneous) polarization of
molecules
 The temporary dipole molecules will be
attracted to each other and these
attractions is known as the London
Forces or London Dispersion forces
177
The formation of London forces
 At any instant, electron distributions

in one molecule may be
unsymmetrical.
 The end having higher electron
density is partially negative and the
other is partially positive.
 An instant dipole moment that exists
in a molecule induces the
neighboring molecule to be polar.
178
Example:
London forces in Br2
Electrons in a molecule
move randomly about the
nucleus
Br Br
At any instant, the
electron density might
be higher on one side The temporary dipole
- molecule induce the
- +
+ neighboring atom to
be partially polar
Br Br Br Br
Temporary
dipole molecule
London forces
179
Factors that influence the strength of
the van der Waals forces.
 The molecular size/molecular mass
Molecules with higher molar mass have
stronger van der Waals forces as they tend to
have more electrons involved in the London
forces.
Example:
CH4 has lower boiling point than C2H6
 Note:
However if two molecules have similar
molecular mass, the dipole-dipole interaction
will be more dominant.
Example: H2S has higher boiling point than
CH3CH3 180
4.4.1.3 Hydrogen intermolecular bond
 Dipole-dipole interaction that acts between a

Hydrogen atom that is covalently bonded to
a highly electronegative atom ; F, O ,N in one
molecule and F,O or N of another molecule.
Example:
+ - + -
 
H F H F
Hydrogen
intermolecular bond
181
Other examples:
NH3 liquid H2O
.. Hydrogen
N intermolecular bond
H
H H .. ..
..
..
Hydrogen O O
.. intermolecular bond H H
H H
N
H
H H ..
..
O
Covalent bond H H
.. .. Hydrogen
O intermolecular bond
H H
182
Consider ethanol, CH3OH
CH3OH CH3OH and methane
H
Hydrogen bond Not a hydrogen
bond
.. C
.. H
..
O H H
O H H .. H
..
..
C in
H C
H H C
H
H H H is not H
bonded to H H
either F, O
or N
183
Example: H2O
___ covalent bond
H ----- hydrogen bond
O H
H H
O H O H O
H
H
H
O H 184
185
Properties of compounds with
Hydrogen intermolecular forces
Boiling point
 Have relatively high boiling point than

compounds having dipole-dipole forces
or London forces
- the Hydrogen bond is the strongest
attraction force compared to the dipole-
dipole or the London forces.
186
Solubility
A. Dissolve in polar solvent
 The molecules that posses
Hydrogen bonds are highly polar.
 They may form interaction with
any polar molecules that act as
solvent.
B. Dissolve in any solvent that can
form Hydrogen bonds
187
Example
 NH3 dissolves in water because it can form

Hydrogen intermolecular bond with water.
..
..
O
Hydrogen bond
H H
..
..
N
N H
H H H
H H
188
Problem:
 Explain the trend of boiling point given by the

graph below:
T/oC
HF
HI
HBr
HCl
Molecular mass
189
Answer
 HF can form hydrogen bonds between molecules

while HCl, HBr and HI have van der Waals forces
acting between molecules. Hydrogen
intermolecular bond is stronger that the van der
Waals forces. More energy is required to break the
Hydrogen bond.
 Boiling point increases from HCl to HI. The strength

of van der Waals forces increases with molecular
mass. Since molecular mass increases from HCl to
HI, thus the boiling point will also increase in the
same pattern.
190
The effect of Hydrogen bond on water
molecules
 The density of water is relatively high
compared to other molecules with similar
molar mass.
Reason:
Hydrogen intermolecular bonds are
stronger than the dipole-dipole or the
London forces. Thus the water molecules
are drawn closer to one another and
occupy a smaller volume.
191
Density
Ice (solid H2O) has lower density

compared to its liquid. Refer to the
structure of ice
Ice form tetrahedral arrangement
Hydrogen bond takes

one of the tetrahedral
orientation and occupy
some space
193
 H2O(l) is denser than H2O(s) because
 the hydrogen bond in ice arrange the
H2O molecules in open hexagonal
crystal
 H2O molecules in water have higher
kinetic energy and can overcome
the hydrogen bond
 V-shaped water molecules slide
between each other.
194
195
196
Fig. 11.13
197
Boiling points of substance with
Hydrogen intermolecular bonds
 The boiling points of these substances are
affected by:
a) the number of hydrogen bonds per
molecule
b) the strength of H intermolecular
forces which directly depends on
the polarity of the hydrogen bond
Example:
Explain the trend of boiling points given below:
The order of the increase in boiling point is:
H2O > HF > NH3 > CH4
198
Answer:
 by looking at the polarity of the bond, we have
(Order of polarity: HF > H2O > NH3)
but H2O has the highest boiling point.
For H2O, the number of hydrogen bonds per molecule
affects the boiling point.
 Each water molecule can form 4 hydrogen bonds with
other water molecules. More energy is required to
break the 4 Hydrogen bonds.
 HF has higher boiling point than NH3 because F is
more electronegative than Nitrogen.
 CH4 is the lowest - it is a non polar compound and
has weak van der Waals forces acting between
molecules.
199
Effects of intermolecular forces on
physical properties
1)Boiling point
 For molecules with similar size, the order of
intermolecular strength:
Hydrogen bond > dipole-dipole forces >
London dispersion forces
 Strength of intermolecular forces ↑
 boiling point ↑
200
201
Why boiling point H2O > HF
and HF > NH3?
 Fluorine is more electronegative than

oxygen, therefore stronger hydrogen
bonding is expected to exist in HF liquid than
in H2O.
 However, the boiling point of H2O is higher

than HF because each H2O molecules has
4 hydrogen bonds.
202
 On the other hand, H-F has only 2 hydrogen
bonds.
 Therefore the hydrogen bonds are stronger
in H2O rather than in H-F.
203
Boiling point HF > NH3
 Fluorine is more electronegative than
nitrogen ,thus the hydrogen bonding in H-F
is stronger than H-N.
204
Vapour Pressure
 Molecules can escape from the surface of liquid
at any temperature by evaporation
 in a closed system :
 vapour molecules which leaves the
surface cannot escape from the system
 the molecules strike the container wall
and exert some pressure
Fig. 11.34
 The pressure exerted by those molecules is
called vapour pressure (or maximum vapour
pressure)
Vapour pressure is the pressure exerted

by a vapour in equilibrium with its liquid
phase.
In a close system ….
Liquid molecules vapourise Molecules have enough energy to
overcome intermolecular forces
Vapour molecules are trapped

in the close container
Volume of liquid becomes less Rate of vaporisation is faster

than the rate of condensation
Some of the vapour molecules may
collide and lose their energy. They
re-enter the liquid surface
System reaches equilibrium Rate of vapourisation is equal to

dynamic equilibrium the rate of condensation
Pressure exerted by the vapour

Volume of liquid remains molecules is known as the vapour
constant pressure
Dynamic equilibrium and vapour pressure
Number of liquid The vapour pressure

molecules leaving the at this stage is
surface is the same as constant and known
the number of vapour as the equilibrium
molecules entering vapour pressure.
the liquid surface.
Dynamic equilibrium is reached when:

Rate of evaporation = rate of condensation
Note:
Equilibrium vapour pressure = saturated vapour pressure
= vapour pressure
Factors that affects vapour pressure
i. Intermolecular forces
Molecules with weak intermolecular forces can easily
vapourise. More vapour molecules will be present and
exert higher pressure.
 the weaker intermolecular forces the higher is
the vapour pressure.
ii. Temperature
Heating causes more molecules to have high kinetic
energies that are higher than their intermolecular
forces. More liquid molecules will form vapour.
 vapour pressure increases with temperature.
Fig. 11.35
Boiling – the process
 Increasing the temperature will increase in the vapour
pressure.
 As heat is applied, the vapour pressure of a system

will increase until it reaches a point whereby the
vapour pressure of the liquid system is equal to the
atmospheric pressure.
 Boiling occurs and the temperature taken at this point

is known as the boiling point.
 At this point, the change of state from liquid to gas

occurs not only at the surface of the liquid but also in
the inner part of the liquid.
 Bubbles form within the liquid.

 Boiling Point: the temperature at
which the vapour pressure of a liquid is
equal to the external atmospheric
pressure.
 Normal Boiling Point: the temperature

at which a liquid boils when the external
pressure is 1 atm (that is the vapour
pressure is 760 mmHg)
Factors affecting the boiling point:
1. Intermolecular forces
A substance with weak intermolecular
forces can easily vapourise and the system
requires less heat to achieve atmospheric
pressure, thus it boils at a lower temperature.
2. Atmospheric pressure
When the external atmospheric pressure is
low, liquid will boil at a lower temperature.
4.5 Metallic bond
LEARNING OUTCOMES
At the end of the lesson, students should be
able to;
1. Explain the formation of metallic bond by using
electron sea model.
2. Relate metallic bond to the properties of metal:
i. malleability
ii. Ductility
iii. Electrical conductivity
iv. Thermal conductivity
3. Explain the factors that affect the strength of metallic
bond
4. Relate the strength of metallic bond to boiling point
Metallic bond
 An electrostatic force between
positive charge metallic ions and the
sea of electrons.
 Bonding electrons are delocalized
over the entire crystal which can be
imagined as an array of the ions
immersed in a sea of delocalized
valence electron.
217
Metallic bonds
Positive
ions are
immersed in
the sea of
e e e
electrons e
e e e e
Free
moving
electrons
e e e e
218
Electrostatic force in a metal
Metallic Bond (Electron-sea Model)
 Metals form giant metallic structure
 Each positive ion is attracted to the
‘sea of electrons’.
 These atoms are closely held by the
strong electrostatic forces acting
between the positive ions and the ‘sea
of electrons’.
 These free moving electrons are
responsible for the high melting point
of metals and the electrical
conductivity. 219
Physical properties of metals
 metals have high melting point

 high energy is required to overcome these
strong electrostatic forces between the
positive ions and the electron sea in the
metallic bond
Metallic bonds formed
e + e + + e + e + e by the electrostatic
e
forces exist between
e + e + e + e + e + e positive ions and the
+ free moving electrons
e + e + e e + e + e
220
The strength of the metallic bonds
 The strength of the metallic bond
increases with the number of valence
electrons and the size of ions.
 The smaller the size of positive ions the

greater is the attractive force acting
between the ions and the valence
electrons
221
Boiling points in metals
Na Mg
ee ee ee ee ee ee ee ee
+1 +1 +1 +1 +1 +1 +2 +2 +2 +2 +2 +2 +2 +2
e e e e e e ee ee ee ee ee ee ee ee
+1 +1 +1 +1 +1 +1 +2 +2 +2 +2 +2 +2 +2 +2
e e e e e e ee ee ee ee ee ee ee ee
ee
+1 +1 +1 +1 +1 +1 +2 +2 +2 +2 +2 +2 +2 +2
Has one valence electron Has 2 valence electrons
Stronger metallic bond due to the

the electrostatic force acting size of Mg being smaller than Na
between positive ions and and the strong electrostatic force
free moving electrons form between +2 ions and the two
metallic bonds valence electrons,
Mg has higher boiling point than Na

222
Example:
Explain the difference in the
boiling point of the two metals
given:
Magnesium – 11300 oC
Aluminum – 24500 oC
223
Answer
 The cationic size of Al is smaller
compared to magnesium and its
charge is higher (+3).
 Mg has two valence electrons
 Al has three valence electrons
involved in the metallic bonding.
 The strength of metallic bond in
Aluminium is greater than that of
Magnesium
 Al has higher boiling point
224
 The strength of metallic bond is
directly proportional to the boiling
point.
 The stronger metallic bond,the
higher the boiling point.
225
CHAPTER 5.0
STATES OF MATTER
5.1 Gas
5.2 Liquid
5.3 Solid
At the end of the lesson, student should be able to :
(a) Explain the general properties of gas in terms of arrangement of

particle, density and compressibility.
(b) Explain qualitatively the basic assumptions of the kinetic
molecular theory of gases for an ideal gas.
(c) Define gas laws
(i) Boyle’s Law
(ii) Charles’s Law
(iii) Avogadro’s Law
(d) Sketch and interpret the graphs of Boyle’s and Charles’s laws
(e) Perform calculations involving gas laws.
(f) derive ideal gas equation based on the gas laws
(g) perform calculations using the ideal gas equation
(h) determine the molar mass and density of a gas using ideal gas
equation
(i) Define:
 Partial pressure
 Dalton's law
(j) perform calculation using Dalton's law
(k) compare the ideal and non-ideal behaviours of gases in terms
of intermolecular forces and molecular volume
(l) explain the conditions at which real gases approach
the ideal behaviour.
(m) explain qualitatively van der Waals equation and relate the
values of a and b to intermolecular forces and molecular volume
of a gas
General
Properties
of Gas
 Particles of gas are far apart and fill the available space.
 Gases assume the volume and shape of their containers.
 can be compressed – due to the particles being

so small and are relatively far apart from one another.
 Gases have relatively low densities.

Kinetic – Molecular Theory of Gases
 Describes the behavior of an ideal gas

 Ideal gas : gases which obey the ideal gas
equation (PV = nRT)

The theory is based on the following assumptions:
1) Gas molecules are very tiny that their size are negligible
compared to the volume of the container.
(having mass but no volume)
2) Gas molecules move in straight lines and are at
a constant motion unless they collide.
3) Molecular collisions are elastic – no energy is lost during
collisions.
4) Attractive and repulsive forces between gas particles are
negligible.
5) The average kinetic energy of the particles is proportional
to the absolute temperature.
The Gas Laws
a) Boyle’s Law :
The volume of fixed amount of gas at constant
temperature is inversely proportional to the gas
pressure
1
V  P (no of mole and temperature are constant)
PV = k Where:
k = constant
V = volume
P = pressure
T = temperature
n = number of moles
 at different pressure and volume :
P1 V1 = P2 V2
Where
P1 = initial pressure
V1 = initial volume
P2 = final pressure
V2 = final volume
Graph of P versus V Graph of P versus 1
V
P
P
1
V V
pressure is inversely pressure is directly
proportional to volume proportional to 1
volume
Graph of PV versus P
PV
PV = constant
P
Example 1
A sample of chlorine gas occupies a volume of 2 L at a pressure

of 1 atm. Calculate the pressure of the gas if the volume is
increased to 5 L at constant temperature.
0.4 atm
Example 2
The pressure of a sample of hydrogen gas in a 50.0 mL container is

765 mmHg. The sample is then transferred into another container and
the measured pressure is 825 mmHg. What is the volume of the second
container?
46.36 mL
a) Charles’s Law :
The volume of a fixed amount of gas at
constant pressure is directly proportional to the
absolute temperature of the gas (in Kelvin).
V  T (no of mole and pressure constant)

V
=k Where :
T
k = constant
T = absolute temperature (K)
V = volume
At different volume and temperature:
T = absolute temperature
in Kelvin (K)
V1 V2

T1 T2 T(K) = T°C + 273.15
Where V1 = initial volume

T1 = initial temperature
V2 = final volume
T2 = final temperature
Graph of volume versus temperature :
V V
0 T(K) -273.15
T(0C)
Example 1
A sample of carbon monoxide gas occupies 3.2 L

At 125 °C. The sample is then cooled at constant
pressure until it contracts to 1.54 L. Calculate the
final temperature in degree Celsius.
-81.54 °C
Example 2
A sample of gas trapped in a capillary tube by a

plug of mercury at 22 oC has a volume of 4.5 mL.
Calculate the volume of the gas when the capillary
tube is heated to 60 oC.
5.08 mL
The Combination of Boyle’s and Charles’s Law
1
Boyle’s law : V
P
Charles’s law : VT
T
V
P
T
V= k
P
PV
=k
T
P1V1 =
P2V2
T1 T2
Example 1
A sample of methane gas occupies 25.5 L at

298.15 K and 153.3 kPa. Find its volume at STP.
Ans : 35.32 L
Example 2
2 moles of chlorine gas kept in a cylinder with

piston occupies a volume of 49 L. When another 3
moles of chlorine gas is pumped into the cylinder
at constant temperature and pressure the piston
moves upwards to accommodate the gas.
Calculate the final volume of the gas.
Ans : 73.5 L
C) Avogadro’s Law
At constant pressure and temperature,
temperature the volume of a
gas is directly proportional to the number of moles of the
gas present
V  n (P and T are constant)
V = k n
V
=k
n
where :
n = number of moles
V1 V2 k= constant

n1 n2
Combination of Boyle's law, Charles's law and Avogadro's law :
1
Boyle's Law: V
P
Charles' Law: VT
Avogadro's Law: Vn
nT
V Where :
P
R = gas constant
V=R
nT
T = Temperature(K)
P
n = number of moles
PV = nRT V = volume
Ideal gas equation P = Pressure
Value of R depend on the unit of pressure and
volume used in the equation.
unit of unit of value of unit of R
pressure volume R
atm L or dm3 0.08206 L atm mol1 K1
Nm2 m3 8.314 Nm mol1 K1

or
J mol1 K1
Pa
Example 1
A steel gas tank has a volume of 275 L and is filled

with 0.485 kg of O2. Calculate the pressure of O2 if
the temperature is 29 oC.
Ans : 1.36 atm

Example 2
A sample of chlorine gas is kept in a 5.0 L container

at 228 torr and 27 °C. How many moles of gas are
present in the sample?
Ans : 0.06 mol

MOLAR MASS and DENSITY CALCULATION
 Molar mass and density of a gas can be calculated

by rearranging the Ideal Gas
Equation:
PV  nRT
 m  m
PV=   RT where: n =
 Mr  Mr
mRT Mr = molar mass of a gas
Mr =
PV
Density of a gas
PV  nRT
m
PV=   RT
 Mr 
mRT
P=
VM r
dRT where,
P=
Mr d = density of a
gas
PM r
d=
RT
Example
1
Calculate the density of ammonia (NH3) in grams
per litre (g/L) at 752 mmHg and 55 C.
Ans : 0.625 gL-1

Example 2
A chemist has synthesized a greenish-yellow compound of

chlorine and oxygen and finds that its density is 7.71 g L-1
at 36 °C and 2.88 atm. Calculate the molar mass of the
compound.
Ans : 67.9 gmol-1

Example 3
What mass of KClO3 is required to produce

2.40 L O2 gas that measured at a pressure of
1 atm and a temperature of 26 oC. The
reaction equation is
2KClO3(s) 2KCl(s) + 3O2(g)
Ans : 8.0 g
Dalton’s Law of Partial Pressure
The total pressure of mixture of non reacting gases is the
sum of the partial pressures exerted by each of the gas in
the mixture
(Partial pressure is the pressure of individual gas component in a
mixture).
- For a mixture of 3 gases, A,B and C :
PT = PA + PB + PC
According to ideal gas equation :
nA RT
pressure exerted by gas A = PA =
V
nBRT
pressure exerted by gas B = PB =
V
 in the mixture of gases A and B :
PT = PA + PB
n A RT nBRT
= 
V V
= (nA + nB )RT n TRT
V  PT =
V
when nA + nB = nT
Mole fraction and pressures
Daltons theory allows us to form a relationship
between Mole fractions, partial pressure and a total
pressure.
Consider the following condition at constant T
and V
If P  n RT
A A  
Ptotal  ntotal(RT )
Thus: PA n A ( RT ) PA nA
  
Ptotal ntotal ( RT ) PTotal nTotal
PA  X A Ptotal XA = mole fraction of gas A

Example
1
A gaseous mixture of 7.00 g N2 and 3.21 g CH4 is placed in
a 12.0 L cylinder at 25 oC.
a) What is the partial pressure of each gas?

b) What is the total pressure in the cylinder?
Ans :a) 0.501 atm , 0.41 atm
b) 0.92atm
Example 2
A mixture of gases contains 4.53 moles of neon, 0.82

moles of argon and 2.25 moles of xenon. Calculate the
partial pressure of the gases if the total pressure is 2.15 atm
at a certain temperature.
Ans : P Ne = 1.28 atm,, P Ar = 0.079 atm, P Xe = 0.63 atm,

Example 3
A sample of gas at 5.88 atm contains 1.2 g CH4, 0.4 g H2 and

0.1 g He. Calculate :
a) The partial pressure of CH4, H2 and He in the mixture.

b) What is the partial pressure of CH4 and H2 if He is removed?
Ans : a) P CH4= 1.74 atm,P H2 = 3.92 atm, P He= 0.49 atm

b) P CH4= 1.6 atm,P H2 = 4.28 atm
 One of the applications of Dalton’s Law is to calculate the pressure
of a gas collected over water ( for gases that not soluble in water).
gas gas + water vapour
The gas collected is actually a mixture of the gas and water vapour.
PT  Pgas  PH 2O
Vapour pressure of water, Pwater = 23.8 torr
Example 1
Consider the reaction below :
2KClO3 2KCl + 3O2

A sample of 5.45 L of oxygen is collected over water at a total
pressure of 735.5 torr at 25 °C. How many grams of oxygen have
been collected?
(at 25°C, Pwater = 23.8 torr)
Ans : 7.011 g
Example 2
Excess amount of hydrochloric acid is added to 2.5 g of pure

zinc. The gas produced is collected over water in a gas cylinder
at 28 oC and 100.0 kNm-2. Calculate :
a) the number of mole of gas produced in the reaction.

b) the volume of gas collected in the cylinder.
Ans : a) 0.038 mol
b) 0.95 L
Ideal gas
any gas that obeys the ideal gas
equation and has the properties as
outlined by the Kinetic Molecular
Theory
Deviation from Ideal Behavior
real gas (non-ideal gas) : gases which do not obey
ideal gas properties
Real gases do not behave ideally because:
i) gas molecules do have its own volume and they occupy
some space.
ii) gas molecules do have intermolecular forces acting
between them
1. Gas molecules have volumes
• The free volume where the molecules move about

is smaller than the volume of the container.
2. There are intermolecular forces between molecules
• Collision between molecules and the container wall

are less frequent
• The actual pressure exerted by the gas is lower than
calculated by ideal gas equation
Real gases behave almost ideally at a
low pressure and high temperature.
Reason:
At low pressure:
• To achieve a low pressure, the volume of
a container is increased.
• Thus, the molecules will be far apart from
another, hence the intermolecular forces
can be neglected.
• At a low pressure the size of a container is
extremely large compared to the size of
molecules, thus the size of molecules can
be neglected.
Reason :
At low pressure
• At low pressure, the volume of a container
is very large
• Thus the molecules will be more far apart
from one another. Hence the
intermolecular forces can be neglected.
• At low pressure, the volume of the
container is extremely large compared to
the size of the molecules, thus the volume
can be neglected
At high temperature
The gas molecules have high kinetic

energies and move at high speed
The molecules are able to free themselves

from the intermolecular forces that act
between them.
The intermolecular forces can be

neglected, thus they behave almost
ideally.
Graph PV/RT against P for N2
at different temperatures
PV
RT 273K
The lines
approach the
600K ideal line when
1000K T increases
The value approaches 1.0

at a very low pressure
9
Van der Waal’s Equation
 Since real gas does not exhibit ideal gas behavior
at high pressure and low temperature :
 the ideal gas equation (PV=nRT) needs to be
adjusted
 adjusting the equation, two parameters need to
be reconsidered :
√ attractive forces between the gas molecules
√ volume of the gas molecules
a) Attractive Forces Between Molecules
 Attractive forces which act between the gas molecules will :
 make the molecules move slower
 give less impact to the wall
 pressure exerted by the real gas is less compared to the ideal
gas
 since Preal < Pideal
2
 the term pressure need to be corrected by adding coefficient 2a
n
V
n=number of moles
P ideal = P real + n2a a=correcting factor for

pressure
V2 V = volume of container
(b) Volume of the gas molecules
• Since the gas occupy a sizeable portion

of a container, the space in which the
molecules are able to move are less
than the volume of the container.
Vreal < V container
• The correction factor done to the
volume is:
nb v
V = volume
V = Vcontainer - nb n = number of moles

b = size factor
• Referring to the ideal gas equation:
PV = nRT
By replacing these into the equation
P ideal = P real + n2a & V = V container - nb

V2
(Preal + n2a ) ( V – nb) = nRT

V2
The van der Waals equation

Value of a :
• a is a positive constant which depends on the

strength of the attractive forces between molecules
• Molecules with a higher value of a have stronger
attractive forces.
Value of b :
• b is a constant to represent the volume occupied
by the molecules.
• Larger molecules have bigger value of b

5.2 Liquids
At the end of this topic, students should
be able to :
a) Explain the properties of liquids : shape,

volume, surface tension, viscosity, compressibility
and diffusion.
b)Explain vaporization process and condensation
process based on kinetic molecular theory and
intermolecular forces.
c) Define vapour pressure and boiling point
d) Relate :
- intermolecular forces to vapour pressure
- vapour pressure to boiling point
The properties of Liquids
1. Volume and Shape
 has a definite volume but not a definite shape
√ the particles are arranged closely but not rigidly
√ held together by a strong intermolecular forces
but not strong enough to hold the particles
firmly in place
√ particles are able to move freely
 thus, a liquid flows to fit the shape of its container
and is confined to a certain volume
2. Surface tension
 Surface tension is the amount of energy
required to stretch or increase the surface of
a liquid by a unit area
• Surface tension is caused by the attractive
forces and the direction of the force acting
between
molecules
√ Molecules within a liquid experienced
intermolecular attractive forces in all
directions by their neighbouring molecules
√ however, molecules at the surface are pulled
inwards and sideways from the neighbouring
molecules
Fig. 11.8
molecule at
the surface
molecule within
the liquid
√ these intermolecular attractive forces will
pull the molecules into the liquid
√ Thus, cause the surface to stretch and
tighten
√ the stronger the intermolecular attractive
forces, the higher the surface tension
3. Viscosity
 is a measure of the resistance of a liquid
to flow
 the greater the viscosity,

viscosity the more slowly
the liquid flows.
 Viscosity may be explained in terms of the

intermolecular forces present in a liquid
The factors affecting the viscosity :
i) The strength of intermolecular forces
Liquids that have strong intermolecular forces have
higher viscosity
ii) The size of the molecules

Liquids with larger size (higher molar mass)
is more viscous because it has stronger
intermolecular forces
iii) The temperature of the liquid
At higher temperature, molecules have
higher
kinetic energy,
 the molecules move faster
 molecules can overcome the intermolecular
attractive forces more easily
 resistance to flow decrease
 Viscosity decrease
4. Compressibility
 in liquid, the particles are packed closely
together
 thus, there is very little empty space
between the molecules
  liquids are much more difficult to
compress than gas
5. Diffusion
 Diffusion is the movement of liquid from one
fluid through another.
 Diffusion can occur in a liquid because molecules
are not tightly packed and can move randomly
around one another.
Vaporisation Process
 a process in which molecules escape from
liquid into gaseous state through a surface
√ molecules in a liquid moves freely, collide
with each other and posses different
magnitudes of kinetic energy
√ when the kinetic energy is sufficient
enough to overcome the intermolecular
forces acting on them, the molecules will
escape as vapour.
 Factors affecting the rate of vaporization :
√ i) Surface area
~ the surface area , the chances for the
molecules to escape from the surface 
 surface area , evaporation rate 
√ ii) Temperature
~ temperature , the kinetic energy 
 more molecules have enough energy to
overcome the attractive intermolecular forces
and escape from the surface of the liquid
~ thus evaporation rate 
Condensation Process
a process whereby gaseous molecules turn to liquid
√ some of the vapour molecules may lose their kinetic
energy during the collision
√ they do not have enough energy to remain as vapour
molecules
√ they reached the surface of the liquid and trapped
by the attractive forces
√ if they cannot overcome the attractive forces,
these vapour molecules return as liquid molecules
√ the process is known as condensation
Vapour Pressure
 molecules escape from the surface of a liquid

: referred as vapour molecules
Pressure exerted by the vapour molecules
on the surface of a liquid is known as the
vapour pressure
√ If evaporation occurs in an open container,

vapour molecules will diffused away until
the liquid dries up
 in a closed system :
√ vapour molecules which leaves the surface are
trapped in the close container
√ these vapour molecules are in constant random
motion
√ the molecules strike the wall of container and
exert some pressure
√ As the quantity of molecules in the vapour phase
increase, some molecules may lose energy and
condense
Eventually,
the rate of evaporation = the rate of condensation.
(The system achieved dynamic equilibrium)
√ At equilibrium, the number of vapour molecules
above liquid are constant.
Factor that affects the vapour pressure
• Temperature
– Applying the heat causes more molecules have high

kinetic energy
– More molecules will be able to overcome the
intermolecular forces and escape from the liquid to
form vapour
– Temperature , vapour pressure 
• Intermolecular forces
– Molecules with weak intermolecular forces can easily

vapourised
– More vapour molecules will exert pressure on the liquid
surface
– Intermolecular forces , vapour pressure 
Boiling
• A process in which liquid molecules

change to vapour at a particular
temperature and at an atmospheric
pressure.
• Happens throughout the liquid.
Evaporation
• liquid molecules change to vapour at
any temperature and pressure.
• Occurs only at the surface of a liquid
Boiling Point: the temperature at
which the vapour pressure of a liquid is
equal to the external atmospheric
pressure.
Normal Boiling Point: the temperature

at which a liquid boils when the external
pressure is 1 atm (that is the vapour
pressure is 760 mmHg)
Boiling Point - process
• Increasing the temperature will increase in the vapour
pressure.
• As heat is applied, the vapour pressure of a system will

increase until it reaches a point whereby the vapour
pressure of the liquid system is equal to the
atmospheric pressure.
• Boiling occurs and the temperature taken at this point

is known as the boiling point.
• At this point, the change of state from liquid to gas

occurs not only at the surface of the liquid but also in
the inner part of the liquid.
• Bubbles form within the liquid.

Factors affecting the boiling point:
1. Atmospheric pressure
W hen the external atmospheric pressure is
low, liquid will boil at a lower temperature
2. Intermolecular forces
A substance with weak intermolecular forces
can easily vapourise and the system requires
less heat to achieve atmospheric pressure,
thus it boils at a lower temperature.
5.3 Solid
OBJECTIVE…
(a) State the properties of solid.
(b) Explain the process of:
- freezing - sublimation
- melting - deposition
(c) Differentiate between amorphous and crystalline
solids.
(d) Describe the types of bonding and the
interparticle/intermolecular forces involved in the
following crystalline solids using appropriate examples.
i. metallic iii. molecular covalent
ii. ionic iv. giant covalent
Properties of solid
1.Particles are closely arranged and regularly in order

2. Rigid arrangement- particles can vibrate, rotate
about fixed position and cannot move freely without
disrupting the whole structure.
3. Has definite shape and volume.
4.Has strong forces between the particles.
5. Has high densities.
6. Incompressible.
7.Diffusion within the solid is extremely slow.
In principle, solid, liquid and gas states are
interconvertible
liquid
sublimation
deposition
solid gas 5
Melting (Fusion) Process
 Solid is changing into a liquid
 When a solid substance is heated :
- its particles gain energy
- therefore able to vibrate more rapidly
- at certain temperature, the kinetic energy is higher
enough to overcome the intermolecular forces of
attraction between solid particles.
– the particles are free to move and the solid start to
melt
• Melting point – the temperature at which solid and
liquid coexist in equilibrium
Freezing (Solidification) Process
 Liquid is changing into a solid

 when the temperature of a liquid is lowered, the
kinetic energy of the liquid particles decreases
 the liquid particles vibrate at a slower rate
 when the intermolecular forces are strong
enough to hold the particles together in a fixed
and orderly arrangement, the liquid freezes.
Freezing point – a temperature at which the liquid and

solid phases of a substances coexist at equilibrium.
Sublimation Process
•The process by which a substance changes
directly from solid to the gaseous state without
passing through the liquid state.
•Occurs on solid with weak intermolecular forces
of attraction
Deposition Process
•The process where molecules from vapour state
change to the solid state.
•The opposite process of sublimation
Types of Solid
crystalline solid amorphous solid

 A solid that has highly ordered  Solid that does not have a
structure where atoms, ions or regular three dimensional
molecules show a regular arrangement of atoms or
repetition in three dimensional molecules
arrangement  Formed when a saturated
 Formed when a saturated liquid is cooled rapidly
liquid is cooled slowly  Example :
 Its atoms, molecules or ions  glass
occupy specific position  plastic material
 Example : ice, sugar, salt
 charcoal
Types of Crystalline Solid
1. Metallic solid
 Close packed structure
 Composed of atoms of the same metal linked
together by metallic bond
 The properties of metal:
– High electrical and thermal conductivity
– Lustre
– Ductile and malleable
 Examples : all metallic elements : Na, Mg, Fe
2. Ionic solids
 consist of ions (cation & anion) held together by ionic
bonds
 Physical properties of ionic solid:
- High melting point
- Hard but brittle
- Does not conduct electricity in the solid state but
does conduct electricity in molten state or in
aqueous state.
 Example: NaCl, CsCl
3. Molecular covalent solid
 composed of molecules held together by
intermolecular forces (van der Waals
and/or hydrogen bonds)
 Example : iodine [I2 (s) ]
4. Giant covalent solids
 very large molecules / gigantic structure
 composed of atoms linked together by

covalent bond
 examples : diamond, graphite, SiO2
5.4 Phase
Diagram
Learning Outcomes :
At the end of this lesson students should be able to:
(a) Define phase .
(b) Sketch the phase diagram of H2O and CO2.
(c) Define triple point and critical point.
(d) Explain the anomalous behaviour of H2O.
(e) Describe the changes in phase with respect to
i. temperature (at constant pressure)
ii. pressure (at constant temperature).

Phase is a homogeneous part of a system
in contact with other parts of the
system but separated from them by a
well-defined boundary
Phase Diagram is a diagram that describes the
stable phases and phase changes of a
substance as a function of temperature and
pressure
• used to predict the phase that exist under a
certain temperature and pressure
(i) Phase Diagram of H2O
B C
8/16/11
Regions of the diagram
- The diagram has three main regions :

Solid, liquid and gas
- Each region corresponds to one phase of the substance.
- A particular phase is stable for any combination of pressure

and temperature.
- Any point along a line shows the pressure and temperature

at which the two phases exist in equilibrium.
8/16/11
Important Points
1. Point T :
- Known as the triple point
- Triple point is the point at which the vapour, liquid and
solid states of a substance are in equilibrium.
- Triple point for water is 0.01°C and 0.06 atm.
2. Point C :
- Known as the critical point
- Critical point is the point on a phase diagram at which
the vapour cannot be condensed to a liquid.
- The liquid – gas line ends at the critical point.
- Above the critical point, the liquid cannot be
distinguished from its vapour form.
8/16/11
(ii) Phase Diagram of CO2
B C
8/16/11
TRIPLE POINT
 At point T, the triple point; solid, liquid and
vapour are in equilibrium
CO2(s) ⇌ CO2(l) ⇌ CO2(g)
 Triple point for CO2 is at 5.2 atm pressure and

temperature 57 OC.
 for most compounds, the TB curve slant to

the right because solid is denser than liquid
8/16/11
ANOMALOUS BEHAVIOR OF H2O
The phase diagram for water is not typical.

The melting temperature line , TB , slopes
slant to the left (negative slope)
i.e. the melting temperature decreases with
pressure.
• This is because ice is less dense than water, the

solid occupies more space than the liquid. An
increase in pressure, favours the formation of
liquid H2O.( the phase that occupy less space)
Thus, the higher the pressure, the lower the
temperature at which solid water melts.
Exercise:
a) Describe the phase change when carbon

dioxide undergoes isobaric heating at 5.2 atm
pressure
Exercises:
b) Describe the phase change when pressure is
applied to water isothermally at 0.01 C
Chemical Equilibrium
Chapter 6
6.0 Chemical Reaction
Chemical reaction may occur in two ways:-

a) a non-reversible reaction
- occurs in one direction
b) a reversible reaction
- occurs in both direction
i.e (forward & reverse reaction)
6.1.1 A non-reversible reaction
Example 1
NaCl + AgNO3 AgCl + NO3
• One/both reactants will be completely

consumed and amount of products formed
depends on the limiting reactant.
• A single arrow (→) is used to represent
reaction.
6.1.2 Reversible Reaction
Example 2
H2(g) + I2(g) ⇌ 2HI(g)
• Occurs in both direction.

• ⇌ shows that reactants react to form product,
and product reacts to form reactants.
• Amount of products formed does not depend
on the amount of reactant used.
• Reaction will reach equilibrium when the
concentration of products & reactants
remained constant.
6.2 Equilibrium System
• A system is at equilibrium when there is

no observable change occurs.
• Equilibrium system can be observed in:

a. Physical Equilibrium
b. Chemical Equilibrium
6.2.1 Physical Equilibrium
Example 3
• vaporisation in a closed container.
H2O (l) ⇌ H2O (g)
• Involves physical change of substance.
• Level of H2O in the container remains

constant at equilibrium because the rate of
evaporation equals the rate of
condensation.
6.2.2 Chemical Equilibrium
Example 4
2NO2(g) ⇌N2O4(g)
• Initially NO2 molecules combine to form N2O4

(brown gas appears)
• As soon as N2O4 is formed, it undergoes

reverse reaction to form NO2.
• At equilibrium, the system contains a constant

amount of NO2 & N2O4.
6.3 Dynamic Equilibrium
A system reaches a dynamic equilibrium when
• the rate of forward reaction equals the rate of

reverse reaction.
• the concentrations of both reactants and

products remain constant.
• no observable change occurs but the

conversions of reactants to products and
products to reactants continue.
concentration After time t1, both concentrations
remain constant.
[N2O4] at equilibrium
[NO2 ]at equilibrium

The reaction does not stop
but the rate of forward
reaction equals the rate of
reverse reaction.
t1 time
6.4 Equilibrium constant, K
• Since concentrations at equilibrium remain
constant, the equilibrium can be expressed by
a constant.
• Consider:
aA (g) + bB (g) ⇌ cC (g) + dD (g)
[C]c[D]d
Kc =
[A]a[B]b
• Kc is known as equilibrium constant
Concentrations of species are expressed in
molar.
Table 6.1
N2O4 (g) ⇌ 2NO2 (g)

[NO2]2
K= = 4.63 x 10-3
[N2O4] constant
6.5 Equilibrium Law: Law of Mass
Action
• When a system has reached equilibrium, the
ratio of multiplied concentrations of products to
the multiplied concentrations of reactants (each
raised to the power of the respective
stoichiometric coefficient) is a constant at
constant temperature.
OR
• Value of equilibrium constant, Kc is a constant at
constant temperature.
6.6 Types of System in Chemical Equilibrium
a) Homogeneous equilibrium
Homogenous equilibrium applies to reactions in
which all reacting species are in the same
phase.
b) Heterogeneous equilibrium
A system in which the reactants and products
are not in the same phase.
6.7 Homogeneous Equilibrium System
6.7.1 Liquid phase

• Important variable: concentration
• Equilibrium constant: Kc
Example 5
CH3COOH (l) + CH3OH (l) ⇌ CH3COOCH3 (l) + H2O (l)
Kc=
Example 6
CH3COOH (aq) ⇌ CH3COO- (aq) + H+ (aq)

Kc=
6.7.2 Gas phase
• The quantitative aspects to be considered are

the concentration and pressure.
• We can use Kcand Kp to represent the

equilibrium constant.
(PC)c (PD)d the pressure of gases are

Kp = expressed in atm or other
(PA)a (PB)b units of pressure
Example 7
Write the equilibrium law in the form of Kp
and Kc for the following reactions:
a) N2(g) + 3H2(g) NH3(g)

b) 2NO(g) + O2(g) N2O4(g)
Answer:
Kp =
Kc =
Expression of Kc
Expression of Kc depends on the equilibrium
equation given
Example 8
2SO3 (g) ⇌ 2SO2 (g) + O2 (g) Kc = [SO2]2 [O2]
[SO3]2
1. SO3 (g) ⇌ SO2 (g) + ½ O2 (g) Kc1 = [SO2] [O2]1/2
[SO3]
2. 2SO2 (g) + O2 (g) ⇌ 2SO3 (g) Kc2 = [SO3]2
[SO2]2 [O2]
Example 9
Find the relationship between Kc1 and Kc2 for the
following equilibrium equations.
1. SO3 (g) ⇌ SO2 (g) + ½ O2 (g) Kc1 = [SO2] [O2]1/2
[SO3]
2. 2SO2 (g) + O2 (g) ⇌ 2SO3 (g) Kc2 = [SO3]2
[SO2]2 [O2]
Example 10
Consider the following reaction:
A(g) + B(g) ⇌ 2C(g)
If 5 moles of A are allowed to mix and react

with 3 moles of B in 1dm3 container, 2 moles
of C are produced at equilibrium. What is the
value of Kc for this reaction?
(Ans: 0.5 )
Example 11
CO(g) + 2H2(g) ⇌ CH3OH(g)
The following equilibrium concentrations are

achieved at 400K:
[CO] = 1.03M
[H2] = 0.332M
[CH3OH] = 1.56M
Determine the equilibrium constant at 400K

(Ans: 13.74 M-2)
Example 12
Nitrogen gas reacts with oxygen gas at high

temperature to form nitrogen monoxide gas,
NO. The equilibrium constant for the reaction is
4.1 x 10-4 at 200oC.
If the concentration for both N2(g) and O2(g) at

equilibrium are 0.40 moldm-3 and 1.3 moldm-3
respectively, calculate the concentration of NO
gas at equilibrium?
(Ans: 0.0146 M)
Example 13
The equilibrium constant Kp for the reaction;

2NO2 (g) ⇌ 2NO (g) + O2 (g)
is 158 at 1000K. What is the equilibrium pressure
of O2 if the P NO2 = 0.400 atm and PNO = 0.270
atm?
Answer;
2
PNO PO
2
Kp =
2
PNO
2
2
PNO
PO = 2
Kp 2
2
PNO
PO2 = 158 x (0.400)2

(0.270)2
= 347 atm
6.7.3 Relationship between Kp and Kc
Consider
aA (g) + bB (g) ⇌ cC (g) + dD (g)
[C]c[D]d
Kc =
[A]a[B]b
Thus, Since P = nRT

V
{PC /(RT)}c {PD / (RT)}d
Kc =
{PA /(RT)}a {PB /(RT)}b
[ ]= P
RT
For the reaction
aA (g) + bB (g) ⇌ cC (g) + dD (g)
PCc PDd (RT) (a + b) – (c+d)

Kc =
PAa PBb
Kc = Kp (RT) (a + b) – (c+d)
Kp = Kc (RT) (c + d) – (a+b)
Kp = Kc (RT)Δn
1. The equilibrium concentrations for the reaction
between carbon monoxide and chlorine to form
COCl2 (g) at 740C are [CO] = 0.012 M, [Cl2] = 0.054
M, and [COCl2] = 0.14 M. Calculate the
equilibrium constants Kc and Kp.
CO (g) + Cl2 (g) ⇌ COCl2 (g)

Answer
;
[COCl2] 0.14
Kc = =
[CO][Cl2] 0.012 x 0.054
= 220 M -1
Kp = Kc(RT)n n = 1 – 2 = -1
Kp = 220 x (0.08206 x 347)–1

= 7.7 atm–1
6.8 Heterogeneous Equilibrium system
• Heterogenous equilibrium applies to

reactions in which reactants and products are
in different phases.
• Kc and Kp can be used to represent the

equilibrium constant.
• The concentration of solids and pure

liquids are not included in the expression
for the equilibrium constant.
1. CH3COOH (aq) + H2O (l) ⇌ CH3COO- (aq) + H3O+ (aq)
[CH3COO-][H3O+]
Kc =
[CH3COOH][H2O]
H2O a pure liquid, has a constant concentration

and thus is not included in the expression.
Therefore, the equilibrium constant is written as,
[CH3COO-][H3O+]
Kc =
[CH3COOH]
Unit : M
2. CH3COOH (aq) + C2H5OH (aq)⇌ CH3COOC2H5 (aq) + H2O (l)
Carboxylic Alcohol Ester
acid
[CH3COOC2H5]
Kc =
[CH3COOH] [C2H5OH]
3. CaCO3 (s) ⇌ CaO (s) + CO2 (g)
[CaO][CO2]
K‘c =
[CaCO3]
[CaCO3] = constant
[CaO] = constant
Kc = [CO2]
Kp = PCO2
CaCO3 (s) ⇌ CaO (s) + CO2 (g)
PCO2 = Kp
PCO2 does not depend on the amount of CaCO3 or CaO

5. Consider the following equilibrium at 295 K:
NH4HS (s) ⇌ NH3 (g) + H2S (g)
The partial pressure of each gas is 0.265 atm.

Calculate Kp and Kc for the reaction?
Answer
;
Kp = PNH PH S = 0.265 atm x 0.265 atm
3 2
= 0.0702 atm2
Kp = Kc(RT)n n = 2 – 0 = 2
T = 295 K
Kc = 0.0702 atm2
(0.08206 atm L mol–1 K–1 x 295 K )2
= 1.2 x 10–4 mol2 L–2

= 1.2 x 10–4 M2
6. The value of Kc for the following equation is 1.0 x 10–3 M
at 200°C.
2NOBr (g) ⇌ 2NO (g) + Br2 (g)
Calculate Kc’ for the following equation at 200°C.
NO (g) + ½ Br2 (g) ⇌ NOBr (g)

Answer;
Kc = [NO]2 [Br2] Kc ’ = [NOBr]
[NOBr]2 [Br2]1/2 [NO]
1
1 = = [NOBr]2
Kc [NO]2 [Br2] [NO]2 [Br2]
[NOBr]2
1 ½ [NOBr]
= = Kc ’
Kc [NO] [Br2] ½
Kc ’ = 1 ½
Kc
Kc ’ = 1 ½
1.0 x 10–3 M
= 31.6 M-½
= 31.6 dm3/2 mol–½

7. At 440 C, the equilibrium constant Kc for reaction,
H2(g) + I2(g) ⇌ 2HI(g)
has a value of 49.5. If 0.200 mole of H2 and 0.200
mole of I2 are placed into a 10.0 L vessel and
permitted to react at this temperature, what will be
the concentration of each substance at
equilibrium?
Answer;
[H2]0 = 0.200 /10.0 = 0.0200 M

[I2]0 = 0.200 /10.0 = 0.0200 M
H2 (g) + I2 (g) ⇌ 2HI (g)

[ ]0 / M 0.0200 0.0200 0
Δ[ ] / M -x -x +2x
[ ]⇌ / M 0.0200 - x 0.0200 - x +2x
Kc = [HI]2
[H2] [I2]
49.5 = (2x)2
(0.0200 – x) (0.0200 – x)
7.036 = 2x
0.0200 - x
x = 0.0156
H2 (g) + I2 (g) ⇌ 2HI (g)
[ ]0 / M 0.0200 0.0200 0
Δ[ ] / M -x -x +2x
[ ]⇌ / M 0.0200 - x 0.0200 - x +2x
= 0.0044 = 0.0044 = 0.0312
Therefore concentration of each substance at equilibrium:
[H2] = 0.0044 M
[I2] = 0.0044 M
[HI] = 0.0312 M
8. A 1.000-L flask is filled with 1.000 mol of H2 and
2.000 mol of I2 at 448°C. The value of the
equilibrium constant, Kp for the reaction,
H2 (g) + I2 (g) ⇌ 2HI (g)
at 448°C is 50.5. What are the partial pressures

of H2 , I2 and HI in the flask at equilibrium.
Answer;
Initial pressures of H2 and I2.
PH = nH RT = (1.000)(0.08206)(721)
2 2
V 1.000
= 59.19 atm
PI = nI2 RT = (2.000)(0.08206)(721)
2
V 1.000
= 118.4 atm
H2 (g) + I2 (g) ⇌ 2HI (g)
P0 59.19 118.4 0
ΔP -x -x +2x
P⇌ 59.19 - x 118.4 - x +2x
Kp = PHI
2
⇒ 50.5 = (2x)2
PH2 P I2 (59.19 – x) (118.4 – x)
46.5x2 – 8969x + 353904 = 0
Partial pressure of gases at equilibrium:

PH2 = 3.89 atm ; P = 63.1 atm ; PHI = 110.6 atm
I2
6.2.6 Degree of Dissociation, α
The fraction of a molecule dissociated.
ΔC ΔC = changes in concentration
α =
C0 C0 = initial concentration
A complete dissociation occurs if α = 1

AB ⇌ A+ + B–
C0 / M a 0 0
ΔC / M -x +x +x
C⇌ / M a-x +x +x
x
α =
a
9. The concentration of H+ ion measured for HCOOH
0.5 M is 0.0089 M. What is the degree of dissociation
of the compound?
a = 0.5 x = 0.0089
HCOOH ⇌ H+ + HCOO–
C0 / M 0.5 0 0
ΔC / M -0.0089 +0.0089 +0.0089
C⇌ / M 0.5-0.0089 0.0089 0.0089
= 0.4911
x 0.0089
α = = = 0.0178 = 1.78%
a 0.5
6.2.7 Predicting the direction of reaction
 For any reversible reaction, we can determine

the direction of a reaction (whether is moving
forward or reverse) by comparing the value of
Q with Kp or Kc.
 Q is the reaction quotient
 Q has the same expression of Kc and Kp but

the numerical value gained is NOT at
equilibrium.
Predicting the direction of reaction:
aA (g) + bB (g) ⇌ cC (g) + dD (g)
[C]c[D]d
Qc =
[A]a[B]b
If Q = K The system is at equilibrium
If Q < K Reaction is moving forward

- more reactants are present in the
mixture at t
If Q > K Reaction is reversed

- more products are present in the
mixture at t
10. At 12800C the equilibrium constant (Kc) for the
reaction
Br2 (g) ⇌ 2Br (g)
is 1.1 x 10-3. If the initial concentrations are [Br2] =
0.063 M and [Br] = 0.012 M, calculate the
concentrations of these species at equilibrium.
Br2 (g) ⇌ 2Br (g)

C0/M 0.063 0.012
[Br]2
Qc = = (0.012)2 = 2.29 x 10–3
[Br2]
0.063
Qc > Kc Equilibrium position shifts
from right to the left.
Br2 (g) ⇌ 2Br (g)
C0/M 0.063 0.012
ΔC/M +x - 2x
C⇌/M 0.063 + x 0.012 - 2x
[Br]2
Kc =
[Br2]
(0.012 – 2x)2
1.1x10-3 =
0.063 + x
4x2 – 0.048x + 1.44x10-4 = 6.93x10-5 + 1.1x10-3x
4x2 – 0.0491x + 7.47x10-5 = 0
x = 0.0105 x = 1.78x10-3
C⇌ [Br] = 0.012 – 2x [Br2] = 0.063 + x
If x = 0.0105 = -0.009 M = 0.0735 M
If x = 1.78x10-3 = 0.00844 M = 0.0648 M

11. The equilibrium constant Kc for the reaction
I2 (g) + H2(g) ⇌ 2HI (g)
is 54.0 at certain temperature. At equilibrium, the conc. of
I2, H2 and HI are 0.200 M, 0.200 M and 1.47 M
respectively. If 0.500M of HI is added, what are the conc.
when equilibrium is re-established?
[HI]2 Since Qc > Kc, the system

Qc =
[H2] [I2] is not at equilibrium
(1.47 + 0.5)2 The net reaction will
= proceed from RIGHT to
(0.200) (0.200)
LEFT until equilibrium is re-
= 97.0 established.
H2 (g) + I2 (g) ⇌ 2HI (g)
C0/M 0.200 0.200 1.47 + 0.500 Kc = 54
ΔC/M +x +x -2x Qc = 97
C⇌/M 0.200 + x 0.200 + x 1.97 – 2x
= 0.2535 = 0.2535 = 1.863
Kc = [HI]2
[H2] [I2]
54.0 = (1.97 – 2x)2 7.35 = 1.97 – 2x
(0.200 + x) (0.200 + x) 0.200 + x
x = 0.0535M
6.3 Factors affecting the equilibrium
position
The position of equilibrium in a system is affected
by:
a) concentration
b) pressure
c) temperature
The effects can be predicted & explained by

the :
Le Chatelier’s Principal
6.3.1 Le Châtelier’s Principle
If an external stress is applied to a

system at equilibrium, the system
adjusts in such a way that the stress is
partially offset as the system reaches
a new equilibrium position.
A) Effect of Concentration:
• Changing the concentration of the reactants or
products causes the equilibrium to shift to the
direction that will reduce the effect .
Example:
• Increasing the concentration of reactant/s causes
the equilibrium position to shift forward in order to
reduce the disturbance (to eliminate the additional
concentration of reactant/s)
• more products will be formed until the equilibrium is

reached again (i.e: composition of equilibrium
reaches Kc value which remains the same at a
fixed temperature).
Example ;
N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
Change Equilibrium Shift
Increase concentration of product(s) To the left

Decrease concentration of product(s) To the right
Increase concentration of reactant(s) To the right
Decrease concentration of reactant(s) To the left
Example :
Consider the reaction below:

Fe 3+(aq) + SCN-(aq) Fe(SCN)2+(aq)
(Yellowish) (Blood red)
Discuss the effect of adding the following

substances to the equilibrium mixture.
a) Iron (III) or Fe+3
b) Sodium hydroxide, NaOH
Answer;
a) When Fe3+ is added to the equilibrium,

the concentration of Fe3+ in the system
increases.
• the position of equilibrium shifts to right in
order to eliminate the effect of the increasing
Fe3+ ions.
• more products will be formed and the
solution turns blood red.
b) When NaOH is added to the system:

• It reacts with Fe3+ to form Fe(OH)3; thus the

concentration of Fe3+ decreases.
• In order to achieve equilibrium, the position of
equilibrium moves to the left to replace the Fe3+
that has reacted.
• More Fe3+ ions will be formed and the solution
becomes yellowish brown.
B) Effect of Temperature:
The effect of temperature on an equilibrium

depends on the type of reactions, whether it
is:
i) an endothermic reaction
or
ii) an exothermic reaction
Temperature is the only factor that affects the

value of Kc
i) Endothermic reaction
• An endothermic reaction is a reaction that
absorbs heat to form products.
Example:
• Consider the following system:
N2O4(g) 2NO2(g) ΔH = +57 kJ
– ‘+’ sign indicates that for the forward reaction

absorbs heat
– If forward reaction absorbs heat, then the
reverse reaction releases heat.
N2O4(g) 2NO2(g) ΔH = +57 kJ
Increasing the temperature:

• Means that heat is added to the system
• Reaction will move forward (forward reaction
absorbs heat) so as to reduce the added heat.
• More NO2 gas will be released.
• Since the amount of product increases, value
of Kc increases
N2O4(g) 2NO2(g) ΔH = +57 kJ
Lowering the temperature:

• Heat is removed from the system
• The position of equilibrium will move from
right to left to replace the heat lost. (since
reverse reaction is exothermic)
• More N2O4 will be formed.
• Since more product is formed, value of Kc
decreases
[ NO2 ]2 Concentration of
Kc 
[ N 2O4 ] N2O4 increases,
thus Kc value
decreases
Example:
Co(H2O)62+(aq)+ 4HCl(aq) CoCl42+(aq) + H2O ΔH = +ve
pink blue
To overcome the
low temperature
reaction should
System at
release heat equilibrium
Disturbance:
High
Low temperature temperature
C) Effect of Pressure
The pressure of a system may be changed by:

i) changing the moles of reactant or product
ii) changing the volume
iii) adding inert gas to the system
Affects only the reversible reaction involving

gaseous reactants/products
i) Changing moles of reactant or product
Adding or removing the gaseous reactant or
product at constant volume has the same effect as
changing the concentration
Example:
Consider the following system at equlibrium
2SO2(g) + O2(g) 2SO3(g)
• When SO2 gas is added to the system, the partial
pressure of SO2 increases (which means [SO2]
increases)
• Equilibrium shifts to the right to reduce the effect
of high concentration of SO2.
ii. Changing the volume of the container:
Decreasing the volume:

• Causes the pressure of the system to
increase
• The position of equilibrium will shift in a
direction that will lower down the pressure
• The pressure can be brought down by having
reaction that produces less number of
molecules
Example
N2(g) + 3H2(g) 2NH3(g)
Consider the above system at equilibrium:
 When the Vol. of the container decreases, the P
of the system increases.
 position of equilibrium will shift in the direction
that brings the pressure down by reducing the
number of moles present in the system
 The equilibrium shifts to the right to produce less
number of moles of gases in the system
 More ammonia is formed
 Value of Kc remains the same
ii. Changing the volume of the container
Increasing the volume:

• Causes the pressure in the system to
decrease
• The equilibrium position will shift in the
direction that will raise the pressure up.
• It moves to the direction that produces more
number of molecules (higher number of
moles)
Example
2SO2(g) + O2(g) 2SO3(g)

• when the volume of the container increases,
the pressure of the system decreases
• Equilibrium position will shift to the direction
that produces more moles
• The equilibrium shifts to the left.
iii) Changing pressure by adding inert gas
a) Adding inert gas at constant volume:
• Adding inert gas causes the total pressure in

the container to increase.
• However the partial pressure of each gas
reacting in the reversible reaction remains
the same.
• Since the partial pressure of the gases
remain the same & Kp is constant at constant
temperature, the equilibrium position does not
change.
b) Adding inert gas at constant pressure:
• Adding inert gas to the system increases the

total pressure.
• In order to keep pressure constant, the
volume of the container has to expand.
• This causes the partial pressures of the
gases to drop.
• System will move in the direction that
produces higher number of moles
Example:
For the following chemical equation,

N2 (g) + O2 (g) ⇌ 2NO (g)
The value of Kc for the reaction is 1x10–3 at high
temperature and 4.8x10–31 at 25°C. Is the forward
reaction exothermic or endothermic?
Kc = [NO]2 T↑ Kc↑ [NO]↑
[N2] [O2] Equilibrium position

shifts from LEFT to the RIGHT
Forward reaction is ENDOTHERMIC.

D) The effect of Catalyst
Catalysts are substances that increase the rate

of a chemical reaction but are not used up in
the reaction.
The rate of forward reaction and reverse

reaction increase.
A catalysts allows a system to reach equilibrium

faster but does not shift the position of an
equilibrium system.
Le Châtelier’s Principle
Change Equilibrium
Change Equilibrium shift Constant, K
Concentration yes no
Pressure yes no
Volume yes no
Temperature yes yes
Catalyst no no
Example :
Consider the chemical reaction at equilibrium given below

CaCO3 (s) ⇌ CaO (s) + CO2 (g) ΔH =+ve
(a) Calculate the values of Kp and Kc for the system

at 525oC, with the equilibrium pressure of CO2 is
0.220 atm.
(b) Predict the equilibrium position when the following
changes are made to the system
(i) some of the CaO is removed from the system
(ii) the pressure of the system is increased
(iii) the temperature of the system is raised
(iv) Helium gas is added at constant volume
(v) Helium gas is added at constant pressure
Kp = PCO = 0.220 atm
2
Kp = Kc(RT)Δn Δn = 1 – 0 = 1
Kp= Kc(RT)
Kc = Kp
(RT)
= 0.220 atm
0.08206 atm L mol –1 K –1 x 798 K
= 3.36 x 10–3 M
(b)(i) Does not change
(the partial pressure of CO2 is not affected by
the removal of SOLID CaO from the system).
(ii) Shifts to the LEFT.

(P↑, ; to the side with less number of moles of gas).
(iii) Shifts to the RIGHT.
(Endothermic, T↑, shifts to the right to reduce heat).
(iv) Does not change
(Addition of inert gas at constant V does not change
the partial pressure of gas).
(v) Shifts to the RIGHT.
(Addition of inert gas at constant P, V increase,
therefore equilibrium position shifts to the side with
greater number of moles of gas).
HABER PROCESS
A process that produces ammonia from

H2 and N2
The process is introduced by German

scientists Fritz Haber and Karl Bosch.
(sometimes called Haber-Bosch) in 1912.
Main objectives of the industry are to obtain a

high yield of the product while keeping the cost
down
Consider
N2(g) + 3H(g) 2NH3(g) ΔH = -92.6 kJ
A higher yield of NH3 can be obtained by carrying
out reaction under high pressures and at the lowest
temperature possible.
However the rate of production is low at a lower
temperature. Commercially, faster production is
preferable.
So combination of high-pressure, high temperature and
proper catalyst is the most efficient way to produce
ammonia on a large scale.
Temperature used = 500oC

Pressure = 500 – 1000 atm
Catalyst = Osmium and Ruthenium
7.0
IONIC EQUILIBRIA
1
7.1 ACIDS AND BASES
Theory of Acids and Bases
Three important theories
1. Arrhenius theory
2. Bronsted-Lowry’s theory
3. Lewis theory
2
Theory of Acids and Bases
1. Arrhenius Theory
Acid:
any substance that produces hydrogen ion (H+) or
hydronium ion (H3O+) when dissociating in water.
Example:
HCl (aq)  H+ (aq) + Cl (aq)
HCl (aq) + H2O (l)  H3O+(aq) + Cl (aq)
3
Base:
any substance that produces hydroxide ions (OH-)
when dissociating in water.
Example:
NaOH (aq)  Na+ (aq) + OH (aq)
4
2. Bronsted-Lowry Theory
Acid:
any substance that can donate a proton, (H+) to
other substance
Example:
HNO3 (aq) + H2O (l)  NO3 (aq) + H3O+ (aq)

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

acid
5
Base:
any substance that can accept a proton from
other substance
Example:
NH3 (aq) + H2O (l) NH4+ (aq) + OH (aq)
base
CO32- (aq) + H2O (l) HCO3- (aq) + OH- (aq)

base
H2O is able to act as an acid or a base : AMPHOTERIC
6
Conjugate Acid-base Pairs
 Conjugate base
◦ A species that remains when one proton has
been removed from the Bronsted acid.
 Conjugate acid
◦ A species that remains when one proton has
been added to the Bronsted base.
7
Example
HCO3 (aq) + H2O (l) CO32 (aq) + H3O+(aq)
acid base conjugate conjugate

base acid
 The stronger the acid, the weaker is its conjugate

base and the stronger the base, the weaker is its
conjugate acid.
8
Exercise
1. In the following reactions, identify the acid-base conjugate
pairs.
a. ClO (aq) + H2O (l) HOCl (aq) + OH (aq)
base acid conjugate conjugate

acid base
b. CH3NH2 (aq) + H2PO4- (aq) CH3NH3+(aq) + HPO42 (aq)

acid base
9
c. HBr(aq) + NH3(aq) NH4+(aq) + Br (aq)
acid base
d. PO43(aq) + H2O(l) HPO42(aq) + OH(aq)

acid base
e. CH3COOH(aq) + H2O(l) CH3COO(aq) + H3O+(aq)

base acid
10
2. Write the conjugate base formula for the following acids.
a) HS d) H3PO4
b) HCN e) H3O+
c) N2H5+ f) CH3NH3+
Answer :
acid conjugate base
a) HS S2- + H+
a) HCN CN- + H+
a) N2H5+ N2H4 + H+
a) H3PO4 H2PO4- + H+
a) H3O+ H2O + H+
a) CH3NH3+ CH3NH2 + H+
11
3. Write the conjugate acid formula for the following bases.
a) HS- d) NH3
b) C6H5COO e) H2O
c) OH f) H2PO4
12
3. Lewis Theory
Acid:
a substance that can accept a pair of electrons to
form a covalent bond.
The species that can be Lewis acid are
 Cations such as H+, Fe2+, Al3+

 molecules with incomplete octet central atom
such as BF3, BeCl2
 Molecules with central atom that can expand
octet such as PCl3
13
Base:
a substance that can donate a pair of electrons to
form a covalent bond.
The species that can be Lewis base are

 anions such as OH-, CN-, Cl-
 molecules with lone pairs electrons at
the central atom such as H2O, NH3, ROH
 molecules with nonpolar multiple bond such as
alkenes
14
Example
1) H3N: + BF3  H3N BF3

Lewis Lewis
base acid
2) H+ + OH-  H2O

Lewis Lewis
acid base
3) 2Cl-(aq) + SnCl4 (aq)  SnCl62-(aq)

Lewis Lewis
base acid
15
Exercise
Classify each of the following species as Lewis acid
or Lewis base.
i. NH3 Lewis base
ii. AlCl3
Lewis acid
iii. BCl3
Lewis acid
iv. Ag+
Lewis acid
v. I-
Lewis base
16
Strength of Acids and Bases
 Strength of acids and bases depend on the extent of

dissociation
[ ]dissociated
% dissociation =  100%
[ ]initial
[ ]dissociate d
Degree of dissociation,  =
[ ]initial
17
Strong Acid
 Strong acid is an acid that ionizes completely in
water.
 3 ways to write the equation for acid dissociation:
a) HCl (aq)  H+ (aq) + Cl (aq)
a) HCl (g) H

2 O (l)
 H+ (aq) + Cl (aq)
a) HCl (g) + H2O (l)  H3O+ (aq) + Cl (aq)
18
 Example : for 0.10 M HCl
HCl (aq) + H2O (l)  Cl (aq) + H3O+ (aq)
[ ]i 0.10 0 0
Δ - 0.10 + 0.10 + 0.10
[ ]f 0.00 0.10 0.10
19
[HCl]dissociated
[HCl]initial
0.10=
 100%
0.10
= 100 %
[HCl]dissociated
[HCl]initial
0.10 =
0.10
= 1.00
20
 The strong acids are ...
◦ The hydrohalic acids HCl, HBr and HI
◦ Oxoacids in which the number of O atoms exceeds

the number of ionizable protons by two or more
e.g: HNO3 and HClO4
21
Strong Base
 Strong base is a base that ionizes completely in
water.
Example : for 0.50 M NaOH
H2O
NaOH (aq) 
 Na+ (aq) + OH (aq)
[ ]i 0.50 0 0
Δ - 0.50 + 0.50 + 0.50
[ ]f 0.00 0.50 0.50
22
[ NaOH ]dissociated
[ NaOH ]initial
0.50=
100%
0.50
= 100 %
[ NaOH ]dissociated
[ NaOH ]initial
0 .50=
0 .50
= 1.00
23
 The strong bases...
◦ M2O or MOH, where M is group 1 element :

Li, Na, K, Rb, Cs
◦ RO or R(OH)2, where R is Ca, Sr, Ba
24
Weak Acid
 Weak acid is an acid that only ionizes partially in
water
Example: CH3COOH, HCOOH
 Generally for any weak acid, HA the dissociation

reaction is:
HA (aq) + H2O (l) A (aq) + H3O+(aq)
 % dissociation < 100%
 <1
25
 Acid dissociation constant expression, Ka
[A  ][H3O  ]
Ka =
[HA]
 Ka value depends on temperature

 Normally Ka is measured at 25 C
 Value of Ka ↓ ;  ↓ strength of acid ↓
26
 The weak acids are ....
◦ The hydrohalic acids HF
◦ Acids in which H is not bonded to O or to halogen

e.g: HCN and H2S
◦ Oxoacids in which the number of O atoms equals or

exceeds by one the number of ionizable protons
e.g: HNO2 and HClO
◦ Organic acids (general formula RCOOH)

e.g: CH3COOH
27
Weak Base
 Weak base is an base that only ionizes partially in
water
Example: NH3, N2H4
 Generally for any weak base, B the dissociation

reaction is:
B (aq) + H2O (l) BH+ (aq) + OH- (aq)
 % dissociation < 100%
 <1
28
 Base dissociation constant expression, Kb
[BH ][OH ]
Kb =
[B]
 Kb value depends on temperature

 Normally Kb is measured at 25 C
 Value of Kb ↓ ;  ↓ strength of base ↓
29
 The weak bases are ...
◦ Ammonia (NH3)
◦ Amines with general formula RNH2, R2NH, R3N

e.g. : CH3CH2NH2; (CH3)2NH; (CH3)3N
30
Example:
At 25 C, 4.2% of 0.10 M formic acid, HCOOH
dissociated in aqueous solution.
Calculate the acid dissociation constant, Ka for
formic acid.
31
Solution:
[4.2]
[HCOOH] dissociated   0.10M
[100]
 0.0042 M
HCOOH + H2O H3O+ + HCOO-
[ ]i 0.10 0 0
Δ -0.0042 +0.0042 +0.0042
[ ] 0.0958 0.0042 0.0042
32
[HCOO - ][H 3O  ]
Ka 
[HCOOH]
[0.0042M]2

[0.0958M ]
 1.8  10 -4 M
Ka for HCOOH is 1.8 x 10-4 M
 Ka or Kb for many weak acids or weak bases < 10,

 ↓↓,
 To simplify the calculation for ionic equilibrium the

following assumption can be made
[ ]initial  [ ]dissociated  [ ]initial

33
 The assumption will give correct answer to at
least 2 significant figures if:
 value of Ka or Kb < 10 or
 % dissociation < 5%
Ka = [H 3O  ] [HCOO  ]
[HCOOH]
[ ]initial  [ ]dissociated  [ ]initial

2
= (0.0042 M)
0.1M
= 1.8  104 M
34
Try this…
1. Acid dissociation constant, Ka for hydrofluoric
acid HF at 25 C is 6.8104 M. For a solution of
0.20 M HF, calculate:
a. the concentration of hydronium ion at
equilibrium
b. degree of dissociation
2. Base dissociation constant, Kb for ammonia

solution, NH3 at 25 C is 1.8105 M. For a
solution of 0.50 M NH3, calculate:
a. the concentration of hydroxide ion at
equilibrium
b. % dissociation
35
Water and the pH Scale
a. The Water Ionization Constant, Kw
◦ When water molecules ionized, transferring a
proton from one water molecule to another
producing a hydroxonium and hydroxide
ion.
2H2O (l) H3O+ (aq) + OH (aq)
36
2H2O (l) H3O+ (aq) + OH (aq)
The equilibrium constant expression can be written as

follows:
Kw = H3O+ OH-
Kw is the ionization constant for water at 25C
37
For pure water, at 25C,
H3O+ = OH = 1 x 10-7 M
Kw = H3O+ OH
= (1 x 10-7) (1 x 10-7)
 Kw = 1 x 10-14 M2
Note:
Temperature ↑, Kw ↑ because the dissociation
of water is an endothermic process
38
a. The pH Scale
◦ The pH scale is used to express acidity.
◦ The pH of a solution is defined as the

negative logarithm (log) of the
hydroxonium ion (hydrogen ion)
concentration.
pH =  log H3O+
39
 In similar way, pOH is the negative logarithm of
the hydroxide ion concentration.
pOH =  log OH
40
In pure water,
Kw = H3O+ OH = 1 x 10-14

M2
H3O+ = OH = 1 x 10-7

M
pH = pOH =  log (1 x
10-7 )
pH = pOH = 7
pH + pOH = 14
41
At 25 oC,
◦ Acidic solution : pH < 7.0 ; pOH > 7.0
◦ Basic solution : pH > 7.0 ; pOH < 7.0
◦ Neutral solution : pH = 7.0 ; pOH = 7.0
42
Example 1
In a NaOH solution, [OH-] is 2.9 x 10-4 M.
Calculate the pH of the solution at 25 oC.
(10.46)
43
Example 2
The pH of rainwater in a certain region was 5.68.
Calculate the H+ ion concentration of the rainwater.
(2.089 x 10-6)
44
Example 3
Calculate the pH of a 0.15 M acetic acid (CH3COOH)
solution, Ka = 1.8 x 10-5.
(2.79)
45
Example 4
What is the pH of a 0.25 M ammonia solution?
Kb = 1.8 x 10-5.
(11.33)
46
Example 5
The pH of 0.06 M solution of formic acid (HCOOH)
is 3.44. Calculate the Ka of the acid.
(2.211 x 10-6)
47
Exercises
1. The Ka for benzoic acid, (C6H5COOH) is 6.5x10-5.
Calculate the pH of a 0.25 M benzoic acid solution.
(2.39)
1. The pH of an acid solution is 6.20. Calculate the Ka

for the acid. The acid concentration is 0.01M.
(3.98 x 10-11)
3. Calculate the pH for 0.5M C5H5N. Kb = 1.7x10-9

(9.47)
48
1. Calculate pH for the following solution.
Answer
a. 0.55 M CH3COOH (Ka = 1.8x10-5) 2.5
b. 0.23 M NH3 (Kb = 1.8x10-5) 11.31
c. 0.15 M HCl 0.82
d. 0.20 M KOH 13.3
e. 0.45 M HCN (Ka = 4.9 x 10-10) 4.8
49
SALTS
 Produced when acid reacts with base.
 3 types of salts are :

1) neutral salts
2) basic salts
3) acidic salts
50
1) Neutral salts
 Produced when strong acid reacts with strong base.
e.g
HCl + NaOH NaCl + H2O
neutral salt
- Na+ comes from strong base

- Na+ does not react with water (does not hydrolyzed)
- Cl- comes from strong acid
- Cl- does not react with water (does not hydrolyzed)
51
 So, pH of a solution depends on the ionization of water
H2O (l) H+ (aq) + OH- (aq)
Kw = H3O+ OH = 1 x 10-14 M2
[H+ ] = [ OH- ] = 1.0 x 10-7 M
pH = 7
52
SALT HYDROLYSIS
 Salt hydrolysis is a chemical reaction between anion
or cation of a salt with water molecules.
 Acidic salts and basic salts have ions that undergo

hydrolysis in aqueous solution.
 The pH value of a solution depends on whether OH- or

H3O+ is produced during hydrolysis.
53
2) BASIC SALTS
 Normally is produced from the reaction of weak acid
and strong base.
 produce OH- when hydrolyzed
 eg : CH3COONa(aq) Na+ (aq) + CH3COO- (aq)
Na+ : comes from strong base

(does not hydrolyzed)
CH3COO- : comes from weak acid and

undergoes hydrolysis
54
Hydrolysis of CH3COO- :
CH3COO-(aq) + H2O (l) CH3COOH(aq) + OH-(aq)
 The solution is basic because the hydrolysis of

CH3COO- produces OH-
 pH of the basic salt solution is > 7.0
55
Example
Sodium cyanide, NaCN is a salt formed when a

strong base, NaOH is reacted with a weak acid, HCN.
a) Write a balanced equation to show the reaction

between NaOH and HCN. Classify the salt
formed.
b) What would be expected pH of the NaCN

solution? Explain the answer using equation(s).
56
3) ACIDIC SALTS
 Normally is produced from the reaction of strong
acid and weak base.
 produce H3O+ when hydrolysed.
 Eg.
NH4Cl(s)  NH4+(aq) + Cl(aq)
Cl- : comes from a strong acid
(does not hydrolyzed)
NH4+ : comes from weak base and
undergoes hydrolysis
57
Hydrolysis of NH4+ :
NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)
 The solution is acidic because hydrolysis of NH4+

produces H3O+
 pH of the acidic salt solution is < 7.0
58
Example
CH3NH3Cl is a salt formed when a weak

base,CH3NH2 is reacted with a strong acid, HCl.
a) Write a balanced equation to show the reaction

between CH3NH2 and HCl. Classify the salt
formed.
b) What would be expected pH of the CH3NH3Cl

solution ? Explain the answer using
equation(s).
59
BUFFER SOLUTION
A solution that maintains its pH when a small amount

of a strong acid or a strong base is added to it.
It contains weak acid or weak base with salt that has

its conjugate pair.
2 types of buffer solution:

a. acidic buffer solution
b. basic buffer solution
60
ACIDIC BUFFER SOLUTION
 Has pH < 7.
 An acidic buffer solution is made up of a weak acid

and its salt (containing its conjugate base)
Example:
A solution of CH3COOH and CH3COONa
61
 The dissociation reactions are:
CH3COOH (aq) H+(aq) + CH3COO-(aq)
CH3COONa(aq) CH3COO-(aq) + Na+(aq)
 CH3COONa dissociates completely and produces

high concentration of CH3COO-.
 The high concentration of CH3COO- will disturb the

equilibrium of the dissociation of ethanoic acid,
CH3COOH.
62
 Equilibrium of acid shifts backward, less
CH3COOH dissociates.
 Solution now has high concentrations of

CH3COOH (from weak base) and its conjugate
base ion CH3COO- (from salt)
63
BUFFER’S ACTION
 Since buffer solution contains CH3COOH that acts
as acid and the conjugate ion CH3COO- that acts
as base, buffer solution will maintain its pH by
performing reactions as follows:
(i) Adding a small amount of acid to the solution:

◦ CH3COO- (conjugate base) will neutralize it.
CH3COO-(aq) + H3O+ (aq) CH3COOH(aq) + H2O(l)
◦ The amount of weak acid, CH3COOH increased

a little but since the dissociation of acid is small,
the pH of the solution is not much affected.
64
(ii) Adding a small amount of base to the solution :
◦ the acid, CH3COOH will neutralize it.
CH3COOH(aq) + OH-(aq) CH3COO-(aq) + H2O(l)
◦ The amount of weak acid, CH3COOH

decreased a little but addition amount CH3COO-
will cause the equilibrium position to move to
the left and replace the amount of acid used
◦ So,the pH of the solution is not much affected.
65
CALCULATION OF pH OF BUFFER SOLUTION
 The pH is obtained by referring to the equilibrium
dissociation of a weak acid, HA.
 Consider buffer solution containing HA and its

conjugate, A-
HA H+ + A-
Comes from Comes from the

weak acids ionisation of a salt
66
We can write the acidic concentration constant,
[ H  ][ A  ] Ka[HA]
Ka  or [H+] =
[ HA ] [A  ]
By applying –log on both sides, we have

[ HA]
-log [H+] = -log Ka + ( - log )
[ A ]

pH
[ A
= pKa + log
]
[HA]
Henderson-Hasselbalch equation
67
Example
a. Calculate the pH of a 1.00 L solution containing

0.30 M CH3OOH and 0.1 M CH3COONa.
(Ka CH3COOH = 1.8 x 10-5)
b. What is the pH when 10 mL of 0.01 M HCl is

added to the buffer solution in (a)?
c. What is the pH when 1 mL of 0.1 M NaOH is

added to the buffer solution in (a)?
68
BASIC BUFFER SOLUTION
 Has pH > 7
 Basic buffer solution is made up of a weak base

and its salt (containing its conjugate)
 Example: A basic buffer solution of NH3 and

NH4Cl
 The dissociation reactions are:
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
NH4Cl(aq) NH4+(aq) + Cl-(aq)
69
 NH4Cl dissociates completely and produce high
concentration of NH4+ ions
 The high concentrations of NH4+ disturb the

equilibrium of the dissociation of NH3.
 Equilibrium of base shift backwards, less NH3

dissociate.
 Solution now has high concentrations of NH3 and

its conjugate acid ion NH4+, originated from salt.
70
BUFFER’S ACTION
 Buffer solution maintains its pH by performing
reactions as follow :
 NH3 acts as base and the conjugate ion, NH4+

acts as an acid.
71
(i) Adding a small amount of acid to the solution
◦ NH3 (base) will neutralize it.
NH3(aq) + H3O+(aq) NH4+(aq) + H2O
◦ The amount of NH4+ will increase a little but

this will cause the equilibrium to shift to the
left and replace the NH3 used, the pH of
solution is not much affected
72
(ii) Adding a small amount of base to the solution
◦ NH4+ (conjugate acid) will neutralize it.
NH4+(aq) + OH-(aq) NH3 (aq) + H2O(l)
◦ The amount of NH3 will increase a little but

since the dissociation of NH3 is small, the pH of
solution is not much affected
73
CALCULATION OF pH OF BUFFER SOLUTION
 The pOH and pH can be calculated by using the

Henderson-Hasselbalch equation.
 Consider the following base dissociation reaction:
B + H2O BH+ + OH-
74
 The base dissociation constant, Kb
[BH ][OH ] [ B]
Kb = or [OH-] = Kb
[B] [ BH  ]
By applying – log on both sides:

[ B]
-log [OH] = -log Kb + ( -log 
)
[ BH ]

pOH = pKb + log [ BH ]
[B ]
Henderson-Hasselbalch equation
75
Example
A buffer solution is prepared by mixing 400mL 1.5 M

NH4Cl solution with 600 mL of 0.10 M NH3 solution.
[ Kb = 1.8 x 10-5 ]
a) Calculate the pH of buffer
b) Calculate the new pH of the buffer after the
addition of 2.0 mL of 0.10 M HCl
c) Calculate the new pH of the buffer after the
addition of 2.0 mL of 0.15 M NaOH
76
Exercises
a) Calculate the pH of a 1 L buffer solution
containing 1.5 M CH3COOH and 0.20 M of
CH3COONa. pH = 3.87
b) Calculate the new pH of the buffer after the
addition of 2.0 mL of 0.1 M HCl. PH = 3.87
a) Calculate the new pH of the buffer after the

addition of 2.0 mL of 0.2 M NaOH. pH = 3.87
[ Ka = 1.8 x 10-5 ]
77
a) Calculate the pH of the solution prepared by mixing
500 mL 0.1 M hydrazinium chloride, N2H5Cl with
500 mL 0.2 M hydrazine, N2H4. pH = 8.53
a) Calculate the new pH of the buffer after the addition

of 2.0 mL of 0.1 M HCl. pH = 8.53
c) Calculate the new pH of the buffer after the addition

of 2.0 mL of 0.2 M NaOH pH = 8.54
[ Kb N2H4 = 1.7 x 10-6 ]
78
7.2 ACID-BASE TITRATIONS
 Titration
◦ a method for determining the
concentration of a solution using
another solution (known concentration),
called standard solution
 Titration Curve
◦ a graph of pH versus volume of titrant
79
Titration apparatus
Titrant
Analyte
80
 The equivalence point
◦ the point at which the number of moles of OH

ions added to a solution is equal to the number
of moles of H+ ions originally present.
 The end point
◦ is the point when the indicator changes colour.
 Indicators
◦ is a weak organic acids or bases that change

colour over a range of pH values.
81
Table 1: Some Common Acid-Base Indicators
Colour
Indicator In Acid In Base pH Range *
Thymol blue Red Yellow 1.2-2.8

Bromophenol blue Yellow Bluish 3.0-4.6
Purple
Methyl orange Orange Yellow 3.1-4.4
Methyl red Red Yellow 4.2-6.3
Chlorophenol blue Yellow Red 4.8-6.4
Bromothymol blue Yellow Blue 6.0-7.6
Cresol Red Yellow Red 7.2-8.8
Phenolphthalein Colourless Reddish 8.3-10.0
pink
82
TYPES OF TITRATIONS
1. Strong acid - strong base titrations

2. Strong acid – weak base titrations
3. Weak acid – strong base titrations
83
Strong acid-strong base titration curves
* The pH starts out
low, reflecting the high

[H3O+] of the strong
acid, and increases
gradually as acid is being
neutralised by the
added base.
84
* The pH rises sharply
when the mole of OH-
that have been added
nearly equal the mole
of H3O+ .
85
* An additional drop or two of
base neutralises the
final tiny excess of acid and
introduces a tiny excess of
base, so pH jumps 6 to 8 unit.
* Beyond this sharp portion, the

pH increases slowly again as
more base is added.
86
Weak acid-strong base titration curves
* The initial pH is higher

than strong acid-strong
base titration curve
because the weak acid
dissociates only slightly,
less H3O+ is present.
87
* A gradually rising portion
of the curve, called the
buffer region, appears
before the sharp rise to
the equivalence point.
88
* The pH at the
equivalence point > 7.0.
The solution contains the
basic salt.
89
Weak base-strong acid titration curves
* The pH starts above 7.0

(~11) because the weak base
dissociates only slightly.
* The pH decreases gradually

in the buffer region.
90
* After the buffer region,
the curve drops vertically
to the equivalence point.
* Beyond the equivalence

point, the pH decreases
slowly as excess H3O+ is
added.
91
How to sketch a titration curve
Steps :
1. Calculate the initial pH of the solution
- identify the analyte (solution in the conical
flask). Whether strong acid, weak acid,
strong base or weak base.
2. Determine the equivalence point :

- Volume and pH
92
3. pH jump (steep portion / sharp portion)
- depends on the type of the titration
Type pH jump
Strong acid-strong base 3-11
Strong acid-weak base 3-7
Weak acid-strong base 7-11
4. Identify the final pH

- depends on the [ ] of the titrant (solution in
the burette).
93
Example 1 :
Sketch the titration curve of 25 mL 0.1 M HCl with
0.1 M NaOH.
Step 1 :
Analyte is a strong acid,
HCl – dissociates completely
HCl(aq) + H2O(l)  Cl (aq) + H3O+(aq)
[H3O+] = [HCl] = 0.1 M

pH = - log [H3O+] = 1.0
94
Step 2 : at equivalence point
- pH equivalence:
- the solution is NaCl (aq)
- both Na+ and Cl- do not hydrolyse
- therefore pH = 7.0
- Volume equivalence:
n HCl = n NaOH
MHCl VHCl = MNaOH VnaOH
VNaOH = 0.1 x 25 = 25 mL
0.1
95
Step 3 :
Type of titration : strong acid-strong base
pH jump : 3 – 11
Step 4 :
Titrant is a strong base, NaOH.
NaOH (aq)  Na+ (aq) + OH (aq)
[OH-] = [NaOH] = 0.1 M

pOH = - log 0.1 = 1
pH = 14 – 1 = 13
Final point approaching pH < 13.
96
Example 2 : Sketch the titration curve of 25 mL 0.2
M HCl and 0.1 M NH3.
Step 1 :
Analyte is a strong acid, HCl
HCl (aq) + H2O (l)  Cl (aq) + H3O+ (aq)
[H3O+] = [HCl] = 0.2

pH = - log [H3O+] = 0.70
97
Step 2:
at equivalence point
HCl(aq) + NH3 (aq) NH4Cl (aq)
- pH equivalence
- the solution is NH4Cl (aq)
- only NH4+ hydrolyses to form H3O+
- therefore pH < 7.0
- Volume equivalence
n NH = n HCl
3
MNH VNH = MHClVHCl

3 3
VNH = 0.2 x 25 = 50 mL
3
0.1
Step 3 :
Type of titration : strong acid-weak base
pH jump : 3 – 7
Step 4 :
Titrant is a weak base, NH3.
Final point approaching pH < 11
99
How to determine the suitable indicator for titrations
 Choose an indicator which the endpoint pH range lies on the
steep portion of the titration curve.
 This choice ensures that the pH at the equivalent point will

fall within the range over which indicator changes color.
Types of Titrations pH jump Suitable Indicators
Strong Acid-Strong 3 – 10 Any Indicator except thymol blue

Base
Weak Acid-Strong 7 – 11 Phenolphthalein, cresol red
Base
Strong Acid-weak Base 3 – 7 Methyl orange, methyl red,
chlorophenol blue, bromophenol
blue
Exercise 1
What is the colour of the solution when 3 drops of the
below indicators are added separately to water (pH = 7)
?
Indicator pH range Colour change
Phenolphthalein 8.2 – 10.0 Colourless reddish

pink
Methyl orange 3.2 – 4.2 Red Yellow
Bromothymol blue 6.0 – 7.6 Yellow Blue
phenol red 6.8 – 8.4 Yellow Red

Exercise 2
The pH range and the colour change for 3 indicator

X, Y and Z is shown in the table below. Determine X,
Y and Z.
Indicator pH range colour change
X 1.2 – 2.8 Red Yellow
Y 6.0 – 7.6 Yellow Blue
Z 8.3 – 10.5 Colourless Yellow

SOLUBILITY EQUILIBRIUM
 Some salts are soluble but most are insoluble or

slightly soluble in water.
 A saturated solution is a solution that contains the

maximum amount of solute that can dissolve in a
solvent.
103
 The solubility of a salt is the amount of solid
that dissolved in a known value of saturated
solution.
 The unit of solubility used may be g L-1 or mol L-1
 Molar solubility is the maximum number of moles

of solute that dissolves in a certain quantity of
solvent at a specific temperature.
104
THE SOLUBILITY PRODUCT CONSTANT, Ksp
 Ksp is the product of the molar concentrations of

the ions involved in the equilibrium, each raised to
the power of its stoichiometric coefficient in the
equilibrium equation.
 Ksp is called the solubility product constant.
 The degree of solubility of a salt is shown by the

value of Ksp.
105
 Consider the equilibrium system below :
MX (s) M+ (aq) + X- (aq)
Kc = [M+] [X-]
[MX]
Kc [MX] = [M+] [X-]
*since [MX] is a constant ;
Ksp = [M+] [X-]
106
 Soluble salt such NaCl and KNO3 has an
extremely high value of Ksp .
 The smaller the value of Ksp the less soluble the

compound in water.
 Temperature ↑ , solubility ↑, Ksp ↑
107
Example
Write the solubility product expression and state

the units of Ksp for each of the following ionic
compounds.
a) Ca3(PO4)2 b) Ag2CO3
108
Example
The solubility product of silver chromate(VI),

Ag2CrO4 is 2.4 x10-12 mol3dm-9. Calculate the
concentration of Ag+(aq) and CrO42-(aq) in the
saturated solution.
Ans: [Ag+] = 1.68 x 10-5 M

[CrO42-] = 8.43 x 10-5 M
109
Example
The solubility of silver sulphide, Ag2S is 5.0x10-17.

Calculate the solubility product of Ag2S.
Ans: 5.0 x 10-49
110
Example
Calculate the solubility of copper (II) hydroxide,

Cu(OH)2, in g L-1.
Ksp Cu(OH)2 = 2 x 10-20 M3,

Mr Cu(OH)2 = 97.57g mol-1
111
Predicting the formation of a precipitate
 Precipitate is an insoluble solid formed in and
separates from the solution.
 A mixture of two solutions will produce a precipitate

or not depending on the ion product, Q present.
 Q has the same form as Ksp but the concentrations

of ions are taken at any given time.
112
 The solubility equilibrium equation for a slightly
soluble salt, MA :
MA (s) M+ (aq) + A- (aq)
Ksp = [M+] [A-]
 If we mix a solution containing M+ ions with one

containing A- ions, the ion product, Q is given by :
Q = [M+] [A-]
113
Three possible situations:
Q < Ksp;
Solution is not saturated.
Solid will dissolve and no precipitate formed.
Q = Ksp;
Saturated solution formed.
System is in equilibrium.
Q > Ksp;
Solution is supersaturated;
Ions will form precipitate until the ionic concentration
product of the system equals the Ksp (until the system
reaches equilibrium).
114
Example
Will precipitate form when 50 mL 0.001 M NaOH

is added to 150 mL of 0.01 M MgCl2.
(Ksp Mg(OH)2 = 2 x 10-11)
115
Example
Exactly 200 mL of 0.0040 M AgNO3 are added to

800 mL of 0.008 M K2SO4. Will a precipitate form?
(Ksp Ag2SO4 = 1.4x10-5 M3)
116
COMMON ION EFFECT
 Common ion is an ion that is common to two or

more components in a mixture of an ionic solution.
 Common ion effect is the shift in equilibrium

caused by the addition of a compound having an
ion in common with the dissolved substances.
117
Example
 Consider a saturated solution of silver chloride, AgCl

in water.
(Ksp AgCl = 1.6 x 10-10)
118
 The equilibrium system is:
AgCl (s) Ag+ (aq) + Cl- (aq)

 If AgNO3 is added to the saturated AgCl solution :
AgNO3 (aq) Ag+ (aq) + NO3- (aq)
(common ion)
- [Ag+] will increase.

- Equilibrium position will shift backward
(according to the Le Chatelier's Principle).
- Solubility of AgCl will decrease.
- So, the addition of a common ion will
reduce the solubility of a slightly soluble salt.
119
Example
Calculate the solubility of AgCl (mol L-1) in :
a. liquid water
b. 0.05 M of silver nitrate solution.
(Ksp AgCl = 1.6 x 10-10)
120
9.0 THERMOCHEMISTRY
Concept of Enthalpy
Important Terms
 Heat is energy transferred between two bodies of
different temperatures
 System is any specific part of the universe
 Surroundings is everything that lies outside the

system
 Open system is a system that can exchange
mass and energy with its surroundings
 Closed system is a system that allows the

exchange of energy with its surroundings
 Isolated system is a system that does not allow

the exchange of either mass or energy with its
surroundings
 Energy is the ability to do work
 SI unit of energy is kg m2 s-2 or Joule (J)
 Non SI unit of energy is calorie (Cal)
 1 Cal = 4.184 J
Thermochemistry
 A study of heat change in chemical reactions.
 Two types of chemical reactions:
 Exothermic
 Endothermic
Exothermic reactions
 Enthalpy of products < Enthalpy of reactants, ΔH is
negative.
 Energy is released from the system to the

surroundings.
 Consider the following reaction:
A (g) + B (g) → C (g) ΔH = ve
(reactants) (product)
reactants
enthalpy
H = -ve
products
reaction pathway
Energy profile diagram for exothermic reaction

Endothermic Reactions
 Enthalpy of products > enthalpy of reactants, ΔH is
positive
 Energy is absorbed by the system from the surrounding

 Consider the following reaction
A (g) + B (g) → C(g) ΔH = + ve
(reactants) (product)
Energy profile of diagram endothermic reactions

Enthalpy, H
 The heat content of a system or total energy in the
system
 Enthalpy, H of a system cannot be measured when

there is a change in the system.
 Example: system undergoes combustion or ionisation.

Enthalpy of Reaction, ∆H and
Standard Condition
 Enthalpy of reaction:
 The enthalpy change associated with a chemical
reaction.
 Standard enthalpy, ∆Hº

 The enthalpy change for a particular reaction that
occurs at 298K and 1 atm (standard state)
Thermochemical Equation
 The thermochemical equation shows the enthalpy changes.
Example : H2O(s) → H2O(l) ΔH = +6.01 kJ
 1 mole of H2O(l) is formed from 1 mole of H2O(s) at 0°C,

ΔH = +6.01 kJ
 However, when 1 mole of H2O(s) is formed from 1 mole of

H2O(l), the magnitude of ΔH remains the same with the
opposite sign of it.
H2O(l) → H2O(s) ΔH = 6.01 kJ
Types of Enthalpies
 There are many kind of enthalpies such as:
 Enthalpy of formation
 Enthalpy of combustion
 Enthalpy of atomisation
 Enthalpy neutralisation
 Enthalpy hydration
 Enthalpy solution
Enthalpy of Formation, ∆Hf
 The change of heat when 1 mole of a compound is
formed from its elements at their standard states.
H2 (g) + ½ O2(g) → H2O (l) ∆Hf = 286 kJ mol1
 The standard enthalpy of formation of any element in

its most stable state form is ZERO.
∆H (O2 ) = 0 ∆H (Cl2) = 0
Enthalpy of Combustion, ∆Hc
 The heat released when 1 mole of substance is
burned completely in excess oxygen.
C(s) + O2(g) → CO2(g) ∆Hc = 393 kJ mol1

Enthalpy of Atomisation, Ha
 The heat change when 1 mole of gaseous atoms is formed
from its element
 Ha is always positive because it involves only breaking of

bonds
 e.g:
Na(s)  Na(g) Ha = +109 kJ mol-1
½Cl2(g)  Cl(g) Ha = +123 kJ mol-1

Enthalpy of Neutralization, ∆Hn
 The heat change when 1 mole of water, H2O is formed from the
neutralization of acid and base .
 HCl(aq)+ NaOH(aq) → NaCl(aq) +H2O(aq) ΔHn = 58 kJ mol1

Enthalpy of Hydration, Hhyd
 The heat change when 1 mole of gaseous ions is
hydrated in water.
 e.g:
Na+(g)  Na+(aq) Hhyd = 406 kJ mol-1
Cl-(g)  Cl-(aq) Hhyd = 363 kJ mol-1
Enthalpy of Solution, Hsoln
 The heat change when 1 mole of a substance is
dissolves in water.
 e.g:
KCl(s)  K+(aq) + Cl(aq) Hsoln = +690 kJ mol-1
Enthalpy of Sublimation, Hsubl
The heat change when one mole of a substance
sublimes (solid into gas).
H subl
I2 (s) → I2(g) Hsubl = +106 kJ mol1

Calorimetry
 A method used in the laboratory to measure the
heat change of a reaction.
 Apparatus used is known as the calorimeter
 Examples of calorimeter
 Simple calorimeter
 Bomb calorimeter
Simple calorimeter
 The outer Styrofoam cup
insulate the reaction
mixture from the
surroundings (it is
assumed that no heat is
lost to the surroundings)
 Heat release by the
reaction is absorbed by
solution and the
calorimeter
A bomb calorimeter
Important Terms in Calorimeter
 Specific heat capacity, c
 Specific heat capacity, c of a substance is the amount of
heat required to raise the temperature of one gram of the
substance by one degree Celsius (Jg 1C1).
 Heat capacity, C
 Heat capacity,C is the amount of heat required to raise
the temperature of a given quantity of the substance by
one degree Celsius (JC1)
Heat released by Heat absorbed
= by calorimeter
substance
q = mc∆T
q = heat released by substance

m= mass of substance
C= specific heat capacity
∆T = temperature change
Basic Principle in Calorimeter
Heat released Heat absorbed

=
by a reaction by surroundings
• Surroundings may refer to
the:
i. Calorimeter itself or;
ii. The water and calorimeter
• qreaction= mcΔT or CΔT
Example 1
In an experiment, 0.100 g of H2 and excess of O2 were compressed

into a 1.00 L bomb and placed into a calorimeter with heat capacity
of 9.08 x 104 J0C1. The initial temperature of the calorimeter was
25.0000C and finally it increased to 25.155 0C. Calculate the
amount of heat released in the reaction to form H2O, expressed in kJ
per mole.
Solution
Heat released = Heat absorbed by the
calorimeter
q = C∆T
= (9.08 X 104 J0C-1) X (0.1550C)
= 1.41 X 104 J
= 14.1 kJ
H2(g) + ½O2(g) → H2O(c)
mole of H2 = 0.100
2.016
= 0.0496 mol
moles of H2O = mole of H2
0.0496 mol of H2O released 14.1 kJ energy

14.1
1 mol H2O released = 0.0496 kJ
= 284 kJ
∆Heat of reaction, ∆H = - 284 kJ mol1
Example 2
1. Calculate the amount of heat released in a reaction in

an aluminum calorimeter with a mass of 3087.0 g and
contains 1700.0 mL of water. The initial temperature of
the calorimeter is 25.0°C and it increased to 27.8°C.
Given:
Specific heat capacity of aluminum = 0.553Jg-1 °C-1
Specific heat capacity of water = 4.18 Jg-1 °C-1
Water density = 1.0 g mL-1
ΔT = (27.8 -25.0 )°C = 2.8°C
Solution
Heat released Heat absorbed by Heat absorbed by
= +
aluminium water
calorimeter
q = mwcwΔT + mcccΔT
= (1700.0 g)(4.18 Jg-1 °C-1)(2.8 °C) +
(3087.0 g)(0.553 Jg-1 °C-1)(2.8°C)
= 24676.71 J
= 24.7 kJ
HESS’S LAW
Hess Law
 Hess’s Law states that when reactants are converted to
products, the change in enthalpy is the same whether the
reaction takes place in one step or in the series of steps.
 The enthalpy change depends only on the nature of the
reactants and products and is independent of the route
taken.
A  H 1 B
 H 2 
H 3
C
H1  H2  H3

Algebraic Method
Step 1
i. List all the thermochemical equations involved
i.C O  CO H  - 393kJmol- 1
(S) 2( g ) 2( g )
ii.H 1 O H O H  -286kJmol- 1
2( g ) 2 2( g ) 2 ( g)
iii.C H 7 O  2CO  3H O H  -1560kJmol -1
2 6( g ) 2 2( g ) 2( g ) 2 ( g)
Algebraic Method
Step 1
i. List all the thermochemical equations involved
i.C O  CO H  - 393kJmol- 1
(S) 2( g ) 2( g )
ii.H 1 O H O H  -286kJmol- 1
2( g ) 2 2( g ) 2 ( g)
iii.C H 7 O  2CO  3H O H  -1560kJmol -1
2 6( g ) 2 2( g ) 2( g ) 2 ( g)
ii. Write the enthalpy of formation reaction for C2H6
H  ?
f
C  3H    C H
(s) 2( g ) 2 6( g )
iii. Add the given reactions so that the result is the desired
reaction.
(i )  2 2C ( S )  2O2( g )  2CO2( g ) H1  2  -393 kJ
( ii )  3 3 H 2( g )  3 O2( g )  3 H 2O( g ) H 2  3  -286kJ

2
reverse (iii) 2CO2(g)  3 H 2O( g )  C 2 H 6( g )  7 O2( g ) H3  1560kJ
2
_______________________________________________________________
H f  ?
2C ( s)  3 H 2( g )    C 2 H 6( g ) - 84kJ
Hf  H1  H 2  H3

 -84kJ
Energy Cycle Method
Draw the energy cycle and apply Hess’s Law to calculate the
unknown value.
HOf
2C(s) + 3H2 (g) C2H6 (g)
HO2 = 3(-286)
HO1 2O2(g) 3/2 O2(g)
7/2 O2(g)
= 2(-393)
HO3 = - (-1560)
2CO2 (g) + 3H2O(g)

° ° ° °
ΔH f = 2( H1 ) + 3(H 2 ) + ΔH3
 -786 - 858  1560
 -84 kJmol - 1
Example 1
The thermochemical equation of combustion of carbon
monoxide is shown as below.
C(s) + ½ O2(g)  CO(g) = ?
H
given :

C(s) + O2(g)  CO2(g) H
∆H= -394 kJ mol-1
CO(s) + ½ O2(g)  CO2(g) ∆H=H-283

kJ mol-1
Calculate the enthalpy change of the combustion of carbon to
carbon monoxide.
Example 2
Calculate the standard enthalpy of formation of methane if the
enthalpy of combustion of carbon, hydrogen and methane are
as follows:
 ∆H [C ] = -393 kJ mol-1
Hc (s)
 ∆H [H2(s)] = -293 kJ mol-1
Hc
∆H [CH ] = -753 kJ mol -1
Hc 4(s)
Example 3
 Standard enthalpy of formation of ammonia, hydrogen
chloride and ammonium chloride is -46.1 kJ mol-1, -92.3 kJ
mol-1, 314.4 kJ mol-1 respectively. Write the thermochemical
equation for the formation of each substance and calculate
the enthalpy change for the following reaction.
NH3(g) + HCl (g)  NH4Cl(s)
Exercise
1.Calculate the enthalpy of formation of benzene
if :
∆H (CO2(g) ) = -393.3 kJ mol-1
∆H (H2O(l) ) = -285.5 kJ mol-1
∆H (C H ) = -3265.3 kJ mol-1
H  6 6(l)
f
H f
H f
Born-Haber
Cycle
Lattice Energy, Hlattice
 is the energy required to completely separate one mole of a
solid (ionic compound) into gaseous ions
 e.g:
NaCl(s)  Na+(g) + Cl-(g) Hlattice = +771 kJ mol-1
(lattice dissociation)
Na+(g) + Cl-(g)  NaCl(s) Hlattice = -771 kJ mol-1

(lattice formation)
 The magnitude of lattice energy increases as
 the ionic charges increase
 the ionic radii decrease
 There is a strong attraction between small ions and
highly charged ions so the H is more negative.
 H for MgO is more negative than H for Na2O

because Mg2+ is smaller in size and has bigger charge
than Na+, therefore
Hºlattice (MgO) > Hºlattice (Na2O)
Hydration Process of Ionic Solid
 Na+ and Cl- ions in the solid crystal are separated from
each other and converted to the gaseous state (Hlattice)
 The electrostatic forces between gaseous ions and polar

water molecules cause the ions to be surrounded by water
molecules (Hhydr)
Hsoln = Hlattice + Hhdyr

Na+ and Cl- ion in
the gaseous state
He
y a
rg to
Ene fH
e yd
ttic ra tio
La n
Heat of Solution
Na+ and Cl- ion in Hydrated Na+ and Cl- ion

the solid state
Born-Haber Cycle
 The process of ionic bond formation occurs in a few stages. At

each stage the enthalpy changes are considered.
 The Born Haber cycle is often used to calculate the lattice
energy of an ionic compound.
 In the Born-Haber cycle energy diagram, by convention,
positive values are denoted as going upwards, negative values
as going downwards.
 Consider the enthalpy changes in the formation of sodium
chloride.
Example :
Na (s)  1
2 Cl 2(g)  NaCl (s)
 Given;
i. Enthalpy of formation NaCl = -411 kJmol-1
ii. Enthalpy of sublimation of Na = +108 kJmol-1
iii. First ionization energy of Na = +500 kJmol-1
iv. Enthalpy of atomization of Cl = +122 kJmol-1
v. Electron affinity of Cl = -364 kJmol-1
vi. Lattice energy of NaCl = ?
Example: A Born-Haber cycle for NaCl
energy
Na+(g) + e + Cl(g)
Ionisation Electron Affinity of Cl

Energy of Na
Na+(g) + Cl- (g)
Na(g) + Cl(g)
HaCl
Na(g) + ½ Cl2(g)
+ve Lattice energy
HaNa
Na(s) + ½ Cl2(g) From Hess’s Law:

E=0
Hf NaCl = HaNa + HaCl +IENa +
Hf NaCl
-ve EACl + Lattice Energy
NaCl(s)
Calculation:
 H 0f   H S  IE   H a ( Cl )  EA   H lattice
 H lattice   H 0f   H S  IE   H a ( Cl )  EA 
 H lattice   411 kJ   108 kJ  500 kJ  122 kJ   364 kJ 
 H lattice   777 kJ
Exercise:
 Construct a Born-Haber cycle to explain why ionic compound
NaCl2 cannot form under standard conditions. Use the data
below:
i. Enthalpy of sublimation of sodium = +108 kJmol-1
ii. First ionization energy of sodium = +500 kJmol-1
iii. Second ionization energy of sodium = +4562 kJmol-1
iv. Enthalpy of atomization of chlorine = +121kJmol-1
v. Electron affinity of chlorine = -364 kJmol-1
vi. Lattice energy of NaCl2 = -2489 kJmol-1
Electrochemistry
Electrochemistry
Is the study of the relationship between electricity
and chemical reaction
Chemical reactions involved in electrochemistry are :
Reduction
REDOX REACTION
Oxidation
One type of reaction cannot occur without

the other.
REDOX Reaction
REDUCTION OXIDATION
gain of electron loss of electron
Oxidation no. decrease Oxidation no. increase
Reaction at cathode Reaction at anode
Example:
Remember…
RED CAT Mg  Mg2+ + 2e-
= REDuction
RED at CAThode
CAT
Example: Oxidation no. 
Cu2+ + 2e-  Cu
Oxidation no. 
Electrochemical reaction consists of reduction
and oxidation.
These two reactions are called ‘half-cell
reactions’
The combination of 2 half reactions are called
‘cell reaction’
Example
Reduction : Cu2+(aq) + 2e-  Cu(s)
Half-cell
Oxidation : Zn(s)  Zn2+(aq) + 2e- reaction
Overall cell 2+ 2+
reaction :
Cu (aq) + Zn(s)  Cu(s) + Zn (aq)
Cells
There are 2 type of cells
Electrochemical Electrolytic
Cells Cells
where chemical reaction Uses electricity to
produces electricity produce chemical
reaction
Also called;
Galvanic cell or Voltaic cell
Chemical Electrical Electrical Chemical
Energy Energy Energy Energy
Component and Operation of
Galvanic cell
Consists of :
1) Zn metal in an aqueous solution of Zn2+
2) Cu metal in an aqueous solution of Cu2+
- The 2 metals are connected by a wire

- The 2 containers are connected by a salt bridge.
- A voltmeter is used to detect voltage generated.
Galvanic cell
Voltmeter
Zn Cu
electrode electrode
Zn2+ Cu2+
CuSO4(aq)
ZnSO4(aq)
solution
solution
Salt
bridge
What happens at the zinc electrode ?
 Zinc is more electropositive than copper.
 Tendency to release electrons: Zn > Cu.
Zn (s)  Zn2+ (aq) + 2e-
 Zinc dissolves.
 Oxidation occurs at the Zn electrode.
 Zn2+ ions enter ZnSO4 solution.
 Zn is the –ve electrode since it is a source of
electrons  anode.
What happens at the copper electrode ?
 The electron from the Zn metal moves out through

the wire enter the Cu metal
 Cu2+ ions from the solution accept electrons.
Cu2+ (aq) + 2e-  Cu (s)
 Copper is deposited.
 Reduction occurs at the Cu electrode.
 Cu is the +ve electrode  cathode
Reactions Involved:
Anode : Zn (s)  Zn2+ (aq) + 2e-

Cathode : Cu2+ (aq) + 2e-  Cu (s)
Overall cell
Zn (s) + Cu2+ (aq)  Zn2+ (aq) + Cu (s)
reaction :
Salt bridge
An inverted U tube containing a gel

permeated with solution of an inert
electrolyte such as KCl, Na2SO4, NH4NO3.
Functions
 Salt bridge helps to maintain electrical neutrality
 Completes the circuit by allowing ions carrying charge
to move from one half-cell to the other.
What happened if there is no salt bridge?
Zn Cu
e
e
e e
Zn2+ e e Cu2+
ZnSO4(aq) CuSO4(aq)
 As the zinc rod dissolves, the concentration of Zn2+

in the left beaker increase.
 The reaction stops because the nett increase in
positive charge is not neutralized.
This excess charge build-up can be reduced by adding a
salt bridge
Zn (s)  Zn2+ (aq) + 2e- Cu2+ (aq) + 2e-  Cu (s)
ANODE (-) CATHODE (+)
E = +1.10 V
Zn - + Cu
e
Zn2+ e
ZnSO4(aq) Cu2+ CuSO4(aq)
Salt bridge
(KCl)
How does the cell maintains its electrical neutrality?
Left Cell Right Cell
Zn (s)  Zn2+ (aq) + 2e- Cu2+ (aq) + 2e-  Cu (s)
Zn2+ ions enter the solution. Cu 2+ ions leave the solution.

Causing an overall excess of Causing an overall excess of
tve charge. -ve charge.
Cl- ions from salt K+ ions from salt

bridge move into Zn bridge move into Cu
half cell half cell
Electrical neutrality is maintained

Electrochemical Cells
anode cathode
oxidation reduction
spontaneous
redox reaction
half 19.2
Cell notation
Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq)
Also can be represented as:

Salt bridge
Phase boundary
Zn (s) | Zn2+ (aq) || Cu2+ (aq) | Cu (s)

anode cathode
Cell notation
Exercise
For the cell below, write the reaction at anode
and cathode and also the overall cell reaction.
Cell notation
Zn (s) | Zn2+(aq) || Cr3+ (aq) | Cr (s)
Anode : 3 Zn(s) → 3Zn2+(aq) + 6e
2e- X3
Cathode : 2 Cr3+(aq) + 6e
3e- → 2Cr(s) X2
Overall cell 3Zn(s) + 2Cr3+(aq) + → 3Zn2+ (aq) +2Cr(s)
reaction:
The difference in electrical potential between the anode
and cathode is called:
• cell voltage
• electromotive force (emf)
measured by a voltmeter
• cell potential
Acts as ‘electrical pressure’ that

pushes electron through the wire.
A measure of the ability of a half-cell to attract electrons towards
it.
Cu2+(aq) + 2e → Cu(s) Eored = +0.34 V
Zn2+(aq) + 2e → Zn(s) Eored = -0.76 V
Standard reduction
potential
•The more positive the half-cell’s electrode potential, the
stronger the attraction for electrons.
Tendency for reduction ↑
(cathode)
Standard reduction potential of copper half-cell is
more positive compared to zinc.
Zinc half-cell becomes anode.
Cu2+(aq) + 2e → Cu(s) Eored = +0.34 V
Zn2+(aq) + 2e → Zn(s) Eored = -0.76 V
Cell Potential (Eocell)= Eocatode — Eoanode
= +0.34 – (-0.76)
= +1.1 V
Zn2+ (aq) + 2e-  Zn (s) E0 = -0.76V
Cu2+ (aq) + 2e-  Cu (s) E0 = +0.34V
E0cell = E0cathode - E0anode

= +0.34 – (-0.76)
= +1.10 V
or E0cell = E0red + E0ox Change the sign
= +0.34 + (+0.76)
= +1.10 V
Half-cell equation at:

Standard Electrode Potentials (Eo)
A measure of the ability of half-cell
to attract electrons towards it
at 25oC, the pressure is 1 atm (for
gases), and the concentration of
electrolyte is 1M.
The sign of E0 changes when the

reaction is reversed
•Changing the stoichiometric

coefficients of a half-cell reaction
does not change the value of E0
For example:
Cl2(g) + 2e-  2Cl-(aq) E0 = +1.36 V
½Cl2(g) + e-  Cl-(aq) E0 = +1.36 V
Cl-(aq)  ½Cl2(g) + e- E0 = -1.36 V

Standard Hydrogen Electrode (SHE)
Made up of a platinum electrode, immersed in an
aqueous solution of H+ (1 M) and bubbled with
hydrogen gas at 1 atm pressure, and temperature at
25oC
H2 gas
at 1 atm
Pt
H+ (aq) electrode
1 M
The standard reduction of SHE is 0 V
Standard reduction potential of Zinc half cell is
measured by setting up the electrochemical
cell as below.
E0 = +0.76
- V + E0 = 0
+
-
H2 (g), 25oC,1 atm.
Zn e
e
e H+(aq),1 M
2+
Zn e
ZnSO4(aq) Pt
1M
Standard Electrode Potentials
Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Anode (oxidation): Zn (s) Zn2+ (1 M) + 2e-
Cathode (reduction): 2e- + 2H+ (aq,1 M) H2 (g,1 atm)
Cell reaction Zn (s) + 2H+ (aq,1 M) Zn2+(aq) + H2 (g,1 atm)
0 = E 0+ - E 0 2+
Ecell H /H2 Zn /Zn
0 2+
0.76 V = 0 - EZn /Zn
0 2+
EZn /Zn = -0.76 V
Zn2+ + 2e- Zn E0 = -0.76 V

Standard reduction potential of Copper half cell is
measured by setting up the electrochemical
cell as below.
+ V- E0 = 0
-
+ H2 (g) 25oC
1 atm.
Cu
H+(aq)
Cu2
1M
CuSO4(aq) Pt
1M
Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)
Anode (oxidation): H2 (1 atm) 2H+ + 2e-
Cathode (reduction): 2e- + Cu2+ (1 M) Cu (s)
H2 + Cu2+ Cu (s) + 2H+
0 = E0
Ecell 0
cathode - Eanode
0 = E 0 2+
Ecell 0
Cu /Cu – EH +/H2
0 2+
0.34 = ECu /Cu - 0
0 2+
ECu /Cu = 0.34 V
The direction of half-reaction of SHE depends on the
other
half-cell connected on it.
The cell notation for SHE is either:
 H+(aq) | H2(g) | Pt(s) when it is cathode
 Pt(s) | H2(g) | H+ (aq) when it is anode
In either case, E0 of SHE remains 0

Zn2+ (aq) + 2e-  Zn (s) E0 = -0.76V
Cu2+ (aq) + 2e-  Cu (s) E0 = +0.34V

= +0.34 – (-0.76)
= +1.10 V
or E0cell = E0red + E0ox Change the sign
= +0.34 + (+0.76)
= +1.10 V
Half-cell equation at:

At standard-state condition
or
E0cell = E0red + E0ox

Exercise
Calculate the standard cell potential of the following
electrochemical cell.
Co(s) | Co2+(aq) || Ag+(aq) | Ag(s)
Ag+(aq) + e-  Ag(aq) E0 = +0.80V
Answer Co2+(aq) + 2e-  Co(s) E0 = -0.28V

+ -
Cathode (Red) : Ag (aq) + e  Ag(aq) E0 = +0.80V
Anode (Ox) : Co(s)  Co2+(aq) + 2e- E0ox = +0.28V

= +0.80 – (-0.28)
= +1.08 V
Refer to the list of Standard Reduction Potential:
Oxidation agent → left of the half cell equation
Reduction agent → right of the half cell equation
Example :
Ni2+ (aq) + 2e- → Ni (s) E0 = -0.25 V Increase
strength as
Cu2+ (aq) + 2e- → Cu (s) E0 = +0.34 V
reducing
Ag+ (aq) + e- → Ag (s) E0 = +0.80 V agent
Oxidation Reducing
agent agent
The more -ve the value of E0 → the stronger

the reducing agent
The more +ve the value of E0 → the stronger
the oxidizing agent
Exercise
Arrange the 3 elements in order of increasing
strength of reducing agents
X3+ + 3e-  X E0 = -1.66 V
Y2+ + 2e-  Y E0 = -2.87 V
L2+ + 2e-  L E0 = +0.85 V
Answer :
L < X < Y
Example
Calculate the E0 cell for the reaction ::
Mg(p) | Mg2+(ak) || Sn4+(ak),Sn2+(ak) | Pt(p)
Given :
E0cell = Ecathode - Eanode
Mg2+(ak) + 2e→ Mg(p) Eθ = -2.38 V
=+0.15- (-2.38)
Sn4+(ak) + 2e → Sn2+(ak) Eθ= +0.15 V
=+2.53V
Oxidation : Mg(p) → Mg2+(ak) + 2e Eoox = +2.38 V
Reduction : Sn4+(ak) + 2e → Sn2+(ak) Eo = +0.15 V
Mg(p) + Sn4+(ak) → Mg2+(ak) + Sn2+(ak) Ecell = +2.53 V
Eθcell = E o red + E o ox
= +2.38 + 0.15
= +2.53 V
Exercise
A cell is set up between a chlorine electrode and a
hydrogen electrode
Pt | H2(g, 1 atm) | H+(aq, 1M) || Cl2(g, 1atm) | Cl-(aq, 1M) | Pt
E0cell = +1.36 V
(a) Draw a diagram to show the apparatus and chemicals

used.
(b) Discuss the chemical reactions occurring in the
electrochemical cell.
Answer
E0cell =1.36V
H2 (g), - V + Cl2 (g),
1 atm. 1 atm.
- +
Pt Pt
H+(aq), 1M Cl-(aq), 1M
1. Show the process occur at anode and
cathode
- Half-cell reaction
2. Overall reaction
Answer
 Reduction (cathode)
Cl2 (g) + 2e-  2Cl- (aq)
 Oxidation(anode)
H2 (g)  2H+ (aq) + 2e- E0 = 0
 Eocell =+1.36 V
Eocell = Eocathode - E0anode
+1.36 = Eocathode – 0
E0cathode = +1.36 V
So the standard reduction potential for
Cl2 is:
Eo = +1.36 V
 Spontaneous & Non-Spontaneous reactions
- Redox reaction is spontaneous when
Ecell is +ve.
- Non spontaneous is when Ecell is –ve.
Eθ cell = 0 The reaction is at equilibrium

Predict whether the following reactions occur
spontaneously or non-spontaneously under standard
condition. EoSn4+/Sn2+=+0.15V
Zn + Sn4+ → Sn2+ + Zn2+
EoZn/Zn2+ = - 0.76V.
The two half-cells involved are:-
Anod : Zn → Zn2+ + 2e Eoox = +0.76 V
Cathode: Sn4+ + 2e → Sn2+ Eo = +0.15 V
Zn + Sn4+ → Zn2+ + Sn2+
Eocell = Eo Sn4+/Sn2+ → Eo Zn/Zn2+ Eocell= Eored + Eoox

= (+0.15) + (0.76)
= +0.15 – (-0.76 ) Or = +0.91 V
= +0.91 V
spontaneous
Pb2+(aq) + 2Cl-(aq) → Pb(s) + Cl2(g)
Reduction
Pb2+(aq) + 2Cl-(aq)
Pb2+(aq) + 2Cl-(aq) →
→ Pb(s) + Cl (g)
→Pb(s)
Pb(s)+ Cl+2(g)
Cl2 (g)
Oxidation
cathode: Pb2+(aq) + 2e → Pb(s) Eo = -0.13 V
anode: 2Cl-(aq) → Cl2(g) + 2e Eoox = -1.36
Pb2+(aq) + 2Cl-(aq) → Pb(s) + Cl2(g)
Eocell= Eored + Eoox

= (-1.36) + (-0.13)
= -1.48 V
Non-spontaneous
No Reaction
Example :
Predict whether the following reactions occur
spontaneously :
2Ag(s) + Br2(aq) 2Ag+(aq) + 2Br-(aq)
0 +
EAg = +0.8 V
/Ag standard reduction
0
EBr potential
2 /Br
- = +1.07 V
Answer :
2Ag(s) 2Ag+(aq) + 2e Eθox = - 0.80 V
Br2(aq) + 2e 2Br -(aq) Eθ = +1.07 V
2Ag(s) + Br2(aq) 2Ag+(aq) + 2Br-(aq) Esel = + 0.27 V
The reaction is spontaneous

Exercise
A cell consists of silver and tin in a solution of 1 M
silver ions and tin (II) ions. Determine the spontaneity
of the reaction and calculate the cell voltage of this
reaction.
Ag+ (aq) + e- → Ag (s) E0 = +0.80 V (cathode)

Sn2+ (aq) + 2e- → Sn (s) E0 = -0.14 V (anode)
= +0.80 – (-0.14)
= +0.94 V
E0cell = +ve ( reaction is spontaneous)
Nernst equation
Nernst equation can be used to calculate the E cell
for any chosen concentration :
Ecell = Eocell – RT ln [ product ]x

nF [ reactant]y
At 298 K and R = 8.314 J K-1 mol-1 , 1 F = 96500 C
Ecell = Eocell – 0.0257 [ product ]x

2.303 log
n [ reactant]y
Ecell = Eocell – 0.0592 [ product ]x
log
n [ reactant]y
[ product ]x
= Q
[ reactant]y
Ecell = Eocell – 0.0592

log Q
n
n = no of e- that are involved

Q = reaction quotient
Example 1
Calculate the Ecell for the following cell
Zn(s) / Zn2+ (aq, 0.02M) // Cu2+(aq, 0.40 M) / Cu(s)
Answer
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Eocell = Eored + Eoox @ Eocell = Eocathode – Eoanode

= +0.34 V + 0.76 V = +0.34 V - (- 0.76 V)
= +1.10 V = +1.10 V
E = Eo – 0.0592 log [ Zn2+]
n [ Cu2+]
E = +1.10 V – 0.0592 log (0.02 )

2 ( 0.40)
= +1.10 V – (-0.0385)
= +1.139 V
At equilibrium:
~ No net reaction occur (Q=K)
~ Ecell = 0
Ecell = Eocell – 0.0592

log K
n
0 = Eocell – 0.0592
log K
n
Eθcell = 0.0592
log K
n
Example 2
Calculate the equilibrium constant (K) for the
following reaction.
Cu(s) + 2Ag+(ak) Cu2+(ak) + 2Ag(s)
Answer
At equilibrium, E cell = 0
Eocell = Eo cathode - Eo anode

= +0.80 – ( +0.34)
= +0.46 V
Ecell = Eocell – 0.0592 log K
2
0 = 0.46 – 0.0592 log K

2
0.0592 log K = 0.46

2
log K = 15.54
K = 3.467 x 1015
Electrolysis
Electrolysis is a chemical process that uses electricity
for a non-spontaneous redox reaction to occur.
Such reactions take place in electrolytic cells.
Electrolytic Cell
 It is made up of 2 electrodes immersed in an
electrolyte.
 A direct current is passed through the electrolyte
from an external source.
 Molten salt and aqueous ionic solution are commonly
used as electrolytes.
Electrolytic Cell
+ -
Oxidation Reduction
Electrolyte
(M+X-)
X-,OH- M+,H+
Anion Cation
A  Positive electrode
n  The electrode which is connected to the
o positive terminal of the battery
d
 Oxidation takes place
e
 Electrons flow from anode to cathode
C
a  Negative electrode
t  The electrode which is connected to the
h negative terminal of the battery
o  Reduction takes place
d
e
Electrode
 as circuit connectors
 as sites for the precipitation of insoluble
products
 example: Platinum , Graphite (inert electrode)
Electrolyte
 a liquid that conducts electricity due to

the presence of +ve and –ve ions
 must be in molten state or in aqueous
solution so that the ions can move freely
example: KCl(l), HCl(aq), CH3COOH(aq)
Comparison between an electrochemical cell
and an electrolytic cell
Electrolytic Cell Electrochemical Cell

+ -
e- e- e- e-
+ - - +
Anode Cathode Anode Cathode

Electrolytic Cell Electrochemical Cell
 Cathode = negative  Cathode = positive
 Anode = positive  Anode = negative
 Non-spontaneous redox  Spontaneous redox
reaction requires energy reaction releases energy
to drive it
Similarities:
 Oxidation occurs at anode, reduction occurs

at cathode
 Anions move towards anode, cations move
towards cathode.
 Electrons flow from anode to cathode in an
external circuit.
Electrolysis of molten salt
 Electrolysis of molten salt requires high temp.
 Electrolysis of molten NaCl
Cation : Na+ Anion : Cl-
Anode : Cl- (l) → Cl2(g) + 2e-
Cathode : Na+ (l) + e- → Na (s)

2Na+ (l) + 2e- → 2Na (s)
Overall : 2Na+ (l) + 2Cl-(l) → Cl2(g) + 2Na(s)

 Electrolysis of molten NaCl gives sodium metal
deposited at cathode and chlorine gas evolved at
anode.
Electrolysis of molten NaCl is industrially important.
The industrial cell is called ‘Downs Cell’
Electrolysis of Aqueous Salt
 Electrolysis of aqueous salt is more complex
because the presence of water.
 Aqueous salt solutions contains anion, cation and water.
 Water is an electro-active substance that may be
oxidised or reduced in the process depending on
the condition of electrolysis.
Reduction :
2H2O (l) + 2e- H2 (g) + 2OH- (aq) E0 = -0.83 V
Oxidation :
2H2O (l) 4H+ (aq) + O2 (g) + 4e- E0 = -1.23 V
Predicting the products of electrolysis
Factors influencing the products :

1. Reduction/oxidation potential of the
species in electrolyte
2. Concentrations of ions
3. Types of electrodes used – active or
inert
Electrolysis of Aqueous NaCl
NaCl aqueous solution contains Na+ cation, Cl- anion
and water molecules
On electrolysis,
 the cathode attracts Na+ ion and H2O molecules
 the anode attracts Cl- ion and H2O molecules
The electrolysis of aqueous NaCl depends on the

concentration of electrolyte.
Electrolysis of diluted NaCl solution
Cathode
Na+ (aq) + e- Na (s) E0 = -2.71 V
2H2O (l) + 2e- H2 (g) + 2OH- (aq) E0 = -0.83 V
E0 for water molecules is more positive.
H2O easier to reduce.
Anode
Cl2 (g) + 2e- 2Cl- (aq) E0 = +1.36 V
O2 (g) + 4H+ (aq) + 4e- 2H2O (l) E0 = +1.23 V
In dilute solution, water will be selected for
oxidation because of its lower Eo.
Reactions involved
Cathode: 2H 2O (l) + 2e - H2 (g) + 2OH- (aq) E0 = -0.83 V

4H2O (l) + 4e- 2H2 (g) + 4OH- (aq)
Anode: 2H2O (l) O2 (g) + 4H+ (aq) + 4e- E0 = -1.23 V
Cell 6H2O(l) O2(g) + 2H2(g) + 4OH-(aq) + 4H+(aq)

reaction:
4 H2O
2H2O(l) O2(g) + 2H2(g) E0cell = -2.06 V

Electrolysis of Concentrated NaCl solution
Cathode
Na+ (aq) + e- Na (s) E0 = -2.71 V
2H2O (l) + 2e- H2 (g) + 2OH- (aq) E0 = -0.83 V
 E0 for water molecules is more positive
 H2O easier to be reduce
Anode
Cl2 (g) + 2e- 2Cl- (aq) E0 = +1.36 V
O2 (g) + 4H+ (aq) + 4e- 2H2O (l) E0 = +1.23 V
In concentrated solution, chloride ions will be
oxidised because of its high concentration.
Reactions involved
Cathode: 2H2O (l) + 2e- H2 (g) + 2OH- (aq) E0 = -0.83 V
Anode: 2Cl- (aq) Cl2 (g) + 2e- E0 = -1.36 V
Cell 2H2O(l) + 2Cl- Cl2(g) + H2(g) + 2OH-(aq)

reaction:
E0cell = -2.19 V
Exercise
Predict the electrolysis reaction when
Na2SO4 solution is electrolysed using platinum electrodes.
Solution
 Na2SO4 aqueous solution contains Na+ ion, SO42- ion
and water molecules
 On electrolysis,
 the cathode attracts Na+ ion and H2O molecules
 the anode attracts SO42- ion and H2O molecules

Cathode
Na+ (aq) + e- Na (s) E0 = -2.71 V
2H2O (l) + 2e- H2 (g) + 2OH- (aq) E0 = -0.83 V
 E0 for water molecules is more positive

H2O easier to reduce
Anode
S2O82- (aq) + 2e- 2SO42- (aq) E0 = +2.01 V
O2 (g) + 4H+ (aq) + 4e- 2H2O (l) E0 = +1.23 V
 E0 for water molecules is less positive

H2O easier to oxidise
Equation
Cathode: 2H2O (l) + 2e- H2 (g) + 2OH- (aq) E0 = -0.83 V
Anode: 2H2O (l) O2 (g) + 4H+ (aq) + 4e- E0 = -1.23 V
Cell 2H2O(l) O2(g) + 2H2(g) E0cell = -2.06 V

Reaction:
 Cathode = H2 gas is produced and solution become

basic at cathode because OH- ions are formed
 Anode = O2 gas is produced and solution become

acidic at anode because H+ ions are formed
Faraday’s Law of Electrolysis
Describes the relationship between the amount of
electricity passed through an electrolytic cell and
the amount of substances produced at electrode.
Faraday’s First Law

States that the quantity of substance formed at an
electrode is directly proportional to the quantity of
electric charge supplied.
Faraday’s 1st Law
mαQ
Q = electric charge in coulombs (C)
m = mass of substance discharged
Q = It
Q = electric charge in coulombs (C)
I = current in amperes (A)
t = time in second (s)
Faraday constant (F)

is the charge on 1 mole of electron
1 F = 96 500 C
Example
An aqueous solution of CuSO4 is electrolysed using a
current of 0.150 A for 5 hours. Calculate the mass
of copper deposited at the cathode.
Answer
Electric charge, Q = Current (I) x time (t)
Q = (0.150 A) x ( 5 x 60 x 60 )s
Q = 2700 C
1 mole of electron Ξ 1 F Ξ 96 500 C

2700
No. of e- passed through = = 0.028 mol
96 500
Cu2+ (aq) + 2e-  Cu (s)
From equation:
2 mol electrons  1 mol Cu
0.028 mol electrons  0.014 mol Cu
Mr for Cu = 63.5
Mass of Copper deposited = 0.014 x 63.5
= 0.889 g
11.0 REACTION KINETICS
Objectives:
1. Define reaction rate, average rate,

instantaneous rate and initial rate.
2. Determine the reaction rate based on a
differential equation.
REACTION KINETICS
Chemical kinetics is the study of the rates of
chemical reactions, the factors that affect these
rates, and the reaction mechanisms by which
reactions occur.
Important
industrial process
-Time
-Optimum yield
-Optimum conditions
control over reaction,
obtain products economically,
using optimum conditions
Rate of reaction
• Reaction rate is the change in the concentration
of a reactant or a product with time.
• Unit of rate (mol L-1 s-1)
1
• rate 
Time
Example; A  B
- d[A] d[A] = change in concentration of A

rate =
dt
dt = period of time
d[B]
rate = dt d[B] = change in concentration of B
Because [A] decreases with time, d[A] is negative.

A B
time
[B] ↑
d[A]
rate = -
dt
d[B]
rate =
dt [A] ↓
Rate of reaction
• The average rate is the rate over a period of time.

• The rate of reaction at a given time is called an
instantaneous rate of reaction.
• The instantaneous rate at the beginning of a
reaction is called the initial rate of reaction.
• Instantaneous rate is determined from a graph of
concentration vs time by drawing a line tangent to
the curve at that particular time.
Rate of reaction
Reaction:
H2O2(aq)  H2O(l) + ½ O2(g)
Reaction rates are obtained
from the slopes of the straight
lines;
purple An average rate from the
purple line.
The instantaneous rate at
t =300 s from the red line.
blue red
The initial rate from the blue
line.
Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)
instantaneous rate = rate at a specific time
d[Br2] [Br2]final – [Br2]initial

average rate = - =-
dt tfinal - tinitial
The differential rate equation
A differential rate equation enables the relationship

between the rate of disappearance of reactants and
the formation of products.
Consider the reaction,

aA + bB  cC + dD
1 d[A] 1 d[B] 1 d[C] 1 d[D]

Rate =    
a dt b dt c dt d dt
a,b,c and d are the stoichiometric coefficients

The differential rate equation
Example:
The formation of NH3,
N2(g) + 3H2(g)  2NH3(g)
The differential rate equation is;

d[N 2 ] 1 d[H 2 ] 1 d[NH 3 ]
Rate =   
dt 3 dt 2 dt
The equation means that the rate of disappearance
of N2 is 1/3 the rate of disappearance of H2 and 1/2
the rate of formation of NH3.
Example 1:
Consider the reaction, 2HI  H2 + I2,
determine the rate of disappearance of HI when
the rate of I2 formation is 1.8 x 10-6 M s-1.
Solution:
1 d[HI] d[H 2 ] d[I 2 ]
Rate =   
2 dt dt dt
d[I 2 ]
= 1.8  10-6
dt
1 d[HI] d[I 2 ]
Rate =  
2 dt dt
d[HI]
= 2  1.8  10-6 = 3.6  10-6 M s-1
dt
EXERCISE 1:
Hydrogen gas produced nonpolluting product is
water vapour when react in O2 due to this reaction
has been used for fuel aboard the space shuttle,
and may be used by Earth-bound engines in the
near future.
2H2(g) + O2(g) 2H2O(g)
• Express the rate in terms of changes in [H2],

[O2] and [H2O] with time.
• When [O2] is decreasing at 0.23 mol L-1 s-1, at

what rate is [H2O] increasing?
(0.46 mol L-1 s-1)
Exercise 2:

NO(g) + O2(g) 2NO2(g).
Suppose that at a particular time during the
reaction nitric oxide (NO) is reacting at the rate of
0.066 M s-1
a) At what rate is NO2 being formed?
b) At what rate is molecular oxygen reacting?
Exercise 3:

N2(g) + 3H2(g)  2NH3(g)
Suppose that at a particular moment during the
reaction molecular hydrogen is reacting at the rate
of 0.074 M s-1
a) At what rate is ammonia being formed?
b) At what rate is molecular nitrogen reacting?
11.1
RATE LAW
Objectives:
At the end of the lesson the students should be able

to:
1. define rate law and write the rate equation
2. define the order of reaction and the rate constant
3. calculate the order with respect to a certain reactant
from experimental data
4. determine the overall order of a reaction from
experimental data
5. calculate the value and determine the units of
rate constants
The Rate Law
The rate law expresses the relationship of the rate of a reaction
to the rate constant and the concentrations of the reactants
raised to some powers.
aA + bB cC + dD
Rate α [reactant]
Rate = k [A]x[B]y
reaction order is x with respect to A
reaction order is y with respect to B
Overall reaction order is (x + y)
The exponents x, y, … can be integers, fractions or
decimal or negative values.
k is called rate constant

Rate Law
• The values of x and y can only be determined
experimentally.
• Reaction order is usually defined in terms of reactant
concentrations.
• The order of a reactant is not related to the stoichiometric
coefficients of the reactants in the balanced chemical
equation.
F2 (g) + 2ClO2 (g) 2FClO2 (g)
rate = k [F2][ClO2] 1
The units of rate constant, k
A Products
Rate, r = k [A]x
i) The reaction is zero order
Rate = k [A]0
Rate = k
unit k = unit rate

= mol L-1 s-1 or M s-1
ii) First order rate
Rate = k [A]1 k=
[A]
M s-1
Unit k =
M
= s-1
iii) Second order
Rate = k [A]2
rate
k=
[A]2
M s-1
Unit k = = M-1 s-1
M2
Example :
S2O82- + 3I- 2SO42- + I3-
The above reaction is first order with respect to iodide ions and
to thiosulphate ions.
a) Write the rate of equation for the reaction.
b) What is the unit of rate constant, k?
Solution :
a) Rate = k [S2O82-]1[I-]1
b) Rate = k [S2O82-]1[I-]1
k= rate Ms-1 M-1 s-1
Unit k = =
[S2O82-]1[I-]1 M2
The order of reaction
For reaction
A Products
Rate = k [A]x
i) If x = 0
Rate = k [A]0
Rate = k
Rate is not dependent on [A]
Therefore this reaction is zero order with respect to A
ii) If x= 1
Rate = k [A]1
Assume [A]i = 1.0M
Rate = k (1.0M)
If the [A] is doubled from 1.0M to 2.0M,
Rate = k (2.0M)
= 2k(1.0M)
hence
Rate = 2k[A]
Doubling the [A] will double the rate of reaction.
Therefore this reaction is first order with respect to A
iii) If x = 2
Rate = k[A]2
Assume [A]i = 1.0 M
Rate = k (1.0 M)2
If the [A] is doubled from 1.0 M to 2.0 M,

Rate = k (2.0 M)2
= 4k(1.0 M)
hence
Rate = 4k[A]
Doubling [A], the rate will increase by a factor of 4.
Therefore the reaction is second order with respect to A
Example
Determining Reaction Order from Rate Law
For each of the following reactions, determine the

reaction order with respect to each reactant and the
overall order from the given rate law.
(a) 2NO(g) + O2(g) 2NO2(g); rate = k[NO]2[O2]
The reaction order respect to NO : 2

The reaction order respect to O2 : 1
overall reaction order = 3
(b) CH3CHO (g) CH4(g) + CO(g);
rate = k[CH3CHO]3/2
Solution:
The reaction order with respect to CH3CHO : 3/2
The reaction order (overall) : 3/2
(c) H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq) + 2H2O(l);
rate = k[H2O2][I-]
Solution:
The reaction of order with respect to H2O2 : 1
The reaction of order with respect to I- : 1
and zero order in H+, while overall order is 2.
Determination of the orders of reaction rate;
O2(g) + 2NO(g) 2NO2(g)
Initial Reactant
Concentrations (molL-1) Initial Rate
Experiment (M s-1)
O2 NO
1 1.10x10-2 1.30x10-2 3.21x10-3
2 2.20x10-2 1.30x10-2 6.40x10-3
3 1.10x10-2 2.60x10-2 12.8x10-3
4 3.30x10-2 1.30x10-2 9.60x10-3
5 1.10x10-2 3.90x10-2 28.8x10-3

Solution:
O2(g) + 2NO(g) 2NO2(g)
rate = k [O2]m[NO]n
Compare 2 experiments in which the concentration of one reactant

varies and the concentration of the other reactant(s) remains
constant.
rate2 k [O2]2m[NO]2n [O2]2m m
[O2]2
rate1 = = =
k [O2]1m[NO]1n [O2]1m [O2]1
6.40x10-3Ms-1 2.20x10-2mol/L m
=
3.21x10-3Ms-1 1.10x10-2mol/L
2= 2m , m = 1 ;
The reaction is first order with respect to O2
Do a similar calculation for the other reactant(s).

To find the order with respect to NO, we compare
experiment 3 and 1, in which [O2] is held constant
and [NO] is doubled:
m [NO] n n
Rate 3 k [O ]
23 3 [NO] 3
= =
Rate 1 k [O2]1m [NO]1n [NO]1
n
12.8 x 10 Ms-3 -1
2.60 x 10-2mol/L
-3 -1
=
3.21 x 10 Ms 1.30 x 10-2mol/L
4 = 2n ; n = 2
The reaction is second order with respect to NO

Thus the rate law is :
Rate = k[O2][NO]2
Exercise:
ClO2(aq) + 2OH- (aq)  products
The results of the kinetic studies are given below.
exp [ClO2] [OH-] Initial rate,
M M Ms-1
1 0.0421 0.0185 8.21 1 0-3
2 0.0522 0.0185 1.26 1 0-2
3 0.0421 0.0285 1.26 1 0-2
a) Explain what is meant by the order of reaction.

b) Reffering to the data determine
(i) rate law /rate equation
(ii) rate constant, k
(iii) the reaction rate if the concentration of both ClO2
and OH- = 0.05 M
Exercise:
Write rate law for this equation,
A + B  C
i) When [A] is doubled, rate also doubles. But
doubling the [B] has no effect on rate.
ii) When [A] is increased 3x, rate increases 3x,
and increasing of [B] 3x causes the rate to
increase 9x.
iii) Reducing [A] by half has no effect on the rate,
but reducing [B] by half causes the rate to be
half the value of the initial rate.
Exercise:
Many gaseous reactions occur in a car engine and exhaust
system. One of the gas reaction is given below.
NO2(g) + CO(g) NO(g) + CO2(g)
Rate = k [NO2]m[CO]n
Use the following data to determine the individual and overall reaction orders:
Experiment Initial Rate(Ms-1) Initial [NO2](M) Initial [CO](M)
0.0050 0.10 0.10

1
2 0.080 0.40 0.10
3 0.0050 0.10 0.20

Integrated Rate Law
Objectives:
1.Write the rate law for zero order, 1st order and
2nd order reaction
2. Define half-life.
3. Draw the respective graphs for the different
order reactions
4. Solve quantitative problems.
Integrated rate equations
Zero Order Reaction
A zero order reaction is a reaction independent of the concentration of reactant.
A product
The rate law is given by

rate = k[A]0
rate = k
rate
[A] M
- d[A] = k
dt
Using calculus,
- d[A] = kdt
- ∫d [A] = k ∫dt
- [A] = kt + c
substituting t=0, [A] = [A]0
- [A]0 = k(0)+c
c = - [A]0
[A]0 -[A] = kt
Unit of k for zero order reaction M s-1

Graphs for zero order reaction
[A]o – [A] = kt
[A]o – [A]
y = mx + c
[A] [A] = -k t + [A]o rate

[A]o
y=m x+c
t [A]
Half-life (t½)
Half life (t½) is the time required for the concentration of a reactant to decrease
to half of its initial value.
zero order reaction

Substituting t = t1/2 , and [A] = [A]0 into the zero
order reaction, gives 2
[A]0 - [A] = kt
[A]0 – [A]0 = kt1/2
2
Solving for t1/2 gives
t1/2 = [A]0
2k
First Order Reactions
A first order reaction is a reaction whereby its rate depends on the

concentration of reactant raised to the first power.
From the rate law,

rate = k[A]
To obtain the units of k
k = rate
[A]
unit k = M s-1
M
= s-1
Rate = k[A]
y = mx + c
Rate
Ms-1
[A] ,M
For first order reaction,
Rate = k[A]
- d[A] substituting
= k[A]
dt t = 0, [A]=[A]0
- d[A]
= k dt
[A] - ln [A]0 = k(0) + c
c =  ln[A]0
- d[A]
∫ = ∫ k dt
[A] -ln [A] = kt – ln[A]0
- ln [A] = kt + c
[A]0
ln = kt
[A]
Characteristic graphs of 1st order reaction
ln[A]o – ln[A] =kt
[A] ln[A] = - kt +ln[A]o
[A]0
ln ------ = kt
[A]
t
ln[A]
ln[A]o
ln[A]o
[A]
t t
Example
The reaction 2A B is first order with respect A with a

rate constant of 2.8 x 10-2 s-1 at 800C. How long will it take
for A to decrease from 0.88 M to 0.14 M ?
[A]0 = 0.88 M
ln[A]o – ln[A] = kt
[A] = 0.14 M
kt = ln[A]0 – ln[A]
[A]0 0.88 M
ln ln
ln[A]0 – ln[A] [A] 0.14 M
t= = = = 66 s
k k 2.8 x 10-2 s-1
Example
Decomposition of H2O2 (aq) is first order, given that k = 3.66 x 10-3 s-1 and [H2O2 ]o
= 0.882 M, determine
a) the time at which [H2O2] = 0.600 M
b) the [H2O2 ] after 225 s.
Solution :
a) [H2O2]0
ln = kt
[H2O2]
0.882
ln = 3.66 x 10-3 s-1 x t
0.600
ln 1.47 = 3.66 x 10-3 s-1 x t
ln 1.47
t=
3.66 x 10-3
= 105.26 s
b) [H2O2]0
ln = kt
[H2O2]
0.882
ln = 3.66 x 10-3s-1x 225 s
[H2O2]
[H2O2] = 0.387 M
Exercise,
The conversion of cyclopropane to propene in the gas phase is a first

order reaction with a rate constant of 6.7 X 10-4 s-1 at 500°C.
CH2
CH2 CH2 CH3-CH=CH2
a) If the initial concentration of cyclopropane was 0.25 M, what is the

concentration after 8.8 minute. (0.18 M)
b) How long will it take for the concentration of cyclopropane to
decrease from 0.25 M to 0.15 M? (13 min)
c) How long will it take to convert 74 percent of the starting material?
(33 min)
Half-life of a first-order reaction
The half-life, t½, is the time required for the concentration of a

reactant to decrease to half of its initial concentration.
t=t½ when [A] = [A]0

2
[A]0
ln
[A]0/2 ln2 0.693
t½ = = =
k k k
What is the half-life of N2O5 if it decomposes with a rate
constant of 5.7 x 10-4 s-1?
t½ = ln2 = 0.693
= 1200 s = 20 minutes
k -4
5.7 x 10 s -1
How do you know decomposition is first order?

units of k (s-1)
First-order reaction
A product
No. of
half-lives [A]o = 8 M
1 4
2 2
3 1
4 1/2
t½ = ln2
k
Example
The decomposition of ethane C2H6 to methyl radicals is a first order reaction
with a rate constant of 5.36 x 10-4 s-1 at 700o C.
C2H6 (g) → 2 CH3 (g)
Calculate the half life of the reaction in minutes.
Solution ln 2
t1/2 =
k
0.693
=
5.36 x 10-4
= 1.29 x 103 s
= 21.5 min
Problem 2
What is the half-life of a compound if 75% of a given sample of the compound

decomposes in 60 min? Assume it is first-order reactions kinetics.
(t1/2=30 min)
Problem 3
The decomposition of SO2Cl2 is a first-order reaction.

SO2Cl2(g) SO2 (g) + Cl2 (g)
i) Write the rate differential equation for the reaction.

ii) Calculate the value of rate constant, k at 500 K if
5.00 % SO2Cl2 decomposed in 6.75 min.
Ans (7.6X10-3)
iii) Specify the half-life for the decomposition reaction. Ans (91.20 )
Second Order Reactions
A second order reaction is a reaction which rate depends on the concentration
of one reactant raised to the second power or on the concentration of two
different reactants each raised to the first power.
Example
A product
Where
d[A]
Rate = - = k[A]2
dt
To obtain the units of k
rate
k =
[A]2
M/s
Unit k =
M2
= M-1 s-1
Using calculus, the following expression can be obtained
1 1
= - + kt
[A] [A]0
Characteristic graphs for second order reaction
Rate = k [A]2
rate
[A]
rate
[A]2
Graphs for second order reaction
1 1
[A] = + kt
[A] [A]o
1/[A] M-1 1/[A] – 1/[A]o
1/[A]o
t t
2nd –order reaction, r = k[A]2
If [A] doubles,
r2 = k (2[A])2
= k ( 4 [A]2 )
= 4 k [A]2
=4r
R will increase by 4 times if [A] doubles

Half life of a second order reaction
1 1
= + kt
[A] [A]0
[A]= [A]o
Substituting t = t1/2
2
1 1
= + kt1/2
[A]0 [A]0
2
1
t1/2=
k[A]0
Detemination of half-life using graph for second order reaction
[A]0
1
t1/2=
k[A]0
[A]0/2
[A]0/4
[A]0/8
x 2x 4x t
Example
Iodine atoms combine to form molecular iodine in
the gaseous phase
I (g) + I (g)  I2(g)

This reaction is a second order reaction , with the rate constant of 7.0 x 109 M-1 s-
1
If the initial concentration of iodine was 0.086 M,

i) calculate it’s concentration after 2 min.
ii) calculate the half life of the reaction if the
initial concentration of iodine is 0.06 M and
0.42 M respectively.
Solution :
1 1
= + kt
i)
[A] [A]0
1 1
= + (7.0 x 109 x 2 x 60 )
[A] [0.086]
= 8.4 x 1011
[A] = 1.190 x 10-12 M
ii) [I2] = 0.06 M

1
1
t1/2= =
k[A]0 7.0 x 109 x 0.060
= 2.4 x 10-10 s
[I2] = 0.42 M
1
t1/2=
k[A]0
1
=
7.0 x 109 x 0.042
= 3.4 x 10-10 s
Using graph
Example,
The following results were obtained from an experimental investigation

on dissociation of dinitrogen pentoxide at 45oC
N2O5(g)  2 NO2(g) + ½ O2(g)
time, t/min 0 10 20 30 40 50 60
[N2O5] x 10-4 M 176 124 93 71 53 39 29
Plot graph of [N2O5] vs time, determine

i) The order of the reaction
ii) the rate constant k
Solution :
180
160
140
120
[N2O5] x 100
10-4 /M
80
60
40
20
10 20 30 40 50 60 70 80
Time ( min)
i) Based on the above graph,
Time taken for concentration of N2O5 to change from 176 x 10-4 M to 88 x

10-4 M is 20 min
Time taken for concentration of N2O5 to change from 88 x 10-4 M to 44 x

10-4 M is also 20 min
The half life for the reaction is a constant and does not depend on the
initial concentration of N2O5
Thus, the above reaction is first order
ln2
ii) = 0.03 min-1
k=
20 min
Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions
Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] = [A]0 - kt t½ =
2k
1 rate = k [A] ln[A] = ln[A]0 - kt t½ = ln2

k
1 1 1
2 rate = k [A]2 = + kt t½ =
[A] [A]0 k[A]0
Zero order 1st order 2nd order
A  product A  product A  product
r = k [A]0 r = k [A]1 r = k [A]2
Unit k = M s-1 Unit k = s-1 Unit k = M-1 s-1
r r r r
[A] [A]
[A] [A]2
Integrated rate law Integrated rate law Integrated rate law
[A]0 – [A] = kt ln([A]0 / [A]) = kt 1/[A] – 1/[A]0 = kt
[A] t1/2 = [A]0/2k [A] ln[A] [A] 1/[A]
[A]0 ln[A]0
1/[A]0
t t t t t
[A]0 - [A]
ln([A]0 / [A]) 1/[A] – 1/[A]0
t1/2 = t1/2 = 1/k[A]0

ln2/k
t t t
11.2 Collision Theory
Objectives
At the end of the lesson the students should be
able to:
1. explain reaction rates in terms of collision
theory.
2. identify factors affecting the effectiveness of
collision.
3. define activation energy.
4. Define and state the characteristics of an
activated complex
Collision Theory
• Collision Theory is the theory to explain the rate of
chemical reactions. It is based on;
Number of effective collisions

Rate 
time
1- molecule must collide to react

2- molecules must possess a certain minimum kinetic energy
(activation energy) to initiate the chemical reaction.
• 3- molecule must collide in the right orientation in order
for the reaction to occur.
• Only effective collisions cause formation of product;

collisions of molecules with Ea and at correct orientation.
• The activation energy (Ea) is the minimum energy that
must be supplied or required by collisions for a reaction to
occur.
The activation energy (Ea)
…..is the minimum

energy is required
to initiate the
chemical reaction.
Importance of Orientation
Orientation is unimportant Orientation is important

Importance of Orientation
Orientation is important
Transition State Theory
• The configuration of the atoms of the

colliding species at the time of the collision is
called the transition state.
• Species formed at transition state is called
activated complex.
Characteristics of Activated Complex
• Very unstable i.e. It has a short half-life.

• Its potential energy is greater than reactants or
products.
• The activated complex and the reactants are in
chemical equilibrium.
• It decomposes to form products or reactants.
Potential energy
- A reaction profile shows
potential energy plotted as a
function of the progress of the
reaction.
Ea - The difference in potential
Reactant energies between the
products and the reactants is -
H for the reaction.
H - Reactant molecules must
have enough energy to
overcome an energy barrier
separating products from
product reactants, Ea.
Progress of reaction
A Reaction Profile: exothermic reaction
Activated complex
Transition state
Ea (Forward reaction)
Ea (reverse reaction)
H
CO(g) + NO2(g) CO2(g) + NO(g)

A Reaction Profile for endothermic process
activated complex.
Ea
(reverse reaction)
Ea
(forward reaction)
Product
H
Reactant
A Reaction profile: endothermic reaction
Ea
H
2NOCl → 2NO + Cl2

Example:
1. For the reaction A + B C + D , the enthalphy
change of the forward reaction is + 21 kJ/mol. The
activation energy of the forward reaction is 84 kJ/mol.
a) What is activation energy of the reverse reaction?
b) Sketch the reaction profile of this reaction
2. Draw a potential energy diagram for an exorthermic

reaction. Indicate on the drawing:
a) Potential energy of the reactants and the products
b) The activation energy for the forward and the reverse
reaction
c) The heat of the reaction
Factors affecting rate of reaction
• CONCENTRATIONS OF REACTANTS:
Reaction rates generally increase as the
concentrations of the reactants are increased.
• TEMPERATURE:
Reaction rates generally increase rapidly
as the temperature is increased.
• CATALYSTS:
Catalysts speed up reactions.
• PARTICLE SIZE:
The rate increases as the smaller the size of
reacting particles .
A) CONCENTRATIONS OF REACTANTS
Reaction rate  collision

time
• The frequency of collision increases increases with the
concentration
4 particle system
(2 and 2)  4 collision
• A concentration of reactants increases, the frequency
of collision increases.
• This would also result in the increase in the quantity of
effective collision. Thus the reaction rate increases.
5 particle system
(3 and 2)  6 collision
• This observation correlates with the RATE LAW that has
been previously discussed…
x y
Reaction rate = k [ A ] [ B ] …
(A & B = reactants)
(x & y = rate order)
• Based on this equation,

Reaction rate  concentration of reactants
(depending on its rate order)
• REMINDER!
Only in zero order reactions, the rate of reaction is not
dependant upon the concentration of the reactants.
Reaction rate = k [ A ]0 = k (constant)
B) TEMPERATURE
• As temperature increases, kinetic energy, of

molecules increases
• So, more collisions occur in a given time
• Furthermore, the higher the kinetic energy, the
higher the energy of the effective collisions.
• So more molecules will have energy greater
than activation energy, Ea
• Thus, the rate of reaction increases
Distribution of Kinetic Energies of Molecules
Represent total number of molecules

with kinetic energy greater than Ea
B) TEMPERATURE
ARRHENIUS EQUATION
• In 1889, Svante Arrhenius proposed the following
mathematical expression for the effect of
temperature on the rate constant, k:
-Ea∕
k = A e RT
Where…
k = rate constant
A = constant known as the collision frequency factor
e = natural log exponent
Ea = activation energy for the reaction
R = universal gas constant (8.314 J mol-1 K-1)
T = absolute temperature
B) TEMPERATURE
ARRHENIUS EQUATION
• The relation ship between the rate constant, k and
temperature can be seen in the k vs T graph:
-Ea∕
k = A e RT
1/T (K-1)
B) TEMPERATURE
ARRHENIUS EQUATION - DERIVATION

• The relationship between k and T is clearer when
we further derive the Arrhenius Equation…
 Ea
RT
k  Ae
 Ea
Natural log both ends… RT
ln k  ln( A .e )
 Ea
RT
ln k  ln A  ln( e )
 Ea
ln k  ln e  ln A (But ln e = 1)
RT
 Ea 1
Thus… ln k  ( )  ln A
R T
See the linear relationship…? y = m x + C
B) TEMPERATURE
Graph Representation Of The Arrhenius Equation
• Plotting a ln k vs 1/T graph would show a clearer
relationship between k (Rate constant) and
temperature
 Ea 1
ln k  ( )  ln A
R T
Where,
Ea = Activation Energy
R = 8.314 Jmol-1K-1
T = Absolute Temp
A = Collision freq. factor
B) TEMPERATURE
• If the value of A (collision frequency factor) is not
known and the same reaction conducted at two
different temperatures.The Arrhenius equation at each
temperature can be written and combined to formed
the equation shown in the box.
 Ea 1  Ea 1
ln k1  ( )  ln A ln k 2  ( )  ln A
and R T2
R T1
Rearranging the equations would give…
Ea 1 Ea 1
ln k 1  ( )  ln A ln k 2  ( )  ln A
R T1 R T2
Since “A” is a constant…
E 1 E 1
ln k 1  a ( )  ln k 2  a ( )
R T1 R T2 k1 Ea 1 1
ln  (  )
Ea 1 Ea 1 k2 R T2 T1
ln k1  ln k 2  ( ) ( )
R T2 R T1
Exercise: the Activation energy
The decomposition of hydrogen iodide,
2 HI (g)  H2(g) + I2(g)
has rate constants of 9.51 x 10-9 L mol-1 s-1 at 500 K and
1.10x10-5 L mol-1 s-1 at 600 K. Find Ea.
DATA: k1 = 9.51 x 10-9 L mol-1 s-1 T1 = 500K

k2 = 1.10 x 10-5 L mol-1 s-1 T1 = 600K
SOLUTION:
k1 Ea 1 1
ln  (  ) 1.10  10 5 1 1 1
k2 R T2 T1 Ea  (8.314 ) ln( 9
)(  )
9.51 10 600 500
k1 1 1
E a   R ln( )(  ) 1
k 2 T 2 T1
Ea = 1.76 x 105 J/mol = 176 kJ/mol
C) CATALYST
• A catalyst is a substance that increases the rate

of a chemical reaction without itself being
consumed.
• Addition of a catalyst increases the reaction rate
by increasing the frequency of effective collision.
That is by
– Decreasing the Ea, and
– Correct orientation
C) CATALYST
• Addition of a catalyst changes the value of k (rate
constant) .
x y
Reaction rate = k [ A ] [ B ]
(A & B = reactants)
(x & y = rate order)
• The catalyst reacts by reducing the Ea and increasing

A, thus increasing the k.
 Ea 1
ln k  ( )  ln A
R T
C) CATALYST
• When Ea decreases, k increases,
REACTION RATE increases
rateuncatalyzed < ratecatalyzed
uncatalyzed catalyzed
Ea > E’a
Reaction pathway
D) PARTICLE SIZE
The smaller the size of reacting particles, the greater is

the total surface area exposed for reaction and
consequently the faster the reaction. In the case of
heterogeneous systems, in which the reactants are in
different phases, the area of contact between the reacting
substances will influence the reaction rate considerably.
Introduction To Organic
Chemistry
Lecture 1
12.1 Introduction
Learning Outcomes:
At the end of the lesson the students should be able to :
1. List the elements that made up organic compounds C, H,
O, N, P, S and halogens.
2. State the ability of carbon to form 4 covalent bonds with
other carbons or elements.
3. Differentiate between saturated and unsaturated organic
compounds.
4. Give examples of organic compounds used in medicine,
engineering, biotechnology and agriculture.
WHAT IS ORGANIC CHEMISTRY?
Organic chemistry is the chemistry of carbon
compounds.
Organic compounds contain H as well as C, while
other common elements are O, N, the halogens, S and
P.
There are many varieties of organic compounds
( more than 10 millions!!!)
They may exist as simple or complex molecules; as
gases, liquids or solid and coloured or colourless.
Examples :-
CH4
methane (a component of natural gas)
OCOCH3
COOH
methyl salicylic acid (aspirin-a drug)

O
CH2 NH S
C
N
O
COOH
penicillin (an antibiotic)
Cl CH Cl
CCl3
dichlorodiphenyltrichloroetane
(DDT- a pesticide component)
All organic compounds consist of carbon atom.
Properties of carbon atom:
-has 4 valence electrons.
-can form 4 covalent bonds.
C C C C C C
Single bond Double bond Triple bond

Hydrocarbons
saturated unsaturated
Contains only single

bonds ( -C-C- ) Contains at least one
carbon-carbon double
Examples: alkanes, bond (-C=C-) or triple
cycloalkanes bond (-C C-).
Examples: alkenes,
alkynes.
Uses of organic compounds
Medicine Antibiotics are used to
fight bacterial and fungal
infections
Engineering Gasoline-as a fuel for
internal combustion
engines.
Biotechnology Genetic information like
DNA
Agriculture DDT-as insectisides to kill
harmful insects.
Lecture 2:
12.2 Molecular and Structural Formulae
Learning Outcomes:
At the end of the lesson the students should
be able to :
Define structural formula.
Draw structural formula in the form of expanded,
condensed and skeletal structures based on the
molecular formula.
Explain primary (1°), secondary (2°), tertiary (3°)
and quaternary (4°) carbon.
Structural formula shows how the
atoms in a molecule are bonded to
each other.
3 types of structural formula:
• condensed structure
• expanded structure
• skeletal structure
2- Dimensional formula
Condensed Structure
Does not show single bonds between carbon
and hydrogen atoms, but double and triple bonds
are shown.
All atoms that are attached to a carbon are
written immediately after that carbon.
C4H9Cl CH3CHCH2CH3
(Condensed structure)
Examples:
ii) Cyclohexane, C6H12 iii) Aldehyde, CH3CHO

H2 O
C
H2C CH3CH
CH2
H2C
CH2
C
H2
Expanded Structure
Expanded structures indicate how atoms are
attached to each other but are not representations
of the actual shapes of the molecules.
H H H H
C4H9Cl
Molecular H C C C C H
Formula H Cl H H
Expanded structure
Examples:
i) Alcohol (C2H6O)
H H
H C C OH
H H
ii) Carboxylic acid (C3H6O2 )

H H O
H C C C OH
H H
Skeletal Structure
Shows only the carbon skeleton.
Hydrogen atoms are not written.
Other atoms such as O, Cl, N etc. are shown.
i) CH3CH(Cl)CH2CH3 =
Cl
H2C CH2
ii) =
H2C CH2
3- Dimensional formula
( wedge – dashed wedge – line formula )
Describes how the atoms of a molecule

are arranged in space.
Example : Bromoethane
Br
H C H
Br H H
C C C
or H Br or H H
H H H Br
H
Indication :-
:bonds that lie in the plane
:bonds that lie behind the plane
:bonds that project out of the plane
Classification of C atoms:
A carbon atom can be classified as

primary carbon(1o) →bonded to 1 C
secondary carbon(2o) → bonded to 2 C
tertiary carbon(3o) → bonded to 3 C
quarternary carbon(4o) → bonded to 4 C
H
H C H
CH3
10 carbon
10 carbon
CH3
H C CH3
CH3
30 carbon
1
1
H H CH3 CH3
1 1
H C C C CH2 C CH3
H H H CH3
1
H H CH3 CH3
2
H C C C CH2 C CH3
2
H H H CH3
H H CH3 CH3
3 4
H C C C CH2 C CH3
H H H CH3
Question
Expanded Condensed Skeletal

Structure Structure Structure
CH3(CH2)CCl(CH3)2
H H CH3
H
C C CH
H H CH3
12.3 FUNCTIONAL GROUPS
AND HOMOLOGOUS SERIES
Lecture 3
Functional Group and Homologous Series
Learning Outcomes:
At the end of the lesson the students should be able
to :
• Define functional group.
• Name functional groups and classify organic
compounds according to their functional groups.
• Define homologous series and explain general
characteristics of its members.
Functional group
is an atom or group of atoms in an organic
molecule which characterised the molecule
and enables it to react in specific ways
which determines its chemical properties.
Functional groups are important for three
reasons:
i. A basic by which organic compounds are

divided into different classes.
ii. A basic for naming organic compounds
iii. A particular functional group will always
undergo similar types of chemical
reactions.
Homologous Series
is series of compounds where each member
differs from the next member by a constant
– CH2 unit
Members of the same homologous series
are called homologs.
Homologs Features
1. Obey a general formula:
Examples:
• Alkane: CnH2n+2
• Alkene: CnH2n
• Alcohol : CnH2n+1OH
2. Differ from the successive homolog by a CH2

unit
3. Show a gradual change in the physical properties
4. Have same functional group
5. Have similar chemical properties
6. Can be prepared by similar general methods
Classification of organic compound
Functional Group
Class of Example
Compound
Structure Name
Alkane CH3-CH3
carbon-carbon
Alkene -C=C- double bond CH3CH=CH2
carbon-carbon
Alkyne -C C- triple bond CH3C CCH3
Aromatic Benzene ring -CH3
Haloalkane X (F, Cl, Br, I) Halogen CH3Cl
Alcohol -OH Hydroxyl CH3-OH
Phenol -OH Hydroxyl -OH
Ether -C-O-C- Alkoxide CH3-O-CH3

-C=O CH3-C=O
Aldehyde H Carbonyl H
R-C=O CH3-C=O
Ketone R Carbonyl CH3
Carboxylic -C=O CH3-C=O

acid OH Carboxyl OH
-C-O-C- CH3-C=O
Ester O Carboalkoxy OCH3
-C=O CH3-C=O
Acyl chloride Cl Cl
O O O O
Anhydride -C-O-C- CH3C-O-CCH3
Amide -C=O Carboxamide CH3-C=O

N- NH2
Amine -NH2 Amino CH3-NH2
Nitrile -C N Cyano group CH3C N

Exercises:
1. Identify the functional group in the following

molecules
a)(CH3)3CCH2CH=CH2
b)(CH3)3CCH=CHCH2-OH
c) O O O
C OH C O C CH3
CH3 CH2 OH CH2 O

CH3 C C C CH C NH2
NH2 CH C O CH3
CH2 O
12.4 Isomerism
Learning Outcomes:
able to :
Define isomerism.
Explain constitutional isomerism.
chain isomers
positional isomers
functional group isomer
Isomerism
Structural/
Stereoisomerism
Constitutional Isomerism
Functional Group diastreomer enantiomer

Chain Positional
Isomerism Isomerism Isomerism
cis-trans other
isomerism diastereomers
Isomerism
is the existence of different compounds with
the same molecular formula but different
structural formulae.
Different structural formula that have the same

molecular formula are called isomers.
1) Constitutional isomers (Structural isomers)
• are isomers with the same molecular formula
but differ in the order of attachment of atoms.
2) Stereoisomers
• are isomers with the same molecular formula
but different arrangement of atoms in space
Constitutional isomerism
Isomerism resulting from different order of
attachment of atoms.
• Three types
a) Chain/skeletal isomerism
b) Positional isomerism
c) Functional group isomerism
a) Chain/skeletal isomerism
The isomers differ in the carbon skeleton
(different carbon chain).
They possess the same functional group and
belong to the same homologous series.
Example:
C5H12
CH3CH2CH2CH2CH3
CH3
CH3CHCH2CH3 CH3CCH3
CH3 CH3
2)Positional isomerism
These isomers have a substituent group/ functional
group in different positions.
Examples
• C3H7Cl
CH3CH2CH2Cl
1-chloropropane
CH3CHCH3
Cl
2-chloropropane
C4H8 CH2=CHCH2CH3 CH3CH=CHCH3
1-butene 2-butene
C8H10
CH3 CH3
CH3
CH3
CH3
CH3
1,2-dimethylbenzene 1,3-dimethylbenzene
1,4-dimethylbenzene
C6H13N
NH2
CH3 CH3
H2N
CH3
CH2NH2
NH2
3)Functional group isomerism
These isomers have different functional groups and
belong to different homologous series with the same
general formula.
Different classes of compounds that exhibit
functional group isomerism :-
General formula Classes of compounds
CnH2n+2O ; n > 1 alcohol and ether
CnH2nO ; n ≥ 3 aldehyde and ketone
CnH2nO2 ; n ≥ 2 carboxylic acid and ester
CnH2n ; n ≥ 3 alkene and cycloalkane

Examples
C2H6O CH3CH2OH CH3OCH3
ethanol dimethyl ether
C3H6O CH3CCH3 CH3CH2CH
O O
propanone propanal
C3H6O2 CH3CH2COH CH3COCH3
O O
propanoic acid methyl ethanoate
Exercise:
1. State how many are isomers with the following molecular

formulae, identify the type of isomerism and draw the
structural formula of the isomers.
a) C5H10
b) C5H10O2
c) CH3CH=C(Cl)CH3
d) C4H6Cl2
e) CH3CH2CH(OH)CH(Br)CH2CH3
Lecture 5
12.4 Isomerism
Learning Outcomes:
be able to :
• Define stereoisomerism.
• Describe cis-trans isomerism due to
restricted rotation about C=C bond and CC
bond in cyclic compounds
• Identify cis-trans isomerism of a given
structural formula.
Stereoisomerism / optical isomerism :
Isomerism that resulting from different
spatial arrangement of atoms
in molecules.
Two subdivisions of stereoisomers:
i) Enantiomers (mirror image)
ii) Diastereomers (non-mirror image)
Diastereomer
Cis-Trans Isomerism
 The requirements for geometric isomerism
:
i) restricted rotation about a C=C,double
bond in alkenes, or a C-C single bond
in cyclic compounds.
ii) each carbon atom of a site of restricted
rotation has two different groups
attached to it.
Examples
H H3C
CH3 CH3
C C C C
H3 C H
H H
trans-2-butene cis-2-butene
H H
CH3 H
H CH3
CH 3 CH 3
cis-1,2-dimethylcyclohexane
trans-1,2-dimethylcyclohexane
If one of the doubly bonded carbons has 2 identical
groups, geometric isomerism is not possible.
Example
H3C
CH3
C C
H3C
H
No cis – trans isomer
Lecture 6
12.4
Learning Outcomes:
Isomerism
At the end of the lesson the students should be able to
:
• Identify cis-trans isomerism of a given structural
formula.
• Define chirality centre and enantiomers.
• Identify chirality centre in a molecule.
• Explain optical activity of a compound.
• Draw a pair of enantiomers using 3-dimensional
formula.
• Define racemate.
• State the applications of chiral compounds in daily
life.
Enantiomer
Optical Isomerism
• Optically active compounds have the ability to
rotate plane-polarized light to the right
(dextrorotary) and to the left (levorotary)
• The angle of rotation can be measured with an
instrument called polarimeter.
Polarimeter
The requirements for optical isomerism :-
i) molecule contains a chiral carbon or chirality centre
or stereogenic centre (a sp3-hybridized carbon atom
with 4 different groups attached to it)
P
PQRS
C* *designates chiral centre
Q S
R
ii) molecule is not superimposable with its mirror
image.
Enantiomers
 a pair of mirror-image that are not superimposable.
Example:-
i) 2-butanol ,
CH3CHCH2CH3
OH
CH2CH3 CH2CH3
C* C
H3C H CH3
H
OH OH
enantiomers
ii) 2-hydroxypropanoic acid, CH3CHCOOH
OH
COOH COOH
H OH HO H
CH3 CH3
enantiomers
12.4.9 Racemate
A racemic mixture or racemate is an
equimolar mixture of enantiomers which is
optically inactive because the two components
rotate plane-polarized light equally (same
degree of rotation) but in opposite directions.
Hence it does not give a net rotation of plane-
polarized light.
Applications of chiral compounds in
daily life.
e.g:
 () Dopa is used for treatment of Parkinson’s

disease but (+) dopa is toxic to human.
 (S)-Ibuprofen the popular analgesic(the active
ingredient in motrin, advil, and many other
nonaspirin analgesics)
REACTIONS OF ORGANIC
COMPOUNDS
Lecture 7
12.5 Reactions of Organic Compounds
Learning Outcomes:
be able to :
Explain covalent bond cleavage:
homolytic
heterolytic
Types of Covalent Bond Cleavage/Fission
 All chemical reactions involved bond

breaking and bond making.
 Two types of covalent bond cleavage :-

 Homolytic cleavage
 Heterolytic cleavage
a) Homolytic Cleavage
Occurs in a non-polar bond involving two

atoms of similar electronegativity.
A single bond breaks symmetrically into

two equal parts, leaving each atom with one
unpaired electron.
Formed free radicals.

Example:
X : X
X + X
free radicals
X X
b) Heterolytic cleavage
• Occurs in a polar bond involving unequal sharing of

electron pair between two atoms of different
electronegativities.
• A single bond breaks unsymmetrically.
• Both the bonding electrons are transferred to the more

electronegative atom.
• Formed cation and anion.

A:- + B+
anion cation
A:B A is more
electronegative.
A+ + B:-
cation anion
B is more
electronegative.
Reaction Intermediates
• a) Carbocation
• b) Carbanion
• c) Free Radical
They are unstable and highly reactive.
a) Carbocation
Also called carbonium ion.

A very reactive species with a positive
charge on a carbon atom.
Carbocation is formed in heterolytic
cleavage.
Example :
 
(CH3)3C — Cl (CH3)3C+ + Cl-
carbocation anion
Chlorine is more electronegative than carbon and the

C—Cl bond is polar.
The C—Cl bond breaks heterolitically and both the

bonding electrons are transferred to chlorine atom to
form anion and carbocation.
b) Carbanion
 is an anion counterpart
 a species with a negative charge on a carbon
atom.
 Carbanion is formed in heterolytic cleavage.
example:
 
• (CH3)3C — Li (CH3)3C- +
Li+ carbanion
kation
b) Free Radical
A very reactive species with an unpaired electron.
Formed in homolytic cleavage.
Examples:
i)
free radicals
Cl
– Cl uv Cl● + Cl ●
ii)
C C ●C + ●C
iii)
H3C H H3C ● + ●H
Lecture 7
Learning Outcomes:
able to:
 State the relative stabilities of primary, secondary
and tertiary free radicals, carbocations and
carbanions.
 Explain the inductive effect of alkyl group
towards the stability of carbocations and
carbanions.
 Define electrophile and nucleophile.
Relative Stabilities of Carbocations,
Carbanions and Free Radicals
Carbocation, carbanion and free radical

can be classified into:
 Primary
 Secondary
 Tertiary
Carbocation Stability
The alkyl groups (electron-releasing group)

stabilise the positive charge on the
carbocation.
The stability of carbocation increases with the

number of alkyl groups present.
Carbocation Stability:
H H R R
H C H < H C R <H C R < R C R
+ + + +
Methyl Primary Secondary Tertiary
cation 10 20 30
Increasing stability
Carbanion Stability
o Alkyl group and other electron-donating

groups destabilise carbanions.
o Electron withdrawing group (e.g: halogen)

stabilise carbanions through the inductive
withdrawal of electron density
Carbanion Stability:
H H R R
H C H < H C R < H C R < R C R
- - - -
Methyl Primary Secondary Tertiary
anion 10 20 30
Free-radical stability
The stability of free radical increases as

more alkyl groups are attached to the carbon
atom with unpaired electron.
Free Radical Stability :
H R
H R
H C
. H < H C
. R < H C
. R <R C
. R
methyl Primary Secondary Tertiary
radical 10 20 30
Reagents and sites of organic
reactions
A) Electrophile
 Means ‘electron loving’.
 An electron-deficient species and accepting
electron from an attacking nucleophile.
 Can be either neutral or positively charged
Examples of electrophiles :
• cations such as H+, H3O+, NO2+ etc.
• carbocations.
• Lewis acids such as AlCl3, FeCl3, BF3 etc.
• oxidizing agents such as Cl2, Br2 and etc.
electrophilic sites are molecules with low
electron density around a polar bond
Examples:
i) ii)
+ - + -
-C = O (carbonyl) ; -C – X (haloalkanes)
iii)
+ -
-C – OH (hydroxy compounds)
b) Nucleophile
means ‘nucleus loving’
An electron-rich species and electron-pair
donor.
A nucleophile can be either neutral or
negatively charged.
Examples of nucleophiles :
 anions such as OH-, RO-, Cl-, CN- etc.
 carbanions( species with a negative charge on

carbon atoms ).
Lecture 7
Learning Outcomes:
be able to explain the main types of organic
reactions:
• addition: electrophilic and nucleophilic
• substitution: electrophilic, nucleophilic and free
radical
• elimination
• rearrangement
4 Types of Organic Reactions
 Addition
 Substitution
 Elimination
 Rearrangement
I) Addition Reaction
 A reaction in which atoms or groups add to

adjacent atoms of a multiple bond.
 Two types of addition :-
a) Electrophilic Addition
b) Nucleophilic Addition
a)Electrophilic Addition
• Initiated by an electrophile accepting electron
from an attacking nucleophile.
• Typical reaction of unsaturated compounds such
as alkenes and alkynes.
Example :
CCl4
CH3CH=CH2 + Br2 Room
CH3CHBrCH2Br
temperature
electrophile
b) Nucleophilic Addition
Initiated by a nucleophile, which attacks an

electrophilic site of a molecule.
• Typical reaction of carbonyl compounds.
O CN

CH3 C CH3 + HCN CH3 C CH3

OH
II) Substitution Reaction
 A reaction in which an atom or group in a
molecule is replaced by another atom or group.
 Three types of substitution :-

a) free radical substitution.
b) electrophilic substitution.
c) nuclephilic substitution.
a) Free-radical Substitution
 Substitution which involves free radicals as
intermediate species.
Example :
CH3CH3 + Cl2 uv light CH3CH2Cl + HCl

b) Electrophilic Substitution
Typical reaction of aromatic compounds.

• The aromatic nucleus has high electron density,
thus it is nucleophilic and is prone to
electrophilic attack.
Example:
Fe
catalyst
+ Br2 Br + HBr
electrophile
c) Nucleophilic Substitution
Typical reaction of saturated organic compounds
bearing polar bond as functional group, such as
haloalkane with alcohol.
Example :
 
Δ
CH3CH2Br + OH-(aq) CH3CH2OH + Br-(aq)
nucleophile
•
III) Elimination Reaction
An atoms or groups are removed from adjacent
carbon atoms of a molecule to form a multiple
bond (double or triple bond).
• Results in the formation of unsaturated molecules.
• Example :
CH3CH2OH conc. H2SO4 CH2= CH2 + H2O


IV) Rearrangement Reaction
 A reaction in which atoms or groups in a molecule

change position.
 Occurs when a single reactant reorganizes the bonds and
atoms.
Example : H
tautomerisme
H C C R H C C R
H OH H O
Exercises
1. Explain how the free radicals are formed

in homolytic cleavage.
2. Write an equation for the bromine-

bromine bond cleavage in the bromination
of methane. State the type of bond
cleavage.
3. Which would you expect to be the
most stable free radical ?
CH2CH3 , (CH3)2 CH , CH3 , 

CH3
Chapter 12.0
HYDROCARBONS
12.1 : ALKANES
Hydrocarbon
are compounds which
contain only carbon and
hydrogen atoms.
HIDROCARBONS
AROMATIC
ALIPHATIC
(contain one or more benzene ring)
ALKANES ALKENES
(saturated) (unsaturated) ALKYNES
contain only contain (unsaturated)
single bond C=C contain
C≡C
CYCLO-ALKANES (saturated) CYCLO-ALKENES

Alkanes which C atoms are (unsaturated)
join in rings
• Saturated hydrocarbons
- compound with C-C
- Example : alkanes and cycloalkanes
– Contain the maximum number of hydrogen

atoms that the carbon compound can
possess.
• Unsaturated hydrocarbons
-compounds with multiple bonds
-Example : alkenes, cycloalkenes, alkynes
and aromatic hydrocarbons
– They posses fewer than the maximum

number of hydrogen atoms.
ALKANES
Alkanes are known as saturated hydrocarbon

which contain only single covalent bonds.
General formula for straight chain of alkanes is

CnH2n+2
where n ≥ 1
General formula for cycloalkanes is CnH2n
where n ≥ 3
Each carbon atom in alkanes is
- sp3 hybridised
- tetrahedral with four sigma bond (formed
by the four sp3 hybrid orbitals.)
- all bond angles are close to 109.5o
Alkanes IUPAC names have the –ane

suffix.
The First Ten Unbranched Alkanes
Molecular Structural formula No .of C Name
formula atoms
CH4 CH4 1 Methane
C2H6 CH3—CH3 2 Ethane
C3H8 CH3—CH2—CH3 3 Propane
C4H10 CH3—(CH2)2—CH3 4 Butane
C5H12 CH3—(CH2)3—CH3 5 Pentane
C6H14 CH3—(CH2)4—CH3 6 Hexane
C7H16 CH3—(CH2)5—CH3 7 Heptane
C8H18 CH3—(CH2)6—CH3 8 Octane
C9H20 CH3—(CH2)7—CH3 9 Nonane
C10H22 CH3—(CH2)8—CH3 10 Decane
• Starting from C4H10 onwards, the alkanes
show the phenomenon of chain isomerism.
• They can exist as linear or branched

alkanes.
Example
C4H10
2-
isobutane
CH3(CH2)2CH3 CH3CH(CH3)2
C5H12
IUPAC NOMENCLATURE
 IUPAC – International Union of Pure

and Applied Chemistry
 Branched - chain alkanes are named

according to the following rules:
Choose the longest continuous chain
of carbon atoms; this chain determines
the parent name for alkanes.
Examples:
CH3CH2CH2CH2CHCH3
|
CH3
Parent name: hexane

CH3CH2CH2CH2CHCH3
CH2
CH3
Parent name : heptane

Number the longest chain beginning
with the end of the chain nearer the
substituent.
Example:
6 5 4 3 2 1
CH3CH2CH2CH2CHCH3
CH3 substituent
7 6 5 4 3
CH3CH2CH2CH2CH CH3 substituent
|
2 CH2
|
1 CH3
Use rule number 2 to locate the position
of the substituent.
 The position and the name of the

substituent must be written in front of
the parent chain.
Examples:
6 5 4 3 2 1
CH3CH2CH2CH2CHCH3
Substituent
CH3 -methyl at C-2
2-methylhexane
Substituent
7 6 5 4 3 -methyl at C-3
CH3CH2CH2CH2CH CH3
|
2 CH
2
|
1 CH
3
3-methylheptane
Some Common Substituent Groups
Alkane name substituent
methane methyl CH3
ethane ethyl CH2CH3
propane propyl CH2CH2CH3

CHCH3
isopropyl
CH3
butane butyl CH2CH2CH2CH3
isobutyl CH2CHCH3
CH3
sec-butyl CHCH2CH3
CH3
tert-butyl CH3
CCH3
CH3
neopentyl CH3
CH2CCH3
CH3
cyclopropyl
cyclobutyl
phenyl
C6H5 or
benzyl
CH2
name substituent
Bromo -Br
Chloro -Cl
Flouro -F
Iodo -I
Hydroxyl -OH
Amino -NH2
Cyano -CN
Nitro -NO2
If two or more substituents are present, give
each substituent a number corresponding
to its location on the longest chain.
 the substituent should be listed

alphabetically.
 In alphabetizing, the prefixes di, tri, tetra,

sec-, tert- are ignored except iso and neo.
Example:
1 2 3 4 5 6
CH3CHCH2CHCH2CH3
| |
CH3 CH2
|
CH3
4-ethyl-2-methylhexane
If two substituents are present on the
same carbon atom, use that number twice
Example:
CH3
|3 4 5 6
CH3CH2CCH2CH2CH3
|
2 CH
2
|
1 CH
3
3-ethyl-3-methylhexane
If two or more identical substituents are
present, use prefixes di-(2 identical
substituents),tri-(3 identical substituents),
tetra-(4 identical substituents).
Commas are used to separate numbers
from each other.
Example:
CH3CH―CH CH3 2,3-dimethylbutane
| |
CH3 CH3
If there are two chains of equal length as
the parent chain, choose the chain with
the greater number of substituents.
7 6 5 4 3 2 1
4 3 2 1
CH3CH2-CH CH CH CHCH3
| | | |
CH3 5 CH2 CH3 CH3
|
6
CH2
|
7
CH3
2,3,5-trimethyl-4-propylheptane
(four substituents)
4-sec-butyl-2,3-dimethylheptane
(three substituents)
If branching occurs at an equal distance from
either end of the longest chain, choose the
name that gives the lower number at the first
point of difference.
6 5 4 3 2 1
CH3CHCH2CH CHCH3
1 2 3 4 5 6
| | |
CH3 CH3 CH3
2,3,5-trimethylhexane
(NOT 2,4,5-trimethylhexane)
CYCLOALKANES
Cycloalkanes – alkanes which carbon atoms are joined
in rings.
Cycloalkanes are known as saturated hydrocarbon,

because it has the maximum number of bonded
hydrogen ( only has single bonds).
General formula:
CnH2n where n = 3, 4, 5, ……
NOMENCLATURE OF
CYCLOALKANES
Cycloalkanes with only one ring are named with

the prefix cyclo- to the names of the alkanes
(contain the same number of carbon atoms)
Examples: Monocyclic compounds
C3H6 cyclopropane
C4H8 cyclobutane
C5H10 cyclopentane
If only one substituent is present, it is not
necessary to designate its position.
Examples:
Chlorocyclopropane
Cl
CH3 Methylcyclohexane
If two substituents are present, number carbon
in the ring beginning with the substituent
according to the alphabetical order
and
number in the direction that gives the next
substituent the lowest number possible.
Examples:
CH3
3
2
4 CH2CH3
1
5 6
1-ethyl-2-methylcyclohexane
NOT
1-ethyl-6-methylcyclohexane
2
Cl 3 1
Cl
4 5
1,3-dichlorocyclopentane
(NOT 1,5-dichlorocyclopentane)
When three or more substituents are
present, begin at the carbon with
substituent that leads to the lowest set of
locants.
Locants
Example:
CH2CH3 chloro 1 4
2 3
1
3 2
4 ethyl 3 2
Cl 4 1 CH3
methyl 4 1
5 6
6 5
1-chloro-3-ethyl-4-methylcyclohexane
4- chloro-2-ethyl-1-methylcyclohexane
H3C CH2CH3
CH3
1-ethyl-1,3-dimethylcyclopentane
(NOT 3-ethyl-1,3-dimethylcyclopentane)
When a single ring system is attached
to a single chain with a greater number
of carbon atoms
or
when more than one ring system is
attached to a single chain, then it is
appropriate to name the compounds as
cycloalkylalkane.
Number of C at
linear chain
Number of C at ring
1 3
1,3-dicyclohexylpropane
Examples:
CH2CH2CH2CH2CH3
1-cyclobutylpentane
Physical properties of alkanes & cycloalkanes
Physical Boiling
state Point
Solubility
Physical state
 At room temperature (25oC) and atmospheric
pressure (1 atm), for unbranched alkanes,
C1 – C4 : gases
C5 – C17 : liquids
C18 - more : solids
Boiling points
 The boiling points of the straight alkanes show a
regular increase with increasing molecular
weight.
 Branching of the alkanes chain, lower the boiling
point.
Mr ↑ boiling point ↑
 C-H is non polar bond
 Intermolecular forces exist – London
dispersion
 The London dispersion forces increase :
 As molecular weight increases,
 Molecular size increases
 Molecular surface area increase
 Therefore, more energy is required to

separate molecules from one another
 Result - a higher boiling point.
Mr ↑ boiling point ↑
 Chain branching :
 makes a molecule more compact
 Surface area reduces
 The strength of the London dispersion forces

reduce
 Lower boiling points.
Isomeric Alkanes
Have different boiling point due to branching
Pentane 2-methylbutane 2,2-

dimethylpropane
CH3CH2CH2CH2CH3 CH3CHCH2CH CH3

CH3 CH3CCH3
CH3
28.5oC 9oC
37oC
For example, butane and 2-methylpropane both
have a molecular formula C4H10, but the atoms
are arranged differently
CH3CH2CH2CH3 butane
CH3CH2CH2CH3
CH3CHCH3 CH3CHCH3
2-methylpropane
CH3 CH3
In butane the C atoms are arranged in a
single chain, but 2-methylpropane is a
shorter chain with a branch
Name Molecular structure
Boiling point
Butane has a higher boiling point because the dispersion

forces are greater.
The molecules are longer (and so set up bigger temporary
dipoles) and can lie closer together than the shorter, fatter
2-methylpropane molecules.
Cycloalkanes
The boiling points of cycloalkanes are 10oC
to 15oC higher than the corresponding straight
chain alkanes.
Cycloalkane Boiling point alkane Boiling
point
Cyclobutane 13oC Butane -0.5oC
Cyclopentane 49oC Pentane 36..3oC

Solubility
 Alkanes – less dense than water
 Alkanes and cycloalkanes are almost totally

insoluble in water
 They are non-polar molecule

 Unable to form hydrogen bond with H2O
 Liquid alkanes and cycloalkanes are soluble in
one another, and they generally dissolve in non-
polar solvents.
 Good solvents for alkanes are benzene, carbon

tetrachloride, chloroform, and other
hydrocarbons.
Nature sources of alkanes;
Natural gas
oil
Natural gas contains primarily methane

and ethane, with some propane and
butane
Oil is a mixture of liquid alkanes and

other hydrocarbons
CHEMICAL REACTION OF
ALKANES
Non-reactivity of alkanes
 Alkanes are generally inert towards many chemical

reagents (bases, acids, dehydrating agents and aqueous
oxidizing agents)
 C and H has nearly the same electronegativity, the C-H

bonds of alkanes are only slightly polarised (non polar)
Reaction of alkanes
 Combustion
 Halogenation
Combustion of alkanes
 Alkanes burnt in air ( oxygen ) to give carbon
dioxide gas, water and heat.
y y
CxHy+ x  O2 → x CO2 + H2O
4 2
+ Heat
Examples:
Combustion of alkane in excess oxygen
C4H8+ 3O2 → 4CO2 + 4H2O

+ Heat
Examples:
Combustion of alkane in limited oxygen
C4H8+ 4O2 → 4CO + 4H2O

+ Heat
 Alkanes are unreactive towards polar or ionic
reagents but can react with non-polar
reagents such as oxygen and bromine.
 The low reactivity of alkanes toward many
reagents explain why alkanes were originally
called paraffins.
(Latin : parum affinis= low affinity).
Halogenation: a free radical
substitution reaction
 Alkanes react with halogen (chlorine & bromine) to
produce haloalkanes in the presence of light or
temperature >> 100 oC.
R–H + X2 hv R–X + HX

 With methane, the reaction produces a mixture of
halomethane and a hydrogen halide.
Examples:
hv CH3Cl + CH2Cl2
i. CH4 + Cl2 
+ CHCl3 + CCl4
+ HCl
hv
ii. CH3CH3 + Cl2  CH3CH2Cl + HCl
CH3 CH3
| |
hv CH CCH Cl + HCl
 3 2
iii. CH3 CCH3 + Cl2
| |
CH3 CH3
(ii) & (iii): 1 product only because all the
hydrogen atoms are identical
CH3CH2CH2Br
hv
iv. CH3CH2CH3 + Br2  ( minor)
+ CH3CHCH3
|
Br
( major)
+ HBr
Reaction mechanism
CH4 + Cl2 hv CH3Cl + HCl


i. Chain initiation step
hv
Cl – Cl  2Cl•
ii. Chain propagation steps
H
H-C H + •Cl  •CH3 + HCl
H
3HC• + Cl Cl_  CH3Cl + Cl•
iii. Chain termination step.
•Cl + •Cl  Cl2
•Cl + •CH3  CH3Cl
•CH3 + •CH3  CH3CH3

Example
 The bromination of 2-methylbutane yields a
mixture of isomers.
CH2Br CH3 CH3
CH3 C CH2 CH3 CH3 C CHBr CH3 CH3 C CH2 CH3
H H Br
Increasing % yield
Exercise
 Chlorination reaction of certain alkanes can be
used for laboratory preparations, for example in
the preparation of chlorocyclopentane from
cyclopentane. Give the mechanism for the
reaction.
12.2 ALKENES
 General formula CnH2n , n  2.
 Functional group  double bond C=C
 Unsaturated hydrocarbon
 Each carbon atom ( C=C ) is sp2 hybridized.
 Restricted rotation of carbon-carbon double

bond causes cis-trans isomerism
IUPAC Nomenclature
Step 1
Determine the parent name by
selecting the longest chain that
contains the double bond and change
the ending ‘-ane’ in alkane to ‘-ene’.
Step 2
When the chain contains more than

three carbon atoms, a number is need
to indicate the location of the double
bond.
The chain is numbered starting from
the end closest to the double bond..
1 2 3 4 5 6 7 8
CH3CH2CH CH CH2CH2CH2CH3
3-octene (not 5-octene)

Step 3
Indicate the position of the substituent by the
number of the carbon atoms to which they
are attached.
CH3
H3 C C CH CH3
1 2 3 4
2-methyl-2-butene
(not 3-methyl-2-butene)
1 2 3 4 5 6
H3C C CH CH2 CH CH3
CH3 CH3
2,5-dimethyl-2-hexene
(not 2,5-dimethyl-4-hexene)
Step 4
The ending of the alkenes with more than

one double bond should be change from -
ene to
 diene – if there are two double bonds

 triene – if there are three double bonds
1 2 3 4
H2C CH CH CH2
1,3-butadiene
1 2 3 4 5 6 7
H2C CHCH CHCH CHCH3
1,3,5-heptatriene
MORE
Step 5
In cycloalkenes :
Number the carbon atoms with a double
bond as 1 and 2, in the direction that gives
the substituent encountered first with a
small number.
CH3
1
5 2
4 3
1-methylcyclopentene
(not 2-methylcyclopentene)
1
6 2
5 3
CH3 CH3
4
3,5-dimethylcyclohexene
(not 4,6-dimethylcyclohexene)
MORE
Step 6
Two frequently encountered alkenyl

groups are vinyl group and allyl group.
RCH=CHR RCH=CH-
-H
alkene alkenyl
CH2=CH- CH2=CHCH2-
vinyl group allyl group
Step 7
When two identical groups are attached:

a) on the same side of the double bond, the
compound is cis
b) on the opposite sides of double bond, it
is trans.
cis / trans
Cl Cl Cl H
C C C C
H H H Cl
cis-1,2-dichloroethene trans-1,2-dichloroethene
Give IUPAC names for the following alkenes
1)
2) CH3
CH3
3)
4) CH2CH3
CH3
5) CH3CH=CHCH2C(CH3)2CH3
Preparation of alkenes
a) Dehydration of alcohols
b) Dehydrohalogenation of alkyl halide
Dehydration of alcohols
 Alcohols react with strong acids in the
presence of heat to form alkenes and water.
H2SO4 (conc.)
C C

C C + H2 O
H OH
 Concentrated sulphuric acid (H2SO4) or
phosphoric acid (H3PO4) : as acidic catalysts
and dehydrating agents.
 The major product is the most stable alkene,

which has greater number of alkyl group
attach to C=C is follow Saytzeff’s rule.
Saytzeff’s Rule
An elimination usually gives the most

stable alkene product, commonly the
most highly substituted alkene.
Examples
H2SO4 (conc.)
(1) CH3CH2OH
H2C CH2

+ H2O
H2SO4 (conc.)
(2) H3C CH CH3 H2C CH CH3

OH + H2O
Mechanism for the
dehydration of alcohol
H3C CH CH2CH3 H SO (conc.) CH 3 CH=CHCH 3
2 4
OH  (major product)
+ CH 2 =CHCH 2 CH 3
(minor product)
+ H 2O
Step 1:
Protonation of alcohol.
H H
H3C C CH2CH3 + +
:O H
:OH H
..
H H
H3C C CH 2 CH 3 + :O H
+ ..
: OH
H
Step 2:
Formation of carbocation
H H
H 3 C C CH 2 CH 3 +
H3 C C CH2 CH3
+:OH
carbocation
H
H
+ :O H
..
Step 3:
Formation of alkenes
H H H H
+
H C C C CH3 :O H
b + ..
H H
a
Root a : major product
Root b : minor product
H H H
C C + +
: O H
H3C CH 3 H
stable alkenes
+ CH 2 =CHCH 2 CH 3
(minor product)
Rearrangement During Dehydration
of Alcohol
Example 1:
CH3 H
H2 SO4 (conc.)
H3C C C CH3

CH3OH
CH3
H 3C C C CH3
CH3
(major product)
CH
3
+ H C C CH CH
2 3
CH
3
(minor product)
Step 1 and Step 2 are similar to
the previous example.
Step 3:
 Now the rearrangement occurs.
 The less stable, secondary carbocation

rearrange to form more stable tertiary
carbocation.
CH CH
3 3
+ +
H C C C CH H C C C CH
3 3 3 3
CH H rearrangement CH H
3 3
2o carbocation 3o carbocation
(less stable) (more stable)
 The rearrangement occurs through the
migration of an alkyl group (methyl) from
the carbon atom adjacent to the one with the
positive charge.
 Because a group migrates from the one

carbon to the next, this kind of
rearrangement is often called a 1,2 shift.
(a) CH
3
HC C CH CH
(a) 2 3
CH
3
H + CH3 H
(minor product)
H C C C CH3 + :O H
.. less stable alkene
H CH H
3
CH
3
(b) HC C C CH
3 3
CH
3
(b) (major product)
more stable alkene
The
The final
final step
step can
can occur
occur in
in two
two ways:
ways:
Path (a): leads to less stable,

disubstituted alkene and produces
the minor product of the reaction.
Path (b): leads to highly stable
tetrasubstituted alkene and produces
the major product according to the
Saytzeff’s rule.
Try this!
CH H CH
3 H2SO4 (conc) 3
H C C C CH H C C CH CH
3 3  3 3
H OH (major product)
CH
3
+ H C C CH CH
2 2 3
(minor product)
(2) Dehydrohalogenation of Alkyl Halides
 The elimination of a hydrogen and a halogen
from an alkyl halide to form an alkene.
alcohol
C C + KOH
reflux
C C
H X
+ HX
 Saytzeff’s rule is used to determine the major
product
Examples:
(1)
Cl
alcohol
H3C CH CH2CH2CH3 + KOH
reflux
H3C CH CH CH2CH3 + H2C CH CH2CH2CH3

(major product) (minor product)
(2)
alcohol
H3C CH CH3 + KOH
reflux
H2C CH CH3
Br
(3)
Br
CH + alcohol CH
KOH
CH reflux CH
3 3
(minor product)
CH2
+
CH3
(major product)
(4)
CH3 H
CH3 C C CH3 + KOH alcohol
CH3 Cl reflux
CH3 H CH3
CH2 C C CH3 CH3 C C CH3
CH3 CH3
2,3-dimethyl-1-butene 2,3-dimethyl-2-butene
(minor product) ( major product)
2 alkyl groups 4 alkyl groups
Chemical Reaction of Alkenes
Comparison of The Reactivity Between
Alkanes and Alkenes
 Alkenes are more reactive compared to alkanes.
 Alkanes have carbon-carbon single bonds (σ bonds)
while alkenes have carbon-carbon double bonds (π
bonds).
 The double bond is a site of high electron density
(nucleophilic).
 Therefore most alkenes reactions are electrophilic
additions.
Electrophilic Additions
Mechanism
H H H
slow +
C C + X Y H C C H
H H X H
-
+ Y
H H H
+ - fast
H C C H + Y H C C H
X H X Y
Example:
i.
H3C CH3
slow
C C + H Cl
H3C CH3
CH3CH3
+
H3C C C CH3 + -
Cl
H
CH3CH3
fast
H3C C C CH3 + Cl-
+
H
CH3CH3
H3C C C CH3
H Cl
Addition Reaction of Alkenes
(1) Hydrogenation
 The reaction of an alkene with hydrogen in the
presence of catalyst such as platinum, nickel and
palladium to form alkane.
Pt or Ni or Pd
C C + H2 C C
H H
Examples:
(1)
Pt /Ni / Pd
H3C C CH2 + H2 H3C CH CH3
CH3 CH3
Pt /Ni / Pd
(2) + H2
(2) Halogenation of Alkenes
(i) In inert solvent (CH2Cl2)

 Alkenes react rapidly with chlorine or bromine
in CH2Cl2 at room temperature to form vicinal
dihalides.
CH2Cl2
C C + X2 C C
X X
Example:
CH3
CH2Cl2
H3C C C CH3 + Cl 2
H
Cl Cl
H3C C C CH3
CH3H
 When bromine is used for this reaction, it can
serve as a test for the presence of carbon-carbon
double bonds.
 If bromine is added to alkene, the reddish

brown color of the bromine disappears almost
instantly as long as the alkene is present in
excess.
Unsaturation test
CH2Cl2
C C + Br2
room temperature
C C
Br Br
Observation: The reddish brown bromine decolourised
(3) Hydrohalogenation : Markovnikov’s rule
 Hydrogen halides (HI, HBr, HCl and HF) add to the
double bond of alkenes to form haloalkanes.
C C + HX C C
H X
 The addition of HX to an unsymmetrical alkenes,
follows Markovnikov’s rule.
 Markovnikov’s Rule:
 Inthe addition of HX to an alkenes, the

hydrogen atom adds to the carbon atom of
the double bond that already has the greater
i. The addition of HBr to propene, could
conceivably lead to either 1-bromopropane or
2-bromopropane.
The main product, however, is 2-
bromopropane
H H
H2C CH CH3 + HBr H C C CH3
H Br
ii. When 2-methylpropane reacts with HBr, the
main product is tert-butyl bromide, not
isobutyl bromide.
Br
H3C C CH2 + HBr H3C C CH3
CH3 CH3
 The addition of HX to an unsymmetrical

alkenes, yield the main product according to
the Markovnikov’s rule.
Mechanism
CH 3
+
slow
CH 3 H Br
C CH CH 3
CH3
CH3 C CH CH3 + Br -
+
30 Carbocation
CH3
-
fast
CH3 C CH CH3 + Br
+
CH3
CH3 C CH CH3
Br H
(4) Addition of HBr to Alkenes in The
Presence of Peroxides
(Anti Markovnikov’s rule)
 When alkenes are treated with HBr in the presence
of peroxides, ROOR (eg: H2O2) the addition
occurs in an anti-Markovnikov manner
 The hydrogen atom of HBr attached to the doubly

bonded carbon with fewer hydrogen atoms.
Example:
ROOR
H2C CH CH3 + HBr
Br CH2CH2CH3
Complete the following reactions:
(1)
H2 O 2
H3C CH2C CH2 + HBr
CH3
(2)
CH2 H2 O2
+ HBr
(ii) In aqueous (Halohydrin Formation)
 If the halogenation of an alkene is carried out in

aqueous solution, the major product of the
overall reaction is a haloalcohol called a
halohydrin.
C C + X2 + H2O C C
X OH
X2 = Cl or Br halohydrin
Example:
H H H H
C C + Br2 + H2O H C C H
H H Br OH
2-bromobutanol
Unsaturated test
Observation : the reddish brown bromine decolourised
 If the alkenes is unsymmetrical, the halogen
ends up on the carbon atom with the greater
Example:
H 3C C CH2 + Br 2 + H2O
CH3
CH3H
H3 C C C H
OH Br
1-bromo-2-methyl-2-propane
Complete the following reaction:
+ Br2 + H2O
CH3
(5) Hydration of Alkene
 The acid-catalyzed addition of water to the
double bond of an alkene (hydration of an
alkene) is a method for the preparation of low
molecular weight alcohols.
 The acid most commonly used to catalyse the

hydration of alkenes are dilute solution of
sulphuric acid and phosphoric acid.
 The addition of water to the double bond
follows Markovnikov’s rule.
+
H3O
C C + H2O C C
H OH
Example:
+
H3 O
H3C C CH2 + H2O
CH3
OH
H3C C CH3
CH3
Complete the following reactions:
(1)
+
CH2 H3 O
+ H2 O
(2)
+
H3O
H2C CH CH3 + H2O
Mechanism
STEP 1
CH3 H
..
CH3 C CH CH3 + H O+ H
CH3
CH3 C CH CH3
+
H
STEP 2
CH3
CH3 C CH CH3 + H2O
..
+ ..
H
CH3
CH3 C CH CH3
H O+ H
..
H
STEP 3
CH3
CH3 C CH CH3
H O+ H
..
CH3
H CH3 C CH CH3 + H3O+

H2O ..
..
..
OH H
(6) Addition of Sulphuric Acid to
Alkenes
 Alkenes dissolve in concentrated sulphuric acid
to form alkyl hydrogen sulphates.
 Alkyl hydrogen sulphates can be easily
hydrolysed to alcohols by heating them with
water.
 The overall result of the addition of sulphuric
acid to alkenes followed by hydrolysis is the
Markovnikov addition of -H and -OH.
CH3CH3
H3 C CH3
conc. H2 SO 4 H3 C C C CH3
C C
H3 C CH3 H OSO 3 H
alkyl hydrogen sulphate
CH3CH3
H2O H3 C C C CH3
heat
H OH
 Example:
OSO3H
conc.H2SO4
H2C CH CH 3 H3C CH CH2
H
OH
H2O
H3 C CH CH2
heat
H
7 ) Oxidation of Alkenes
 Alkenes undergo a number of reactions in
which the C=C is oxidized
KMnO4 ozonolysis
 basic,cold,dilute
 acidic,hot,concentrated
i) With cold and dilute potassium
permanganate, KMnO4
 Potassium permanganate in alkaline solution

can be used to oxidise alkenes to 1,2-diols
(glycols).
-
OH ,cold
C C + KMnO4
(purple)
C C + MnO2
OH OH (brown precipitate)
Observation: Purple colour of KMnO4 decolourised and

brown precipitate formed.
 This reaction is called Baeyer’s test.
 It is a test for the presence of C=C where the

purple colour of the KMnO4 decolourised, and
brown precipitate of MnO2 is formed.
Example:
-
OH ,H2 O
H2C CH2 + KMnO4
cold
H H
H C C H + MnO2
OH OH
ii) With hot potassium permanganate
solutions to alkenes
 When oxidation of the alkene is carried out in

acidic solution of KMnO4, cleavage of the double
bond occurs and carbonyl-containing products are
obtained.
If the double bond is tetrasubstituted,
tetrasubstituted the
two carbonyl-containing products are
ketones
CH3 -
(i) OH ,heat
H3C C C CH3 + KMnO4
(ii) H3O
+
CH3
O O
H3C
C
CH3
+ H3C
C
CH3
 If a hydrogen is present at double bond, one
of the carbonyl-containing products is a
carboxylic acid;
 If two hydrogens are present on one carbon,

CO2 is formed.
2)
-
(i) OH ,heat
H2C CH CH3 + KMnO4
(ii) H3O
+
HO
C
CH3
+ CO2 + H2 O
 The oxidative cleavage of alkenes can be
used to establish the location of the double
bond in an unknown alkene.
Example:
 An unknown alkene with the formula C7H14
undergoes oxidation with hot basic potasium
permanganate solution to form propanoic acid
and butanoic acid. What is the structure of this
alkene?
(i) OH-,heat
C7 H14 + KMnO4
(ii) H3 O
+
O O
H3C
CH2
C
OH
+ H3C
CH2 C
CH2 OH
Answer:
O O
H3C C CH2 C
CH2 OH H3C CH2 OH
propanoic acid butanoic acid
H H
H3C CH2C C CH2CH2CH3
3-heptene
Example
 An unknown alkene undergoes oxidation in hot
basic KMnO4 followed by acidific to give the
following product:
O O
CH3CCH2CH2CH2CH2C OH
Deduce the structural formula for the unknown

alkene.
iii) Ozonolysis of Alkenes
 A more widely used method for locating the

double bond of an alkene is the use of ozone
(O3).
 Ozone reacts vigorously with alkenes to form
unstable compounds called molozonides,
which rearrange spontaneously to form
compounds called ozonides.
O
C C
C C + O3
O O
ozonide
 Ozonides:
 very unstable compounds
 can easily explode violently
 they are not usually isolated but are

reduced directly by treatment with water
and in the presence of zinc and acid
(normally acetic acid) to give carbonyl
compounds (either aldehydes or ketones).
O H
+
H2 O,H
C C
+ Zn
R
O O
ozonide
H
C=O + O=C
R
Example:
CH3 (i) O3
+
H3C C CH CH3 (ii) Zn,H2O/H
CH3 CH3
H3C
C
O
+ H
C
O
Exercise
1. Write the structure of alkene that would
produce the following products when
treated with ozone followed by water, zinc
and acid
CH3COCH3 and CH3CH(CH3)CHO
Example
 Deduce the structural formula of an alkene
that gives the following compound when it
reacts with ozone in the presence of Zn / H+.
O=CH-CH2-CH2-CH(CH3)CH=O
2. Acid-catalyzed dehydration of neopentyl
alcohol, (CH3)3CCH2OH, yields 2-methyl-
2-butene as the major product. Outline a
mechanism showing all steps in its
formation.
Exercise
 Compounds A, B, C and D are isomers with the
molecular formula C4H8. A and B give a positive
Baeyer test, while C and D do not. A exists as
cis- and trans- isomers, while B does not have
geometrical isomers. C has only secondary
hydrogen, while D has primary, secondary and
tertiary hydrogen. Give the IUPAC names for A,
B, C, and D.
The origin of August Kekulé’s view of benzene structure:
“There I sat and wrote my

textbook, but things did not
go well; my mind was occupied
with other matters, I turned the
chair towards the fireplace and
began to doze.
“Once again the atoms danced
before my eyes. This time
smaller groups modestly
remained in the background.
My mental eye, sharpened by
repeated apparitions of similar
kind, now distinguished larger
units of various shapes.”
“Long rows, frequently joined

more densely; everything in
motion, twisting and turning
like snakes. And behold, what
was that? One of the snakes
caught hold of its own tail and
mockingly whirled around my
eyes.
“1 awoke, as if by lightening;
this time, too, I spent the rest of
the night working out the
consequences of this
hypothesis”
“Let us learn to dream, gentlemen,
then perhaps we shall find the truth”
AUGUST KEKULÉ
Edison, Einstein and many others have used the
subconscious mind to give them the insight and the
“know-how” to bring about their great achievements.
August Kekulé
“In variably, my device works
as I imagined it should.
In twenty years there has not been
single exception.”
NIKOLA TESLA
“Imagination is more important
than knowledge.”
ALBERT EINSTEIN
AROMATIC COMPOUNDS
Introduction to
14.1
aromatic Compounds
Arenes = aromatic compounds:

the word aromatic has nothing to do with odour.
KEYWORDS
aromatic Kekulé structure
ortho meta para

resonance structure
Friedel-Craft acylation
electrophilic substitution
oxidation of
activating and alkylbenzene
deactivating group
substitution of
ortho-para and meta director toluene
DISCOVERY OF BENZENE
1825 Michael Faraday

(British)
Isolated a pure compound of

boiling point 80oC
Empirical formula = CH
Named “bicarburet of hydrogen”

1834 Eilhard Mitscherlich (German)
Prepared benzene from benzoic acid

heat
C6H5CO2H + CaO  C6H6 + CaCO3
Molar mass = 78, molecular formula = C6H6
named “benzin”
benzene benzin benzoin
benjoin Luban Jawi

gum benzoin
(French) (Arabic)
1866 Friedrich August Kekulé (German)
Proposed a cyclic structure for benzene.
AROMATIC COMPOUNDS
In earlier time, compounds are called
aromatic because of their pleasant odours.
Benzene has strong

pleasant odour.
Today, we use the word aromatic to refer to

benzene and its structural relatives.
AROMATIC COMPOUNDS
Aromatic compound is a cyclic conjugated

molecule or ion that is stabilized by ∏ electron
delocalisation.
it is characterised by substitution reactions.

KEKULÉ’S STRUCTURE
 Kekule was the first to formulate a

reasonable representation of benzene
H
H C C H
C
or
C C
H C H
H
The Kekule structure suggests alternating double

and single carbon-carbon bonds
RESONANCE STRUCTURE
Benzene is actually a resonance hybrid of the
two Kekulé structures.
equivalent to
resonance hybrid
All C–C bond length equal = 139 pm
Shorter than typical C–C (148 pm)
Longer than typical C=C (134 pm)

The six  electrons completely delocalized around the ring
The circle represents the six
 electrons, distributed over
the six atoms of the ring!
All six C atoms and six p orbitals are equivalent

THE CRITERIA FOR AROMATICITY
4 structural criteria must be satisfied for

compound to be aromatic
Cyclic Planar
Conta
in par
numb ticula
e r of r
pl e t e ly electr ∏
Com ted on
nju g a  obe
co ys HÜ
Rule ckel’s
HÜckel’s Rule
* cyclic, planar and completely
conjugated compounds that
contain [4n+2] ∏ electron
(n=0,1,2…..) are said to be
aromatic
Erich HÜckel
(1896-1980)
 planar monocyclic rings with 2,6,10,14 and so forth

∏ electrons are aromatic
EXAMPLE OF AROMATIC COMPOUNDS
1. Aromatic compounds with a single ring
Benzene
aromatic
Benzene is aromatic because:
 contains 6∏ electrons
(obeys HÜckels Rule)
[4n+2] ∏ = [4(1) + 2]∏
 cyclic, planar and has double
= 6 ∏ electrons bond in the ring
2. Aromatic compounds with more than one ring
EXAMPLE
Aromatic
naphthalene
4n+2= 4(2)+ 2
10 ∏ electrons
* Two benzene rings joined together forms naphthalene

AROMATIC COMPOUNDS
Nomenclature of benzene
14.2
and its derivatives

NAMING BENZENE DERIVATIVES
Many organic molecules contain a benzene
ring with one or more substituents.
Many common name are

recognized by the IUPAC system
EXAMPLE:
CH3
Common: toluene
IUPAC: methylbenzene
MONO SUBSTITUTED BENZENE
Benzene is the parent name and the substituent
is indicated by a prefix.
F Cl Br
fluorobenzene chlorobenzene bromobenzene
NO2 CH2CH3
nitrobenzene ethylbenzene
IUPAC rules allow some common names
to be retained.
CH3 OH NH2
toluene phenol aniline
COOH CHO
benzoic acid benzaldehyde

DISUBSTITUTED BENZENE
Two Same Substituents
Relative position of subsituents are indicated by
prefixes ortho, meta, and para ( o–, m–, and p–)
or by the use of number.
Br
Br 1
1 Br 2
2 Br
1
2 3
4
3
Br Br
1,2–dibromobenzene 1,4–dibromobenzene
or 1,3–dibromobenzene or
o–dibromobenzene or p–dibromobenzene
m–dibromobenzene
NO2 NO2
1 NO2 1
2
2
3
NO2
1,2–dinitrobenzene 1,3–dinitrobenzene
or or
o–dinitrobenzene m–dinitrobenzene
NO2
1
2
3
4
NO2
1,4–dinitrobenzene
or
p–dinitrobenzene
DISUBSTITUTED BENZENE
Two Different Substituents
Select one of the substituent that give

new parent name and numbered as C1.
COOH
COOH 1
1 2
2 NO2 COOH
1
2 3
4
3
NO2
NO2
2–nitrobenzoic acid 4–nitrobenzoic acid
or 3–nitrobenzoic acid or
o–nitrobenzoic acid or p–nitrobenzoic acid
m–nitrobenzoic acid
THREE OR MORE SUBSTITUENTS
Position of substituents must be indicated by
numbers.
The substituents are listed alphabetically when

writing the name.
Cl
Br
1 2 Br Br
3 I
4
2–bromo–1–chloro–3–iodobenzene
Br
1,2,4–tribromobenzene
C atom bearing the subtituent that define the
new parent name is numbered as C1.
OH
COOH
1
2 NO2 1
6 2
3 5 3
4 OH
HO 4
NO2
3,5–dihydroxybenzoic acid
2,4–dinitrophenol
3
Br 4 2 CH3
1 CH3
4–bromo–1,2–dimethylbenzene
3
Br 4 2 CH3
1 CH3
4–bromo–1,2–dimethylbenzene correct
4–bromo–o–dimethylbenzene
o–, m– and p– naming system is used

for arenes with 2 substituents only!
14.2-11
PHENYL GROUP
Benzene ring as substituent.
If alkyl substituent is larger than the ring
(more than 6 C), the compound is named as
phenyl-substituted alkane.
1 CH2
3 4 5 6 7
2 CH–CH
2–CH2–CH2–CH2–CH3
2–phenylheptane
Phenyl = C6H5– = Ph
14.2-12
If the chain is unsaturated (have C═C or C≡C)

or contains important functional group, the
benzene ring is considered as
phenyl substituent.
1 2 3 4 2 1
CH2–C C–CH3 CH2–CH2–OH
1–phenyl–2–butene 2–phenylethanol
14.2-13
BENZYL GROUP
CH2—
phenyl group benzyl group
CH2Br CH2OH
benzyl bromide benzyl alcohol

AROMATIC COMPOUNDS
Chemical properties of benzene

14.3
and its derivatives

14.3-01
UNUSUAL REACTIONS OF BENZENE
Br2 / CCl4
no addition of Br2
(no decolorization)
BENZENE KMnO4 / H2O

no oxidation
(no decolorization)
H2 / Ni
slow addition at high
temperature and pressure
Alkenes readily undergo addition

reaction, benzene does not!
14.3-03
REACTION OF ARENES
Involves the benzene ring itself
Electrophilic aromatic substitution
Br
FeBr3
+ Br2
benzene bromobenzene
Involves substituents attached to the ring

CH3CH2CH2CH3 KMnO COOH
4
H2O
butylbenzene benzoic acid

14.3-04
ELECTROPHILIC SUBSTITUTION
Most characteristic reaction of benzene.
A H atom is replaced by an electrophile.
H E
+ E+ + H+
electrophile
14.3-05
X2, FeX3 X
(X = Cl Br) + HX halogenation
HONO2
NO2
+ H2O nitration
H2SO4
RCl , AlCl3 R Friedel-Crafts

+ HCl Alkylation
(R can rearrange)
O
O
RCCl , AlCl3
C–R Friedel-Crafts
+ HCl Acylation
14.3-07
GENERAL MECHANISM
STEP 1 Formation of arenium ion

H
H H E+
H H
H
H H H
E E E
H H H
+ H H H
+ +
H H H H H H
H H arenium ion H
14.3-08
ARENIUM ION
+
E+ E
H
benzene ring arenium ion
Electrophile takes two electrons of six–electrons

 system to form  bond.
This interrupts of cyclic system of  electrons.
Benzene ring  arenium ion

(aromatic) (nonaromatic)
The four  electrons delocalized through these
the five C atom (p orbitals)
14.3-09
STEP 2 Loss of H+
H H
E
H H E
+ H
H H H H
H H
Substitution reaction allow

aromatic six  electrons to
be regenerated.
+
E+ E – H+
H E
6  electrons 4  electrons 6  electrons

14.3-10
Kekulé structures are more appropriate for writing

mechanisms.
For simplicity, however, we can show the mechanism
in the following way:
E
STEP 1
H
+ E+ +
arenium ion
STEP 2 E
E
H + H+
+
14.3-11
HALOGENATION
Reactants: benzene and halogens (Cl2 or Br2).
Conditions:
Lewis acid such as FeCl3 and FeBr3
+ Br2 no reaction
(decolorization not observed)
Br
FeBr3
+ Br2 + HBr
bromobenzene
14.2-13
MECHANISM
STEP 1 Formation of Br+
+ –
Br–Br + FeBr3 Br—Br–FeBr3 Br+ + FeBr4–
complex
STEP 2 Formation of arenium ion Br

H
+
+ Br+
STEP 3 Loss of H+
Br FeBr4– Br
H + HBr + FeBr3
+
14.3-14
FUNCTION OF LEWIS ACIDS
Increase polarity of halogen molecules.

Produce positive halogen ions (Br+ or Cl+).
14.3-15
NITRATION
Reactants: benzene and concd. HNO3.
Conditions:
Concd. H2SO4
HNO3 NO2
H2SO4
nitrobenzene
+ H+ + HSO4–
12.5-49
MECHANISM
STEP 1 Formation of nitronium ion (NO2+)

H
..
+-NO –
H-O-NO2 +
.. H-OSO3H .. 2
H-O + HSO 4
H2O + NO2+
nitronium ion
NO2
H
+ NO2+ +
STEP 3 Loss of H+
NO2 HSO4–
NO2
H + H2SO4
+
12.5-51
FRIEDEL–CRAFT ALKYLATION
Reactants: benzene and haloalkane.
Conditions:
Catalyst: Lewis acid such as AlCl3.
R
AlCl3
+ R–X + HCl
alkylbenzene
Alkylation = transfer an
alkyl group to benzene
12.5-52
12.5-53
EXAMPLE:
Cl
CH(CH3)2
AlCl3
+ CH3CHCH3 + HCl
2–chloropropane
isopropylbenzene
C(CH3)3
AlCl3
+ (CH3)3C–Cl + HCl
2–chloro–2–methylpropane
tert–butylbenzene
12.5-54
MECHANISM
STEP 1 Formation of carbocation
+ -
: :
: :
(CH3)2CHCl: + AlCl3 (CH3)2CH–Cl–AlCl3
(CH3)2CH+ + AlCl4–
carbocation
CH(CH3)2
+CH(CH ) H
+ 3 2 +
STEP 3 Loss of H+
AlCl4–
CH(CH3)2
CH(CH3)2
H
+ + HCl
OTHER FACTS ABOUT 12.5-55
FRIEDEL–CRAFT ALKYLATION
Rearrangement can occur, especially when
1o haloalkanes are used.
CH2CH2CH2CH3
EXAMPLE:
35%
CH3CH2CH2CH2Cl butylbenzene
CH3
AlCl3 +
CHCH2CH3
65%
Rearrangement: sec–butylbenzene
H
+ +
CH3—CH2—CH—CH2 CH3—CH2—CH—CH3
1o carbocation 2o carbocation
12.5-56
FRIEDEL–CRAFT ACYLATION
Reactants: benzene and acid chloride.
Product: ketone.
Conditions:
Catalyst: Lewis acid such as AlCl3.
EXAMPLE:
O
O
AlCl3 CCH3
+ CH3C—Cl + HCl
acetyl chloride
acetophenone
12.5-57
ACYL GROUP
O
RC—
acyl group
EXAMPLE:
O
O
–C—
CH3C—
acetyl group benzoyl group
Acylation = transfer an
acyl group to benzene
12.5-59
MECHANISM
STEP 1 Formation of acylium ion
:O: :O:
R–C–Cl + AlCl3 R–C–Cl–AlCl3
: :
R–C+═O R–C≡O+ + AlCl4–
acylium ion
Formation of arenium ion R
STEP 2
C=O
+ R–C+═O H
+
STEP 3 Loss of H+
R AlCl4– R
C=O
C═O
H
+ + HCl
12.5-61
SUBSTITUENT EFFECT
But, what would happen if we were to carry out a reaction

on aromatic ring that already has a substituent?
12.5-62
EFFECT ON REACTIVITY
Activating groups:
Substituents that activate the ring,
making it more reactive than benzene.
Deactivating groups:
Substituents that deactivate the ring,
making it less reactive than benzene.
EXAMPLE:
NO2 Cl H OH
relative rate
6 x 10–8 0.033 1 1000
of nitration
reactivity
12.5-63
EFFECT ON ORIENTATION
Ortho–para directors
Tend to direct the incoming group into
ortho and para positions.
Meta directors
Tend to direct the incoming group into
meta position.
EXAMPLE: ortho-para director
CH3 CH3 CH3 CH3
HNO3 NO2
+ +
H2SO4 NO2
(59%) (37%) NO2 (4%)
12.5-64
CLASSIFICATION OF SUBSTITUENTS
ortho– , para– directing

activators
ortho– , para– directing

deactivators
meta– directing deactivators

ORTHO– , PARA– 12.5-65
DIRECTING ACTIVATORS
Increasing activation
●● ●● ●●
—NH2 —NHR —NR2
●●
—OH
●●
●● General structure:
—OR
●● —R or —Z● ●
●●
—NHCOR
Alkyl groups or have
nonbonded electron pair
—R on the atom bonded to
benzene ring
12.5-66
EXAMPLE:
CH2CH3 CH2CH3 CH2CH3

Br
Br2
+
FeBr3
ethylbenzene (38%) (62%) Br
ORTHO– , PARA– 12.5-67
DIRECTING DEACTIVATORS
●● ●●
—F ●
● —Cl●
●
●● ●●
●● ●●
—Br●● — I●
●
●● ●●
General structure
●●
—X●● (halogens)
●●
12.5-68
EXAMPLE:
Cl Cl Cl
NO2
HNO3
+
H2SO4
chlorobenzene (35%) (64%) NO2
12.5-69
META– DIRECTING ACTIVATORS
—CHO
—COR
—COOR General structure:
—Y (+ or –)
—COOH
—CN
Have a full or partial
—SO3H positive charge on the
atom bonded to
—NO2 benzene ring
+
—NR3
Increasing deactivation
12.5-69
EXAMPLE:
NO2
NO2
HNO3
H2SO4
NO2
nitrobenzene
(93%)
12.5-70
INDUCTIVE EFFECT
Due to:
Electronegativity of the atoms in the
substituent.
Polarisability of the substituent.
EXAMPLE:
Cl CH3
Cl— CH3—
electron–withdrawing electron–donating
12.5-71
Activating Groups
CH3
Release electrons to the ring NO2
Stabilise arenium ion +

Form faster
Deactivating Groups
Cl
Withdraw electrons from the ring NO2
Destabilise arenium ion +

Form slower
12.5-72
EXAMPLE:
CF3 CH3
(trifluoromethyl)benzene benzene toluene

increasing rate of nitration
CF3 CH3
NO2 NO2
NO2
+ +
+
CF3 withdraws e-, CH3 releases e-,

 arenium ion less stable  arenium ion more stable
 ring less reactive  ring more reactive
12.5-75
OXIDATION OF SIDE CHAIN
Reactants: arene with benzylic H.

Conditions:
Strong oxidizing agent such as KMnO4
and Na2Cr2O7.
Heat.
benzylic H
CH3
CH3 CH(CH3)2
EXAMPLE: 12.5-76
CH3 COOH
KMnO4
heat
toluene benzoic acid
Na2Cr2O7
O2N CH3 O2N COOH
heat
p–nitrotoluene p–nitrobenzoic acid
KMnO4
CH3 CH(CH3)2 HOOC COOH
heat
isopropyl toluene terepththalic acid
12.5-77
KMnO4
CH3 CH(CH3)2 HOOC COOH
heat
Alkyl group, regardless their chain length are

converted to –COOH.
Compounds without a benzylic H are inert to oxidation.
KMnO4
CH3 C(CH3)3 HOOC C(CH3)3
heat
12.5-78
HALOGENATION OF TOLUENE
Free radical substitution reaction

Take place at high temperature or in the
presence of uv light.
Mechanism: free–radical substitution
Cl or Br replaces H atom of alkyl group
EXAMPLE: (dichloromethyl)benzene
CH3 CH2Cl CHCl2 CCl3
Cl2 Cl2 Cl2
heat or heat or heat or
light light light
toluene benzyl chloride (trichloromethyl)benzene

HALOGENATION OF TOLUENE
Electrophilic aromatic substitution reaction
CH3
CH3
CH3
Br2 Br2 +
FeBr3
toluene Br2
●
CH2 12.5-79
benzylic
radical
Benzylic radicals are even more stable than 3o radicals!

12.5-34
CARCINOGENIC EFFECT
CH3
benzene toluene
Many aromatic compounds are carcinorgenic

and toxic.
Example: benzene, benzo[a]pyrene.

12.5-35
At one time, benzene was widely used as solvent.

Studies revealed benzene is carcinorgenic
(can cause cancer).
Replaced by toluene.
12.5-36
benzo[a]pyrene
Benzo[a]pyrene is found in cigarette smoke, automobile

exhaust, and the fumes from charcoal grills.
When ingested or inhaled, it oxidised to carcinogenic

products.
12.5-21
12.5-20
Benzoic acid, the simplest organic acid, prevent the

growth of many organism.
12.5-22
widely used as a food preservative.

12.5-19
Fresh wild berries

END OF
SLIDE SHOW
CHAPTER 15
HALOALKANES
FJ / Chemistry Unit, KMPk / Mac 2006 1
15.1 : Introduction
 Haloalkanes or alkyl halides
- compounds that contains halogen atom bonded
to an sp3 hybridized carbon atom.
 General formula : R-X

or CnH2n+1X (acyclic)
or CnH2n-1X (cyclic)
where X : halogen atom

(F, Cl, Br or I)
2
15.1.1 : Classification of Haloalkanes
 Haloalkanes are classified according to the nature of
carbon atom bonded to the halogen.
General Formula Classification
methyl halide
CH 3 X - halogen is bonded to
methyl group
Primary (10) halide
R CH 2 X - halogen is bonded to 10
carbon atom
Secondary (20) halide
R
- halogen is bonded to 20
R CH X carbon atom 3
General Formula Classification
R Tertiary (30) halide

R C X - halogen is bonded to 30 carbon
R atom
X Aryl halide
- halogen is bonded to aromatic
ring
CH 2 X
** Not a aryl halide
4
Example :
 Classify the following haloalkanes :
No. Haloalkanes Classification
i. CH 3 CH 2 Br 10
ii. CH 3 CH (Cl)CH 3 20
iii. (CH 3 ) 3 C(Br) 30
H3C Cl
iv. 30
5
15.1.2 : IUPAC Nomenclature
 Haloalkanes are named as alkanes with halogen as

substituents.
 Locate and number the parent chain from the direction

that gives the substituent encountered first the lower
number.
 Show halogen substituents by the prefixes flouro-,

chloro-, bromo- and iodo-, and list them in alphabetical
order along with other substituents.
6
Example :
i. CH 3 CHCH 2 CH 3
Br
2-bromobutane
ii. Cl
BrCH 2 CH 2 CHCHCH 2 CH 3
CH 3
1-bromo-3-chloro-4-methylhexane
7
Example :
iii. CH 2 CH 2 F
CH 3 CH 2 CH 2 CHCH 2 CH 2 CH 3
4-(2-flouroethyl)heptane
iv. H3C CH 3
Cl
2-chloro-1,1-dimethylcyclopentane 8
Example :
v. Br
4-bromocyclohexene
vi. CH 2 Cl vii. CH 3
Cl
(chloromethyl)benzene 2-chlorotoluene
9
15.1.3 : Structure of Haloalkane
 The carbon – halogen bond in haloalkene is polar
because halogens is more electronegative than carbon.
δ+ δ- electrophilic
C X
site
 The polar C – X bond causes the carbon bearing the

halogen is susceptible to nucleophilic attack.
 Haloalkanes are reactive and undergo nucleophilic

substitution and elimination reaction.
10
15.2 : Chemical Properties
15.2.1 : Nucleophilic Substitution Reaction
 Haloalkanes undergo nucleophilic substitution

reactions in which the halogen atom is replaced by a
nucleophile.
 In this reaction, the nucleophile attacks the partially

positive charge (δ+) carbon atom bonded to the halogen
(δ-).
 General reaction :
_ _ _
R X + N u: R _N u + X:
11
(a) : Hydrolysis of Haloalkane with Aqueous Solution
of NaOH (H2O/NaOH)
 Alkaline hydrolysis is carried out by boiling R-X with

NaOH(aq) to form alcohol.
H2 O
R_ X + NaOH R_ OH + NaX
 Example :
CH3 CH3
_ _ H2 O
CH3 C Br + NaOH CH3 _ C _OH + NaBr
CH3 CH3
12
(b) : Reaction of Haloalkane with Potassium Cyanide
(KCN)
 When R-X is refluxed with KCN in alcohol, the halogen

atom is substituted by the CN- to produce a nitrile
compound.
_ _ alcohol _
R X + CN R_ CN + X
reflux
 Example :
CH 3 CH 2 Br + KCN alcohol CH 3 CH 2 CN + KBr

reflux
13
(c) : Reaction of Haloalkane with Ammonia (NH3)
 When R-X is heated with excess concentrated NH3, the

halogen atom is replaced by the amino group, NH2-.
NH 3 _ NH 3 _
R_ X +
RNH 3 X _ +
R N H2 + NH 4 X
(amine)
 Example :
+ _
CH 3 CH 2 Cl + excess NH 3 CH 3 CH 2 NH 2 + NH 4 Cl
14
15.2.2 : Mechanisms of Nucleophilic
Substitution Reaction
 They are 2 important mechanisms for the substitution

reaction:
(A). Unimolecular Nucleophilic Substitution Reaction

(SN1)
(B). Bimolecular Nucleophilic Substitution Reaction

(SN2)
15
(A) : Unimolecular Nucleophilic Substitution Reaction
(SN1)
 The term unimolecular means there is only one

molecule involved in the transition state of the rate-
limiting step.
 SN1 reactions are governed mainly by the relative

stabilities of carbocations.
 Relative reactivities of haloalkanes in an SN1 reaction :

R-X < R-X < R-X
1o 2o 3o
increasing reactivity
16
 The rate of SN1 reaction does not depend on the
concentration of nucleophile.
 The rate depends only on the concentration of the

substrate, alkyl halide.
 rate = k [R3C-X]
* SN1 is a first order reaction
17
 The mechanism of SN1 reaction involves 2 steps.
Step 1 : Formation of a carbocation (rate determining

step)
R R
s low _
R_ C _ X _
R C+ + X
R R
3o alkyl halide carbocation halide ion
Step 2 : Nucleophilic attack on the carbocation
R R
_ _ fas t
R C + + N u: R_ C _ N u
R R 18
 Example 1 :
Reaction of 2-bromo-2-methylpropane with H2O.
CH 3 CH 3
CH 3 _ C _ Br + H 2 O CH 3 _ C _ OH + HBr
CH 3 CH 3
 SN1 mechanism :
Step 1 : Formation of a carbocation
CH 3 CH 3
s low _
CH 3 _ C _ Br CH 3 _ C + + Br
CH 3 CH 3 19
 Step 2 : Nucleophilic attack on the carbocation
CH 3 CH 3
fa s t H
CH 3 _ C + + H2O _ _
CH 3 C O
+ H
CH 3 CH 3
Loss of proton, H+ to solvent
CH 3 CH 3
H
_ _
CH 3 C O + H2O CH 3 _ C _ OH + H 3 O +
+ H
CH 3 CH 3
20
 Example 2 :
Write the mechanism for the following reaction.
CH3 CH3
CH3 _C _CH2Br + NaOH(aq) CH3 _ C _CH2CH3 + NaBr
CH3 OH
 SN1 Mechanism :
Step 1 : Formation of carbocation
CH 3 CH 3
_
CH 3 _ C _ CH 2 _Br s low _ _
CH 3 C CH 2 + Br
+
CH 3 CH 3 21
Rearrangement :
CH 3 CH 3
CH 3 _ C _ CH 2 1,2-meth yl s hift CH 3 _ C _ CH 2
+ +
CH 3 CH 3
Step 2 : Nucleophilic attack on the carbocation
CH 3 CH 3
_
CH 3 _ C _ CH2 + OH fas t CH 3 _ C _ CH 2 CH 3
+
CH 3 OH
22
Exercise 1 : (Feb 2003)
Write a reasonable structures of products formed when 1-

iodobutane reacts with
i. KCN
ii. NaOH/H2O
iii. excess NH3
Write the mechanism for the reaction in (ii).
23
Exercise 2 : (Mac 2002)
The structure of compound A is as follows:
CH3
CH3 C Br
CH3
i. Give IUPAC name for A
ii. Compound A react with OH- forming an alcohol. Write

the mechanism for the formation of this alcohol and
name the reaction.
24
(B) : Bimolecular Nucleophilic Substitution
Reaction (SN2)
 The term bimolecular means that the transition state of

the rate limiting step involves the collision of two
molecules.
 SN2 reactions are governed mainly by steric factors

(steric effect).
 Steric effect
- is an effect on relative rates caused by the space-
filling properties of those parts of a molecule
attached at or near to the reacting site.
25
 The reactivity on SN2 reaction depends on the size of
atoms or groups attached to a C – X.
 The presence of bulky alkyl groups will prevent the

nucleophilic attack and slow the reaction rate.
 Relative reactivities of haloalkanes in an SN2 reaction :
R-X < R-X < CH3-X

2o 1o
increasing reactivity
26
 The rate of reaction depends on the concentration of
the haloalkane and the concentration of nucleophile.
 rate = k [R-X] [Nu:-]
* SN2 is a second order reaction.
 The mechanism of SN2 occurs in a single step.
General Mechanism :
R R R
slow fast Nu C
C X Nu C X + X-
Nu:- H H
H H H H
27
transition state
 In SN2 reaction, the nucleophile attacks from the back
side of the electrophilic carbon, that is, from the side
directly opposite bonded to the halogen.
 The transition state involves partial bonding between

the attacking nucleophile and the haloalkane.
 Back-side attack causes the product formed has inverse

configuration from the original configuration.
* turns the tetrahedron of the carbon atom inside

out, like umbrella caught by the wind.
28
 Example 3 :
Reaction of ethyl bromide with aqueous sodium
hydroxide.
CH3 CH2 Br + NaOH(aq) CH3 CH2 OH + NaBr
 SN2 Mechanism :
CH3 CH3 CH3

:OH- C Br slow OH C Br
fast
OH C + Br-
H H
H H H H
transition state
29
Comparison of SN1 and SN2 Reactions
SN1 SN2
A two-step mechanism A one-step mechanism

A unimolecular rate- A bimolecular rate-
determining step determining step
Second order : First order :
rate = k [RX] [Nu] rate = k [RX]
Strong nucleophile Weak nucleophile
No carbocation
Carbocation rearrangement
rearrangement
Reactivity order : Reactivity order :
3o > 2o > 1o methyl > 1o > 2o 30
15.2.3 : Elimination Reaction
(dehydrohalogenation of haloalkanes)
 Halogen can be removed from one carbon of a

haloalkane and hydrogen from an adjacent carbon to
form a carbon-carbon double bond in the presence of a
strong base.
 General reaction :
H
_C_C_ _ _ _
+ :B C C + X
X
alkene
haloalkane base
31
 Example :
Br
CH 3 CH 2 ON a
i. CH 3 CHCHCH 3 CH 3 C CHCH 3
CH 3 CH 2 OH
CH 3 CH 3
major
+
CH 3 CHC CH 2
CH 3
minor
ii.
Br CH 3 CH 2 ON a CH 3 CH 2
CH 3 CH 3 CH 2 OH +
major minor 32
15.2.4 : Synthesis of Organomagnesium
Compound ( Grignard Reagent )
 Prepared by the reaction of haloalkanes with

magnesium metal in anhydrous ether as a solvent.
R-X + Mg ether R-MgX

Grignard Reagent (
alkylmagnesium halide)
 Example :
i. CH 3 CH 2 CH 2 Br + Mg ether CH 3 CH 2 CH 2 MgBr
ii.
ether
Cl + Mg MgCl
33
15.2.4.1 : Synthesis of Alkanes, Alcohols and
Carboxylic Acids from Grignard
Reagents.
 The Grignard reagents undergo many reactions that
make them useful as a starting materials in the
synthesis of other organic compounds.
(i). Synthesis of alkane
The Grignard reagent is hydrolyzed to an

alkane when warmed with H2O.
H+
RMgX + H 2 O R-H + Mg(OH)X
34
Example :
H +
i. CH 3 CH 2 MgBr + H 2 O CH 3 CH 3 + Mg(OH)Br
ii.
CH 3 CH-MgBr + H 2 O H+
CH 3 CH 2 CH 3 + Mg(OH)Br
CH 3
iii.
H 2 O/H +
CH 2 MgCl CH 3
+ Mg(OH)Cl
35
(ii). Synthesis of 1o alcohol
Methanal reacts with the Grignard reagent,

followed by the hydrolysis produces primary
alcohol.
O H
R-MgX + H-C-H R-C-OMgX
H
H 2 O,H +
H
R-C-OH + Mg(OH)X
36
H
 Example :
i.
O H
H 3 O+
CH 3 MgBr + H-C-H CH 3 -C-OH + Mg(OH)Br
H
ii.
MgBr O CH 2 OH
H 3 O+
+ H -C-H + Mg(OH)Br
37
(iii). Synthesis of 2o alcohol
Grignard reagent reacts with aldehydes to

produce secondary alcohol.
O R'
R-MgX + H-C-R' R-C-OMgX
H
H 2 O,H +
R'
R-C-OH + Mg(OH)X
H 38
 Example :
O
i. CH 3 CH 2 MgBr + CH 3 CH 2 -C-H
H 2 O/H +
H
CH 3 CH 2 -C-CH 2 CH 3 + Mg(OH)Br
OH
ii.
CH 3
O
MgCl H 2 O/H + C-OH
+ CH 3- C-H + Mg(OH )Cl
H
39
(iv). Synthesis of 3o alcohol
Grignard reagent reacts with ketons to produce

the tertiary alcohol.
O R'
R-MgX + R'-C-R" R-C-OMgX
R"
H 2 O,H +
R'
R-C-OH + Mg(OH)X
40
R"
 Example :
i. O
CH 3 CH 2 MgBr + CH 3 -C-CH 3
H 2 O/H +
CH 3
CH 3 CH 2 -C-CH 3 + Mg(OH)Br
OH
ii.
CH 3
O
MgCl
H 3 O+ C-OH
+ CH 3- C-CH 3 + Mg(OH )Cl
CH 3 41
(v). Synthesis of carboxylic acid
Grignard reagent reacts with carbon dioxide

(CO2) followed by hydrolysis to form carboxylic
acid.
O
RMgX + O C O R-C-O-MgX
O O
H+
R-C-O-MgX + H 2 O R-C-OH + Mg(OH)X
42
 Example :
O
CH 3 CH 2Mg I + CO 2 CH 3 CH 2- C-O-MgI
O O
H+
CH 3 CH 2- C-O-MgI + H 2 O CH 3 CH 2 COH + Mg(OH)I
43
15.2.5 : Wurtz Reaction
 Reaction of haloalkane (RX) with an alkali metal

(usually Na) to synthesise longer alkane.
i. To prepare an even number of carbon atoms

alkane
dry ether
2RX + 2Na  RR + 2NaX
Example:
2CH3CH2Br + 2Na  CH3CH2CH2CH3 + 2NaBr

44
ii. To prepare a odd number of carbon atoms
alkane
RX + R’X + 6Na  RR + RR’ + R’R’

+ 6NaX
Example:
CH3CH2Br + CH3Br + 6Na  CH3CH2CH2CH3

+ CH3CH2CH3
+ CH3CH3 + 6NaBr
45
15.2.6 : Importance of Haloalkanes as Inert
Substance
Haloalkanes Uses
CCl4 solvent for dry

cleaning, spot
(carbon tetrachloride) removing
CHCl3 solvent for cleaning
(chloroform) and degreasing work
CF2Cl2 , Freon-12 propellants in aerosol
(dichlorodifluoromethane) sprays
CFC
refrigerant gas
(chloroflourocarbons)
DDT
insecticide protects
46
(DichloroDiphenylTrichloroethane)
HYDROXY COMPOUNDS
(ALCOHOLS)
Click me
for intro!
1
INTRODUCTION
 Alkane with hydroxyl group (–OH)
 General formula for aliphatic alcohol,
CnH2n+1OH
 Aromatic alcohol – phenol (-OH attached
to the benzene rings)
2
INTRODUCTION
OH CH2-OH
CH3CH2-OH
ALIPHATIC ALCOHOL (–OH group attached

directly to the alkyl group)
3
INTRODUCTION
OH OH OH
CH3
Br
AROMATIC ALCOHOL (–OH group attached

directly to the aryl group)
4
CLASSIFICATION
 Methyl alcohol CH3-OH
 10 Alcohols R-CH2-OH
R
 20 Alcohols R-CH-OH
R
 30 Alcohols R-C-OH
R
5
NOMENCLATURE
Structure General name IUPAC name
CH3-OH methyl alcohol methanol
CH3CH2-OH ethyl alcohol ethanol
CH3CH(OH)CH3 isopropyl alcohol 2-propanol
OH cyclohexyl cyclohexanol
alcohol
6
Naming the alcohol
1. The suffix ‘–e’ in the alkane parent name is
replaced by ‘–ol’
2. The location of the –OH on the longest chain
is given by the smallest possible number
7
IUPAC rules for naming alcohols
1. Determine parent name
2. Give the lowest number to the carbon
bearing the –OH group
3. Identify substituent groups and their position
4. Name the alcohol
8
Naming Alcohols, R-O-H:
CH3 CH3
CH3CHCH2CHCH3 CH3CCH2CH2CH3
OH OH
4-methyl-2-pentanol
2-methyl-2-pentanol
2o 3o
CH3
HO-CHCH2CH3 CH3CH2CH2-OH
sec-butyl alcohol n-propyl alcohol

2-butanol 1-propanol
2o 1o 9
Naming Alcohols
10
For phenol, C attach to the –OH group is C 1
OH OH OH
CH3
CH2CH3 Br
3-ethylphenol 3-bromophenol 2-methylphenol
11
Alcohol with 2 hydroxy groups
Structure General name IUPAC name
CH2(OH)CH2-OH
ethylene glycol 1,2-ethanediol
CH3CH(OH)CH2-OH
propylene glycol 1,2-propanediol
HO-CH2CH2CH2-OH trimethylene 1,3-propanediol
glycol
OH-CH2CHCH2-OH
OH
glycerol 1,2,3-propanetriol
12
Benzene derivatives with 2 –OH groups are
name as benzenediol
OH OH OH
OH
OH
OH
1,4-benzenediol 1,3-benzenediol 1,2-benzenediol

(hydroquinone) (resorcinol) (catechol)
13
EXCERCISE
1. Name the following compounds using IUPAC nomenclature
(a)
-CH2CH(CH3)CH2-OH
(b)
-OH
NO2
(b)
-OH
Br
14
PHYSICAL PROPERTIES
 Most simple alcohols are liquids
 MeOH & EtOH are volatile liquids, b.p.
65oC & 78oC respectively
 Mr , b.p.
 ROH with C > 12 are solids
15
PHYSICAL PROPERTIES
 No. of –OH , b.p.

 b.p. ROH > alkane & RX because of H-
bonding
 b.p. ROH straight chain > ROH branch
 b.p. 1o ROH > 2o ROH > 3o ROH
16
PHYSICAL PROPERTIES
(ii) Boiling point
 As molecular weight increase, van der Waals
forces increase, boiling point will increase too.
For isomeric alcohol (same molecular

formula)
 increase in boiling point with increasing carbon
number.
 decrease in boiling point with branching.
 boiling point in descending order:-
 1° alcohol  2° alcohol  3° alcohol
17
PHYSICAL PROPERTIES (Solubility)
Alcohols and water have the ability to form

inter-molecular H-bonding
Methanol, ethanol & propanol are completely
soluble in water
Solubility decreases with relative Mr because of
the bigger hydrophobic area
Solubility increases with the no. of -OH groups
18
δ+
H
δ-
R O
Hydrophilic area
δ- H Hydrogen
O δ+ bonding
H
R OH
H
δ- δ+
R O Hydrophobic area
H
O δ+
H
δ-
19
Phenol is not completely soluble in water below
66oC, but completely soluble above this temp.
Phenol is a colourless crystalline solid which is
hygroscopic
4-nitrophenol is more soluble in water than 2-
nitrophenol because can form H-bonding with
water molecules
20
2-nitrophenol 4-nitrophenol
δ-
δ- O
δ+ O δ+ O H H
H δ- δ+
N
O
δ- O
N
δ+
O
O δ+ δ-
δ- H O
Intramolecular H-bonding δ+
H H
Intermolecular H-bonding
21
Acidity of phenol & alcohol
phenol > water > alcohol

 Ethanol, very weak acid & only can react with
strong base such as Na or K to produce a
conjugate base (ethoxide ion)
CH3CH2-OH CH3CH2-O- + H+
22
 CH3CH2O- is e- richer than OH-, thus
H2O > acidic than CH3CH2OH
 Phenol > acidic than H2O & CH3CH2OH
because phenoxide ion formed is more
stable
 The phenoxide ion formed is stabilised
by resonance effect
23
O H O -
release proton
+ H+
Phenoxide ion
24
Phenoxide ion stability
O - O O O
- -
Oδ-
δ- δ-
δ-
25
Example:
OH CH2CH2-OH CH2-OH OH
acidity increase
26
Example:
COOH OH
> > CH CH -OH

3 2
ACIDITY
DECREASE
Na2CO3 KOH K, Na
NaHCO3 NaOH NaH
Weak bases Strong bases Very strong bases
27
EXCERCISE
1. Arrange the following compounds in the order of increasing

boiling point. Explain your answer.
1,2-ethanediol , n-butane , 1-propanol , 1,3-propanediol
2. Predict which of the compound is more soluble in water.

Briefly explain your answer.
(a) propane & 1-propanol

(b) 1-propanol & 1,2-propanediol
(c) 2-propanol & 2-pentanol
28
PREPARATION OF ALCOHOLS
1. Fermentation of carbohydrate
-fermentation of sugars by yeast to
form ethanol
C6H12O6 2CH3CH2OH + 2CO2
29
2.Hydration of Alkenes
follows Markovnikov’s rule
Example:-
CH3CH=CH2 H2O / H2SO4

CH3CH-CH3
OH
30
Mechanism
CH3CH=CH2 + H+ CH3CH-CH3 2o carbonium

+
●●
● -
● OH
CH3CH-CH3
●
● OH
●●
31
3. Hydrolysis of Haloalkanes
RX + OH- (aq) ROH + X-
CH2Cl CH2OH
+ NaOH(aq)
32
4. Addition of Grignard reagent to
carbonyl compounds
10, 20 & 30 alcohols can be prepared by

addition of Grignard reagent with carbonyl
compounds followed by hydrolysis
33
(a) Formation of 1o alcohols (Grignard reagent + methanal)
CH3CH2-MgCl + H2C=O CH3CH2CH2-OMgCl

methanal
H3O+
1o Alcohol CH3CH2CH2-OH
+ Mg(OH)Cl
34
(b) Formation of 2o alcohols (Grignard reagent + aldehyde)
CH3 CH3
CH3CH2-MgCl + HC=O CH3CH2CH-OMgCl
ethanal
H3O+
CH3
2o Alcohol CH3CH2CH-OH
+ Mg(OH)Cl
35
(c) Formation of 3o alcohol (Grignard reagent + ketone)
O O-MgCl
CH3-MgCl + CH3-C-CH3 CH3-C-CH3
propanone CH3
H3O+
O-H
3o Alcohol CH3-C-CH3 + Mg(OH)Cl
CH3
36
EXCERCISE
1. Write the chemical equation for the following reaction:

i. tert-butyl alcohol from an alkene
ii. isopropyl alcohol from an alkyl halide
2. Draw the structure of A, B and C:
i. CH3 O
CH3-C-MgCl + -C-H A
CH3
ii.
H2O / H+
-CH=CH-CH3 B + C
37
ALCOHOL REACTIONS
(a) As an acid
In an aqueous solution alcohol reacts as a very weak acid
ROH + H2O RO- + H3O+
Reacts with Na or NaH & form a very strong base

alkoxide ion
CH3CH2OH + Na CH3CH2O-Na+ + 1/2H2
38
ALCOHOL REACTIONS
(a) As a base
With the presence of lone pair of e- at the O atom,

alcohol can accept proton from an acid
●● ●●
CH3CH2-O-H
●●
+ HA CH3CH2O+-H + A-
H
39
ALCOHOL REACTIONS
(1) Esterification
Alcohol reacts with carboxylic acid under reflux & is

catalysed by mineral acids (H2SO4 or HCl)
General reaction:-
O O
H+,
R-C-OH + R’-OH R-C-OR’ + H-O-H
acid alcohol ester water
40
ALCOHOL REACTIONS
(1) Esterification
Example:-
O H+, O
CH3C-OH + CH3-OH CH3C-OCH3 + H-O-H
ethanoic acid methanol methyl ethanoate
41
ALCOHOL REACTIONS
(1) Esterification
Alcohol reacts with acyl chloride to form ester
O O
base
CH3C-Cl + CH3-OH CH3C-OCH3 + HCl
ethanoil chloride methanol methyl ethanoate
42
ALCOHOL REACTIONS
(2) Dehydration of alcohol
•Involve formation of carbocation
•Possible of rearrangement
H2SO4(con.)
CH3CH2CH2OH CH3CH=CH2
1800C
propanol propene
43
ALCOHOL REACTIONS
(3) Formation of haloalkane
•ROH reacts with HX to form RX

•The reaction rates are in the order
HI > HBr > HCl (HF non-reactive)
•Reactivity of alcohols
3o ROH > 2o ROH > 1o ROH > phenol
44
ALCOHOL REACTIONS
Example:-
• ROH + HX RX + H2O
• CH3CH2CH2OH + HBr CH3CH2CH2Br + H2O
45
ALCOHOL REACTIONS
(3) Formation of haloalkane
•ROH reacts with PX3, PX5 , SOCl2
General reaction:
(i) 3ROH + PX3 3RX + H3PO3
(ii) ROH + PCl5 RCl + POCl3 + HCl
(iii)ROH + SOCl2 RCl + SO2 + HCl
46
ALCOHOL REACTIONS
(4) Oxidation of alcohols
• Common oxidising agents are potassium

permanganate (KMnO4/H+) and potassium
dichromate (K2Cr2O7/H+)
• Oxidation product depends on the class of
alcohol used
47
ALCOHOL REACTIONS
(4) Oxidation of 1o alcohol
• 1o R-OH can be oxidised to give an aldehyde.

Further oxidation would give a carboxylic acid
O O
[O] [O]
RCH2OH RC-H RC-OH
1o alcohol aldehyde carboxylic acid
48
ALCOHOL REACTIONS
Example:-
O O
K2Cr2O7 /H+ K2Cr2O7/H+
CH3CH2OH CH3C-H CH3C-OH + Cr3+
green
orange
49
ALCOHOL REACTIONS
• Sarett-Collins reagent is a special oxidation
agent to change a 1o alcohol to an aldehyde
• CrO3 is added to excess pyridine to form
pyridinium chlorochromate (PCC)
O
CH3CH2CH2OH + PCC CH3CH2C-H
propanol propanal
50
ALCOHOL REACTIONS
• form ketone which cannot be oxidised further
under normal conditions
R R
[O]
R’CH-OH R’C=O + H2O
2o alcohol ketone
CH3 +
CH3
KMnO4/H
CH3CH-OH CH3C=O + H2O
2-propanol propanone
51
ALCOHOL REACTIONS
• Does not undergo oxidation under normal
condition
R
[O]
R’-C-OH no reaction
R’’
3o alcohol
52
Chemical test for R-OH
 Lucas test
• Lucas reagent : HCl(con.) + ZnCl2
• 3o R-OH + Lucas reagent – reacts
immediately to form cloudy haloalkane
• 2o R-OH + Lucas reagent –takes about 5-10
minutes
• 1o R-OH + Lucas reagent – no visible
changes unless heated
53
Example: OBSERVATIONS :
CH2OH
HCl / ZnCl2 Does not turn
cloudy
OH
HCl / ZnCl2 Turn cloudy
within 5 minute
54
OBSERVATIONS :
CH3
OH Turn cloudy
HCl / ZnCl2 immediately
55
Haloform Reaction
 Methyl carbinol cleavage to give Carboxylic
acids and Haloform
H
X2 , H+
CH 3 C H HCX 3 + H C OH
OH-
OH O
H
X2 , H+
CH 3 C R HCX 3 + R C OH
OH-
OH O
56
IODOFORM TEST
OH
CH3CH2CCH3 + 3I2 base (OH-)
2-butanol
CH3CH2COO- + CHI3↓
yellow precipitate
(iodoform)
57
PHENOL
Manufacture of phenol by Cumene process
(a) Friedel-Crafts reaction
CH3-CH-CH3
AlCl3
+ CH3CH=CH2
Isopropylbenzene
(cumene)
58
PHENOL
(b) Oxidation of Cumene
O -OH
CH3-CH-CH3
CH3-C-CH3
1200C
+ O2 Cumene
hydroperoxide
(c) Decomposition & rearrangement

CH3 O
H2SO4
-C-O-OH -OH + CH3CCH3
CH3
59
Phenol reactions
1. Reaction at functional group -OH
(a) Reaction with Na
OH O-Na+
+ Na + ½ H2
60
Phenol reactions
1. Reaction at functional group -OH
(b) Reaction with NaOH
OH O-Na+
+ NaOH + H2O
CH3CH2OH + NaOH no reaction
61
Phenol reactions
2. Electrophilic substitution reactions
(a) Halogenation (Bromination)
-OH is ortho-para director
in Br2, aqueous solution, white precipitate 2,4,6-
tribromophenol will form
OH OH
Br Br
+ 3Br2 / H2O + 3HBr
Br
62
Phenol reactions
(a) Bromination to get monobromination (catalyst:
FeBr3 or CS2)
OH OH OH
Br
CS2
+ Br2 + + HBr
50C
Br
63
Phenol reactions
(b) Nitration
OH OH
Dilute HNO3 NO2
+
Room temp.
OH
NO2
OH
O2N NO2
Concentrated HNO3 Yellow
precipitate
NO2
64
Phenol reactions
3. Esterification
phenol is a weaker nucleophile than alcohol since
the lone pair e- of O atom are delocalised to the
benzene ring
reacts with an acid derivative such as acid chloride
to form an ester
CH3
OH O-C=O
Cl
+ CH3-C=O + Cl-
65
Phenol reactions
4. Identification test for phenols
phenol reacts with aqueous solution of iron (III)
chloride giving a light purple complex
OH OH
+ FeCl3 (aq)
FeCl3
Purple
complex
66
EXERCISE 1
Suggest a chemical test to differentiate the following pairs of

compounds. State the reagents, observations and write
chemical equations involved.
(a) methanol from ethanol

(b) 2-methyl-1-propanol from 2-methyl-2-propanol
(c) cyclohexanol from cyclohexane
(d) phenol from benzyl alcohol
(e) o-methylphenol from 2-methylcyclohexanol
67
EXERCISE 2
Compound A (C4H10O) undergoes oxidation to form compound

B (C4H8O). Oxidation of B gives compound C (C4H8O2).
Reaction of A with hot concentrated sulphuric acid yields
compound D (C4H8). Hydration of D gives compound E
(C4H10O) which cannot be oxidised. A and E are isomeric.
Suggest the structure of A, B, C, D and E. Rasionalise your
answer.
68
Common used of alcohol and
phenol
 Ethyl alcohol is a poison. LD50 =
~10g/Kg orally in mice.- Nausea,
vomiting, flushing, mental excitement or
depression, drowsiness, impaired
perception, loss of coordination, stupor,
coma, death may occur. (intoxication)
 Phenol is an important industrial
chemical. Major use is in phenolic resins
for adhesives and plastics.
69
Phenols in Medicine
 Many phenols are used as antiseptics and
disinfectants.
OH OH OH
OH OH
CH2CH2CH2CH2CH2CH3
Phenol Resorcinol 4-Hexylresorcinal

(antiseptic) (antiseptic)
70
Derivatives of Phenol
 Compounds of phenol are the active ingredients in the
essential oils of cloves, vanilla, nutmeg, and mint.
71
17.0 CARBONYL COMPOUNDS:
ALDEHYDES AND KETONES
17.1 Introduction
 Aldehydes and ketones are carbonyl compounds
 The functional group : C
Aldehyde ketone
O O
R C H R C R
1
17.2 Nomenclature
 The longest continuous carbon chain with

-CHO group gives the parent name.
 Aldehydes : the -e ending is replaced by –al
 Ketones : the –e ending is replaced by –one.
 The chain is numbered in the direction that

provides the lower number for the functional
group.
2
Example
O
butanal
CH3CH2CH2C H
CH3 O
2-ethyl-4-methylpentanal CH3CH CH2CH C H
CH2 CH3
CH3 O
3,5-dimethyl-2-hexanone CH3CH CH2CH C CH3
CH3
3
IUPAC nomenclature and common names of some carbonyl
compounds.
Compound Structure IUPAC Common name

formula nomenclature
Aldehyde H2C=O Methanal Formaldehyde
CH3CH=O Ethanal Acetaldehyde
CH3CH2CH=O Propanal Propionaldehyde

CH3CH2CH2CH=O Butanal Butyraldehyde
Ketone CH3COCH3 Propanone Acetone

CH3CH2COCH3 2-butanone Ethyl methyl ketone
CH3CH2CH2COCH3 2-pentanone n–propyl methyl ketone
CH3CH2COCH2CH3 3-pentanone Diethyl ketone

4
Example
i) 2- methylpentanal
O
CH3CH2CH2CH C H
CH3
ii) 3- hexanone
CH3CH2C CH2CH2CH3
iii) 5-methyl-3- heptanone
CH3CH CH2 C CH2CH3

CH2CH3
5
iv) 3-ethylcyclopentanone
CH3 CH2 O
v) 3-cyclohexylpropanal
CH2 CH2 C H
O
6
17.3 Synthesis of Aldehydes and Ketones
a) Oxidation Alcohols
 When 1o alcohols are oxidised using

pyridinium chlorochromate (PCC) in CH2Cl2,
aldehydes are formed.
 2o alcohols are oxidised to ketones using

oxidation agent such as chromic acid (H2CrO4),
acidified potassium dichromate (K2Cr2O7,
H+), acidified potassium permanganate
(KMnO4,H+).
7
Example
1.
H O
PCC
CH3 C OH CH2Cl2
CH3 C H
H
ethanol ethanal
(alcohol 10) (aldehyde)
2.
CH3 O
KMnO4, H+
CH3 C OH CH3 C CH3
heat
H
2-propanol propanone
(alcohol 20)
8
3.
CH3
no reaction
CH3 C OH
CH3
2-methyl-2-propanol
(alcohol 30)
9
b) Ozonolysis of Alkenes
R R1 O O
i. O3
C C ii. H2O/Zn
R C H + R1 C H
H H
R R1 O O
i. O3
C C ii. H2O/Zn
R C R2 + R1 C R3
R2 R3
Example:
1.
H 3C CH2 CH3
i. O3
C C ii. H2O/Zn
H H
2-pentene
10
2.
CH2CH3
i. O3
CH3 C CH CH2 CH3 ii. H2O/Zn
3-methyl-3-hexene
3.
CH3
i. O3
ii. H2O/Zn
4-methylcyclopentene
11
c) Hydration of Alkynes (keto-enol tautomerism)
 Alkynes react with water in the presence of

mercury sulphate and sulphuric acid.
OH O
H2SO4
R C C R 1 + H 2O R C CH R1 R C CH2 R1
HgSO4
Enol Keto
Example:
H2SO4
H C C H + H 2O
HgSO4
ethyne
H2SO4
H 3C C C H + H 2O
HgSO4
propyne
12
d) Friedel- Crafts Acylation
 Acyl chloride or anhydride acid reacts with
benzene in the presence of Lewis acid to form
ketone.
Example :
O
AlCl3
+ CH3 C Cl
O O
AlCl3
+ R C O C R'
13
e) Hydrolysis Geminal Dihalides
 Hydrolysis of aromatic gem- dihalides to

produce aromatic aldehyde.
CHO
CH3 CHCl2
2Cl2 H2O
uv
 Hydrolysis can be carried out by adding one of

the following reagents:
a) aqueous calcium carbonate

b) aqueous sodium carbonate
c) 70 % H2SO4
Example :
14
17.4 Chemical Properties
A) Nucleophilic addition
 Aldehydes and ketones undergo nucleophilic

addition reaction.
R + -
C O
R1
aldehyde or ketone
(R or R1 may be H)
 The positive charge on the carbonyl carbon

atom is exposed to attack by a nucleophile.
General reaction :
OH
R
C O + Nu R C Nu
H
H
15
General Mechanism
 The nucleophile attacks the partially positive

carbonyl group and breaking the carbonyl  bond.
16
a) Addition of Hydrogen Cyanide
 Hydrogen cyanide adds to the carbonyl

groups of aldehydes and ketones to form
compounds called cyanohydrins.
OH
R
C O + HCN R C CN
H
H
cyanohydrins
OH
R
C O + HCN R C CN
R1
R1
 HCN can be obtained from the reaction of NaCN

or KCN with diluted sulphuric acid.
NaCN + H2SO 4 HCN + NaHSO 4
17
Example:
CN
CHO H C OH
NaCN
H2SO 4
Mechanism:
18
Exercises.
1.
O NaCN
H3C C H
H2SO 4
2.
O NaCN
H3C C CH3
H2SO 4
19
b) Addition of Grignard Reagent
General mechanism :
20
 Grignard reagents react with carbonyl
compounds to yield alcohol.
 Reaction of Grignard reagent with methanal
gives primary alcohol
+
H
CH3CH2CH2CH2MgX
+ HCOH
21
 Reaction of Grignard reagent with aldehyde
other than methanal gives secondary alcohol
CH2CH2CH3
H+
CH3 CH2MgX + HC O
 Reaction of Grignard reagent with ketone gives
tertiary alcohol
CH2CH3
H+
CH3CH2CH2MgX + C O
CH3
22
c) The Hydration Reaction
 The gem-diol results from a nucleophilic

addition of water to the carbonyl group of the
aldehyde.
O R
H+
H C R + H2O HO C H
OH
O R
H+
R' C R + H2O HO C R'
OH
23
Example:
1.
O
H+
H C CH3 + H2O
ethanal
2.
O
H+
H C H + H2O
methanal
3.
O
H+
CH3 CH2C CH3 + H2O
2-butanone
24
Mechanism :
O
H+
H 3C C CH3 + H2O
propanone
25
d) The Addition Of Alcohols: Hemiacetals and
Hemiketals
i. Hemiacetals and hemiketals
 Aldehyde reacts with alcohol to form
hemiacetal.
O OH
R C H + R'OH R C OR'
H
hemiacetal
 A hemiacetal or hemiketal has both – OR and
–OH groups attached to the same carbon
atom.
26
 Ketone undergoes similar reaction to give
hemiketal.
O OH
R C R' + R''OH R C OR''
R'
hemiketal
 A hemiacetal or hemiketal in acidic medium
can reacts further to produce an acetal or
ketal.
OH + OR''
H
R C OR' + R''OH R C OR'
H H
hemiacetal acetal
27
OH + OR'''
H
R C OR'' + R'''OH R C OR''
R' R'
hemiketal ketal
 An acetal has two – OR groups attached to
the same carbon atom.
28
Example:
1.
H
HCl
CH3 CH2 CH2 C O + CH3CH2CH2OH
2.
OCH2CH2CH3
HCl
CH3 CH2 CH2 C OH + CH3CH2CH2OH
H
29
3.
CH3
HCl
CH3 CH2 C O + CH3CH2CH2OH
4.
OCH2CH2CH3
HCl
CH3 CH2 C OH + CH3CH2CH2OH
CH3
30
e) Addition of Sodium bisulfite
 Addition of sodium bisulfite (NaHSO3) to

aldehyde or ketone give bisulfite salt.
_
+
O Na OH
_ +
C O + NaHSO3 C SO3H C SO3 Na
Example:
1.
CH3
C O + NaHSO3
31
2.
H
CH3 CH2 C O + NaHSO3
32
Addition of Ammonia and its derivatives.
 General reaction
H3O+
C O + H2N-Z C N-Z + H2O
aldehyde Z = -H, -OH,

or
-NH2 ,etc.
ketone
Example:
33
R NH2 C NR
amine 10 imine
H2N NH2 C NNH2
hydrazone
hidrazina
H2N OH C NOH
oxime
C O hidroxylamine
H 2N NH C NNHC6H5
phenylhydrazine phenylhydrazone
O O
H2N NH C NH2 C NNH C NH2
semicarbazide semicarbazone
H2N NH NO2
C N NH NO2
O2N
O2 N
2,4-dinitrophenylhydrazine
2,4-dinitrophenylhydrazone
34
(Brady’s reagent)
35
 When react with hydrazine, phenylhydrazine or
2,4-dinitrophenylhydrazine gives yellow precipitate
which is used as a test to determine the carbonyl
compounds.
a) Oxidation
 Aldehydes are oxidized to carboxylic acid

while ketone are hardly oxidized.
Example :
O O
H+
CH3 (CH2)4 C H + K2Cr2O7 CH3 (CH2)4 C OH
36
b) Reduction
 Aldehydes are reduced to primary alcohols and

ketones to secondary alcohols.
 Reducing agents are :
a) H2, Ni @ Pt
b) NaBH4 (sodium borohydride)
c) LiAlH4 (litium aluminium hydride)
O OH
H2, Ni
R C H R C H
aldehyde H
alcohol 10
37
O OH
H2, Pt
R C R1 R C R1
ketone H
alcohol 20
 Example:
1.
O
LiAlH4
CH3 C H
H+
ethanal
2.
O
NaBH4/H+
CH3 C CH3
or H2/pt
propanone
38
Some tests to determine carbonyl compounds
Test Purpose Observation

1 Brady’s To determine + : yellow /
carbonyl orange
H2N NH NO2 functional precipitate
O2N group
2,4-
dinitrophenylhydrazine
2 Fehling’s To determine + : brick-red

/Benedict aliphatic precipitate
Cu2+, OH - aldehyde
39
3 Tollens’ To determine + : silver
[Ag(NH3)2] +,OH -
aldehyde mirror
4 Schiff’s To determine + : pinkish

aldehyde & purple
propanone solution
5 Iodoform To determine + : yellow

I2, OH- methyl precipitate
carbonyl &
methyl alcohol
structure,
CH3
|
-C=O
40
CH3
|
-C-OH
|
41
CARBOXYLIC ACID AND
ITS DERIVATIVES
1
Structure
R C OH
RCOOH or RCO2H
(R ≡ alkyl, aryl or H)
2
NOMENCLATURE
3
IUPAC Nomenclature &
Common Name
HCOOH CH3COOH CH3CH2COOH

Methanoic acid Ethanoic acid Propanoic acid
Formic acid Acetic acid Propionic acid
CH3CH2CH2COOH CH3CH2CH2CH2COOH
Butanoic acid Pentanoic acid
Butyric acid Valeric acid
4
IUPAC Nomenclature
•The longest chain must contain the carboxyl group.
•The carboxyl group is at the terminal, therefore the carbon

of the carboxyl group is not numbered.
One COOH – carboxyl group is at one end
Two COOH – carboxyl groups are at both ends
•Name the compound as alkane, drop ‘e’ in alkane and

add ‘oic acid’ (eg: methanoic acid)
5
Br CH3 O
CH3 CH CH CH2 C OH
4-bromo-3-methylpentanoic acid
CH3 O
HO CH CH2 CH2 CH2 C OH

5-hydroxyhexanoic acid
O CH3
HO C CH2 CH CH CH CH3
5-methyl-3-hexenoic acid
6
• Two COOH groups, the compound will be named as
alkanedioic acid’
(Example: ethanedioic acid, propanedioic acid and etc)
O O
HO C CH2 CH2 CH2 C OH

pentanedioic acid
7
O CH3 O
HO C CH2 CH CH2 CH2 C OH

3-methylhexanedioic acid
H CH2 COOH
C C
HOOC CH2 H
trans 3-hexenedioic acid
8
• When R is an aryl group, the parent name is benzoic
acid
Cl COOH
4-chlorobenzoic acid
9
• An aromatic dicarboxylic acid is named as
1,x-benzenedicarboxylic acid
HOOC
COOH
1,3-benzenedicarboxylic acid HOOC

CH3
CH CH3
COOH
2-isopropyl-1,4-benzenedicarboxylic acid
10
• A cyclic carboxylic acid is named as cycloalkanecarboxylic
acid
• The C atom which is attached to —COOH is numbered as

C1
1 COOH
cyclopentanecarboxylic acid
11
1 COOH
cyclohexanecarboxylic acid
CH3
Br 1 COOH
4-bromo-2-methylcyclohexanecarboxylic acid
12
A cyclic dicarboxylic acid is named as
1,x-cycloalkanedicarboxylic acid
COOH
COOH
1,2-cyclohexanedicarboxylic acid
COOH
Cl COOH
4-chloro-1,2-cyclohexanedicarboxylic acid
13
• When a compound contains a carboxyl group and other
functional group(s), the priority is given to the carboxylic
acid as the parent name.
COOH
CH3
3-methyl-2-cyclohexenecarboxylic acid
14
PHYSICAL PROPERTIES OF
CARBOXYLIC ACIDS
15
Boiling Point
The boiling point of carboxylic acid is higher than an
alcohol, a ketone or an aldehyde (with Mr that almost the
same) because:
i. it exists as stable dimers that form hydrogen
bond.
ii. molecules in dimers are arranged closely
packed, therefore the hydrogen bonds are
relatively strong.
iii. high energy is needed to overcome the
intermolecular forces ,
 boiling point 
16
Hydrogen bond
O H O
R C C R
O H O
Hydrogen bond
17
Solubility
a) Solubility in water
• Carboxylic acids are soluble in water due to the

formation of hydrogen bond between the water
molecules and carboxylic acid molecules.
Hydrogen Bonds H
O H O H O
R C H C R
O H O H O
18
• The solubility of carboxylic acid in water is almost
the same as alcohol.
• Aliphatic carboxylic acids with C > 5 are insoluble in

water. Size of R ↑, hydrophobic area ↑.
O
hydrophilic
hydrophobic R C OH
19
• Aromatic carboxylic acids are slightly soluble in
water due to the huge aromatic ring.
• Dicarboxylic acids are relatively more soluble since

more hydrogen bonds are formed.
20
Example : Descending order of solubility
COOH COOH COOH

> >
CH3 CH CH2 CH2 CH3 CH2 CH2
COOH COOH
>
CH3 CH2 CH2 CH2
21
b. Solubility in non polar solvent
• Carboxylic acids are soluble in non polar solvent such as

benzene due to the Van der Waals forces between the
benzene and alkyl group of carboxylic acids .
O H O
R C C R
O H O
Van der Waals forces Van der Waals forces

Hydrogen bonds
22
Acidity of Carboxylic Acid
• The acidity of carboxylic acid is influenced by:
i. Resonance effect
ii.Inductive effect
23
Resonance Effect
O
Carboxylate ion : R C O-
O-
Phenoxide ion :
24
• Carboxylic acids are more acidic due to the resonance
stabilisation of the carboxylate ion.
• The electrons in carboxylate ion are delocalised

between two oxygen atoms, whereas in phenoxide
ion, the electrons are delocalized in the benzene ring.
• The C=O group in carboxylic acid is a electron-

withdrawing group which reduce the electron density
of –OH, therefore the –OH bond becomes weaker.
• Thus H+ is easily donated and carboxylic acid is more

acidic than phenol.
25
• Carboxylic acid is relatively a weak acid, however it is
stronger than phenol & alcohol
OH
> H2O
R C OH > > R OH
26
-
O O O
R C + H2O ⇌ R C
-
R C + H3O+
OH O O
carboxylic acid carboxylate ion
(resonance structure)
-
OH + H2O ⇌ O +
H3O+
phenol phenoxide ion
(resonance structure)
R—O—H + H2O ⇌ R—O– + H3O+

alcohol alkoxide ion
27
Inductive Effect
O O
EWG C EDG C
- -
O O
An electron withdrawing An electron donating
group (deactivating group) group, (activating group)
that attached to a will destabilise the
carboxylate ion will carboxylate ion and
delocalise the negative decreases acidity.
charge, thereby stabilises
the carboxylate ion and
increases acidity. 28
i. The inductive effect
electron-withdrawing group in the
compound
• electron-withdrawing groups
(e.g –NO2 ,-F,-Cl,-Br, -I ) reduce the electron
density of
–O H.
• Thus the O-H bond becomes weaker and H+

can be easily released.
• The compound is said to be more acidic

 Electron- withdrawing group increases the
acidity.
29
• Example:
CH3CHCl-COOH and CH3CH2COOH
• Cl is an electron-withdrawing groups, therefore reduce

the electron density of –OH.
• Thus the O-H bond becomes weaker and H+ can be

easily released.
• Acidity :
– CH3CHCl-COOH > CH3CH2COOH
• Electron-withdrawing groups increase the acidity.

30
ii) The electronegativity of electron-
withdrawing group in the compound
• Example:
CH3CHF-COOH and CH3CHCl-COOH
• Both F and Cl are electron-attracting group.
• The electronegativity of F > Cl
• The electron density of –OH in CH3CHF-COOH is

less, thus the –OH bond is weaker than in
CH3CHCl-COOH. Therefore, H+ is easily donated.
• Acidity : CH3CHF-COOH > CH3CHCl-COOH
31
iii) Number of electron-attracting group in
the compound.
• Example:
CH3C(Cl)2-COOH and CH3CHCl-COOH
• CH3C(Cl)2-COOH contains 2 Cl atoms that make the

bond of –OH weaker than CH3CHCl-COOH (with only
one Cl atom). Thus, H+ is easily donated.
• Acidity : CH3C(Cl)2-COOH > CH3CHCl-COOH
32
iv) The position of electron-attracting group
• Example:
CH3CH2CH(Cl)COOH and CH2(Cl)CH2CH2COOH
• The distance between Cl atom and carboxyl group in

CH3CH2CHCl-COOH is nearer compare to in
CH2ClCH2CH2-COOH.
• The –OH bond in CH3CH2CH(Cl)COOH is weaker than

in CH2ClCH2CH2-COOH, so H+ is easily donated.
• Acidity :
CH3CH2CH(Cl)COOH > CH2(Cl)CH2CH2COOH
33
(v ) The inductive effect of electron- releasing
(electron-donating) group in the compound
• Example:
CH3COOH and CH3CH2COOH
• -R is an electron –releasing group.
• The size of –R group in CH3CH2COOH is larger than in

CH3COOH, so CH3CH2- is a stronger releasing group
than CH3-.
• The electron density of –OH in CH3CH2COOH

increases and H+ is difficult to be donated.
•  Electron-releasing groups reduce the acidity of a

carboxylic acid. 34
SYNTHESIS OF
CARBOXYLIC ACIDS
35
1. Oxidation of primary alcohol and aldehyde
H R R
oxidizing oxidizing
R C OH agent C O agent C O
H H HO
1o alcohol aldehyde carboxylic acid
Common oxidizing agents are :

•KMnO4 / H2SO4
potassium permanganate
•K2Cr2O7 @ Na2Cr2O7 /H2SO4

potassium /sodium dichromat (VI)
36
2. Oxidation of Alkyl Benzene
oxidizing
R agent COOH
Cl Cl
CH3
KMnO4 , H+
CH CH3 Δ COOH
+ CO2 + H2O
37
3. Formation and Hydrolysis of nitrile
NaCN H2O,H+
R CH2 X R CH2 CN R CH2 COOH
CH2 Br CH2 CN CH2 COOH
NaCN H2O,H+
38
4. Carbonation of Grignard Reagents
R—MgX O C O R—COOH + Mg(OH)X

H2O, H+
CH2 MgBr CH2 COOH
CO2
H2O, H+ + Mg(OH)Br
39
CHEMICAL PROPERTIES OF
CARBOXYLIC ACIDS
40
• Main reactions of carboxylic acid,
a. The reaction that involves the donation of H+
from –OH group.
b. The reaction that involves the substitution of OH
group
c. The reaction that involves the reduction with
LiAlH4 to primary alcohol
41
a. The reaction that involves the donation of
H+ from –OH group
1. Neutralisation
• Carboxylic acids are acidic, it can react with base such as
NaOH (aq) to give metal carboxylate salts,
O O
R C + NaOH R C + H2O
-
OH O Na+
42
COOH COO– Na+
+ NaOH + H2O
Sodium benzoate
43
2. Reaction with electropositive metals such as Na,
K, Ca, Mg and Fe.
O O
R C OH + M R C O M + H2
Exercise:
Cl O
C
OH
+ K
44
b. The reaction that involves the substitution
of –OH group (to form its derivatives)
1. Acid chloride formation
Acid chloride can be prepared from the reaction of
carboxylic acids with thionyl chloride, SOCl2 ; phosphorous
pentachloride, PCl5 ; phosphorous trichloride, PCl3
O
SOCl2
R C Cl + SO2 + HCl
O O
PCl5
R C OH R C Cl + POCl3 + HCl
O
PCl3
R C Cl + H3PO3 45
Exercise :
SOCl2
O
PCl5
CH3 CH C OH
CH3
PCl3
46
2. Esterification
Carboxylic acids react with alcohols in the presence of mineral
acid catalyst to produce esters.
O O
H+
R C OH + H—OR’ ⇌ R C O R' + H2O
carboxylic acid alcohol ester
O O
H+ CH3 CH2 C OCH2 CH3

CH3 CH2 C OH + HOCH2CH3
⇌
propanoic acid ethanol ethyl propanoate
+ H2O
47
3. Acid anhydride formation
Acid anhydrides can be prepared from carboxylic acids by
the loss of water through heating.
O O O O
R C OH + HO C R heat R C O C R + H2O
acid anhydride
O O O O
heat CH3 C O C CH3
CH3 C OH + CH3 C OH
ethanoic anhydride
+ H2O
48
4. Amides formation
Reaction of carboxylic acids with an
ammonia or amine give amide.
O
NH3
R C NH2 + H2O
1o amide
O O
RNH2
R C Cl R C NHR + H2O
(1o amine) 2o amide
O
R2NH
R C NR2 + H2O
(2o amine)
(3o amide)
49
Exercise :
NH3
CH3 O
CH3 NH2
CH C Cl
CH3
CH3 NH
CH3
50
c. The reaction that involves the reduction with
LiAlH4 to primary alcohol
Carboxylic acid are reduced to primary alcohols by

reaction with lithium aluminium hydride, LiAlH4 .
O
LiAlH4
R C O R' R CH2 OH + R’OH
ether
1o alcohol
O
LiAlH4
CH3 CH C O CH2 CH3 ether CH3 CH CH2 OH
CH3 CH3
+ HO—CH2CH3 51
Methanoic acid, HCOOH as a reducing agent
• Methanoic acid molecule, H C OH has both
O O
and
C OH H C
carbonyl
carboxylic
• It shows the properties of both carboxylic acid and aldehyde.
• It also shows reducing properties in reactions with acidified

KMnO4 or K2Cr2O7 and Tollens’ reagent.
52
KMnO4 / H+
O CO2 + H2O + MnO2
(Brown)
H C OH
Ag(NH3)2+ Ag + CO2 + H2O
53
DERIVATIVES OF
CARBOXYLIC ACIDS
54
Reactions of carboxylic acid derivatives
i. Hydrolysis of acid chlorides
O O
H2O
R C Cl R C OH + HCl
acid chloride carboxylic acid
ii. Hydrolysis of acid anhydrides
O O O
H2O
R C O C R 2 R C OH
acid carboxylic acid
anhydride
55
Reactions of carboxylic acid derivatives
iii. Hydrolysis of esters
H2O
O H+ + ROH
carboxylic acid alcohol
R C OR
O
ester
H2O -
NaOH R C O Na
+ + ROH
alcohol
56
Example :
O
H2O
C Cl
benzoyl chloride
O O
H2O
CH3 C O C CH3
ethanoic anhydride
57
Example :
O
H2O
CH3 C O CH3
H+
methyl ethanoate
58
Relative Reactivity Of Carboxylic Acid
Derivatives
• The reactivity of a carboxylic acid derivative depends
on the basicity of the substituent (leaving group) that
attached to the acyl group
• The less basic the substituent, the more reactive the

carboxylic acid derivative.
59
Relative basicities of the leaving group (substituent)
Cl– < RCOO– < RO– < HO– < NH2–
O O O O O O
R C Cl , R C O C R , R C OR , R C OH , R C NH2
acid acid ester carboxylic amide
chloride anhydride acid
reactivity increases
60
ACYL CHLORIDE
• Acyl chloride is the most reactive because of its

electropositive carbonyl group is attach to the
electronegative Cl atom (which is a releasing group).
61
ANHYDRIDE ACID
• Anhydride acid is more reactive than ester and

amide because the carboxyl group of anhydride is
attached to the carbonyl carbon.
O O
R C O C R'
• This makes the carbonyl carbon becomes more
electropositive and can be easily attack by
nucleophile.
62
ESTER
• Ester is less reactive towards nucleophile because the

delocalization of electron makes the positive charge of
carbon can be shifted to oxygen.
• That makes the carbonyl carbon less electropositive.
H3C H3C H3C

+ - -
C O C O C O
+
R O R O R O
63
AMIDE
• Amide is the least reactive because, NH2 group is an

electron-donating group that makes the carbonyl less
electropositive.
• The resonance structure of amide shows that the

carbonyl carbon is not electropositive.
R H R H
+
N N
-
O H O H
64
The Uses of Carboxylic Acid
Carboxylic acid / derivatives Uses
Polyamide (Nylon) carpet, apparel
Ester Artificial flavors
Acetic acid Vinegar
Ethanoic anhydride Drug aspirin
Salicylic acid analgesic
65
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties
19.1 Introduction
Amines are organic derivatives of
ammonia, NH3
Classification of Amines
Primary amines H N H
Secondary amines H N R'
Tertiary amines R'' N R'
R
19.1 Classify the following amines:

i. CH3CH2CH2NH2 1°
ii. CH3CH2 N H
2° Aliphatic amines
CH3
iii. CH3CH2 N CH3 3°
CH3
iv. N CH3
2°
H
v. NH2 1° Aromatic amines
vi. N CH3
3°
CH2CH3
19.2 IUPAC Nomenclature

In primary amines, the suffix ‘amine’
replaces the ‘e’ in the name of the parent
alkane
i. CH3CH2CH2NH2 propanee
amine
3 2 1
Secondary and tertiary amines are named

as N-substituted derivatives of primary
amines
2°
ii. CH3CH2 N H
2 1 N-methylethaneamine
CH3
19.2 Examples:
Structure IUPAC Name

CH3NH2 Methanamine
CH 3 CH(NH 2 )CH 3 2-propanamine
NH2 Cyclopentanamine
CH 3CH 2CHCH2CH3 N-methylpentanamine

NHCH3
CH3 N-ethyl-N-methyl
CH3CH2 N CH2CH3
ethanamine

When multiple functional groups are
present and the –NH2 group does not
take priority, it is named as an “amino”
substituent
Examples:
NH2CH2COOH 2-aminoethanoic acid
2 1
H 2N 4
1 OH
3 2 2,4-diaminophenol
NH2

Aromatic amines are named as
derivatives of aniline
N-ethyl-N-methylaniline
19.2 Common Name

Most primary amines are named as
alkylamines
Structure IUPAC Name

CH3NH2 methylamine
CH 3CH 2NH 2 ethylamine
CH3CH2CH2NH2 propylamine
CH 3 NHCH 3 dimethylamine
CH3NHCH2CH3 methylethylamine
19.3 (i) Boiling Point
Boiling point Both primary and secondary amines

can form intermolecular hydrogen
Solubility bonds.
CH3 CH3
Basicity H HCH3
CH3
CH3N NCH H N CH3
CH3 N H CH3 NN CH
CH3
3
3
CH3 H
H
no hydrogen bond
hydrogen bonds hydrogen bonds
1° amines 3° amines 2° amines

Tertiary amines cannot form hydrogen
bonds to each other.
Examples:
The table below compares the boiling points of isomeric

amines.
Amines Class Relative Boliling
molecular points/oC
mass
CH3CH2CH2NH2 1° 59 49
CH3CH2-NH-CH3 2° 59 37
CH3 3° 59 4
|
CH3-N-CH3
Boiling Point : CH3CH2CH2NH2 > CH3CH2NH(CH3) > (CH3)3N

Boiling point Amines have higher boiling points than

alkanes or haloalkanes of similar relative
Solubility molecular mass due to intermolecular
hydrogen bonding Example
Basicity
Amines have lower boiling points than
alcohols or carboxylic acids of
comparable molecular weight because
H- bond in RNH2 is weaker than the
H- bond in ROH and RCOOH
(Nitrogen is less electronegative than the
Oxygen)
Examples: The table below compares the boiling points of organic
compounds of comparable relative molecular mass.
Amines Type Relative Boliling
molecular mass points/oC
CH3CH2CH2CH3 Alkane 58 -0.5
butane
CH3CH2Cl 12.5
Haloalkane 64.5
chloroethane
CH3CH2CH2NH2
Amine 59 48.6
1-propanamine
Boiling point Amines have higher boiling points than

alkanes or haloalkanes of similar relative
Solubility molecular mass due to intermolecular
hydrogen bonding Example
Basicity
Amines have lower boiling points than
alcohols or carboxylic acids of
comparable molecular weight because
H- bond in RNH2 is weaker than the
H- bond in ROH and RCOOH
(Nitrogen is less electronegative than the
Oxygen) Example
Examples: The table below compares the boiling points of organic
compounds of comparable relative molecular mass.
Amines Type Relative Boiling
molecular mass points/oC
CH3CH2CH2CH3 Alkane 58 -0.5
butane
CH3CH2Cl 12.5
Haloalkane 64.5
chloroethane
CH33CH
CH CH22CH22NH
NH22
1-propanamine Amine 59 48.6
CH3CH2CH2OH Alcohol
1-propanol
60 97.2
CH3COOH Carboxylic 60 118
ethanoic acid acid
Boiling Point : Carboxylic acid > Alcohol > Amine >

Haloalkane > Alkane
19.3 (ii) Solubility
Boiling point All amines including tertiary amines,

are capable of forming hydrogen
Solubility bonds with water molecules. Thus
Basicity simple amines (amines of fewer than
5 carbons) are generally water
soluble and dissolve to form basic
aqueous solutions
Comparison the solubility between 1°,2° and 3°amine
R N R : N3°H< 2 ° < 1R ° N R
TheHsolubility
H R R
o
1 Increasing2osolubility 3o
O H O H
O H
H H
H
R N H O H R N H O H
H H R H R N R
O H R
H : hydrogen bonds
3 hydrogen bonds 2 hydrogen bonds 1 hydrogen bond
per a 1° amine per a 2° amine per a 3° amine
molecule molecule molecule
19.3 Basicity
 An amine is a nucleophile (a Lewis base)
base
Boiling point
because its lone pair of non-bonding
Solubility electrons on nitrogen
H H
Basicity
+ -
H N + H OH H N H + OH
H H
Ammonia Ammonium ion
19.3 Basicity – (i) Inductive effect

 An alkyl group is electron donating
Boiling point group, and it stabilises the
Solubility alkylammonium ion by dispersing its
positive charge
Basicity H H
+ -
R N + H OH R N H + OH
H H
1° Amine alkylammonium ion
Stabilised by the
alkyl group Stronger base
19.3 H H
+ -
Boiling point
H H
Solubility 1° Amine alkylammonium ion
Basicity R R
+
H H
2° Amine alkylammonium ion
Strength as a base : Methyl, 1°, 2°

Increasing
19.3 Basicity – (ii) Resonance effect

 Aromatic amines (e.g., aniline) are
Boiling point
weaker bases than the corresponding
Solubility aliphatic and cyclic amines
Basicity Example:
NH2 NH2
Cyclohexylamine Aniline
pKb = 3.36 pKb = 9.42
19.3 Basicity – (ii) Resonance effect

Aromatic amines are less basic
Boiling point The lone pair electrons of nitrogen atom
are delocalised and overlapped with the
Solubility
aromatic ring π electrons system make it
Basicity less available for bonding to H+
NH2
NH2 NH2 NH2
arylamines are stabilised due to the 4

resonance structures
19.4 Reduction of nitro compounds
Reduction of  Aromatic amines can be prepared by

nitro compound reduction of nitro compounds using
Zn/H+ or SnCl2/H+
Reduction of
nitriles
Zn/H+ or
Reduction of NO2 NH2
amides SnCl2/H+
nitrobenzene Aniline
anline
Hoffmann’s
degradation of
amides
19.4 Reduction of nitriles
Reduction of  Nitriles are reduced to primary amines

nitro compound by H2 / catalyst, LiAlH4 / H+ or
NaBH4 / H+.
Reduction of
H2
nitriles R C N RCH2NH2
catalyst (Pt, Ni, Pd)
Reduction of
amides Example :
Hoffmann’s 1. LiAlH 4 OH
OH
degradation of
+
amides CN 2. H CH 2 NH 2
19.4 Reduction of amides
Reduction of  Reduction of an amide using LiAlH4 / H+

nitro compound or NaBH4 / H+ can yield a primary,
secondary, or tertiary amine
Reduction of depending on the type of amide used
nitriles
O 1. LiAlH 4 H
Reduction of
R C NH 2 2. H + R C NH 2 + H 2O
amides
H
Hoffmann’s
degradation of
amides
19.4 Example :
Reduction of O H
i.
1. LiAlH 4
nitro compound CH3 C NH 2 CH3 C NH 2 + H2O
+
2. H
Reduction of H
Ethanamide
nitriles Ethanamine
(2o amide)
(1o amine)
Reduction of
amides ii.
O CH3 1. NaBH4
H CH
3
+ CH3 C NH + H2O
Hoffmann’s CH3 C NH 2. H
H
degradation of
amides N-methylethanamide N-methylethanamine
(2o amine)
(2o amide)
19.4 Hoffmann’s degradation of amides
Reduction of  On warming a primary amide with bromine

nitro compound in solution of NaOH, a primary amine is
formed.
Reduction of
 This reaction is used to synthesise
nitriles
primary alkyl and aryl amines.
Reduction of O Br2 , NaOH 2-
RNH2 + CO3
amides R C NH2 H2O
Hoffmann’s amide amine
degradation of  The elimination of carbonyl group is
amides shortening the length of carbon chain by
one carbon atom.
atom
19.4 Example :
Reduction of CONH2 NH2

nitro compound
Br2, OH-
Reduction of + CO32-
nitriles H2O
Reduction of
amides
Hoffmann’s
degradation of
amides
19.5 Reaction with acyl chlorides

Reaction with :  1° and 2° amines are acylated to form
N-substituted amides
Acyl chloride O
H H O +
+ RNH3 Cl -
Acid anhydride 2 R N H + Cl C CH 3 R N C CH3
Benzenesulphonyl 1o amine 2o amide

chloride
O
Nitrous acid R R O
-
+ R2NH+2 Cl
2 R N H + Cl C CH3 R N C CH3
Bromine water 3o amide
2o amine
Formation of dye  3° amines are not acylated because they

do not have a H atom attached to N atom.
19.5 Reaction with acid anhydride

Reaction with :  1° and 2° amines are acylated to form
N-substituted amides
Acyl chloride H O O H O
R N H + CH3 C O C CH 3 R N C CH 3
Acid anhydride
1o amine acid anhydride 2o amide
Benzenesulphonyl
chloride + CH3COO H
R O O R O
Nitrous acid
R N H + CH 3 C O C CH 3 R N C CH3
Bromine water 2o amine acid anhydride 3o amide
+ CH3COO H
Formation of dye  3° amines are not acylated because they

do not have a H atom attached to N atom.
19.5 Reaction with benzenesulphonyl chloride

Reaction with : Hinsberg’s test
Acyl chloride  This reaction is used to differentiate
Acid anhydride between 1°, 2° and 3° amines.
Benzenesulphonyl
chloride
Nitrous acid
Bromine water
Formation of dye
19.5 1° amines
Reaction with :  Benzenesulphonyl chloride reacts with a
1° amine to form a white precipitate
Acyl chloride (N-substituted sulphonamides)Acidic hydrogen
Acid anhydride H O H O
-
+ OH R-N -S-
Benzenesulphonyl R-N-H Cl-S-
chloride (-HCl)
O
1o amine O
Nitrous acid N-substituted
Na O benzenesulphonamides
Bromine water R-N -S- (precipitate)
 N-substituted sulphonamides have an
O
acidic hydrogen, N-H.NaOH
Formation of dye wateritsoluble salt in aqueous NaOH.
 Therefore, dissolve
(clear solution)
19.5 2° amines
Reaction with :  Benzenesulphonyl chloride reacts with a
2° amines to form a white precipitate
Acyl chloride (N,N-disubstituted sulphonamide)
R' O R' O
Acid anhydride -
+ OH
Benzenesulphonyl R-N-H Cl-S- R-N -S-
chloride (-HCl)
o O
2 amine O
Nitrous acid N,N-disubstituted
benzenesulphonamides
Bromine water (precipitate)
 N,N-disubstituted sulphonamides do not
No reaction
have an acidic hydrogen, N-H.NaOH
Formation of dye
 Therefore, it dissolve in aqueous NaOH.
19.5 3° amines
Reaction with :  3° amine do not gives visible reaction
with benzenesulphonyl chloride
Acyl chloride
Summary of Hinsberg’s test:
Acid anhydride
NaOH
Benzenesulphonyl 1° amines  white precipitate  clear
chloride solution
NaOH
Nitrous acid 2° amines  white precipitate  do not
dissolved
Bromine water
3° amines  do not give any visible
Formation of dye change
19.5 Reaction with nitrous acid (NaNO2 + HCl)

Reaction with :  Nitrous acid (HNO2) is a weak and
unstable acid.
Acyl chloride
 It is always prepared in situ, by treating
Acid anhydride cold sodium nitrite (NaNO2) with an
Benzenesulphonyl aqueous solution of a cold dilute
chloride hydrochloride acid (-5°C).
Nitrous acid  Nitrous acid reacts with all classes of
amines
Bromine water
Nitrous acid test can be used to distinguish:
• 1° aliphatic and 1° aromatic amines
Formation of dye
• 1° and 2° aliphatic amines
19.5 1° amines (Aliphatic)

Reaction with :  Primary aliphatic amines react with
nitrous acid to yield highly unstable
Acyl chloride aliphatic diazonium salts
Acid anhydride H
NaNO2, HX + -N2 + -
Benzenesulphonyl R-N-H [ R-N NX ] R +
X
o
-5 to 0 C
chloride o aliphatic carbocation
1 amine diazonium salt
Nitrous acid (unstable)
Bromine water Observation :

Formation of gas bubbles C=C +
ROH +
RX
Formation of dye (N2)
19.5 1° amines (Aromatic)

Reaction with :  Primary arylamines react with nitrous
acid to give arenediazonium salts
Acyl chloride
Acid anhydride NH2 N2+Cl
Benzenesulphonyl NaNO2, HCl

chloride + NaCl + H2O
cold
Nitrous acid arenediazonium salt
Bromine water
Formation of dye
19.5 1° aliphatic amines and 2° aliphatic amines

Reaction with : Primary Form a mixture of alkenes,
aliphatic alcohols, alkyl halides and
Acyl chloride
amines nitrogen gas.
Acid anhydride Secondary Form secondary N-
Benzenesulphonyl aliphatic nitrosamines as yellow oil,
chloride amines which is stable under the
Nitrous acid reaction conditions.
Bromine water
Formation of dye
19.5 Identification
Reaction with bromine water
test
Reaction with : Aniline reacts with aqueous bromine to
yield white precipitates
Acyl chloride
NH2 group is an activating and ortho-
Acid anhydride para directors group
Benzenesulphonyl NH2 NH2
chloride
3Br2(aq) Br Br
Nitrous acid
room temperature + 3HBr
Bromine water
Br
(2,4,6-tribromoaniline)
Formation of dye
Observation: White precipitate formed
19.5 Formation of dye

Reaction with : Primary arylamines react with nitrous acid
to give arenediazonium salts which are
Acyl chloride stable at 0 C
Acid anhydride Arenediazonium salts also undergo coupling
Benzenesulphonyl reaction with aromatic compounds with
chloride strong electron donating group, such as –OH
Nitrous acid and –NR2 at the para position to yield azo
compounds
Bromine water
Azo compounds are usually intensely
coloured and relatively inexpensive
Formation of dye compounds, they are used as dyes
19.5
Reaction with :
Acyl chloride OH
N=N OH
Acid anhydride (orange)

+
-
Benzenesulphonyl N N: X CH3
CH3
chloride
N CH3 N=N N CH3
Nitrous acid (yellow)
Bromine water
Formation of dye
Chapter 20 : Amino Acids and Proteins
20.1 : Introduction 20.2 : Chemical Properties

20.1
-amino acid
20 amino acids
Naming
Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI
20.1 Amino acid:

acid a compound that contains
both an amino group, -NH2 and a
-amino acid
carboxyl group, -COOH
20 amino acids H
Naming CH 3 CH 2 C COOH
Zwitterion NH 2
Isoelectric point -amino acid: an amino acid in which
the amino group is on the carbon
Structures in:
adjacent to the carboxyl group
H
Acidic

Basic NH 2 C COOH
pI CH 2 CH 3
20.1
Name Structure
-amino acid
20 amino acids Glycine H CH COOH
Naming Gly NH2
Zwitterion
Alanine H3C CH COOH
Isoelectric point
Ala NH2
Structures in: CH 3
Valine
Acidic Val HC CH COOH
Basic CH 3 NH 2
pI
20.1
Name Structure
-amino acid
C H
20 amino acids Leucine 3
C H C H C H C O O H
Naming Leu 2
C H 3 N H 2
Zwitterion
Isoleucine CH 3CH 2CH CH COOH
Isoelectric point Ile CH 3
NH2
Structures in:
Phenylalanine
Acidic Phe CH2 CH COOH
NH2
Basic
pI
20.1
Name Structure
-amino acid
OH
20 amino acids Threonine
CH 3 C CH COOH
Naming Thr
H NH 2
Zwitterion CH 2 CH 2 COOH
Cysteine
Isoelectric point C
Cys CH 2 NH
Structures in: H
Methionine
Acidic HO CH2 CH COOH
Met
Basic NH2
pI
20.1
Name Structure
-amino acid
O
20 amino acids Tryptophan
OH
Naming Trp NH2
NH
Zwitterion CH 2 CH 2 COOH
Proline
Isoelectric point C
Pro CH 2 NH
Structures in: H
Serine
Acidic HO CH2 CH COOH
Ser
Basic NH2
pI
20.1
Name Structure
-amino acid
Threonine OH
20 amino acids CH3 C CH COOH
Thr
Naming H NH 2
Zwitterion Cysteine HS CH2 CH COOH
Isoelectric point Cys NH2
Structures in:
Methionine CH S CH CH CH COOH
3 2 2
Acidic
Met NH2
Basic
pI
20.1
Name Structure
-amino acid
20 amino acids Tyrosine HO CH2 CH COOH
Naming Tyr NH2
Zwitterion
Asparagine NH2─C─CH2─CH ─COOH
Isoelectric point ║ │
Asn O NH2
Structures in:
Glutamine NH2─C─CH2CH2─CH─COOH
Acidic ║ │
Gln O NH2
Basic
pI
20.1
Name Structure
-amino acid
Aspartic HOOC─CH2─CH─COOH
20 amino acids
acid │
Naming NH2
Asp
Zwitterion Glutamic HOOC─CH2CH2─CH─COOH
Isoelectric point acid │
NH2
Structures in: Glu
Acidic Lysine H2N─CH2CH2CH2CH2─CH ─COOH
Lys │
Basic NH2
pI
20.1
Name Structure
-amino acid
Arginine H2N─C─NH─(CH2)3─CH─COOH
20 amino acids │ │
Arg NH NH2
Naming
Zwitterion
Histidine HC─C=CH2─CH ─ COOH
│ │ │
His N NH NH2
Isoelectric point
Structures in: CH
Acidic
Basic
pI
20.1 IUPAC Name

i) H
-amino acid
H C COOH 2-amino ethanoic acid
20 amino acids 2 1
NH2
Naming
Zwitterion ii) CH3
3
Isoelectric point H C COOH 2-amino propanoic acid

2 1
Structures in: NH2
iii) CH2OH
Acidic 3
H C COOH 2-amino-3-hydroxy
Basic 2 1
propanoic acid
NH2
pI
20.1 IUPAC Name
-amino acid CH2CH2CH2NH2

iv) 3 4 5
20 amino acids H C COOH
2 1
Naming
NH2 2,5-diamino pentanoic acid
Zwitterion
Isoelectric point
v) CH2CH2CH2COOH
Structures in: 3 4 5 6
H C COOH
2 1
Acidic
NH2
Basic 2-amino hexanedioic acid
pI
20.1 Zwitterion
-amino acid Amino acids can undergo an
internal acid-base reaction, in which a
20 amino acids proton is transferred from the
Naming carboxyl (-COOH) to the amino group
(-NH2) to form dipolar ion called
Zwitterion
zwitterion.
Isoelectric point
CH2CH2CH3 CH2CH2CH3
Structures in: -
H C COOH H C COO
Acidic NH2 +
NH3
Basic
(neutral) (dipolar ion @
pI zwitterion)
20.1 Isoelectric Point (pI)

-amino acid In general, zwitterion is electrically
20 amino acids neutral and exists at specific pH
Naming This particular pH is called isoelectric

points
Zwitterion
Each amino acid has it’s specific pI
Isoelectric point
Lysine H2N─(CH2)4─CH ─COOH 9.7
Example: │
(Lys) NH2
Structures in: Amino Acid Structure pI
Aspartic HOOC─CH ─CH─COOH 2.9
Acidic Glycine H CH 2 COOH 6.1
acid │
Basic (Gly) N H 2 NH2
(Asp)
pI

In Acidic
20.1 The cation, H3N+— CH2 — COOH
-amino acid predominates (Amino acids as base)
c
In Basi
20 amino acids The anion, H2N— CH2 — COO-
predominates (Amino acids as acid)
Naming
I n pI
Zwitterion The zwitterion, H3N+—CH2—COO-
Isoelectric point predominates (Amino acids as
amphoteric)
Structures in: NH2CH2COOH
Gly (pI = 6.1)
Acidic + - -
+
NH3CH2COOH ↔NH3CH2COO ↔ NH2CH2COO
Basic
pI at pH < 6.1 at pH = 6.1 at pH > 6.1
20.2
Reactions of
–NH2 group:
HCl
HNO2
Reactions of
-COOH group:
NaOH
ROH
Peptide bond
Importance
20.2 a) Reaction with HCl

Reactions of R' R' _
+
–NH2 group: R C NH2 + HCl R C NH3Cl
HCl COOH COOH
HNO2
Example:
Reactions of CH2CH3 CH2CH3
-COOH group: + _
H C NH2 + HCl H C NH3Cl
NaOH COOH COOH
ROH
Peptide bond
Importance
20.2 b) With Nitrous Acid (HNO2)

R' R'
Reactions of NaNO2 / HCl +
R C NH2 R C N N
–NH2 group: -5 to 0 C o
COOH COOH
HCl diazonium ion
HNO2 elimination of N2(g)
Observation: Bubbling R'

Reactions of
of gas (N2)
-COOH group: R C+
NaOH COOH
carbocation
ROH H 2O - +
+ Cl -H
Peptide bond 2-hydroxy halocarboxylic Alkenoic
carboxylic acid acid acid
Importance
Example: CH3 CH3

NaNO2 / HCl +
H C NH2 H C N N
COOH COOH
diazonium ion
elimination of N2(g)
CH3
H C+
COOH
carbocation
+
H 2O - -H
+ Cl
CH3
CH3 CH2
H C OH
H C Cl H C
COOH
COOH COOH
20.2 c) Reaction with NaOH

Reactions of R' R'
–NH2 group: R C NH2 + NaOH R C NH2
_
HCl COOH COO Na+
HNO2
Example:
Reactions of
CH2CH3 CH2CH3
-COOH group:
H C NH2 + NaOH H C NH2
NaOH _
COOH COO Na+
ROH
Peptide bond
Importance
20.2 d) Reaction with ROH + HCl (catalyst)

Reactions of R' R'
–NH2 group: R C NH2 + R''OH R C NH2 + H 2O
HCl COOH COOR''
HNO2
Example:
Reactions of
CH2CH3 R'
-COOH group: HCl
H C NH2 + CH3OH R C NH2 + H 2O
NaOH
COOH COOR''
ROH
Peptide bond
Importance
20.2 Peptide Bond

Reactions of 2 amino acids react together, H2O
–NH2 group: is eliminated.
This is condensation reaction.
HCl
Peptides are amino acid polymers
HNO2 in which the individual amino acid
Reactions of units, are linked together by amide
-COOH group: bonds, or peptide bonds
NaOH •2 amino acids form dipeptide
ROH •3 amino acids form tripeptide
•15 – 30 amino acids form oligopeptide
Peptide bond •> 30 amino acids form polypeptide
Importance
20.2 Formation of dipeptide bond:

O H
Reactions of
–NH2 group: H2N CH2 C OH + H N C COOH
H CH3
HCl
HNO2 O H
Notes:
Reactions of H2N CH2 C N C COOH + H O
N-terminal (with free –NH2) 2is
-COOH group: H CH3
always written on the left and
NaOH C-terminal
amide bond(with
/ free –COOH) at
thepeptide
right side
bond
ROH
A dipeptide
Peptide bond
Importance
Formation of tripeptide bond:

O H CH2 OH
H2N CH2 C OH H N C COOH H N C COOH
H CH3 H H
Gly Ala Tyr
Write the structural formula of tripeptide with the following

sequence Gly-Ala-Tyr :
O H O CH2 OH
H2N CH2 C N C C N C COOH
H CH3 H H
A tripeptide
20.2 Importance of amino acids :

Reactions of  Human beings can synthesize about half
–NH2 group: of the amino acids needed to make
proteins.
HCl
 Other amino acids, called the essential
HNO2 amino acids,
acids must be provided in the
Reactions of diet.
-COOH group:  The ten essential amino acids are :
NaOH
arginine (Arg) valine (val) methionine (Met)
ROH threonine (Thr) leucine (Leu) phenylalanine (Phe)
histidine (His) isoleucine (Ile) lysine (Lys)
Peptide bond trypthophan (Trp)
Importance
20.2 Importance of proteins :

Reactions of  Proteins are the most abundant organic
–NH2 group: molecules in animals, playing important
roles in all aspects of cell structure and
HCl function.
HNO2  Examples of protein functions :
Reactions of
Class of protein Examples Functions
-COOH group:
structural protein collagen, keratin tendons, skin
NaOH
hair, nails
ROH
enzymes DNA polymerase repair DNA
Peptide bond
transport protein hemoglobin transport O2
Importance
CHAPTER 21
POLYMERS
FJ/Chemistry Unit, KMPk/Mac 2006 1
21.1 : Introduction
Polymer
- is a macro molecule that is made up of many small
repeating units called monomers linked together by
covalent bond.
nA -A-A-A-A-A-A-A-A-n
monomer polymer
- polymer can be represented by their repeating unit in

the long chain.
nA -A-n
polymer
(repeating unit)
Monomer
- is a basic molecular units that can joined to many others
to form a polymer.
2
Homopolymer
- a polymer formed from only one types monomer units.
nA -A-n
- Example :
nCH2 CH2 -CH2CH2-n
ethene polyethene
(ethylene) (polyethylene)
3
Copolymer
- a polymer formed from two or more different monomers.
nA + nB -A-B-n
- Example :
nCH2 CCl2 + nCH2 CHCl -CH2-CCl2-CH2-CHCl-n
1,1-dichloroethene 1-chloroethene Saran®
4
21.2 : Structures of Polymers
21.2.1 : Linear Polymers
Linear polymer is a polymer consist of monomers that are
linked in straight and long continuous chain.
Linear or straight-chain polymer can be folded back upon
themselves in a random fashion.
Linear polymer is recycleable because it is soft and can be
reformed when heated.
-A-A-A-A-A-A-A-A-n
monomers link together
in a straight chain
folded linear polymer
in a random fashion
5
21.2.2 : Cross-linked Polymers
Cross-linked polymer contains branches that connect linear

polymer chain, as shown in the figures below.
-A-A-A-A-A-A-A-A-A-A-A-A-
X X
-A-A-A-A-A-A-A-A-A-A-A-A-
• Long polymer chain cross-linked by branched
Cross-linked polymer is harder (rigid) and more elastic

polymer compared to linear polymer.
It also cannot be remelted or remolded again.
The equation below shows the chemical reaction for the

rubber vulcanization process.
6
In a vulcanization process, long chain of polyisoprene are
cross-linked by sulphur atoms.
CH3 CH3
-CH2C CH-CH2- + -CH2C CH-CH2-
sulphur
CH3 CH3
-CHC CH-CH2-CHC CH-CH2-
S S
-CHC CH-CH2-CHC CH-CH2-
CH3 CH3
After vulcanization rubber becomes more stable over wide
ranges of temperature and far more durable than natural
rubber.
7
21.3 : Types of Polymers
21.3.1 : Natural Polymers
Natural polymers are polymers that synthesized in nature
or naturally occurring polymers.
i. Proteins
Protein are the most abundant organic molecules in animals
such as enzymes, hormones, hemoglobin and many other
things.
It is a natural polymer built from amino acids linked by
amide bonds.
H O
HN-C-C
R n
8
ii. Carbohydrates
Carbohydrates such as starch is also a polymer.
i. Starch (amylose)
CH2OH CH2OH
O O
H H HH H H
O OH H O OH H O
H OH H OH
n
α-(1,4)-glycosidic linkages
ii. Starch (amylopectin)

- contains α-(1,4)-glycosidic and α-(1,6)-glycosidic
linkages.
9
iii. Natural Rubber
Natural rubber is a polymer of 2-methyl-1,3-butadiena,
also known as isoprene.
n CH2=C-CH=CH2 -CH2-C=CHCH2-
CH3 CH3 n
isoprene cis-polyisoprene
Another name for natural rubber is cis-1,4-polyisoprene.

All the double bond in natural rubber are cis-
configuration.
Natural rubber is soft, not strong or elastic and sticky,
that makes it less useful.
In order to make it more useful rubber has to undergo a
vulcanization process.
10
21.3.2 : Synthetic Polymers
Synthetic polymers are polymers that are prepared in

industries from monomers that have gone through
polymerization process.
Polymerization is a process that combines monomers to
form polymers.
Synthetic polymers can be classified base on their method
of preparation ( polymerization process ).
21.3.2.1 : Addition Polymerization
Addition polymerization is the addition reaction in which

unsaturated monomers are joined together by covalent
bonds to form a polymer without elimination of a small
molecule.
Polymers obtained by addition polymerization are called
addition polymers.
11
Therefore, addition polymer always involves the
polymerization of monomers which have double bond within
the monomers.
Peroxide is used as initiator in addition polymerization.
i. Formation of polyethene
n CH2 CH2 ROOR -CH

( 2-CH2-
)n
ethene polyethene
ii. Formation of polyvinyl chloride
n HC CH2 ROOR (
-HC-CH 2-
)n
Cl Cl
chloroethene polychloroethene
(polyvinyl chloride or PVC)
12
iii. Formation of polystyrene
n HC CH2 ROOR (
-HC-CH 2-
)n
phenylethene Polyphenylethene
(styrene) (polystyrene)
iv. Formation of polyisopropene
n CH 2 =C-CH=CH 2 -CH 2 -C=CHCH 2-

CH 3 CH 3 n
isoprene polyisoprene
13
21.3.2.2 : Condensation Polymerization
Condensation polymerization is a process that combines the

monomers with elimination of a small molecule such as
water, methanol, hydrogen chloride or ammonia to form a
polymer.
The polymers obtained from condensation polymerization

are called condensation polymers.
The monomers involves in this polymerization must have at

least two identical or different functional group in the
molecule.
When a carboxylic acid with two –COOH group reacts with

an amine with two –NH2 groups, a polyamide is formed.
When a carboxylic acid with two –COOH group reacts with

an alcohol with two –OH groups, a polyester is formed.
14
(A). Polyamides
i. Formation of Nylon 6,6
O O
n H2N-(CH2)6-NH2 + n HO-C-(CH2)4-C-OH
hexane-1,6-diamine hexane-1,6-dioic acid
H H O O
(
-N-(CH 2)6-N-C-(CH2)4-C-
)n + n H2O
Nylon 6,6
ii. Formation of Nylon 6

O O
n H2N-(CH2)5-C-OH (
-NH-(CH 2)5-C-
)n + n H2O
6-aminohexanoic acid Nylon 6
15
iii. Formation of Kevlar
H H O O
n H-N- -N-H + n Cl-C- -C-Cl
1,4-diaminobenzene terephthalic acid
H H O O
N- -N-C- -C n + n HCl
Kevlar
(B). Polyester
The repeating functional groups in this polymer chain are

ester.
The most familiar polyester is polyethylene terephthalate
known as Dacron and Terylene. 16
The polymer is formed by the reaction of ethylene glycol
with methyl ester or tetephtalic acid.
In this process, a molecule of methanol is split out for
each new ester group formed.
i. Formation of Dacron
O O
n CH3O-C- -C-OCH3 + n HO-CH2CH2-OH
1,2-ethanediol
dimethyl terephthalate
(ethylene glycol)
O O
(
-O-CH 2CH2-O-C- -C-
)n + n CH3OH
Dacron or poly(ethylene terephthalate) metanol
17
ii. Formation of Terylene
O O
n HO-CH 2CH 2-OH + n HO-C- -C-OH
ethane-1,2-diol benzene-1,4-dicarboxylic acid
O O
(
-O-CH 2CH 2-O-C- -C-
)n + n H 2O
water
Terylene
18
21.4 : Uses of Synthetic Polymers
No. Polymer Uses

1 Polyethene plastics, drinking bottles, toys
piping, floor tiles, clothing, toys,
2 Polyvinyl chloride
wire covering
3 Polystyrene containers, thermal insulation-ice buckets
4 Nylon 6 Textile
5 Nylon 6,6 Sweater
6 Kevlar Bullet proof vest
7 Dacron Fabric
8 Terylene Fiber-optic material
19

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 CHEMISTRY – The Central Science, 9th Ed. Theodore

 GENERAL CHEMISTRY – Principle & Structure, 6th Ed.

 ORGANIC CHEMISTRY, 7th Ed – T.W.Graham

 ORGANIC CHEMISTRY, 4th Ed – L.G. Wade, Jr,

 ORGANIC CHEMISTRY, 6th Ed – John

(a) Describe proton, electron and neutron in

 Matter may consists of atoms, molecules or

 A mixture is a combination of two or

A compound is a substance composed of

SOLID LIQUID GAS

 Electrons move around the region of the atom.

 Proton number (Z)  is the number of

 Nucleon number (A)  is the total number

Particle Mass Charge Charge

(gram) (Coulomb) (units)

Proton (p) 1.67 x 10-24 +1.6 x 10-19 +1

Neutron (n) 1.67 x 10-24 0 0

Z = Proton number of X (p)

The number of neutrons

Symbol Number of : Charge

Species Number of : Notation

(b) Calculate the average atomic mass of an

i. Relative Atomic Mass, Ar

Mass of one atom of element

 Atomic mass unit, amu is defined to be one

 Mass of a 12C atom is given a value of exactly 12

 The relative isotopic mass is the mass of an

Relative molecular mass, Mr

Calculate the relative molecular mass of

shows that Mg consists of 3

 The height of each line is

At the end of this topic, student should be able

(a) Calculate the average atomic mass of an

Average atomic  (% abundance  isotopic mass)

Relative atomic mass Ne = 20.2

Copper occurs naturally as mixture of

Relative atomic mass Cu = 63.55

Naturally occurring iridium, Ir is composed

respectively. Calculate the relative atomic

Average atomic =  abundance  isotopic mass 

(5  191 .021 u)  (8  193 .025 u)

Relative atomic mass Ir = 192.254

a) Define mole in terms of mass of

 Atoms and molecules are so small – impossible

 A unit called mole (abbreviated mol) is devised

 A mole is the amount of matter that contains

 The number of atoms in 12 g of 12C is called

1 mol of O2 contains 6.02  1023 O2 molecules

1 mol of NH3 contains 6.02  1023 NH3 molecules

Mass of 1 mol C atoms consists of 6.02 x 1023 C atoms

From the periodic table, Ar of nitrogen, N is 14.01

3.01110 23 molecules  1 mol

= 0.5000 mol of O2 molecules

= 0.4000 mol of N atoms

0.25 mol Cl2  2  35.45 g  0.25 mol

1.60 mol Cl2 occupies 1.60 mol  22.4 L

Calculate the volume occupied by 19.61 g of

Mass of 0.50 mol CH4 16=.05 g  0.50 mol

0.50 mol CH4 gas occupies 22.4 L  0.50 mol