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CHEMISTRY
CHEMISTRY
CHEMISTRY

CHEMISTRY SK016
Chapter

1.0
2.0
3.0
4.0
5.0
6.0
7.0

08/16/11

Topics

Hours

Matter
Atomic Structure
Periodic Table
Chemical Bonding
State of Matter
Chemical Equilibrium
Ionic Equilibria
Total

7
7
4
2
7
5
12
54

matter

CHEMISTRY SK026
Chapter

Topic

8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0

Thermochemistry
Electrochemistry
Reaction Kinetics
Intro To Organic Chemistry
Hydrocarbons
Aromatic Compounds
Haloalkanes (Alkyl halides)
Hydroxy compounds

08/16/11

matter

Hours

4
6
7
4
8
3
4
3
3

CHEMISTRY SK026
Chapter

16.0
17.0
18.0
19.0
20.0

08/16/11

Topic

Carbonyl
Carboxylic acids & Derivatives
Amines
Amino acids and Proteins
Polymers

matter

Hour

4
4
5
2
1

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 Astructured)


(Part
B-long structured)
-100%
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matter

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.

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matter

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

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matter

Chapter 1 : MATTER
1.1 Atoms and Molecules
1.2 Mole Concept
1.3 Stoichiometry

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1.1 Atoms and Molecules

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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.
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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.

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matter

11

Classifying Matter

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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

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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
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LIQUID
matter

GAS
15

1.1 Atoms and Molecules


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)

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matter

16

Modern Model of the Atom

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Electrons move around the region of the atom.


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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

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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.

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20

Examples:

1
1

235
92

2
1

H (D)

238
92

3
1

H (T)

Isotope Notation
An atom can be represented by an isotope
notation ( atomic symbol )

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X=

Element symbol

Z =

Proton number of X (p)

A=
=

Nucleon number of X
p+n

matter

22

Nucleon number of
mercury, A = 202

Total charge on
the ion

The number of neutrons


=AZ
= 202 80
= 122

Proton number
of mercury,
Z = 80

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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 :
Proton

200
80

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Neutron Electron

Hg

63
29

Cu

17
8

O 2

59
27

Charge

Co 3
matter

25

Exercise 2
Write the appropriate notation for each of the
following nuclide :
Species

A
B
C
D
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Number of :
Notation
Proton
Neutron Electron for nuclide
2
1
1
7

2
2
1
7
matter

2
0
1
10
26

b) Molecules
A molecule consists of a small number of
atoms joined together by bonds.

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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

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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.
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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

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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 = 1.660538710-24 g

The relative isotopic mass is the mass of an


atom, scaled with 12C.

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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:

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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

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1
12

molecular
mass, Mr
Mass of one molecule
x Mass of one atom of

matter

12

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

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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

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36

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37

Mass Spectrum of Monoatomic Elements

Modern mass
spectrum converts
the abundance into
percent abundance

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38

Relative abundance

Mass Spectrum of Magnesium

The mass spectrum of Mg


shows that Mg consists of 3
isotopes: 24Mg, 25Mg and
26Mg.

The height of each line is


proportional to the abundance
of each isotope.

63
8.1 9.1
24

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25 26

m/e
(amu)

matter

24Mg

is the most abundant of


the 3 isotopes

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.

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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


elements isotope as found in a particular
environment is the relative atomic mass, Ar of
the atom.
(isotopicmass abundance
)

Averageatomicmass
abundance

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41

Example 1:
Calculate the relative atomic mass of neon
from the mass spectrum.

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42

Solution:
Average atomic
mass of Ne
=

(% abundance isotopic mass)


=
% abundanc e

(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.

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44

Solution:
Average atomic
mass of Cu
=
=

(%abundance isotopicmass)

=
% 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

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46

Solution:

Average atomic = abundance isotopic mass


abundance

mass of Ir
=
=

(5 191 .021 u) (8 193 .025 u)


(5 8 )

192.254 u

Relative atomic mass Ir = 192.254


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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+

Cl2 + e

Cl2+

+ 2e

Cl2 + e 2Cl+ + 2e

35Cl-37Cl+
37Cl-37Cl+
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
At the end of this topic, students should be
able to:

a) Define mole in terms of mass of


carbon-12 and Avogadros constant, NA

Avogadros 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
Avogadros 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
23 atoms
6.02 10N
23 atoms
3 6.02 10H

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 =


The molar mass of N atom =

14.01 g

14.01 g mol1

The molar mass of nitrogen gas = 28.02 g mol1

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 mol1

Learning Outcome
At the end of this topic, students should be
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.
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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

3.011 x 1023

1 mol of O2 molecules

3.01110 23 molecules 1 mol


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

1.204 x

1023

1mol of N2 molecules
2 mol of N atoms

molecules of N2

23
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

7.528 x

1023

23
16
.
05
g

7.528

10
CH4 molecules
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

273.15 K
0 C

and Pressure
1 atm

101325 N m-2
101325 Pa

760 mmHg

Standard Molar Volume

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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

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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 g
2(14.01) g mol 1

19.61

mol 22.4 L
2(14.01)
of N2 occupies
1 mol

= 15.7 L
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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:
16.05
g
(a) Mass of 1 mol CH4
=
Mass of 0.50 mol CH4 16=.05 g 0.50 mol

1 mol

= 8.0 g
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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
2 mol of H atoms

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MATTER

6.02 x 1023 atoms


2 x 6.02 x 1023 atoms
1.2 x 1024 atoms
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:
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1 dm3
1 dm3

= 1000 cm3
=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.
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MATTER

74

The relationship between empirical formula


and molecular formula is :
Molecular formula = n ( empirical formula )

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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.

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MATTER

76

Solution:
C

Mass

85.7

14.3

Number
of moles

85.7
12.01

14.3
1.01

Simplest ratio

= 7.1357

= 14.1584

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

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MATTER

79

Learning Outcome
At the end of this topic, students should be
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
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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

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MATTER

solvent
81

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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

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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

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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:

MNaCl

nNaCl
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

= 0.500 mol L1 250.00 103 L

mass of CaCl2 nCaCl x molar mass


2

= (0.500 250.00 103) mol


(40.08 + 2(35.45)) g mol1

= 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

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MATTER

89

Example:
What is the molality of a solution
prepared by dissolving 32.0 g of CaCl2 in
271 g of water?

Solution:

nCaCl 2

32.0 g

40.08 2(35.45) g mol-1

32.0 mol

Molality of CaCl2 110.98 3


271 10 kg

1.06 mol kg1

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
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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.

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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

nwater

Xethanol

200.0 g
(2(12.01) 5(1.01) 16.00) g mol1

150.0 g
1
(2(1.01) 16.00) g mol

200.0 mol

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
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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.

%v

volume of solute

x 100
v volume of solution

Note:

mass of solution
Density of solution
volume of solution
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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
Vethanol

35.5% 250.00 mL

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 C. 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;
Vsolution

mass solution
=
solution

masssolution = massNaOH + masswater


massNaOH = nNaOH molar mass of NaOH
= 6.25 mol (22.99 + 16.00 + 1.01) g mol1
= 250 g

masssolution = 250 g + 1000 g


= 1250 g
Vsolution =

1250 g
1

1.33 g mL

MNaOH

6.25 mol
=
3
1250
10 L

1.33

= 6.65 mol L1

(b) XNaOH =

nNaOH
nNaOH n water

1 kg of water contains 6.25 mol of NaOH

nwater

mass water
=
molar mass of water
1000 g

(2(1.01) 16.00) g mol


XNaOH =

6.25 mol
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.

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MATTER

114

Example:

xA +

yB

zC +

Reactants

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wD

Products

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

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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 nonmetallic 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.

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MATTER

117

Example:
Balance the chemical equation by applying the
inspection method.
NH3 + CuO Cu + N2 + H2O

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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

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MATTER

119

Redox Reaction

Mainly for redox (reduction-oxidation)


reaction

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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

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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 BrSn4+ + 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

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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

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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)
number for halogen = +ve

oxidation

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

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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-

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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.

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MATTER

127

Balancing Redox Reaction In Acidic


Solution
Fe2+ + MnO4- Fe3+ + Mn2+
1. Separate the equation into two halfreactions: reduction reaction and oxidation
reaction
i. Fe2+ Fe3+
ii. MnO4- Mn2+
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MATTER

128

1. Balance atoms other than O and H in each


half-reaction separately

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i.

Fe2+ Fe3+

ii.

MnO4- Mn2+

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
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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.

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i.

5 x (Fe2+ Fe3+ + 1e)


5Fe2+ 5Fe3+ + 5e

ii.

MnO4- + 8H+ + 5e Mn2+ + 4H2O

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+


Total charge reactant
= 5(+2) + (-1) + 8(+1)
= + 10 - 1 + 8
= +17

5Fe3+ + Mn2+ + 4H2O


Total charge product
= 5(+3) + (+2) + 4(0)
= + 15 + (+2)
= +17

Exercise: In Acidic Solution


C2O42- + MnO4- + H+ CO2 + Mn2+ + H2O
Solution :

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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.

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MATTER

135

Example: In Basic Solution


Cr(OH)3 + IO3- + OH- CrO32- + I- + H2O

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MATTER

136

Exercise:
1.
2.
3.
4.

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H2O2 + MnO4- + H+ O2 + Mn2+ + H2O


(acidic medium)
Zn + SO42- + H2O Zn2+ + SO2 + 4OH(basic medium)
MnO4- + C2O42- + H+ Mn2+ + CO2 + H2O
(acidic medium)
Cl2 ClO3- + Cl(basic medium)

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.

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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 C 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 +
(b)

O2

CO2 +

H2O

22.4 dm3 is the volume of 1 mol CO2

20.0 dm3 is the volume of

20.0 dm 1 mol

2 mol CO2 produced by 1 mol C2H422.4 dm


mol CO2 produced by
C2H4

20.0
22.4

CO2

20.0

mol

1 mol
22.4

2 mol

massethane

20.0

22.4 mol x [2(12.01) 4(1.01)] g mol-1


2

= 12.5 g

Learning Outcome
At the end of this topic, students should be
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

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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

6 mol H2 produce

2 mol NH3

6 mol 2 mol
3 mol

= 4 mol NH3

or
1 mol N2
6 mol N2

react with 3 mol H2


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

6 mol N2

produce

2 mol NH3

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?

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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

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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

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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

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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 Bohrs Atomic Model

Learning Outcomes
At the end of this topic students should be able
to:a) Describe the Bohrs atomic model.
b) Explain the existence of electron energy
levels in an atom.
c) Calculate the energy
of electron at 18
its level
1

E n= R H

(orbit) using.

, R H = 2.18x10

Learning Outcomes
d) Describe the formation of line spectrum of
hydrogen atom.
e) Calculate the energy change of an electron
1 1
RH
2
duringE =transition.
2
n1 n2

f)

where RH = 2.18 10

18

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
1 Pfund
1
7
1
Brackett
and
series:
= RH

where
R
=
1.097
10
m
H
2
2
n1

n2

n1 n2

g) Calculate the ionisation energy of hydrogen


atom from the Lyman series.

Learning Outcomes
i)

State the weaknesses of Bohrs atomic


model.

j)

State the dual nature of electron using de


Broglies postulate and Heisenbergs
uncertainty principle.

Bohrs Atomic Model


In 1913, a young
Dutch physicist, Niels
Bhr 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.

Bohrs Atomic Model


Bhr 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.

Bohrs Atomic Model


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

Bohrs Atomic Model


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

Bohrs Atomic Model


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)

Bohrs Atomic Model


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 = h = E3-E1

n =1

n=2 n=3 n=4

Electron falls from higher to lower energy level .


A photon is emitted.
E = h = 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:

Ef = RH

1
2
nf

1
1
E = R H 2 R H 2

n
n
f
i

E i= R H

1
2
ni

1
1
Thus, E = R H 2 2
n

n
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
Thus :

E =

hc

Rydberg Equation
Wavelength emitted by the transition of
electron between two energy levels is
calculated using Rydberg equation:

= RH

1
1
2
2
n1 n2

where R H = 1.097 10 m
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
Spectra

Line
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.

Formation of Atomic / Line


Spectrum

Formation of Atomic / Line


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
A spectrum that
contains all
wavelength without
any blank spots.
Example: Rainbow.

Line Spectrum
A spectrum that contain
only specific
wavelengths.
A spectrum of discrete
lines with certain
wavelengths.
Example: Emission
spectrum an element.

Formation of Line Spectrum


(Lyman Series)
n=
n=5
n=4
Energy

n=3
n=2

n=1

Emission of photon

Line
spectrum

Lyman Series

Formation of Line Spectrum


(Balmer Series)
n=
n=5
n=4
Energy

n=3
n=2

n=1

Emission of photon

Line
spectrum

Lyman Series

Balmer Series

Energy Level in Hydrogen Atom

Example
Complete the following table
Spectrum
region

Series

nf

ni

Lyman

2,3,4,

ultraviolet

Balmer

3,4,5,

Visible/uv

Paschen

4,5,6,

Infrared

Brackett

5,6,7,

Infrared

Pfund

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

C D E

Line
spectrum

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

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

C B A

Line
spectrum

(a)

Paschen series

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 =
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)
E= R H

1
1
2
2
n1 n2
1
1
2
2
1

18

= 2.18 10

18

2.18 10

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/

= 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 Bohrs 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 cant define the
precise location of a wave because a wave
extends in space.

de Broglies 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 Broglies Postulate
h
=
m
h = Planck constant (J s)
m = particle mass (kg)
= velocity (m/s)
= wavelength of a matter wave

Heisenbergs 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,

x
where

h
p
4

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 threedimensional 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

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)

Angular Momentum Quantum


Number, l
Letters are assigned to different numerical
values of
Value of l
0
1
2
3

Symbol Orbital shape


s
spherical
p
dumbbell
d
cloverleaf
f

Angular Momentum Quantum


Number, l
value is depend on n. (i.e., 0 l < n).
One subshell
If n = 1, l = 0 (s-orbital)
(s orbital)
If n = 2, l = 0 (s-orbital)
two subshells
(s and p orbitals)
= 1 (p-orbital)
If n = 3, l = 0 (s-orbital)
= 1 (p-orbital)
= 2 (d-orbital)

three subshells
(s, p, and dorbitals)

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 : + and -

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

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

dxy

dz2

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 = + and -
Can be simplified as (2,0,0,+)
or (2,0,0,-)
n, l , m, s
n, l , m, s

Exercise

Shell n
1
2

1
2

Orbital
notation

No. of orbitals

1s

2s

2p

-1,0,+1

Exercise
Predict the following quantum numbers whether
they are allowed or not
(a) (1,0,0,-)
(b) (2,0,1,1)
(c) (0,1,1,+)
(d) (4,1,0,-)

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

Electronic Configuration
Method 2: s,p,d,f notation
Example: 8O
2
1s

Principal quantum
number, n

2
2s

Number of electrons
in the subshells
4
2p

Azimuthal quantum
number, l

Electronic Configuration
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
3d

energy

Energy

n=4
4s
n=3

3p
3s

n=2

2p
2s

n=1
1s

Orbital energy levels


in a many-electron atom

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)

Hunds 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.

Element

Expected (Aufbau
Principle)

Observed/actual

Cr (Z=24)

1s22s22p63s23p6 4s2
3d4

1s22s22p63s23p6 4s1 3d5

Cu (Z=29)

1s22s22p63s23p6 3d9
4s2

1s22s22p63s23p6 3d10
4s1

Orbital diagram
24Cr

18[Ar]
3d

4s

3d orbital with a half filled orbital arrangement are more


stable.
24Cr

Actual

18[Ar]
3d

4s

2 2s2 2p6 3s2 3p6


Ar
:
1s
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
2 2s2 2p6 3s2 3p6
Ar
:
1s
18

4s

3.0 PERIODIC TABLE

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.

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
Group 2
Group 3-11
Group 17
Group 18
Group 12

:
:
:
:
:
:

alkali metals (except H)


alkaline earth metals
transition metals
halogens
inert/ noble gases
Zn, Cd, Hg

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

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.

s- block
Group 1 and 2
The filling of valence electrons involve the s
orbital
Configuration of the valence electrons :
ns1 to ns2
Eg:
2 2s2 2p6 3s1
Na
:
1s
11
2 2s2 2p6 3s2 3p6 4s2
Ca
:
1s
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.
2 2s2 2p6 3s2 3p1
Al
:
1s
13
2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2
Te
:
1s
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

2 2s2
K
:
1s
19
2p6 3s2 3p6
2
1
Mg
:
1s
12 4s
2 2p62 3s22
2s
P
15 : 1s 2s
2p6 3s2 3p3
2 2s2
Bv
:
1s
35
2p6 3s2 3p6
2 2s52
2
10
Ni
:
1s
4s
4p
28 3d
2p6 3s2 3p6
2 3d
8 2 2s2
Zr
:
1s
4s
40
2p6 3s2 3p6
4s2 3d10 4p6
5s2 3d2

s
p

3
3

2
15

Numbe
r of
velenc
1
e
electro
2
n
5

17

10

10

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

18

Inert gas / block p


Block p

B
C
D

17

Block s
Transition element/
block d
Inert gas / block p

18

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 ()
Size

volume

V = 4/3 r3 , V r

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
of P
Both Si and P are in the third period and Si is
to the left of P.
Atomic radius decreases as we move from
left to right.
Therefore, the radius of P is smaller than Si.
Thus the order of increasing radius :

Group
14

Group
15
N

Si

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
P315
proton
S216
Cl17
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- H = 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
B

N
O

37

Anomalous cases in Period 2


a) Between group 2 and 13

2 2s2 2p1 in group 13 has a lower IE


B
:
1s
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 )
2 2s2 2p4( the partially-filled 2p orbital)
O
:1s
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
899

IE2
1757

IE3
14850

IE4
21005

43

The ratio between the ionization energies are:


IE 2
IE 1
IE 3
IE 2
IE 4
IE 3

1757

1.95
899
14850

8.45
1757
21005

1.41
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
800

IE2
1580

IE3
3230

IE4
IE5
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
Melting
point
(oC)
Boiling
point
(oC)

Na
98

Mg Al
Si
P S
Cl
Ar
650 660 1410 44 120 -101 -189

890 1120 2450 2360 280 445 -34 -186

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.

The more valence


electrons, the stronger
the metallic bond and
the higher the melting
/ boiling point

Na+ Na+

Na+
e

Na+
Na+

Na+
e

Na+ Na+

Na+
e

Na+ Na+

Na+

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.

metal

Metalloids
(semimetal)

nonmetal

60

Acid-base behavior of oxides of Period 3


For Period 3:
Na Mg
Al

Si

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

13

14

15

16

17

18

Valence
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
+

Example 3: LiF
+

Lewis structure and formation of ionic compounds

1) CaCl2
+

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

7e-

F F

7e-

8e- 8e-

Lewis structure of F2
single covalent bond

lone pairs

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

Double bond two atoms share


two pairs of electrons

O
8e-

8e-

8e-

double bonds

or O

double bonds

Triple
bond

two
atoms
share
+
three pairs of electrons

N
8e-

or

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 :
3H :
Total :

5e
3e
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

1.54

1.34

C C

1.20

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.
ii.
iii.

64

VSEPR theory
5 basic shapes
polarity

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 pairlone pair
repulsion

> Lone pair-bonding > Bonding pair-bonding


pair repulsion
pair 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.

69

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
minimize repulsion.

A.

Molecules with 2 bonding pairs


shape

Example: BeCl2
Lewis structure
Be : 2e

180

2Cl :14e
Total : 16 e
..
..
Cl:
Cl Be
..

..

:
70

Linear

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 :
..

..

:
71

..
Cl

..

Cl

Trigonal planar

C. Molecules with 4 bonding pairs


Example: CH4
Lewis structure

Equal repulsion
between bonding pairs
equal angle

H
H

109.5

Tetrahedral
72

D. Molecules with 5 bonding pairs


Example: PCl5
Lewis structure
:

90

..
..

..

..

Cl

73

..
Cl :

120

..

..
Cl :
..

..
Cl

..

Cl

Shape:

Trigonal bipyramidal

E. Molecules with 6 bonding pairs


Example: SF6
Lewis structure
S :
6e
6F : 42e
Total
: 48e

F
F
F

S
F
F

74

Octahedral
90o
90o

2 electron pairs in the valence shell


of central atom:
Class of
molecules

Number
of bonding
pairs

Number
of lone
pairs

AB2

Shape

180

Linear
75

3 electron pairs in the valence shell


of central atom:
Class of
molecules

Number
of bonding
pairs

Number
of lone
pairs

AB3

Shape

120

76

trigonal planar

4 electron pairs in the valence shell


of central atom:
Class of
molecules

Number
of bonding
pairs

Number
of lone
pairs

AB4

Shape

109.5o

77

Tetrahedral

5 electron pairs in the valence shell


of central atom:
Class of
molecules

Number
of bonding
pairs

Number
of lone
pairs

AB5

Shape

90

120

78

Trigonal pyramidal

6 electron pairs in the valence shell


of central atom:
Class of
molecules

Number
of bonding
pairs

Number
of lone
pairs

AB6

Shape

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 pairlone pair
repulsion

> Lone pairbonding


pair repulsion

> Bonding pairbonding 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

Number of electron pair : 4


Example : NH3
Class of molecules : AB3E
Molecular shape : Trigonal pyramidal

84

Number of electron pair : 4


Example : H2O
Class of molecules : AB2E2
Molecular shape : Bent / V-shaped

85

Number of electron pair : 5


Example : SF4
Class of molecules : AB4E
Molecular shape : Distorted tetrahedron /
seesaw

86

Number of electron pair : 5


Example : ClF3
Class of molecules : AB3E2
Molecular shape : T-shaped

87

Number of electron pair : 5


Example : I3 Class of molecules : AB2E4
Molecular shape : Linear

88

Number of electron pair : 6


Example : BrF5
Class of molecules : AB5E
Molecular shape : Square pyramidal

89

Number of electron pair : 6


Example : XeF4
Class of molecules : AB4E2
Molecular shape : Square planar

90

Shape of molecules which the central


atom has one or more lone pairs
Class of
molecules

Number
of bonding
pairs

Number
of lone
pairs

AB2E

Shape

Bent / V-shaped
91

Bond angle : < 120o

4 electron pairs in the valence shell


of central atom:

92

Class of
molecules

Number
of bonding
pairs

Number
of lone
pairs

AB3E

Shape

Trigonal pyramidal
Bond angle : < 109.5o

4 electron pairs in the valence shell


of central atom:
Class of
molecules

Number
of bonding
pairs

Number
of lone
pairs

AB2E2

Shape

Bent / V-shaped
Bond angle : < 109.5o
93

5 electron pairs in the valence shell


of central atom:

94

Class of
molecules

Number
of bonding
pairs

Number
of lone
pairs

AB4E

Shape

Distorted tetrahedral
(see-saw)
Bond angle : < 90o

5 electron pairs in the valence shell


of central atom:

95

Class of
molecules

Number
of bonding
pairs

Number
of lone
pairs

AB3E2

Shape

T-shaped
Bond angle : < 90o

5 electron pairs in the valence shell


of central atom:

96

Class of
molecules

Number
of bonding
pairs

Number
of lone
pairs

AB2E3

Shape

Linear
Bond angle : 180o

6 electron pairs in the valence shell


of central atom:

97

Class of
molecules

Number
of bonding
pairs

Number
of lone
pairs

AB5E

Shape

Square pyramidal
Bond angle :90o and
180o

5 electron pairs in the valence shell


of central atom:

98

Class of
molecules

Number
of bonding
pairs

Number
of lone
pairs

AB4E2

Shape

Square planar
Bond angle : 90o

99

COMPARISON OF BOND ANGLE


IN CH4, NH3 AND H2O

109.5o

100

107.3o

104.5o

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 ( ).

= Qr

Where : = 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
105

The consequent charge separation can be


represented by :
+ : partial positive charge
- : 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:

109

Carbon dioxide, CO2


Carbon tetrachloride, CCl4
Chloromethane, CH3Cl
Ammonia, NH3

(a) Carbon dioxide, CO2

110

molecular geometry : linear


oxygen is more electronegative than carbon,
Dipole moment can cancell each other
has no net dipole moment ( = 0)
therefore CCl4 is a nonpolar molecule.

(b) Carbon tetrachloride, CCl4

111

molecular geometry : tetrahedral


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

( c) Chloromethane, CH3Cl

- molecular geometry : tetrahedral


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

(d ) Ammonia, NH3

- molecular geometry : tetrahedral


- N is more electronegative than H,
- Dipole moment cannot cancell each other
- has a net dipole moment ( 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
MOLECULES
Symetrical molecules
- basic molecular shape with the
same terminal atom
- molecules with lone pairs linear
(from trigonal bipyramidal) and
square planar with the same
terminal atom
115

POLAR
MOLECULES
Non-symetrical molecules
- basic molecules with different
terminal atom
- molecules with lone pairs except
linear and square planar

Exercises :
Predict the polarity of the following molecules:

116

SO2 ; HBr ; SO3 ; CH2Cl2 ; ClF3 ; CF4 ; H2O ;


XeF4 ; NF3 ; Cis-C2H2Cl2 ; trans-C2H2Cl2

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:
H

The s-orbital of the


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 ()
b) pi bond ()

121

a) bond
formed when orbitals overlap along its
internuclear axis (end to end overlapping)
Example:
i. overlapping s orbitals

bond
122

ii.

Overlapping of s and p orbitals

Px orbital
H

bond

123

iii. Overlapping of p orbitals

bond

124

b) bond
Formed when two p-orbitals of the same
orientation overlap sideways
y

125

bond

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:
O : 1s2 2s2 2p4

Two unpaired electrons to be used in


bonding.

y
1s

2s

2p

Overlapping occurs between


the p-orbitals of each atom

129

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
1s

2s

Lewis Structure

H
H C H
H

2p

Excitation: to have 4
unpaired electrons

H
sp3

Excited state :
1s

2s

2p

C
sp3

sp3 hybrid
shape: tetrahedral
138

sp3

sp3
H

Fig. 10.8

sp3-Hybridized C atom in CH4

sp3
1s

sp3

sp3
sp3

1s
139

1s

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
sp3

1s
141

1s

Example:
3) H2O
Lewis structure

Valence orbital diagram;


O ground state :
O hybrid :
Orbitals overlap:

142

2
sp

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

px

sp2

py

144
one
s orbital + two p orbitals

sp2

sp2

three sp2 orbitals

simplified drawing of sp2 orbitals:

Shown together
(large lobes only)

145

Example:
1) BF3
Lewis structure

Valence orbital diagram;


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
Lewis structure

Valence orbital diagram;


C ground state :
C excited :
C hybrid :
Orbital overlap:

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
Lewis structure

Valence orbital diagram;


Cl :
Be ground state :
Be excited :
Be hybrid :
Orbital overlap:
153

Fig. 10.11

154

Example:
2) C2H2
Lewis structure

Valence orbital diagram;


C ground state :
C excited :
C hybrid :
Orbital overlap:

155

Fig. 10.19a-c

156

Example:
3) CO2
Lewis structure

Valence orbital diagram;


O:
C ground state :
C excited :
C hybrid :
Orbital overlap:
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
Lewis structure

Valence orbital diagram;


Cl :
P ground state :
P excited :
P hybrid :
Orbital overlap:
160

Example:
2) ClF3
Lewis structure

Valence orbital diagram;


F:
Cl ground state :
Cl excited :
Cl hybrid :
Orbital overlap:
161

3
2
sp d

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
Lewis structure

Valence orbital diagram;


F:
S ground state :
S excited :
S hybrid :
Orbital overlap:
164

Example:
2) ICl5
Lewis structure

Valence orbital diagram;


Cl :
I ground state :
I excited :
I hybrid :
Orbital overlap:
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

sp

BeCl2

sp2

BF3

sp3

CH4, NH3, H2O

sp3d

PCl5

sp3d2

SF6

166

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.

2.
3.

1.

Describe intermolecular forces


i. van der Waals forces :
- dipole-dipole interactions or permanent
dipole
- London forces or dispersion forces
ii. Hydrogen bonding
Explain factors that influence the strength of van der Waals
forces
Explain the effects of hydrogen bonding on
i. boiling point
ii. Solubility
iii. Density of water compared to ice
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
Forces

Hydrogen
Bond

Between
covalent
molecules

Between
covalent
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:

Cl

Chlorine is more
electronegative,
thus it has higher
electron density

Cl

Dipole-dipole forces; the


partially positive end attracts
the partially negative end

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

At any instant, the


electron density might
be higher on one side
+

Br

Temporary
dipole molecule

Br

Br

Br

Br

The temporary dipole


molecule induce the
neighboring atom to
be partially polar

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:

Hydrogen
intermolecular bond
181

Other examples:
NH3 liquid

H2O

..
H
Hydrogen
intermolecular bond

..
N

..
H

H
H

..

..

..

..

Hydrogen
intermolecular bond

Covalent bond

..

..

..
H

Hydrogen
intermolecular bond

182

Consider ethanol, CH3OH


CH3OH

CH3OH and methane

Hydrogen bond
..
..
H
O
O

..
O

..

in

Not a hydrogen
bond

..

..

H
H

H is not
bonded to
either F, O
or N

C
H

H
H

183

Example: H2O

___ covalent bond


----- hydrogen bond

H
O H

H
O H

O 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 dipoledipole 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.

..

..

Hydrogen bond

..

..

N
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


dynamic equilibrium
Volume of liquid remains
constant

Rate of vapourisation is equal to


the rate of condensation
Pressure exerted by the vapour
molecules is known as the vapour
pressure

Dynamic equilibrium and vapour pressure


Number of liquid
molecules leaving the
surface is the same as
the number of vapour
molecules entering
the liquid surface.

The vapour pressure


at this stage is
constant and known
as the equilibrium
vapour pressure.

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.
2.

3.
4.

Explain the formation of metallic bond by using


electron sea model.
Relate metallic bond to the properties of metal:
i. malleability
ii. Ductility
iii. Electrical conductivity
iv. Thermal conductivity
Explain the factors that affect the strength of metallic
bond
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
electrons

Free
moving
electrons
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
+ e + e + e
e + e +
e
e + e + e + e + e + e
+
e + e + e
e

+ e + e

Metallic bonds formed


by the electrostatic
forces exist between
positive ions and the
free moving electrons

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


Mg

Na
+1

+1
e

e
+1

e
+1

+1
e

e
+1

+1

+1

e
e
+1 +1

+1
e

+1

+1
e

+1

+1

e
e
e
+1 +1 +1

Has one valence electron

the electrostatic force acting


between positive ions and
free moving electrons form
metallic bonds

ee ee ee ee ee
+2 +2 +2 +2 +2
ee ee ee ee ee
+2 +2 +2 +2 +2
ee ee ee ee ee
ee
+2 +2 +2 +2 +2

ee ee ee
+2 +2 +2
ee ee ee
+2 +2 +2
ee ee ee
+2 +2 +2

Has 2 valence electrons


Stronger metallic bond due to the
size of Mg being smaller than Na
and the strong electrostatic force
between +2 ions and the two
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
5.2
5.3

Gas
Liquid
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)
Boyles Law
(ii)
Charless Law
(iii) Avogadros Law
(d) Sketch and interpret the graphs of Boyles and Charless 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) Boyles Law :
The volume of fixed amount of gas at constant
temperature is inversely proportional to the gas
pressure
1

V P
PV = k

(no of mole and temperature are constant)


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 1

Graph of P versus V

P
P

1
V

pressure is inversely
proportional to volume

pressure is directly
1
proportional to

volume

Graph of PV versus P

PV

PV = constant

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) Charless 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
T

Where :
k = constant
T = absolute temperature (K)
V = volume

At different volume and temperature:

V1 V2

T1 T2
Where V1 = initial volume
T1 = initial temperature
V2 = final volume
T2 = final temperature

T = absolute temperature
in Kelvin (K)
T(K) = TC + 273.15

Graph of volume versus temperature :


V

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 Boyles and Charless Law


1
Boyles law :
P
Charless law :
VT
V

T
P
T
V= k
P
PV
=k
T
V

P1V1
T1

P2V2
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) Avogadros 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

V1 V2

n1 n2

where :
n = number of moles
k= constant

Combination of Boyle's law, Charles's law and Avogadro's law :


1
Boyle's Law:
V
P
Charles' Law:
VT

Avogadro's Law:
V
V=R

Vn

nT
P
nT
P

PV = nRT
Ideal gas equation

Where :
R = gas constant
T = Temperature(K)
n = number of moles
V = volume
P = Pressure

Value of R depend on the unit of pressure and


volume used in the equation.
unit of
pressure
atm
Nm2
or

Pa

unit of
volume

value of
R

unit of R

L or dm3 0.08206 L atm mol1 K1


m3

8.314

Nm mol1 K1
J mol1 K1

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
Equation:

the

Ideal

Gas

PV nRT
m
PV=
RT
Mr
mRT
Mr =
PV

m
where: n =
Mr
Mr = molar mass of a gas

Density of a gas

PV nRT
m
PV= RT
Mr
mRT
P=
VM r
dRT
P=
Mr
PM r
d=
RT

where,
d = density of a
gas

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

Daltons 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

pressure exerted by gas B = PB

nBRT
=
V

in the mixture of gases A and B :


PT = PA + PB
n A RT
nBRT

=
V
V

= (nA + nB )RT
V
when nA + nB = nT

n TRT
PT =
V

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

Ptotal ntotal(RT )
Thus:

PA
n A ( RT )

Ptotal ntotal ( RT )

PA X A Ptotal

PA
nA

PTotal
nTotal

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 Daltons 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 25C, 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
273K

RT

600K
1000K

The lines
approach the
ideal line when
T increases

The value approaches 1.0


at a very low pressure
P

Van der Waals 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
n
the term pressure need to be corrected by adding coefficient 2a
V

n=number of moles

P ideal = P real + n2a


V2

a=correcting factor for


pressure
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 = 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
V2

& V = V container - nb

(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

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
A solid that has highly ordered

amorphous solid
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

liquid is cooled slowly


Its atoms, molecules or ions

occupy specific position


Example : ice, sugar, salt

Formed when a saturated


liquid is cooled rapidly
Example :
glass
plastic material
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

and/or hydrogen bonds)

Example : iodine [I2 (s) ]

(van

der

Waals

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

T
A

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 0.01C 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

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.

After time t1, both concentrations


remain constant.

concentration

[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)
Kc =

cC (g) + dD (g)

[C]c[D]d
[A]a[B]b

Kc is known as equilibrium constant


Concentrations of species are expressed in
molar.

Table 6.1

N2O4 (g)
K=

[NO2]2
[N2O4]

2NO2 (g)
= 4.63 x 10-3

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
Kp =

(PA)a (PB)b

the pressure of gases are


expressed in atm or other
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) + 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) + 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
Consider the reaction:
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

Kp =

PO =
2

2
PNO
2
2
PNO
2
Kp
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)
Kc =

cC (g) + dD (g)

[C]c[D]d
[A]a[B]b

Thus,
Kc =

{PC /(RT)}c {PD / (RT)}d


{PA /(RT)}a {PB /(RT)}b

Since P = nRT
V
[ ]=

P
RT

For the reaction


aA (g) + bB (g)
Kc =

cC (g) + dD (g)

PCc PDd (RT) (a + b) (c+d)


PAa PBb

Kc = Kp (RT) (a + b) (c+d)
Kp = Kc (RT) (c + d) (a+b)

Kp = Kc (RT)n

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
;
0.14
[COCl2]
=
Kc =
0.012 x 0.054
[CO][Cl2]
= 220 M -1
Kp = Kc(RT)n

n = 1 2 = -1

Kp = 220 x (0.08206 x 347)1


= 7.7 atm1

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)


Alcohol

Carboxylic

Ester

acid

Kc =

[CH3COOC2H5]
[CH3COOH] [C2H5OH]

3.

CaCO3 (s)

CaO (s) + CO2 (g)

[CaO][CO2]
Kc =
[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
2
3
= 0.0702 atm2
Kp = Kc(RT)n

n = 2 0 = 2
T = 295 K

Kc =

0.0702 atm2
(0.08206 atm L mol1 K1 x 295 K )2

1.2 x 104 mol2 L2

1.2 x 104 M2

6. The value of Kc for the following equation is 1.0 x 103 M


at 200C.
2NOBr (g) 2NO (g) + Br2 (g)
Calculate Kc for the following equation at 200C.
NO (g) + Br2 (g) NOBr (g)

Answer;
Kc = [NO]2 [Br2]

Kc =

[NOBr]2
1 =
Kc

1
[NO]2 [Br2]

[NOBr]
[Br2]1/2 [NO]

[NOBr]2
[NO]2 [Br2]

[NOBr]2
1
Kc

[NOBr]
= Kc
[NO] [Br2]

Kc =

1
Kc

Kc =

1
1.0 x 103 M

= 31.6 M-
= 31.6 dm3/2 mol

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)

[ ]0 / M
[ ] / M
[ ] / M

0.0200
-x
0.0200 - x

+ I2 (g)

2HI (g)

0.0200

-x
0.0200 - x

+2x
+2x

Kc =

[HI]2
[H2] [I2]

49.5 =

7.036 =

(2x)2
(0.0200 x) (0.0200 x)
2x
0.0200 - x

x = 0.0156

H2 (g)

I2 (g)

2HI (g)

[ ]0 / M

0.0200

[ ] / M

-x

[ ] / M

0.0200 - x

0.0200 - x

+2x

= 0.0044

= 0.0044

= 0.0312

0.0200
-x

0
+2x

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 448C. The value of the
equilibrium constant, Kp for the reaction,
H2 (g) + I2 (g) 2HI (g)
at 448C 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

= (2.000)(0.08206)(721)
1.000
= 118.4 atm

H2 (g)
P0
P
P

Kp

= PHI
PH2 P I2

59.19
-x
59.19 - x
50.5 =

+ I2 (g)

2HI (g)

118.4

-x
118.4 - x

+2x
+2x

(2x)2
(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,

The fraction of a molecule dissociated.


C
=
C0

C = changes in concentration
C0 = initial concentration

A complete dissociation occurs if = 1

AB

C0 / M
C / M
C / M

A+

-x

+x

+x

a-x

+x

+x

x
=
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?
x = 0.0089
a = 0.5

H+
0

C0 / M

HCOOH
0.5

C / M

-0.0089

+0.0089

C / M

0.5-0.0089

0.0089

HCOO
0

+0.0089
0.0089

= 0.4911

x
a

0.0089
=
= 0.0178 = 1.78%
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)
Qc =

cC (g) + dD (g)

[C]c[D]d
[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)
C0/M
[Br]2
Qc =
[Br2]

Qc > Kc

0.063
=

2Br (g)
0.012

(0.012)2 = 2.29 x 103


0.063

Equilibrium position shifts


from right to the left.

Br2 (g)

C0/M

0.063

C/M

+x

C/M

0.063 + x

2Br (g)

0.012
- 2x

0.012 - 2x

[Br]2
Kc =
[Br2]
1.1x10-3

(0.012 2x)2
=
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

[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?

Qc =
=

[HI]2
[H2] [I2]
(1.47 + 0.5)2
(0.200) (0.200)

= 97.0

Since Qc > Kc, the system


is not at equilibrium
The net reaction will
proceed from RIGHT to
LEFT until equilibrium is reestablished.

H2 (g)

+ I2 (g)

2HI (g)

C0/M

0.200

0.200

1.47 + 0.500

C/M
C/M

+x
0.200 + x

+x
0.200 + x

-2x
1.97 2x

= 0.2535

= 0.2535

= 1.863

Kc =
54.0 =

Kc = 54
Qc = 97

[HI]2
[H2] [I2]
(1.97 2x)2
(0.200 + x) (0.200 + x)

7.35 =

1.97 2x
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 Chateliers Principal

6.3.1

Le Chteliers 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)
(Yellowish)

+ SCN-(aq)

Fe(SCN)2+(aq)
(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;
Consider the reaction below:
Fe 3+(aq)
+ SCN-(aq)
(Yellowish)

Fe(SCN)2+(aq)
(Blood red)

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:

Consider the reaction below:


Fe 3+(aq) + SCN-(aq)
(Yellowish)

Fe(SCN)2+(aq)
(Blood red)

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)

H = +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)

H = +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)

H = +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
Kc
[ N 2O4 ]

Concentration of
N2O4 increases,
thus Kc value
decreases

Example:
Consider the reaction:
Co(H2O)62+(aq)+ 4HCl(aq)
pink
To overcome the
low temperature
reaction should
release heat

Disturbance:
Low temperature

CoCl42+(aq) + H2O H = +ve


blue

System at
equilibrium

High
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
Consider the reaction:
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 1x103 at high


temperature and 4.8x1031 at 25C. Is the forward
reaction exothermic or endothermic?
Kc =

[NO]2
[N2] [O2]

Kc

[NO]

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 Chteliers Principle
Change

Equilibrium shift

Change Equilibrium
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)
H =+ve
(a)

(b)

Calculate the values of Kp and Kc for the system


at 525oC, with the equilibrium pressure of CO2 is
0.220 atm.
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

Kp = Kc(RT)n

n = 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 103 M

(b)(i)

(ii)

Does not change


(the partial pressure of CO2 is not affected by
the removal of SOLID CaO from the system).
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)

H = -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

7.1

ACIDS AND BASES

Theory of Acids and Bases


Three important theories
1. Arrhenius theory
2. Bronsted-Lowrys theory
3. Lewis theory

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)

Base:
any substance that produces hydroxide ions (OH-)
when dissociating in water.
Example:
NaOH (aq)

Na+ (aq) + OH (aq)

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

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

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.

Example
HCO3 (aq) + H2O (l)
acid

base

CO32 (aq) + H3O+(aq)


conjugate
base

conjugate
acid

The stronger the acid, the weaker is its conjugate


base and the stronger the base, the weaker is its
conjugate acid.

Exercise
1. In the following reactions, identify the acid-base conjugate
pairs.
a. ClO (aq) + H2O (l)
base

HOCl (aq) +

acid

b. CH3NH2 (aq) + H2PO4- (aq)


base

acid

OH (aq)

conjugate
acid

conjugate
base

CH3NH3+(aq) + HPO42 (aq)


conjugate
acid

conjugate
base

NH4+(aq) + Br (aq)

c. HBr(aq) + NH3(aq)
acid

conjugate
acid

base

d. PO43(aq) + H2O(l)
base

HPO42(aq) + OH(aq)
conjugate
acid

acid

e. CH3COOH(aq) + H2O(l)
acid

conjugate
base

base

conjugate
base

CH3COO(aq) + H3O+(aq)
conjugate
base

conjugate
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) HSd) 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:

Lewis
base

2) H+
Lewis
acid

BF3

H3N BF3

H2O

Lewis
acid

OHLewis
base

3) 2Cl-(aq) + SnCl4 (aq)


Lewis
base

SnCl62-(aq)

Lewis
acid

15

Exercise
Classify each of the following species as Lewis acid
or Lewis base.
Lewis base

i. NH3
ii.

AlCl3

iii.

BCl3

Lewis acid
Lewis acid

iv.

Ag+

v.

I-

Lewis acid
Lewis base
16

Strength of Acids and Bases

Strength of acids and bases depend on the extent of


dissociation

% dissociation =

[ ]dissociated
100%
[ ]initial

Degree of dissociation, =

[ ]dissociate d
[ ]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)
a) HCl (g)

H+ (aq) + Cl (aq)

2 O (l)
H

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

- 0.10

+ 0.10

+ 0.10

[ ]f 0.00

0.10

0.10

19

[HCl]dissociated
% dissociation =
[HCl]initial

100%

0.10=
100%
0.10
= 100 %

[HCl]dissociated
Degree of dissociation, =
[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


NaOH (aq)

H2O

Na+ (aq) + OH (aq)

[ ]i

0.50

- 0.50

+ 0.50

+ 0.50

[ ]f

0.00

0.50

0.50

22

[ NaOH ]dissociated
% dissociation =
[ NaOH ]initial

100%

0.50=
100%
0.50
= 100 %
Degree of dissociation, =

[ 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)

% dissociation < 100%

<1

A (aq) + H3O+(aq)

25

Acid dissociation constant expression, Ka

Ka =

[A ][H3O ]
[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)

% dissociation < 100%

<1

BH+ (aq) + OH- (aq)

28

Base dissociation constant expression, Kb

Kb =

[BH ][OH ]
[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

-0.0042

+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
= 1.8 104 M

34

Try this
1.

Acid dissociation constant, Ka for hydrofluoric


acid HF at 25 C is 6.8104 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 1.8105 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 25C

37

For pure water, at 25C,


H3O+ = OH = 1 x 10-7 M
Kw

Kw

= H3O+ OH
= (1 x 10-7) (1 x 10-7)
=

1 x 10-14 M2

Note:
Temperature , Kw because the dissociation
of water is an endothermic process

38

The pH Scale

a.

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.

a.
b.
c.
d.
e.

Answer
0.55 M CH3COOH (Ka = 1.8x10-5)
2.5
0.23 M NH3 (Kb = 1.8x10-5)
11.31
0.15 M HCl
0.82
0.20 M KOH
13.3
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)
Cl-

NH4+(aq) + Cl(aq)

: 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

BUFFERS 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 CH3COOwill 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, AHA

Comes from
weak acids

H+

A-

Comes from the


ionisation of a salt

66

We can write the acidic concentration constant,


Ka

[ H ][ A ]

[ HA ]

or

[H+]

Ka[HA]
=
[A ]

By applying log on both sides, we have


-log

[H+]

pH

[ HA]
= -log Ka + ( - log
[ A ]

[
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)
NH4Cl(aq)

NH4+(aq) + OH-(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

BUFFERS 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 ]
Kb =
[B]

[OH-] = Kb

or

[ B]
[ BH ]

By applying log on both sides:


-log [OH] = -log Kb + ( -log

pOH

[ B]
)

[ BH ]

[
BH
]
= pKb + log
[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 *

Red

Yellow

1.2-2.8

Yellow

Bluish
Purple

3.0-4.6

Orange

Yellow

3.1-4.4

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

Colourless

Reddish
pink

8.3-10.0

Thymol blue
Bromophenol blue
Methyl orange
Methyl red

Phenolphthalein

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 OHthat 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
MHCl VHCl

= n NaOH
= MNaOH VnaOH

VNaOH = 0.1 x 25
0.1

= 25 mL

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
MNH VNH = MHClVHCl
VNH = 0.2 x 25 = 50 mL
0.1
3

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
Base
Weak
Acid-Strong
Base
Strong Acid-weak Base

3 10

Any Indicator except thymol blue

7 11

Phenolphthalein, cresol red

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

Phenolphthalein

8.2 10.0

Colour change
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

1.2 2.8

Red

6.0 7.6

Yellow

8.3 10.5

Colourless

Yellow
Blue
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:


Ag+ (aq) + Cl- (aq)

AgCl (s)

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, H is


negative.

Energy is released from the system to the


surroundings.

Consider the following reaction:


A (g) + B (g) C (g)
(reactants)
(product)

H = ve

reactants
enthalpy
H = -ve
products
reaction pathway

Energy profile diagram for exothermic reaction

Endothermic Reactions

Enthalpy of products > enthalpy of reactants, H is


positive

Energy is absorbed by the system from the surrounding

Consider the following reaction


A (g) + B (g) C(g)
H = + 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, H
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)

H = +6.01 kJ

1 mole of H2O(l) is formed from 1 mole of H2O(s) at 0C,


H = +6.01 kJ

However, when 1 mole of H2O(s) is formed from 1 mole of


H2O(l), the magnitude of H remains the same with the
opposite sign of it.
H2O(l) H2O(s) H = 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) + O2(g) H2O (l)

Hf = 286 kJ mol1

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 mol1

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

Cl2(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) Hn = 58 kJ mol1

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 mol1

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 1C1).
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 (JC1)

Heat released by
substance

Heat absorbed
by calorimeter

q = mcT
q = heat released by substance
m= mass of substance
C= specific heat capacity
T = temperature change

Basic Principle in Calorimeter


Heat released
by a reaction

Heat absorbed
by surroundings

Surroundings may refer to


the:
i. Calorimeter itself or;
ii. The water and calorimeter
qreaction= mcT or CT

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 J0C1. 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

= CT
= (9.08 X 104 J0C-1) X (0.1550C)
= 1.41 X 104 J
= 14.1 kJ
H2(g) + O2(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


1 mol H2O released

14.1
= 0.0496

Heat of reaction, H

= 284 kJ
= - 284 kJ mol1

kJ

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 25.0C and it increased to 27.8C.

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
T = (27.8 -25.0 )C = 2.8C
Solution
Heat released

Heat absorbed by
aluminium
calorimeter

q = mwcwT + mcccT
= (1700.0 g)(4.18 Jg-1 C-1)(2.8 C) +
(3087.0 g)(0.553 Jg-1 C-1)(2.8C)
= 24676.71 J
= 24.7 kJ

Heat absorbed by
water

HESSS LAW

Hess Law

Hesss 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.
H 1

A
H 2

H 3

H1 H2 H3

Algebraic Method
Step 1
i. List all the thermochemical equations involved
i.C

O
CO
(S)
2( g )
2( g )

1 O
H O
2
2( g )
2( g )
2 ( g)
iii.C H
7 O
2CO
3H O
2
2 6( g )
2( g )
2( g )
2 ( g)
ii.H

H - 393kJmol- 1
H -286kJmol- 1
H -1560kJmol

-1

Algebraic Method
Step 1
i. List all the thermochemical equations involved
i.C

O
CO
(S)
2( g )
2( g )

1 O
H O
2
2( g )
2( g )
2 ( g)
iii.C H
7 O
2CO
3H O
2
2 6( g )
2( g )
2( g )
2 ( g)
ii.H

H - 393kJmol- 1
H -286kJmol- 1
H -1560kJmol

-1

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 )
2

H 2 3 -286kJ

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 Hesss Law to calculate the
unknown value.

HOf
2C(s)

3H2 (g)

C2H6 (g)

HO2 = 3(-286)
HO1
= 2(-393)

2O2(g)

3/2 O2(g)

2CO2 (g) + 3H2O(g)

7/2 O2(g)
HO3 = - (-1560)

H f = 2( H1 ) + 3(H 2 ) + H3
-786 - 858 1560
1
-84 kJmol

Example 1
The thermochemical equation of combustion of carbon
monoxide is shown as below.
C(s) + O2(g) CO(g)
= ?
H
given :

H
C(s) + O2(g) CO2(g)
H= -394 kJ mol-1

CO(s) + 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:
-1

H
[C
]
=
-393
kJ
mol
(s)
Hc
H [H2(s)]
= -293 kJ mol-1

Hc
-1
H
[CH
]
=
-753
kJ
mol
4(s)

Hc

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
-1
H
(C
H
)
=
-3265.3
kJ
mol

6
6(l)
H
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)

Na+(g) + Cl-(g) NaCl(s)

Hlattice = +771 kJ mol-1


(lattice dissociation)

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
Hlattice (MgO) > Hlattice (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

ne

La

He
a

y
rg

E
e
ttic

to
fH
yd
ra

tio

Heat of Solution
Na+ and Cl- ion in
the solid state

Hydrated Na+ and Cl- ion

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

i.
ii.
iii.
iv.
v.
vi.

(s)

Cl

2(g)

NaCl

Given;
Enthalpy of formation NaCl
Enthalpy of sublimation of Na
First ionization energy of Na
Enthalpy of atomization of Cl
Electron affinity of Cl
Lattice energy of NaCl

=
=
=
=
=
=

(s)

-411 kJmol-1
+108 kJmol-1
+500 kJmol-1
+122 kJmol-1
-364 kJmol-1
?

Example: A Born-Haber cycle for NaCl


energy
Na+(g) + e

+ Cl(g)

Ionisation
Energy of Na
Na(g)

Electron Affinity of Cl
Na+(g) + Cl- (g)

+ Cl(g)

HaCl
+ve

Na(g) + Cl2(g)

Lattice energy

HaNa
E=0
-ve

Na(s) + Cl2(g)

From Hesss Law:


Hf

Hf NaCl
NaCl(s)

NaCl

= HaNa + HaCl +IENa +


EACl + Lattice Energy

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:

i.
ii.
iii.
iv.
v.
vi.

Construct a Born-Haber cycle to explain why ionic compound


NaCl2 cannot form under standard conditions. Use the data
below:
Enthalpy of sublimation of sodium
=
+108 kJmol-1
First ionization energy of sodium
=
+500 kJmol-1
Second ionization energy of sodium
=
+4562 kJmol-1
Enthalpy of atomization of chlorine
=
+121kJmol-1
Electron affinity of chlorine
=
-364 kJmol-1
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

Remember
RED CAT

Example:

Mg Mg2+ + 2e-

= REDuction
at CAThode
RED
CAT
Oxidation no.

Example:

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)
Oxidation :

Zn(s) Zn2+(aq) + 2e-

Overall cell
2+
2+
Cu
+
Zn

Cu
+
Zn
(aq)
(s)
(s)
(aq)
reaction :

Half-cell
reaction

Cells
There are 2 type of cells

Electrochemical
Cells
where chemical reaction
produces electricity

Electrolytic
Cells
Uses electricity to
produce chemical
reaction

Also called;
Galvanic cell or Voltaic cell
Chemical
Energy

Electrical
Energy

Electrical
Energy

Chemical
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

Cu
electrode

Zn
electrode
Zn2+
ZnSO4(aq)
solution

Cu2+

Salt
bridge

CuSO4(aq)
solution

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 :
Cathode :
Overall cell
reaction :

Zn (s) Zn2+ (aq) + 2eCu2+ (aq) + 2e- Cu (s)

Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s)

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?


V
Cu

Zn

ZnSO4(aq)

Zn2+

e
e
e
e

e
e

Cu2+

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)


CATHODE (+)

ANODE (-)
E = +1.10 V

Zn

ZnSO4(aq)

Zn2+

Cu

e
e

Cu2+
Salt bridge
(KCl)

CuSO4(aq)

How does the cell maintains its electrical neutrality?


Left Cell
Zn (s) Zn2+ (aq) + 2eZn2+ ions enter the solution.
Causing an overall excess of
tve charge.
Cl- ions from salt
bridge move into Zn
half cell

Right Cell
Cu2+ (aq) + 2e- Cu (s)
Cu 2+ ions leave the solution.
Causing an overall excess of
-ve charge.
K+ ions from salt
bridge move into Cu
half cell

Electrical neutrality is maintained

Electrochemical Cells

anode
oxidation

cathode
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 :
Cathode :

2e3 Zn(s) 3Zn2+(aq) + 6e


3e- 2Cr(s)
2 Cr3+(aq) + 6e

X3
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)
cell potential

measured by a voltmeter

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-cells 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

or

= +0.34 (-0.76)
= +1.10 V

E0cell = E0red + E0ox

Change the sign

= +0.34 + (+0.76)
= +1.10 V
Half-cell equation at:

Anode :

Zn (s) Zn2+ (aq) + 2e-

Cathode :

Cu2+ (aq) + 2e- Cu (s)

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

Cl2(g) + e- Cl-(aq)

E0 = +1.36 V

Cl-(aq) Cl2(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

H+ (aq)
1 M

Pt
electrode

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
Zn

e
e
e
2+
Zn e

ZnSO4(aq)
1M

E0 = 0

+
+

H2 (g), 25oC,1

H+(aq),1 M
Pt

atm.

Standard Electrode Potentials


Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)
Anode (oxidation):
Cathode (reduction):

Zn2+ (1 M) + 2e-

Zn (s)
2e- + 2H+ (aq,1 M)

Cell reaction Zn (s) + 2H+ (aq,1 M)

H2 (g,1 atm)
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.

+
+
Cu

E0 = 0

V-

H2 (g) 25oC
1 atm.

H+(aq)
1M

Cu2
CuSO4(aq)
1M

Pt

Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)


Anode (oxidation):

H2 (1 atm)

Cathode (reduction): 2e- + Cu2+ (1 M)


H2 + Cu2+

0
0 = E0
Ecell
cathode - Eanode
0 = E 0 2+
0
Ecell
Cu /Cu EH +/H2
0 2+
0.34 = ECu
/Cu - 0
0 2+
ECu
/Cu = 0.34 V

2H+ + 2eCu (s)


Cu (s) + 2H+

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

E0cell = E0cathode - E0anode

or

= +0.34 (-0.76)
= +1.10 V

E0cell = E0red + E0ox

Change the sign

= +0.34 + (+0.76)
= +1.10 V
Half-cell equation at:

Anode :

Zn (s) Zn2+ (aq) + 2e-

Cathode :

Cu2+ (aq) + 2e- Cu (s)

At standard-state condition

E0cell = E0cathode - E0anode


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)

Answer

Co2+(aq) + 2e- Co(s)

+
Cathode (Red) : Ag (aq) + e Ag(aq)

Anode (Ox) : Co(s) Co2+(aq) + 2e-

E0cell = E0cathode - E0anode


= +0.80 (-0.28)
= +1.08 V

E0 = +0.80V
E0 = -0.28V
E0 = +0.80V
E0ox = +0.28V

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
Cu2+ (aq) + 2e- Cu (s) E0 = +0.34 V
Ag+ (aq) + e- Ag (s)
E0 = +0.80 V
Reducing
Oxidation
agent
agent

Increase
strength as
reducing
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 :
Mg2+(ak) + 2e
Sn4+(ak)

E = -2.38 V

Mg(p)

+ 2e Sn2+(ak) E= +0.15 V

Oxidation

: Mg(p)

Mg2+(ak)

Reduction

: Sn4+(ak)

+ 2e

= +2.38 + 0.15
= +2.53 V

E o ox

=+2.53V

+ 2e

Eoox = +2.38 V

Sn2+(ak)

Eo = +0.15 V

Mg(p) + Sn4+(ak) Mg2+(ak) + Sn2+(ak)

Ecell = E o red

E0cell = Ecathode - Eanode


=+0.15- (-2.38)

Ecell = +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),
1 atm.

+
+

Pt

Cl2 (g),
1 atm.

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.

E 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+


= +0.15 (-0.76 )
= +0.91 V
spontaneous

Or

Eocell= Eored + Eoox


= (+0.15) + (0.76)
= +0.91 V

Pb2+(aq) + 2Cl-(aq) Pb(s) + Cl2(g)

Reduction
Pb2+(aq) + 2Cl-(aq)

Pb(s) + Cl (g)

Pb(s)
Pb(s)
Cl2 (g)
Pb2+(aq) + 2Cl-(aq)
+ Cl+2(g)
Oxidation

cathode: Pb2+(aq) + 2e Pb(s)


anode: 2Cl-(aq) Cl2(g) + 2e

Eo = -0.13 V
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+(aq)

2Ag(s) + Br2(aq)
0 +
EAg

Br2(aq)

= +0.8 V

0
EBr
- = +1.07 V
2 /Br

Answer :
2Ag(s)

/Ag

2Ag+(aq)
+ 2e

2Ag(s) + Br2(aq)

+ 2Br-(aq)
standard reduction
potential

2e

Eox = - 0.80 V

2Br -(aq)

E = +1.07 V

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
Sn2+ (aq) + 2e- Sn (s) E0 = -0.14 V

(cathode)
(anode)

E0cell = E0cathode - E0anode

E0cell

= +0.80 (-0.14)
= +0.94 V
= +ve ( reaction is spontaneous)

Nernst equation
Nernst equation can be used to calculate the E
for any chosen concentration :
Ecell = Eocell

RT
nF

ln

[ product ]x
[ reactant]y

At 298 K and R = 8.314 J K-1 mol-1 , 1 F = 96500 C


Ecell = Eocell

0.0257
n

2.303 log

[ product ]x
[ reactant]y

cell

Ecell = Eocell 0.0592

log

[ product ]x
[ reactant]y

[ product ]x
[

reactant]y

Ecell = Eocell

0.0592

log Q

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)

Eocell = Eored + Eoox

Zn2+(aq)

+ Cu(s)

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+]
[ Cu2+]

E = +1.10 V 0.0592 log (0.02 )


2

= +1.10 V (-0.0385)
= +1.139 V

( 0.40)

At equilibrium:
~ No net reaction occur (Q=K)
~ Ecell = 0

Ecell = Eocell 0.0592

log K

n
0

= Eocell 0.0592
n

Ecell

0.0592
n

log K

log K

Example 2
Calculate the equilibrium constant (K) for the
following reaction.
Cu(s) +

2Ag+(ak)

Cu2+(ak)

Answer
At equilibrium, E cell = 0
Eocell = Eo cathode -

Eo anode

= +0.80 ( +0.34)
= +0.46 V

2Ag(s)

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-

Anion

M+,H+

Cation

A
n
o
d
e

Positive electrode
The electrode which is connected to the
positive terminal of the battery
Oxidation takes place
Electrons flow from anode to cathode

C
a
t
h
o
d
e

Negative electrode
The electrode which is connected to the
negative terminal of the battery
Reduction takes place

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
+

e-

e+

Anode

Electrochemical Cell

Cathode

e-

Anode

e-

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+
Anode :

Anion : Cl-

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) + 2eO2 (g) + 4H+ (aq) + 4e-

2Cl- (aq)
2H2O (l)

E0 = +1.36 V
E0 = +1.23 V

In dilute solution, water will be selected for


oxidation because of its lower Eo.

Reactions involved
2H
O
(l)
+
2e
2
Cathode:

4H2O (l) + 4e-

H2 (g) + 2OH- (aq) E0 = -0.83 V


2H2 (g) + 4OH- (aq)
E0 = -1.23 V

Anode: 2H2O (l)

O2 (g) + 4H+ (aq) + 4e-

Cell
6H2O(l)
reaction:

O2(g) + 2H2(g) + 4OH-(aq) + 4H+(aq)

2H2O(l)

4 H2O
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) + 2eO2 (g) + 4H+ (aq) + 4e-

2Cl- (aq)
2H2O (l)

E0 = +1.36 V
E0 = +1.23 V

In concentrated solution, chloride ions will be


oxidised because of its high concentration.

Reactions involved
Cathode: 2H2O (l) + 2eAnode:

2Cl- (aq)

Cell
2H2O(l) + 2Clreaction:

H2 (g) + 2OH- (aq) E0 = -0.83 V


Cl2 (g) + 2e-

E0 = -1.36 V

Cl2(g) + H2(g) + 2OH-(aq)


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) + 2eO2 (g) + 4H+ (aq) + 4e-

2SO42- (aq)
2H2O (l)

E0 = +2.01 V
E0 = +1.23 V

E0 for water molecules is less positive


H2O easier to oxidise

Equation
Cathode: 2H2O (l) + 2eAnode:

2H2O (l)

Cell
2H2O(l)
Reaction:

H2 (g) + 2OH- (aq) E0 = -0.83 V


O2 (g) + 4H+ (aq) + 4eO2(g) + 2H2(g)

E0 = -1.23 V

E0cell = -2.06 V

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

Faradays Law of Electrolysis


Describes the relationship between the amount of
electricity passed through an electrolytic cell and
the amount of substances produced at electrode.

Faradays First Law


States that the quantity of substance formed at an
electrode is directly proportional to the quantity of
electric charge supplied.

Faradays 1st Law

mQ
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 1 F 96 500 C
No. of

e-

passed through =

2700
96 500

= 0.028 mol

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.
2.

Define reaction rate, average rate,


instantaneous rate and initial rate.
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;

d[A]
rate =
dt

d[A] = change in concentration of A

d[B]
rate = dt

d[B] = change in concentration of B

dt = period of time

Because [A] decreases with time, d[A] is negative.

time

d[A]
rate = dt
rate =

d[B]
dt

[B]

[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) + 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


[Br2]final [Br2]initial
d[Br2]
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

Rate =

cC + dD

1 d[A]
1 d[B] 1 d[C] 1 d[D]

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:
Consider the reaction,
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:
Consider the reaction,
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 [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


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

determined

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]
Unit k =

M s-1
M

= s-1
iii) Second order

Rate = k [A]2
rate
k=

[A]2

M s-1
Unit k =
M2

= M-1 s-1

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
rate
k=
[S2O82-]1[I-]1

Unit k =

Ms-1
M2

M-1 s-1

The order of reaction


For reaction

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)
Experiment

O2

NO

Initial Rate
(M s-1)

1.10x10-2

1.30x10-2

3.21x10-3

2.20x10-2

1.30x10-2

6.40x10-3

1.10x10-2

2.60x10-2

12.8x10-3

3.30x10-2

1.30x10-2

9.60x10-3

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
rate1 =

k [O2]2m[NO]2n
k [O2]1m[NO]1n

6.40x10-3Ms-1

3.21x10-3Ms-1

2=

[O2]2m

[O2]1m

2.20x10-2mol/L

[O2]2
[O2]1

1.10x10-2mol/L
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:
n
m [NO] n
k
[O
]
[NO]
Rate 3
23
3
3
=
=
[NO]1
Rate 1
k [O2]1m [NO]1n
n
-3
-1
12.8 x 10 Ms
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.

[ClO2]
M
0.0421

[OH-]
M
0.0185

8.21 1 0-3

0.0522

0.0185

1.26 1 0-2

0.0421

0.0285

1.26 1 0-2

exp

Initial rate,
Ms-1

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

0.080

0.40

0.10

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

t
[A]
[A]o

rate

[A] = -k t + [A]o
y=m x+c

[A]

Half-life (t)
Half life (t) 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]
=

k[A]

dt
- d[A]

t = 0, [A]=[A]0
=

k dt
- ln [A]0 = k(0) + c
c = ln[A]0

[A]
- d[A]

substituting

= k dt

[A]

-ln [A] = kt ln[A]0

- ln [A] = kt + c
ln

[A]0
[A]

kt

Characteristic graphs of 1st order reaction


ln[A]o ln[A] =kt

ln[A] = - kt +ln[A]o

[A]

[A]0
ln -----[A]

kt

ln[A]
ln[A]o
[A]

ln[A]o

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]
ln[A]0 ln[A]
=
t=
k

ln

[A]0
[A]
k

ln
=

0.88 M
0.14 M

2.8 x

10-2

s-1

= 66 s

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)

ln

[H2O2]0

kt

[H2O2]
ln

0.882
0.600

3.66 x 10-3 s-1 x t

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)
ln

[H2O2]0

kt

3.66 x 10-3s-1x 225 s

[H2O2]
0.882
ln
[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 500C.

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, t, is the time required for the concentration of a


reactant to decrease to half of its initial concentration.
t=t when [A] = [A]0
2
[A]0
ln
[A]0/2
ln2
0.693
t =
=
=
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?
0.693
t = ln2 =
= 1200 s = 20 minutes
-4
-1
k
5.7 x 10 s
How do you know decomposition is first order?
units of k (s-1)

First-order reaction
A

product

No. of
half-lives
1

[A]o = 8 M
4

1/2
t = 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 = dt

= k[A]2

To obtain the units of k


rate
k

=
[A]2

Unit k

M/s
M2
= M-1 s-1

Using calculus, the following expression can be obtained


1
=
[A]

1
[A]0

+ kt

Characteristic graphs for second order reaction

Rate = k [A]2
rate

[A]
rate

[A]2

Graphs for second order reaction

[A]

[A]

+ kt

[A]o

t
1/[A] 1/[A]o

1/[A] M-1

1/[A]o
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

+ kt

=
[A]

[A]0
[A]= [A]o

Substituting t = t1/2
1

2
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

2x

4x

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 s1

If the initial concentration of iodine was 0.086 M,


i)
calculate its 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
i)

1
=

[A]

+ kt

[A]0

+ (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
t1/2=

1
=
7.0 x 109 x 0.060

k[A]0
=

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) + O2(g)

time, t/min

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


ii)

ln2
k=

= 0.03 min-1
20 min

Summary of the Kinetics of Zero-Order, First-Order


and Second-Order Reactions

Order
0

Rate Law
rate = k

rate = k [A]

[A]2

rate = k

Concentration-Time
Equation
[A] = [A]0 - kt
ln[A] = ln[A]0 - kt
1
1
=
+ kt
[A]
[A]0

Half-Life
t =

[A]0
2k

t = ln2
k
1
t =
k[A]0

1st order
A product
r = k [A]1
Unit k = s-1

Zero order
A product
r = k [A]0
Unit k = M s-1

r
[A]

[A]

Integrated rate law

[A]0

[A]2

Integrated rate law

ln([A]0 / [A]) = kt

1/[A] 1/[A]0 = kt

ln[A]

t1/2 = [A]0/2k [A]

[A]

Integrated rate law

[A]0 [A] = kt
[A]

2nd order
A product
r = k [A]2
Unit k = M-1 s-1

[A]

1/[A]

ln[A]0
1/[A]0

[A]0 - [A]

ln([A]0 / [A])

t1/2 =
ln2/k

t
1/[A] 1/[A]0

t1/2 = 1/k[A]0
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;
Rate

Number of effective collisions


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

Ea
Reactant

product
Progress of reaction

- A reaction profile shows


potential energy plotted as a
function of the progress of the
reaction.
- The difference in potential
energies
between
the
products and the reactants is H
for
the
reaction.
- Reactant molecules must
have enough energy to
overcome an energy barrier
separating
products
from
reactants, Ea.

A Reaction Profile: exothermic reaction


Activated complex
Transition state

Ea (Forward reaction)
Ea (reverse reaction)

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) CONCENTRATIONS OF REACTANTS
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

A) CONCENTRATIONS OF REACTANTS
This observation correlates with the RATE LAW that has
been previously discussed
x

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:

k = A

-Ea
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:

k = A

-Ea
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
k Ae
Natural log both ends

Ea

ln k ln( A .e

RT

Ea

RT

Ea

RT
ln k ln A ln( e
)
Ea
ln k
ln e ln A
RT

Thus
See the linear relationship?

Ea 1
ln k
( ) ln A
R T
y = m x + C

(But ln e = 1)

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
ln k1
( ) ln A
R T1

and

ln k 2

Ea 1
( ) ln A
R
T2

Rearranging the equations would give

Ea 1
ln k 1
( ) ln A
R T1
Since A is a constant
E
1
E
1
ln k 1 a ( ) ln k 2 a ( )
R T1
R T2

Ea 1
Ea 1
ln k1 ln k 2
( )
( )
R T2
R T1

Ea 1
ln k 2
( ) ln A
R T2

k1 Ea 1 1
ln
( )
k2
R T2 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

k2 = 1.10 x 10-5 L mol-1 s-1

T1 = 500K
T1 = 600K

SOLUTION:

k1 Ea 1 1
ln
( )
k2
R T2 T1
E a R ln(

k1 1
1
)(
) 1
k 2 T 2 T1

1.10 10 5
1
1 1
Ea (8.314 ) ln(
)(

)
9
9.51 10
600 500
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

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 > Ea

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
O

N
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

Single bond

Double bond

Triple bond

Hydrocarbons

saturated
Contains only single
bonds ( -C-C- )
Examples: alkanes,
cycloalkanes

unsaturated
Contains at least one
carbon-carbon double
bond (-C=C-) or triple
bond (-C C-).
Examples: alkenes,
alkynes.

Uses of organic compounds


Medicine

Engineering

Biotechnology
Agriculture

Antibiotics are used to


fight bacterial and fungal
infections
Gasoline-as a fuel for
internal combustion
engines.
Genetic information like
DNA
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

H2C

H2
C
CH2

H2C
C
H2

CH2

iii) Aldehyde, CH3CHO


O
CH3CH

Expanded Structure
Expanded structures indicate how atoms are
attached to each other but are not representations
of the actual shapes of the molecules.
C4H9Cl
Molecular
Formula

H H

Cl

Expanded structure

Examples:
i) Alcohol (C2H6O)
H

OH

ii) Carboxylic acid (C3H6O2 )


H

OH

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

ii)

H2C

CH2

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

or

Br

or

Indication ::bonds that lie in the plane


:bonds that lie behind the plane
:bonds that project out of the plane

Br

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

CH3
10 carbon

10 carbon

CH3
H

C
CH3

30 carbon

CH3

H H CH3

CH3
1

H C C C CH2 C CH3
H H H

CH3
1

H H CH3

CH3

H C C C CH2 C CH3
2

H H H

CH3

H H CH3
3

CH3
4

H C C C CH2 C CH3
H H H

CH3

Question
Expanded
Structure

Condensed
Structure

Skeletal
Structure

CH3(CH2)CCl(CH3)2
O

H H

CH3
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.

ii.
iii.

A basic by which organic compounds are


divided into different classes.
A basic for naming organic compounds
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.
3.

Differ from the successive homolog by a CH2


unit
Show a gradual change in the physical properties

4.
5.
6.

Have same functional group


Have similar chemical properties
Can be prepared by similar general methods

Classification of organic compound

Class of
Compound

Functional Group
Example
Structure

Alkane

Alkene

Alkyne

Name
CH3-CH3

-C=C-

carbon-carbon
double bond
CH3CH=CH2

-C C-

carbon-carbon
triple bond
CH3C CCH3

Aromatic

Haloalkane

Benzene ring

X (F, Cl, Br, I) Halogen

Alcohol

-OH

Hydroxyl

Phenol

-OH

Hydroxyl

-C-O-C-

Alkoxide

Ether

-CH3

CH3Cl

CH3-OH

-OH

CH3-O-CH3

Aldehyde

-C=O
H

Ketone

R-C=O
R

Carboxylic
acid

-C=O
OH

Ester

-C-O-CO

Acyl chloride

-C=O
Cl

Carbonyl

CH3-C=O
H

Carbonyl

CH3-C=O
CH3

Carboxyl

CH3-C=O
OH

Carboalkoxy

CH3-C=O
OCH3
CH3-C=O
Cl

Anhydride

O O
-C-O-C-

Amide

-C=O
N-

Amine

-NH2

Nitrile

-C N

O O
CH3C-O-CCH3
Carboxamide CH3-C=O
NH2
Amino
Cyano group

CH3-NH2
CH3C

Exercises:
1. Identify the functional group in the following
molecules
a)(CH3)3CCH2CH=CH2
b)(CH3)3CCH=CHCH2-OH

c)

O
C

OH C O C

CH3 CH2 OH CH2


CH3

NH2 CH C
CH2 O

CH3

CH

CH3

NH2

12.4 Isomerism
Learning Outcomes:
At the end of the lesson the students should be
able to :
Define isomerism.
Explain constitutional isomerism.
chain isomers
positional isomers
functional group isomer

Isomerism

Structural/
Constitutional Isomerism

Chain
Isomerism

Positional
Isomerism

Stereoisomerism

Functional Group
Isomerism

diastreomer enantiomer

cis-trans
isomerism

other
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
CH3

CH3CCH3
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

1,2-dimethylbenzene 1,3-dimethylbenzene

CH3
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
CH3CH2OH
C2H6O
ethanol

C3H6O

CH3CCH3
O

propanone

C3H6O2

CH3CH2COH
O
propanoic acid

CH3OCH3
dimethyl ether

CH3CH2CH
O

propanal

CH3COCH3
O
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:
At the end of the lesson the students should
be able to :
Define stereoisomerism.
Describe cis-trans isomerism due to
restricted rotation about C=C bond and CC
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

CH3
C

H3 C

cis-2-butene

CH3 H
H

CH 3 CH 3

CH3
C

trans-2-butene

H3C

CH3

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

H3C

H
No cis trans isomer

Lecture 6
12.4
Isomerism
Learning Outcomes:

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
Q

C*

PQRS
*designates chiral centre

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

H3C

CH2CH3

CH2CH3

C*

H
OH

enantiomers

CH3
OH

ii) 2-hydroxypropanoic acid,

CH3CHCOOH
OH

COOH
H

OH

COOH
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 planepolarized light.

Applications of chiral compounds in


daily life.

e.g:

() Dopa is used for treatment of Parkinsons


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:
At the end of the lesson the students should
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

A:+
B+
anion
cation
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+ +
Clcarbocation
anion

Chlorine is more electronegative than carbon and the


CCl bond is polar.
The CCl 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
Li+
kation

(CH3)3C- +
carbanion

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)

iii)

H3C

H3C + H

Lecture 7
12.5 Reactions of Organic Compounds
Learning Outcomes:
At the end of the lesson the students should be
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.

Electron withdrawing group (e.g: halogen)


stabilise carbanions through the inductive
withdrawal of electron density

Carbanion Stability:
H
H
R
R
< R C R
H C H < H C
<
H
R
R
C
Methyl
anion

Primary
10

Secondary
20

Increasing stability

Tertiary
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 :


R
H

H
H
R
H
C
H C
H
<
<
.
.
methyl
radical

Primary
10

C
.

R
R <R C
. R

Secondary
20

Increasing stability

Tertiary
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:
ii)
i)
+ + -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
12.5 Reactions of Organic Compounds
Learning Outcomes:
At the end of the lesson the students should
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)
b)

Electrophilic Addition
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 :

CH3CH=CH2 + Br2

CCl4

CH3CHBrCH2Br

Room
temperature

electrophile

b)

Nucleophilic Addition

Initiated by a nucleophile, which attacks an


electrophilic site of a molecule.
Typical reaction of carbonyl compounds.

O
CH3

CN

C CH3 + HCN

CH3 C
OH

CH3

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:

+ Br2
electrophile

Fe
catalyst

Br + HBr

c)

Nucleophilic Substitution
Typical reaction of saturated organic compounds
bearing polar bond as functional group, such as
haloalkane with alcohol.

Example :

CH3CH2Br + OH-(aq)
nucleophile

CH3CH2OH + Br-(aq)

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 :

tautomerisme
C R
H C

OH

C R
O

Exercises
1.

Explain how the free radicals are formed


in homolytic cleavage.

2. Write an equation for the brominebromine 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
(contain one or more benzene ring)

ALIPHATIC

ALKANES
(saturated)
contain only
single bond

ALKENES
(unsaturated)
contain
C=C

CYCLO-ALKANES (saturated)
Alkanes which C atoms are
join in rings

CYCLO-ALKENES
(unsaturated)

ALKYNES
(unsaturated)
contain
CC

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
formula
CH4
C2H6
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22

Structural formula
CH4
CH3CH3
CH3CH2CH3
CH3(CH2)2CH3
CH3(CH2)3CH3
CH3(CH2)4CH3
CH3(CH2)5CH3
CH3(CH2)6CH3
CH3(CH2)7CH3
CH3(CH2)8CH3

No .of C
atoms
1
2
3
4
5
6
7
8
9
10

Name
Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
Nonane
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

CH3CH2CH2CH2CHCH3
CH3

substituent

CH3CH2CH2CH2CH CH3
|
2 CH2
|
1 CH3

substituent

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

CH3CH2CH2CH2CHCH3
CH3
2-methylhexane

Substituent
-methyl at C-2

Substituent
7

-methyl at C-3

CH3CH2CH2CH2CH CH3
|
2 CH
2
|
1 CH
3
3-methylheptane

Some Common Substituent Groups


Alkane
methane
ethane
propane

name
methyl
ethyl
propyl
isopropyl

butane

butyl

substituent

CH3
CH2CH3
CH2CH2CH3
CHCH3
CH3
CH2CH2CH2CH3

isobutyl

CH2CHCH3
CH3

sec-butyl

tert-butyl

CHCH2CH3
CH3
CH3
CCH3

neopentyl

CH3
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

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:
CH3CHCH CH3
|
|
CH3 CH3

2,3-dimethylbutane

If there are two chains of equal length as


the parent chain, choose the chain with
the greater number of substituents.

4
4

3
3

2
2

1
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

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

1
5

CH2CH3

1-ethyl-2-methylcyclohexane
NOT
1-ethyl-6-methylcyclohexane

Cl

Cl

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:
2

Cl

3
2

4
1

5
6

CH2CH3

CH3

chloro 1

ethyl 3

methyl 4

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

3
2

1,3-dicyclohexylpropane

Examples:

CH2CH2CH2CH2CH3

1-cyclobutylpentane

Physical properties of alkanes & cycloalkanes

Boiling
Point

Physical
state

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

2,2dimethylpropane

CH3CH2CH2CH2CH3

CH3CHCH2CH
CH3

CH3
CH3CCH3
CH3
9oC

37oC

28.5oC

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 nonpolar 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 +


+ Heat

4H2O

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.
RH + X2

hv RX + HX

With methane, the reaction produces a mixture of


halomethane and a hydrogen halide.

Examples:
i.

CH4 + Cl2

hv

CH3Cl + CH2Cl2
+ CHCl3 + CCl4
+ HCl

ii.

hv
CH3CH3 + Cl2 CH3CH2Cl + HCl

CH3

CH3

|
iii. CH3 CCH3 + Cl2
|
CH3

|
hv CH CCH Cl + HCl

3
2
|
CH3

(ii) & (iii): 1 product only because all the


hydrogen atoms are identical

CH3CH2CH2Br
iv.

CH3CH2CH3

hv
+ Br2

( minor)
+ CH3CHCH3
|
Br
( major)
+ HBr

Reaction mechanism
CH4 + Cl2
i.

hv CH3Cl + HCl

Chain initiation step

Cl Cl

hv

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

C
H

CH2

CH3

CH3

CH3

CH3

CHBr

Increasing % yield

CH3

CH3

C
Br

CH2

CH3

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..

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

CH CH3

1
2
3
4
2-methyl-2-butene

(not 3-methyl-2-butene)

H3C

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

H2C

CH CH

CH2

1,3-butadiene
1

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

1-methylcyclopentene
(not 2-methylcyclopentene)

1
6

CH3

CH3

3,5-dimethylcyclohexene
(not 4,6-dimethylcyclohexene)
MORE

Step 6
Two frequently encountered alkenyl
groups are vinyl group and allyl group.
RCH=CHR
alkene
CH2=CHvinyl group

-H

RCH=CHalkenyl
CH2=CHCH2allyl 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
C
H

Cl
C
H

cis-1,2-dichloroethene

Cl
C
H

H
C
Cl

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

OH

Dehydration of alcohols
Alcohols react with strong acids in the
presence of heat to form alkenes and water.

H2SO4 (conc.)

H2 O

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 Saytzeffs rule.

Saytzeffs Rule
An elimination usually gives the most
stable alkene product, commonly the
most highly substituted alkene.

Examples
(1) CH3CH2OH

(2) H3C CH CH3


OH

H2SO4 (conc.)

H2SO4 (conc.)

H2C CH2

H2C

H2O

CH CH3
H2O

Mechanism for the


dehydration of alcohol
H3C CH CH2CH3
OH

H SO (conc.)
2

CH 3 CH=CHCH 3
(major product)

CH 2 =CHCH 2 CH 3
(minor product)

H 2O

Step 1:
Protonation of alcohol.
H
H3C C CH2CH3
:OH
..

H
+
:O H
H

H
H3C

C
+

: OH
H

CH 2 CH 3

:O
..

Step 2:
Formation of carbocation
H
H 3 C C CH 2 CH 3
+:OH
H

H3 C

H
+
C CH2 CH3

carbocation
H
+

:O
..

Step 3:
Formation of alkenes
H

H H H
+
H C C C CH3
b

Root a : major product


Root b : minor product

:O H
..

H
C

H3C

H
+

C
CH 3

+
: O

stable alkenes
+

CH 2 =CHCH 2 CH 3
(minor product)

Rearrangement During Dehydration


of Alcohol
Example 1:
CH3 H
H3C

CH3OH

CH3

H2 SO4 (conc.)

CH3
H 3C

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
H C
3

CH

CH

CH H
3

H C

rearrangement

CH

CH H
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.

CH

(a)
HC
2

(a)

3
CH CH

CH

H + CH3
H C C C CH3
H CH H
3

3
(minor product)

:O H
..

less stable alkene


CH
HC
3

(b)

(b)

3
C CH

CH
3
(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
Saytzeffs rule.

Try this!
CH H
3
H C C C CH
3
3
H OH

CH
3
H C C CH CH
3
3
(major product)

H2SO4 (conc)

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
KOH

reflux

C C

H X

HX

Saytzeffs rule is used to determine the major


product

Examples:
(1)

Cl
H3C

CH CH2CH2CH3

H3C CH

CH CH2CH3

(major product)

KOH

alcohol
reflux

H2C CH CH2CH2CH3
(minor product)

(2)

H3C CH CH3
Br

KOH

alcohol
reflux

H2C

CH CH3

(3)

Br
+
CH
CH
3

KOH

alcohol
reflux

CH
CH
3
(minor product)

CH2
CH3
(major product)

(4)
CH3

CH3 H
C C CH3
CH3 Cl

CH2

CH3 H
C C CH3
CH3

2,3-dimethyl-1-butene
(minor product)
2 alkyl groups

+ KOH

CH3

alcohol
reflux

CH3
C C CH3
CH3

2,3-dimethyl-2-butene
( major product)
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 ( bonds)
while alkenes have carbon-carbon double bonds (
bonds).
The double bond is a site of high electron density
(nucleophilic).
Therefore most alkenes reactions are electrophilic
additions.

Electrophilic Additions
Mechanism
H

H
C

C
H

slow

C
X

H
H

C
X

C H

fast

C H

Example:
i.

H3C

CH3
C

H3C

Cl

slow

CH3
CH3CH3
H3C

C
H

CH3

Cl

CH3CH3
H3C

C
H

CH3

Cl-

fast

CH3CH3
H3C

H Cl

CH3

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.

C C

H2

Pt or Ni or Pd

C C
H H

Examples:
(1)

H3C

CH2

H2

Pt /Ni / Pd

CH3

CH3

(2)

H3C CH CH3

H2

Pt /Ni / Pd

(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.

X2

CH2Cl2

Example:
CH3
H3C C C CH3

CH2Cl2

Cl 2

H
Cl Cl
H3C

CH3H

CH3

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
C C

Br2

CH2Cl2
room temperature
C C
Br Br

Observation: The reddish brown bromine decolourised

(3) Hydrohalogenation : Markovnikovs

rule

Hydrogen halides (HI, HBr, HCl and HF) add to the


double bond of alkenes to form haloalkanes.

HX

C C
H X

The addition of HX to an unsymmetrical alkenes,


follows Markovnikovs rule.

Markovnikovs Rule:

In

the addition of HX to an alkenes, the


hydrogen atom adds to the carbon atom of
the double bond that already has the greater
number of hydrogen atoms.

i.

The addition of HBr to propene, could


conceivably lead to either 1-bromopropane or
2-bromopropane.
The main product, however, is 2bromopropane

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
CH3

HBr

H3C C CH3
CH3

The addition of HX to an unsymmetrical


alkenes, yield the main product according to
the Markovnikovs rule.

Mechanism
CH 3
CH 3

CH

CH 3

slow
H

Br

CH3
CH3

C
+

CH

30 Carbocation

CH3

+ Br -

CH3
CH3

C
+

CH

CH3

Br

fast

CH3
CH3

CH

Br

CH3

(4) Addition of HBr to Alkenes in The


Presence of Peroxides
(Anti Markovnikovs 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:
H2C CH CH3

HBr

ROOR
Br CH2CH2CH3

Complete the following reactions:

(1)

H3C

CH2C

CH2

HBr

H2 O 2

CH3
(2)

CH2

HBr

H2 O2

(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

+ Br2 + H2O

C C
H

H H

H
H

Unsaturated test

H C C H
Br OH
2-bromobutanol

Observation : the reddish brown bromine decolourised

If the alkenes is unsymmetrical, the halogen


ends up on the carbon atom with the greater
number of hydrogen atoms.

Example:
H 3C

CH2

Br 2

H2O

CH3
CH3H
H3 C

OH Br
1-bromo-2-methyl-2-propane

Complete the following reaction:

+
CH3

Br2

H2O

(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 Markovnikovs rule.

C C

H2O

H3O

C C
H OH

Example:
H3C

CH2

H3 O

H2O

CH3
OH
H3C

C
CH3

CH3

Complete the following reactions:

(1)

CH2

H2 O

H3 O

(2)

H2C

CH CH3

H2O

H3O

Mechanism
STEP 1
CH3
CH3

..
CH

CH3

O+

CH3
CH3

C
+

CH
H

CH3

STEP 2
CH3
C
+

CH

CH3

H2O

..

CH3

..

CH3
CH3

CH

O+

..

CH3

STEP 3

CH3
CH3

CH

O+

..

CH3
CH3

CH

OH

..

H2O

CH3

..

CH3

H3O+

..

(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.

H3 C

CH3
C

H3 C

CH3CH3
conc. H2 SO 4

H3 C

CH3

H OSO 3 H
alkyl hydrogen sulphate

CH3

CH3CH3
H2O
heat

H3 C

OH

CH3

Example:

H2C CH CH 3

OSO3H

conc.H2SO4

H3C CH CH2
H

H2O
heat

OH
H3 C

CH CH2
H

7 ) Oxidation of Alkenes

Alkenes undergo a number of reactions in


which the C=C is oxidized

KMnO4
basic,cold,dilute
acidic,hot,concentrated

ozonolysis

i)

With cold and dilute potassium


permanganate, KMnO4

Potassium permanganate in alkaline solution


can be used to oxidise alkenes to 1,2-diols
(glycols).

KMnO4
(purple)

OH OH

OH ,cold

MnO2
(brown precipitate)

Observation: Purple colour of KMnO4 decolourised and


brown precipitate formed.

This reaction is called Baeyers 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:
-

H2C

CH2

+
H

KMnO4
H

OH OH

OH ,H2 O
cold

MnO2

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
H3C

CH3

(i) OH ,heat

KMnO4

(ii) H3O

CH3
O
H3C

O
CH3

H3C

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)
-

H2C

CH CH3

KMnO4

(i) OH ,heat
(ii) H3O

O
HO

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?

C7 H14

KMnO4

O
H3C

CH2

(i) OH-,heat
(ii) H3 O

O
OH

CH2 C
H3C
CH2 OH

Answer:
O
H3C

CH2

O
CH2 C
H3C
CH2 OH

OH

propanoic acid

butanoic acid

H H
H3C

CH2C

CH2CH2CH3

3-heptene

Example

An unknown alkene undergoes oxidation in hot


basic KMnO4 followed by acidific to give the
following product:
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.

O3
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).

Zn

H2 O,H

ozonide
H

C=O

O=C
R

Example:
CH3
H3C

(i) O3
CH CH3

(ii) Zn,H2O/H

CH3
H3C

CH3

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-methyl2-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 Kekuls 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 KEKUL

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 Kekul

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

14.1

Introduction to
aromatic Compounds

Arenes = aromatic compounds:


the word aromatic has nothing to do with odour.

KEYWORDS
aromatic

resonance structure

Kekul structure
ortho meta para
Friedel-Craft acylation

electrophilic substitution
activating and
deactivating group

ortho-para and meta director

oxidation of
alkylbenzene

substitution of
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


C6H5CO2H + CaO

heat

C6H6 + CaCO3

Molar mass = 78, molecular formula = C6H6


named benzin
benzene

gum benzoin

benzin
benjoin
(French)

benzoin

Luban Jawi
(Arabic)

1866

Friedrich August Kekul (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.

KEKULS STRUCTURE
Kekule was the first to formulate a
reasonable representation of benzene
H
H
H C C
C
H

or

H
The Kekule structure suggests alternating double
and single carbon-carbon bonds

RESONANCE STRUCTURE
Benzene is actually a resonance hybrid of the
two Kekul structures.

equivalent to

resonance hybrid

All CC bond length equal = 139 pm


Shorter than typical CC (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

ly
e
t
e
l
p
Com
ted
a
g
u
j
n
co

Planar

Conta
in par
ticula
numb
r
e r of

electr
on
obe
ys H
Rule ckels

THE CRITERIA FOR AROMATICITY


Hckels Rule
* cyclic, planar and completely
conjugated compounds that
contain [4n+2] electron

(n=0,1,2..) are said to be


aromatic
Erich Hckel
(1896-1980)
planar monocyclic rings with 2,6,10,14 and so forth
electrons are aromatic

THE CRITERIA FOR AROMATICITY


EXAMPLE OF AROMATIC COMPOUNDS

1. Aromatic compounds with a single ring

Benzene

aromatic
Benzene is aromatic because:
contains 6 electrons
(obeys Hckels Rule)

[4n+2] = [4(1) + 2]
= 6 electrons

cyclic, planar and has double


bond in the ring

THE CRITERIA FOR AROMATICITY


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

14.2

Nomenclature of benzene
and its derivatives

Arenes = aromatic compounds:


the word aromatic has nothing to do with odour.

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.
Cl

fluorobenzene

Br

chlorobenzene

NO2

nitrobenzene

bromobenzene
CH2CH3

ethylbenzene

IUPAC rules allow some common names


to be retained.
CH3

toluene
COOH

benzoic acid

OH

NH2

phenol

aniline
CHO

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
2
1
Br
2 Br
1

2
3

3
4

Br

Br

1,2dibromobenzene
1,4dibromobenzene
or
or
1,3dibromobenzene
odibromobenzene
pdibromobenzene
or
mdibromobenzene

NO2
1

NO2
NO2

1
2
3

NO2
1,2dinitrobenzene
or
odinitrobenzene
NO2
1

1,3dinitrobenzene
or
mdinitrobenzene

2
3
4

NO2
1,4dinitrobenzene
or
pdinitrobenzene

DISUBSTITUTED BENZENE
Two Different Substituents

Select one of the substituent that give


new parent name and numbered as C1.
COOH
1
2 NO2

COOH
1

COOH
1

2
4

NO2

NO2

2nitrobenzoic acid
4nitrobenzoic acid
or
or
3nitrobenzoic acid
onitrobenzoic acid
pnitrobenzoic acid
or
mnitrobenzoic 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

Br

3
4

Br
1,2,4tribromobenzene

Br
I
2bromo1chloro3iodobenzene

C atom bearing the subtituent that define the


new parent name is numbered as C1.
OH
1

COOH
2

NO2

HO

NO2
2,4dinitrophenol

Br 4

OH

3,5dihydroxybenzoic acid
3

CH3

CH3

4bromo1,2dimethylbenzene

Br 4

CH3

CH3

4bromo1,2dimethylbenzene

correct

4bromoodimethylbenzene
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
2 CHCH

2CH2CH2CH2CH3

2phenylheptane

Phenyl = C6H5 = Ph

14.2-12

If the chain is unsaturated (have CC or CC)


or contains important functional group, the
benzene ring is considered as
phenyl substituent.

CH2C

3 4

CCH3

1phenyl2butene

CH2CH2OH

2phenylethanol

14.2-13

BENZYL GROUP
CH2

phenyl group

CH2Br

benzyl bromide

benzyl group

CH2OH

benzyl alcohol

AROMATIC COMPOUNDS

14.3

Chemical properties of benzene


and its derivatives

Arenes = aromatic compounds:


the word aromatic has nothing to do with odour.

14.3-01

UNUSUAL REACTIONS OF BENZENE


Br2 / CCl4

BENZENE

KMnO4 / H2O
H2 / Ni

no addition of Br2
(no decolorization)
no oxidation
(no decolorization)
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
+ Br2
benzene

Br

FeBr3

bromobenzene

Involves substituents attached to the ring


CH3CH2CH2CH3 KMnO
4
H2O
butylbenzene

COOH

benzoic acid

14.3-04

ELECTROPHILIC SUBSTITUTION
Most characteristic reaction of benzene.
A H atom is replaced by an electrophile.

E
+

E+
electrophile

H+

14.3-05

X2, FeX3
(X = Cl Br)

X
+ HX

HONO2

NO2
+ H2O

H2SO4

RCl , AlCl3
(R can rearrange)

O
RCCl , AlCl3

halogenation

nitration

R
+ HCl

Friedel-Crafts
Alkylation

O
CR
+ HCl

Friedel-Crafts
Acylation

14.3-07

GENERAL MECHANISM
Formation of arenium ion

STEP 1

H
H

E+

H
H
H

E
H
H

H
H

E
H

H
H
H arenium ion

H
H

14.3-08

ARENIUM ION
+
E+

benzene ring

E
H
arenium ion

Electrophile takes two electrons of sixelectrons


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)

Loss of

STEP 2
H
H

E
H

14.3-09

H+

H
H

Substitution reaction allow


aromatic six electrons to
be regenerated.

E+
6 electrons

E
H
4 electrons

H+

E
6 electrons

14.3-10

Kekul structures are more appropriate for writing


mechanisms.
For simplicity, however, we can show the mechanism
in the following way:
E

STEP 1
+ E+

arenium ion
E

STEP 2

E
H

+ H+

14.3-11

HALOGENATION
Reactants: benzene and halogens (Cl2 or Br2).
Conditions:
Lewis acid such as FeCl3 and FeBr3
no reaction
(decolorization not observed)

+ Br2

+ Br2

FeBr3

Br
+ HBr
bromobenzene

14.2-13

MECHANISM
STEP 1

Formation of Br+
+

BrBr

STEP 2

BrBrFeBr3
complex

+ FeBr3

Br+

+ FeBr4

Br

Formation of arenium ion

+ Br+
STEP 3

Loss of H+
Br
FeBr4

Br
+ 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
NO2

HNO3
H2SO4

nitrobenzene
+ H+

+ HSO4

12.5-49

MECHANISM
STEP 1

..
..

H-O-NO2 +

Formation of nitronium ion (NO2+)

H-OSO3H

+-NO

H-O
+
HSO
.. 2
4

H2O + NO2+
nitronium ion

STEP 2

Formation of arenium ion


NO2
NO2+

STEP 3

Loss of H+
HSO4
NO2

NO2
+ H2SO4

12.5-51

FRIEDELCRAFT ALKYLATION
Reactants: benzene and haloalkane.
Conditions:
Catalyst: Lewis acid such as AlCl3.

+ RX

AlCl3

R
+ HCl
alkylbenzene

Alkylation = transfer an
alkyl group to benzene

12.5-52

12.5-53

EXAMPLE:
Cl

CH(CH3)2

AlCl3

+ CH3CHCH3
2chloropropane

+ HCl
isopropylbenzene

+ (CH3)3CCl

AlCl3

C(CH3)3
+ HCl

2chloro2methylpropane
tertbutylbenzene

12.5-54

MECHANISM
Formation of carbocation

(CH3)2CHCl: +

AlCl3

+ (CH3)2CHClAlCl3

: :

: :

STEP 1

(CH3)2CH+

+ AlCl4

carbocation

Formation of arenium ion

STEP 2

CH(CH3)2
+

+CH(CH )
3 2

Loss of H+

STEP 3

AlCl4
CH(CH3)2

CH(CH3)2
+ HCl

12.5-55
OTHER FACTS ABOUT
FRIEDELCRAFT ALKYLATION

Rearrangement can occur, especially when


1o haloalkanes are used.
CH2CH2CH2CH3
EXAMPLE:

35%

CH3CH2CH2CH2Cl
AlCl3

butylbenzene
CH3
CHCH2CH3

secbutylbenzene

Rearrangement:
H

65%

CH3CH2CHCH2
1o carbocation

CH3CH2CHCH3
2o carbocation

12.5-56

FRIEDELCRAFT ACYLATION
Reactants: benzene and acid chloride.
Product: ketone.
Conditions:
Catalyst: Lewis acid such as AlCl3.
EXAMPLE:
O

O
+

CH3CCl

AlCl3

CCH3

acetyl chloride
acetophenone

+ HCl

12.5-57

ACYL GROUP
O
RC
acyl group
EXAMPLE:
O

O
CH3C
acetyl group

C
benzoyl group

Acylation = transfer an
acyl group to benzene

12.5-59

MECHANISM
Formation of acylium ion

STEP 1
:O:

AlCl3

RCClAlCl3

: :

RCCl

:O:

RC+O

RCO+

acylium ion

+ AlCl4

STEP 2

Formation of arenium ion

C=O
+ RC+O
STEP 3

Loss of H+
R
C=O

AlCl4

R
CO
+ 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:

relative rate
of nitration

NO2
6 x 108

Cl
0.033
reactivity

H
1

OH
1000

12.5-63

EFFECT ON ORIENTATION
Orthopara directors
Tend to direct the incoming group into
ortho and para positions.
Meta directors
Tend to direct the incoming group into
meta position.
EXAMPLE:
CH3
HNO3
H2SO4

ortho-para director
CH3
CH3
NO2
+
+

CH3

NO2
(59%)

(37%)

NO2

(4%)

12.5-64

CLASSIFICATION OF SUBSTITUENTS
ortho , para directing
activators

ortho , para directing


deactivators

meta directing deactivators

ORTHO , PARA
DIRECTING ACTIVATORS

12.5-65

Increasing activation

NH2

NHR NR2

OH

OR

General structure:
R or Z

NHCOR
R

Alkyl groups or have


nonbonded electron pair
on the atom bonded to
benzene ring

12.5-66

EXAMPLE:

CH2CH3

CH2CH3

CH2CH3

Br
Br2

FeBr3
ethylbenzene

(38%)

(62%)

Br

12.5-67
ORTHO , PARA
DIRECTING DEACTIVATORS

Br

Cl

General structure

(halogens)

12.5-68

EXAMPLE:

Cl

Cl

Cl
NO2

HNO3

H2SO4
chlorobenzene

(35%)

(64%)

NO2

12.5-69

META DIRECTING ACTIVATORS


CHO
COR
COOR
COOH
CN
SO3H
NO2
+
NR3
Increasing deactivation

General structure:
Y (+ or )

Have a full or partial


positive charge on the
atom bonded to
benzene ring

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

Cl
electronwithdrawing

CH3

CH3
electrondonating

12.5-71

Activating Groups
Release electrons to the ring
Stabilise arenium ion

CH3

NO2

Form faster

Deactivating Groups
Withdraw electrons from the ring
Destabilise arenium ion
Form slower

Cl

NO2

12.5-72

EXAMPLE:
CF3

CH3

(trifluoromethyl)benzene

benzene

toluene

increasing rate of nitration


CF3

NO2

NO2

+
CF3 withdraws e-,
arenium ion less stable
ring less reactive

CH3

NO2

+
CH3 releases e-,
arenium ion more stable
ring more reactive

OXIDATION OF SIDE CHAIN

12.5-75

Reactants: arene with benzylic H.


Conditions:
Strong oxidizing agent such as KMnO4
and Na2Cr2O7.
Heat.
benzylic H
CH3
CH3

CH(CH3)2

12.5-76

EXAMPLE:
CH3

COOH
KMnO4
heat

toluene

O2N

benzoic acid
CH3

Na2Cr2O7
heat

pnitrotoluene

CH3

CH(CH3)2

isopropyl toluene

O2N

COOH

pnitrobenzoic acid

KMnO4
heat

HOOC

COOH

terepththalic acid

12.5-77

CH3

CH(CH3)2

KMnO4
heat

HOOC

COOH

Alkyl group, regardless their chain length are


converted to COOH.
Compounds without a benzylic H are inert to oxidation.

CH3

C(CH3)3

KMnO4
heat

HOOC

C(CH3)3

12.5-78

HALOGENATION OF TOLUENE
Free radical substitution reaction
Take place at high temperature or in the
presence of uv light.
Mechanism: freeradical substitution
Cl or Br replaces H atom of alkyl group
EXAMPLE:
CH3

toluene

(dichloromethyl)benzene
CH2Cl

CHCl2

Cl2

Cl2

Cl2

heat or
light

heat or
light

heat or
light

benzyl chloride

CCl3

(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!

CARCINOGENIC EFFECT

12.5-34

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

15.1 : Introduction
Haloalkanes or alkyl halides

compounds that contains halogen atom


to an sp3 hybridized carbon atom.

General formula :

bonded

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
CH 3 X

R CH 2 X

R
R CH X

Classification
methyl halide
- halogen is bonded
methyl group

to

Primary (10) halide


- halogen is bonded to 10
carbon atom
Secondary (20) halide
- halogen is bonded to 20
3
carbon atom

General Formula

Classification

Tertiary (30) halide


- halogen is bonded to 30 carbon
atom

R C X
R

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

iv.

Cl

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

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.


+ C X

electrophilic
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 (+) carbon atom bonded to the halogen


(-).
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.

R_ X + NaOH

H2 O

R_ OH + NaX

Example :

CH3
H2 O
_
_
CH3 C Br + NaOH
CH3

CH3
CH3 _ C _OH + NaBr
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.

_
_
R X + CN

alcohol
reflux

R_ CN

+ X

Example :
CH 3 CH 2 Br + KCN

alcohol
reflux

CH 3 CH 2 CN

+ KBr
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-.

R_ X

NH 3

_
+
RNH 3 X

NH 3

_
_
+
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
(SN1)

Reaction

(B). Bimolecular Nucleophilic Substitution


(SN2)

Reaction

15

(A) : Unimolecular Nucleophilic Substitution


(SN1)

Reaction

The term unimolecular means there is only one

molecule involved in the transition state of the ratelimiting 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_ C _ X

s low

R
3o alkyl halide

R
_
_
R C+ + X
R
carbocation

halide ion

Step 2 : Nucleophilic attack on the carbocation

R
_
_
R C + + N u:
R

fas t

R
R_ C _ N u
R

18

Example 1 :

Reaction of 2-bromo-2-methylpropane with H2O.


CH 3
CH 3 _ C _ Br + H 2 O
CH 3

CH 3
CH 3 _ C _ OH + HBr
CH 3

SN1 mechanism :

Step 1 : Formation of a carbocation


CH 3
CH 3 _ C _ Br
CH 3

s low

CH 3
CH 3 _ C +
CH 3

+ Br

_
19

Step 2 : Nucleophilic attack on the carbocation

CH 3
CH 3 _ C +

fa
s
t
H2O

CH 3

CH 3
H
_
_
CH 3 C O
+ H
CH 3

Loss of proton, H+ to solvent

CH 3
H
_
_
CH 3 C O
+ H
CH 3

H2O

CH 3
CH 3 _ C _ OH + H 3 O +
CH 3
20

Example 2 :

Write the mechanism for the following reaction.


CH3
CH3 _C _CH2Br + NaOH(aq)
CH3

CH3
CH3 _ C _CH2CH3 + NaBr
OH

SN1 Mechanism :

Step 1 : Formation of carbocation


CH 3
CH 3 _ C _ CH 2 _Br
CH 3

s low

CH 3
_
_
_
CH 3 C CH 2 + Br
+
CH 3

21

Rearrangement :
CH 3
CH 3 _ C _ CH 2
+
CH 3

1,2-meth yl s hift

CH 3
CH 3 _ C _ CH 2
+
CH 3

Step 2 : Nucleophilic attack on the carbocation


CH 3
CH 3 _ C _ CH2
+
CH 3

+ OH

fas t

CH 3
CH 3 _ C _ CH 2 CH 3
OH
22

Exercise 1 : (Feb 2003)


Write a reasonable structures of products formed when 1iodobutane reacts with
i.
ii.
iii.

KCN
NaOH/H2O
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


Reaction (SN2)

Substitution

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 spacefilling 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
Nu:-

C X
H

R
slow

Nu C X
H H

transition state

fast Nu C

+ X27

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
:OHH

C Br
H

slow

OH C Br
H H

fast

CH3
OH C
H

+ Br-

transition state
29

Comparison of SN1 and SN2 Reactions


SN1

SN2

A two-step mechanism

A one-step mechanism

A unimolecular
ratedetermining step
Second order :
rate = k [RX] [Nu]

A bimolecular
ratedetermining step
First order :
rate = k [RX]

Strong nucleophile

Weak nucleophile

Carbocation rearrangement
Reactivity order :
3o > 2o > 1o

No carbocation
rearrangement
Reactivity order :
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_

_
C C

base

alkene

:B

X
haloalkane

31

Example :
Br

i.

CH 3 CHCHCH 3

CH 3 CH 2 ON a
CH 3 CH 2 OH

CH 3 C CHCH 3
CH 3

CH 3

major
+
CH 3 CHC CH 2
CH 3

minor
ii.
Br
CH 3

CH 3 CH 2 ON a

CH 3

CH 2
+

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.

Cl + Mg

ether

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.
RMgX + H 2 O

H+

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.
CH 2 MgCl

H 2 O/H +

CH 3
+ Mg(OH)Cl
35

(ii).

Synthesis of 1o alcohol
Methanal reacts with the Grignard reagent,
followed by the hydrolysis produces primary
alcohol.
H

O
R-MgX + H-C-H

R-C-OMgX
H
H 2 O,H +

H
R-C-OH
H

Mg(OH)X
36

Example :

i.
O
CH 3 MgBr + H-C-H

H 3 O+

H
CH 3 -C-OH

+ Mg(OH)Br

ii.
MgBr

O
+ H -C-H

H 3 O+

CH 2 OH
+ Mg(OH)Br

37

(iii).

Synthesis of 2o alcohol
Grignard reagent reacts
produce secondary alcohol.

with

aldehydes

to

R'

O
R-MgX + H-C-R'

R-C-OMgX
H
H 2 O,H +

R'
R-C-OH
H

+ Mg(OH)X
38

Example :

O
CH 3 CH 2 MgBr + CH 3 CH 2 -C-H

i.

H 2 O/H +
H
CH 3 CH 2 -C-CH 2 CH 3 + Mg(OH)Br
OH

ii.
MgCl

O
+ CH 3- C-H

CH 3
H 2 O/H +

C-OH
H

+ Mg(OH )Cl
39

(iv).

Synthesis of 3o alcohol

Grignard reagent reacts with ketons to


the tertiary alcohol.

produce

R'

O
R-MgX + R'-C-R"

R-C-OMgX
R"

H 2 O,H +
R'
R-C-OH
R"

+ Mg(OH)X
40

Example :

i.

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.
MgCl

CH 3

O
+ CH 3- C-CH 3

H 3 O+

C-OH
CH 3

+ Mg(OH )Cl
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
O
R-C-O-MgX + H 2 O

H+

R-C-O-MgX
O
R-C-OH + Mg(OH)X
42

Example :
O
CH 3 CH 2Mg I + CO 2

O
CH 3 CH 2- C-O-MgI + H 2 O

CH 3 CH 2- C-O-MgI

H+

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
2RX + 2Na

dry ether

RR + 2NaX

Example:
2CH3CH2Br + 2Na CH3CH2CH2CH3 + 2NaBr
44

ii.

To prepare a odd number of carbon atoms


alkane
RX + RX + 6Na RR + RR + RR
+ 6NaX

Example:
CH3CH2Br + CH3Br + 6Na CH3CH2CH2CH3
+ CH3CH2CH3
+ CH3CH3 + 6NaBr

45

15.2.6 : Importance of Haloalkanes as Inert


Substance
Haloalkanes

Uses

CCl4
(carbon tetrachloride)

solvent for dry


cleaning, spot
removing

CHCl3
(chloroform)
CF2Cl2 , Freon-12
(dichlorodifluoromethane)
CFC
(chloroflourocarbons)
DDT
(DichloroDiphenylTrichloroethane)

solvent for cleaning


and degreasing work
propellants in aerosol
sprays
refrigerant gas
46
insecticide protects

HYDROXY COMPOUNDS
(ALCOHOLS)
Click me
for intro!

INTRODUCTION

Alkane with hydroxyl group (OH)


General formula for aliphatic alcohol,
CnH2n+1OH
Aromatic alcohol phenol (-OH attached
to the benzene rings)

INTRODUCTION
OH

CH2-OH

CH3CH2-OH

ALIPHATIC ALCOHOL (OH group attached


directly to the alkyl group)

INTRODUCTION
OH

OH

OH

CH3

Br

AROMATIC ALCOHOL (OH group attached


directly to the aryl group)

CLASSIFICATION

Methyl alcohol CH3-OH

10 Alcohols

R-CH2-OH

20 Alcohols

R
R-CH-OH

30 Alcohols

R
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
alcohol

cyclohexanol

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

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

Naming Alcohols, R-O-H:


CH3
CH3CHCH2CHCH3
OH
4-methyl-2-pentanol

CH3
CH3CCH2CH2CH3
OH
2-methyl-2-pentanol

2o

3o

CH3
HO-CHCH2CH3

CH3CH2CH2-OH

sec-butyl alcohol
2-butanol

n-propyl alcohol
1-propanol

2o

1o

Naming Alcohols

10

For phenol, C attach to the OH group is C 1

OH

OH

OH
CH3

CH2CH3
3-ethylphenol

Br
3-bromophenol

2-methylphenol

11

Alcohol with 2 hydroxy groups


Structure
CH2(OH)CH2-OH
CH3CH(OH)CH2-OH
HO-CH2CH2CH2-OH
OH-CH2CHCH2-OH
OH

General name

IUPAC name

ethylene glycol

1,2-ethanediol

propylene glycol

1,2-propanediol

trimethylene
glycol
glycerol

1,3-propanediol
1,2,3-propanetriol

12

Benzene derivatives with 2 OH groups are


name as benzenediol

OH

OH

OH
OH

OH
1,4-benzenediol
(hydroquinone)

OH
1,3-benzenediol
(resorcinol)

1,2-benzenediol
(catechol)

13

EXCERCISE
1. Name the following compounds using IUPAC nomenclature
(a)

(b)

-CH2CH(CH3)CH2-OH

-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 Hbonding
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

PHYSICAL PROPERTIES (Solubility)


+

O
-

H
R

O
-

Hydrophilic area

OH

H
H

Hydrogen
bonding

Hydrophobic area

19

PHYSICAL PROPERTIES (Solubility)


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 2nitrophenol because can form H-bonding with
water molecules

20

PHYSICAL PROPERTIES (Solubility)


4-nitrophenol

2-nitrophenol

H
- O

O + O
N

N
+

Intramolecular H-bonding

O +
- H

O
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

Acidity of phenol & alcohol

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

Acidity of phenol & alcohol

O -

H
release proton

+ H+
Phenoxide ion

24

Phenoxide ion stability


O -

O
-

O-

25

Example:
OH

CH2CH2-OH

CH2-OH

OH

acidity increase

26

Example:
COOH

OH

>

> CH CH -OH
3

Na2CO3

KOH

K, Na

NaHCO3

NaOH

NaH

Weak bases

Strong bases

ACIDITY
DECREASE

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

PREPARATION OF ALCOHOLS
2.Hydration of Alkenes
follows Markovnikovs rule
Example:CH3CH=CH2

H2O / H2SO4

CH3CH-CH3
OH

30

PREPARATION OF ALCOHOLS
Mechanism
CH3CH=CH2 + H+

CH3CH-CH3 2o carbonium
+

OH

CH3CH-CH3

OH

31

PREPARATION OF ALCOHOLS
3. Hydrolysis of Haloalkanes
RX + OH- (aq)

CH2Cl

ROH + X-

CH2OH

+ NaOH(aq)

32

PREPARATION OF ALCOHOLS
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

PREPARATION OF ALCOHOLS
(a) Formation of 1o alcohols (Grignard reagent + methanal)

CH3CH2-MgCl + H2C=O

CH3CH2CH2-OMgCl

methanal

H3O+
1o Alcohol

CH3CH2CH2-OH
+ Mg(OH)Cl

34

PREPARATION OF ALCOHOLS
(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

PREPARATION OF ALCOHOLS
(c) Formation of 3o alcohol (Grignard reagent + ketone)
O-MgCl

O
CH3-MgCl + CH3-C-CH3
propanone

CH3-C-CH3
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 +
ii.

-C-H

CH3
-CH=CH-CH3

H2O / H+

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-

39

ALCOHOL REACTIONS
(1) Esterification
Alcohol reacts with carboxylic acid under reflux & is
catalysed by mineral acids (H2SO4 or HCl)
General reaction:O

H+,

R-C-OH + R-OH
acid

alcohol

R-C-OR + H-O-H
ester

water
40

ALCOHOL REACTIONS
(1) Esterification
Example:O

H+,

CH3C-OH + CH3-OH
ethanoic acid

methanol

CH3C-OCH3 + H-O-H
methyl ethanoate

41

ALCOHOL REACTIONS
(1) Esterification
Alcohol reacts with acyl chloride to form ester
O

base

CH3C-Cl + CH3-OH
ethanoil chloride

methanol

CH3C-OCH3 + HCl
methyl ethanoate

42

ALCOHOL REACTIONS
(2) Dehydration of alcohol
Involve formation of carbocation
Possible of rearrangement

CH3CH2CH2OH
propanol

H2SO4(con.)
1800C

CH3CH=CH2
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

CH3CH2CH2OH + HBr

RX + H2O
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

RCH2OH
1o alcohol

[O]

O
RC-H
aldehyde

[O]

O
RC-OH
carboxylic acid

48

ALCOHOL REACTIONS
(4) Oxidation of 1o alcohol
Example:-

CH3CH2OH

K2Cr2O7

/H+

O
CH3C-H

K2Cr2O7/H+

O
CH3C-OH + Cr3+

green

orange

49

ALCOHOL REACTIONS
(4) Oxidation of 1o alcohol
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)

CH3CH2CH2OH + PCC
propanol

O
CH3CH2C-H
propanal
50

ALCOHOL REACTIONS
(4) Oxidation of 2o alcohol
form ketone which cannot be oxidised further
under normal conditions
R
RCH-OH
2o alcohol

[O]

R
RC=O + H2O
ketone

CH3
CH3
+
KMnO4/H
CH3CH-OH
CH3C=O + H2O
2-propanol

propanone
51

ALCOHOL REACTIONS
(4) Oxidation of 3o alcohol
Does not undergo oxidation under normal
condition

R
R-C-OH

[O]

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

OBSERVATIONS :

Example:

CH2OH
HCl / ZnCl2

Does not turn


cloudy

HCl / ZnCl2

Turn cloudy
within 5 minute

OH

54

CH3
OH
HCl / ZnCl2

OBSERVATIONS :
Turn cloudy
immediately

55

Haloform Reaction

Methyl carbinol cleavage to give Carboxylic


acids and Haloform
H
CH 3 C H
OH

X2 , H+
OH-

HCX 3 + H

C OH
O

H
CH 3 C R
OH

X2 , H+
OH-

HCX 3 + R

C 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
+ CH3CH=CH2

AlCl3

Isopropylbenzene
(cumene)

58

PHENOL
(b) Oxidation of Cumene
CH3-CH-CH3
+ O2

O -OH
CH3-C-CH3

1200C

Cumene
hydroperoxide

(c) Decomposition & rearrangement


CH3
-C-O-OH

H2SO4

O
-OH + CH3CCH3

CH3
59

Phenol reactions
1. Reaction at functional group -OH
(a) Reaction with Na

O-Na+

OH
+ Na

+ H2

60

Phenol reactions
1. Reaction at functional group -OH
(b) Reaction with NaOH
O-Na+

OH
+ NaOH

CH3CH2OH + NaOH

+ H2O

no reaction

61

Phenol reactions
2. Electrophilic substitution reactions
(a) Halogenation (Bromination)
-OH is ortho-para director
in Br2, aqueous solution, white precipitate 2,4,6tribromophenol will form

OH

OH
Br

Br

+ 3Br2 / H2O

+ 3HBr
Br
62

Phenol reactions
2. Electrophilic substitution reactions
(a) Bromination to get monobromination (catalyst:
FeBr3 or CS2)
OH

OH
+ Br2

OH
Br

CS2
50C

+ HBr

Br
63

Phenol reactions
2. Electrophilic substitution reactions
(b) Nitration
OH

OH

NO2

Dilute HNO3

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

+ Cl65

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
(antiseptic)

4-Hexylresorcinal
(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
O

The functional group :

Aldehyde
O
R C H

ketone
O
R C

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.

Example

butanal

O
CH3CH2CH2C H
CH3

2-ethyl-4-methylpentanal

CH3CH CH2CH C H
CH2 CH3
CH3

3,5-dimethyl-2-hexanone

CH3CH CH2CH C CH3


CH3

IUPAC nomenclature and common names of some carbonyl


compounds.
Compound

Structure
formula

Aldehyde

H2C=O

Ketone

IUPAC
nomenclature

Common name

Methanal

Formaldehyde

CH3CH=O

Ethanal

Acetaldehyde

CH3CH2CH=O

Propanal

Propionaldehyde

CH3CH2CH2CH=O

Butanal

Butyraldehyde

CH3COCH3

Propanone

Acetone

CH3CH2COCH3

2-butanone

Ethyl methyl ketone

CH3CH2CH2COCH3

2-pentanone

npropyl methyl ketone

CH3CH2COCH2CH3

3-pentanone

Diethyl ketone
4

Example
i)

2- methylpentanal
O
CH3CH2CH2CH C H
CH3

ii) 3- hexanone
O
CH3CH2C CH2CH2CH3

iii) 5-methyl-3- heptanone


O
CH3CH CH2 C CH2CH3
CH2CH3

iv) 3-ethylcyclopentanone
CH3 CH2

v) 3-cyclohexylpropanal
CH2 CH2 C H
O

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+).

Example
1.
H

CH3 C

OH

PCC
CH2Cl2

CH3 C

H
ethanol

ethanal

(alcohol 10)

(aldehyde)

CH3

2.

CH3 C

OH

H
2-propanol

KMnO4, H+
heat

CH3 C

CH3

propanone

(alcohol 20)

3.
CH3
CH3 C

OH

no reaction

CH3
2-methyl-2-propanol
(alcohol 30)

b) Ozonolysis of Alkenes

R1
C

R1
C

R2

O
i. O3
ii. H2O/Zn

R C

H + R1

ii. H2O/Zn

R C

O
i. O3

R2 + R1

R3

R3

Example:
1.
CH2 CH3

H 3C
C
H

i. O3
ii. H2O/Zn

2-pentene
10

2.
CH2CH3
CH3 C

i. O3

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.
O

OH
R C

C R 1 + H 2O

H2SO4
HgSO4

R C

CH R1

Enol

R C CH2 R1
Keto

Example:
H C

C H + H 2O

H2SO4
HgSO4

ethyne

H 3C C

C H + H 2O

propyne

H2SO4
HgSO4

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
+ R

C O C

R'

AlCl3

13

e) Hydrolysis Geminal Dihalides


Hydrolysis of aromatic gem- dihalides to
produce aromatic aldehyde.
CH3

CHO

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

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 :

R
H

OH
C

O + Nu

R C

Nu

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
O + HCN

R C CN
H
cyanohydrins

OH
O + HCN

R1

R C CN
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
H C OH

CHO
NaCN
H2SO 4

Mechanism:

18

Exercises.
1.
O
H3C

NaCN

C H
H2SO 4

2.
O
H3C

NaCN

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
CH3 CH2MgX + HC O

H+

Reaction of Grignard reagent with ketone gives


tertiary alcohol

CH2CH3

CH3CH2CH2MgX + C O

H+

CH3

22

c) The Hydration Reaction

The gem-diol results from a nucleophilic


addition of water to the carbonyl group of the
aldehyde.

O
H

R + H2O

H+

HO

OH
R

O
R'

R + H2O

H+

HO

R'

OH

23

Example:
1.
O
H

H+

CH3 + H2O

ethanal

2.
O
H

H+

+ H2O

methanal

3.
O
CH3 CH2C

CH3 + H2O

H+

2-butanone
24

Mechanism :
O
H 3C

H+

CH3 + H2O

propanone

25

d) The Addition Of Alcohols: Hemiacetals and


Hemiketals
i.

Hemiacetals and hemiketals


Aldehyde reacts with alcohol to form
hemiacetal.

O
R

OH
H

R'OH

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
R

OH
R'

R''OH

OR''

R'

hemiketal
A hemiacetal or hemiketal in acidic medium
can reacts further to produce an acetal or
ketal.
OH
R

C OR'
H

hemiacetal

R''OH

OR''

C OR'
H

acetal

27

OH
R

OR'''

OR''

H
R'''OH

R'

hemiketal

OR''

R'

ketal

An acetal has two OR groups attached to


the same carbon atom.

28

Example:
1.
H
CH3 CH2 CH2 C

O + CH3CH2CH2OH

HCl

2.
OCH2CH2CH3
CH3 CH2 CH2 C

OH + CH3CH2CH2OH

HCl

29

3.
CH3
CH3 CH2 C

+ CH3CH2CH2OH

HCl

4.
OCH2CH2CH3
CH3 CH2 C

OH + CH3CH2CH2OH

HCl

CH3

30

e) Addition of Sodium bisulfite


Addition of sodium bisulfite (NaHSO3) to
aldehyde or ketone give bisulfite salt.
_
O
C

O + NaHSO3

+
Na
SO3H

OH
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

O + H2N-Z

aldehyde
or
ketone

H3O+

N-Z + H2O

Z = -H, -OH,
-NH2 ,etc.

Example:

33

R NH2
amine 10
H2N NH2
hidrazina
C O

C NR
C NNH2

imine
hydrazone

H2N OH
hidroxylamine

C NOH

H 2N

NH

C NNHC6H5

phenylhydrazine

phenylhydrazone
O

O
H2N NH C NH2
semicarbazide
H2N

NH
O2N

NO2

2,4-dinitrophenylhydrazine

oxime

C NNH C NH2
semicarbazone
C N

NH
O2 N

NO2

2,4-dinitrophenylhydrazone
34

(Bradys 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
CH3 (CH2)4 C H + K2Cr2O7

O
H+

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)

OH

O
R

C H

aldehyde

H2, Ni

C H
H

alcohol 10

37

OH

O
R

C R1

H2, Pt

ketone

C R1
H

alcohol 20

Example:
1.
O
CH3 C H

LiAlH4
H+

ethanal

2.
O
CH3 C CH3
propanone

NaBH4/H+
or H2/pt

38

Some tests to determine carbonyl compounds


Test
1

Purpose

Bradys
H2N

NH
O2N

NO2

Observation

To determine
carbonyl
functional
group

+ : yellow /
orange
precipitate

To determine
aliphatic
aldehyde

+ : brick-red
precipitate

2,4dinitrophenylhydrazine

Fehlings
/Benedict
Cu2+, OH -

39

Tollens
[Ag(NH3)2] +,OH

Schiffs

Iodoform
I2, OH-

To determine
aldehyde

+ : silver
mirror

To determine
aldehyde &
propanone

+ : pinkish
purple
solution

To determine + : yellow
methyl
precipitate
carbonyl &
methyl alcohol
structure,
CH3
|
-C=O

40

CH3
|
-C-OH
|

41

CARBOXYLIC ACID AND


ITS DERIVATIVES

Structure
O
R

OH

RCOOH or RCO2H
(R alkyl, aryl or H)

NOMENCLATURE

IUPAC Nomenclature &


Common Name
HCOOH
Methanoic acid
Formic acid

CH3CH2CH2COOH
Butanoic acid
Butyric acid

CH3COOH
Ethanoic acid
Acetic acid

CH3CH2COOH
Propanoic acid
Propionic acid

CH3CH2CH2CH2COOH
Pentanoic acid
Valeric acid

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)

CH3

Br

CH3

CH

CH

O
CH2 C

OH

4-bromo-3-methylpentanoic acid
CH3
HO

CH CH2 CH2 CH2 C

OH

5-hydroxyhexanoic acid
O
HO

C CH2 CH

CH3
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)

HO

CH2 CH2 CH2 C

OH

pentanedioic acid

HO

CH3

C CH2

CH CH2 CH2 C

OH

3-methylhexanedioic acid

CH2 COOH
C

HOOC CH2

C
H

trans 3-hexenedioic acid


8

When R is an aryl group, the parent name is benzoic


acid

Cl

COOH

4-chlorobenzoic acid

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

COOH

cyclopentanecarboxylic acid

11

COOH

cyclohexanecarboxylic acid
CH3
Br

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

COOH
Cl
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
R

O
C

C
O

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

O
R

H
O

C
O

C
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

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
CH3 CH

COOH

CH2 CH2

COOH

>
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
R

O
C

C
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

O-

OPhenoxide 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 electronwithdrawing 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
O
R

OH

>

>

H2O

>

OH

26

+ H2O

+ H3O+

O
O
carboxylate ion
(resonance structure)

OH
carboxylic acid

OH

+ H2O

ROH + H2O

+
H3O+

phenoxide ion
(resonance structure)

phenol

alcohol

RO
alkoxide ion

H3O+
27

Inductive Effect
O
EWG

EDG
O

An electron withdrawing
group (deactivating group)
that attached to a
carboxylate ion will
delocalise the negative
charge, thereby stabilises
the carboxylate ion and
increases acidity.

An electron donating
group, (activating group)
will destabilise the
carboxylate ion and
decreases 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 electronwithdrawing 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

C
H
1o alcohol

R
OH

oxidizing
agent

R
C

oxidizing
agent

H
aldehyde

HO
carboxylic acid

Common oxidizing agents are :


KMnO4 / H2SO4
potassium permanganate
K2Cr2O7 @ Na2Cr2O7 /H2SO4
potassium /sodium dichromat (VI)
36

2. Oxidation of Alkyl Benzene

oxidizing
agent

Cl

COOH

Cl
CH3
CH

CH3

KMnO4 , H+

COOH

+ CO2 + H2O
37

3. Formation and Hydrolysis of nitrile


R CH2 X

NaCN

CH2 Br

R CH2 CN

H2O,H+

CH2 CN

NaCN

R CH2 COOH

CH2 COOH

H2O,H+

38

4. Carbonation of Grignard Reagents

RMgX

C
O
H2O, H+

CH2 MgBr

RCOOH + Mg(OH)X

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
R

O
+ NaOH

OH

+ H2O
-

O Na+

42

COO Na+

COOH

+ NaOH

+ H2O
Sodium benzoate

43

2. Reaction with electropositive metals such as Na,


K, Ca, Mg and Fe.
O

O
R

C OH

C O M

H2

Exercise:
Cl

O
C
OH

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

O
R

C OH

C Cl + SO2 + HCl
O

PCl5

C Cl + POCl3 + HCl
O

PCl3

C Cl + H3PO3

45

Exercise :

SOCl2
O
CH3 CH C OH

PCl5

CH3
PCl3

46

2. Esterification
Carboxylic acids react with alcohols in the presence of mineral
acid catalyst to produce esters.
O
R

O
OH + HOR

carboxylic acid

H+

alcohol

O R' + H2O

ester

O
CH3 CH2 C OH + HOCH2CH3
propanoic acid

ethanol

H+

CH3 CH2 C OCH2 CH3


ethyl propanoate

+ H2O
47

3. Acid anhydride formation


Acid anhydrides can be prepared from carboxylic acids by
the loss of water through heating.
O
R

C OH + HO C

heat

R C

C R + H2O

acid anhydride

CH3 C

OH + CH3 C

O
OH

heat

CH3 C

O
O

C CH3

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
R

C Cl

RNH2

(1o amine)

NHR + H2O

2o amide

O
R2NH
(2o

amine)

NR2 + H2O

(3o amide)
49

Exercise :
NH3

CH3

CH C

Cl

CH3 NH2

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
R

R'

LiAlH4
ether

R CH2 OH + ROH
1o alcohol

O
CH3 CH C O CH2 CH3
CH3

LiAlH4
ether

CH3 CH CH2 OH
CH3
+ HOCH2CH3

51

Methanoic acid, HCOOH as a reducing agent


O

Methanoic acid molecule, H C OH has both


O
and
C OH
carboxylic

O
H C
carbonyl

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+

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

R C Cl

H2O

acid chloride

R C OH + HCl
carboxylic acid

ii. Hydrolysis of acid anhydrides

R C O C R
acid
anhydride

O
H2O

2 R C OH
carboxylic acid
55

Reactions of carboxylic acid derivatives


iii. Hydrolysis of esters

H2O
H+

+ ROH
carboxylic acid

R C OR
ester

alcohol

O
H2O
+
NaOH R C O Na

+ ROH
alcohol

56

Example :
O
C Cl

H2O

benzoyl chloride

CH3 C O C CH3

H2O

ethanoic anhydride

57

Example :

O
CH3 C O CH3

H2O
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

R C Cl , R C O C R , R C OR , R
acid
chloride

acid
anhydride

ester

< NH2

O
C

O
OH , R

carboxylic
acid

NH2

amide

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
R

O
O

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
C
R

O
R

H3C

C
R

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.

N
-

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

Secondary amines

R'

Tertiary amines

R''

N
R

R'

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.1

Classify the following amines:


i. CH3CH2CH2NH2

ii. CH3CH2

Aliphatic amines

CH3

iii. CH3CH2

CH3

CH3
iv.

CH3

H
v.

NH2

vi.

CH3

3
CH2CH3

Aromatic amines

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.2

IUPAC Nomenclature
In primary amines, the suffix amine
replaces the e in the name of the parent
alkane
i. CH3CH2CH2NH2
3 2
1

propanee
amine

Secondary and tertiary amines are named


as N-substituted derivatives of primary
amines
ii. CH3CH2
2 1

2
N

CH3

N-methylethaneamine

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.2

Examples:
Structure

CH3NH2
CH 3 CH(NH 2 )CH 3
NH2

CH 3CH 2CHCH2CH3

IUPAC Name
Methanamine
2-propanamine
Cyclopentanamine
N-methylpentanamine

NHCH3
CH3
CH3CH2

CH2CH3

N-ethyl-N-methyl
ethanamine

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.2

IUPAC Nomenclature
When multiple functional groups are
present and the NH2 group does not
take priority, it is named as an amino
substituent
Examples:

NH2CH2COOH
2

H 2N

1
3

2-aminoethanoic acid

OH

NH2

2,4-diaminophenol

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.2

IUPAC Nomenclature
Aromatic amines are named as
derivatives of aniline

N-ethyl-N-methylaniline

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.2

Common Name
Most primary amines are named as
alkylamines
Structure

CH3NH2

IUPAC Name
methylamine

CH 3CH 2NH 2

ethylamine

CH3CH2CH2NH2

propylamine

CH 3 NHCH 3

CH3NHCH2CH3

dimethylamine
methylethylamine

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3
Boiling point
Solubility
Basicity

(i) Boiling Point


Both primary and secondary amines
can form intermolecular hydrogen
bonds.
H
CH3 N

HCH3
CH3
H CH3 NN CH
3

H
hydrogen bonds

CH3

CH3

CH3N NCH H

CH3
N

CH3

no hydrogen bond

hydrogen bonds

1 amines 3 amines 2 amines


Tertiary amines cannot form hydrogen
bonds to each other.

CH3

Examples:
The table below compares the boiling points of isomeric
amines.
Amines

Class

Relative
molecular
mass

Boliling
points/oC

CH3CH2CH2NH2

59

49

CH3CH2-NH-CH3
CH3
|
CH3-N-CH3

2
3

59
59

37
4

Boiling Point : CH3CH2CH2NH2 > CH3CH2NH(CH3) > (CH3)3N

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3
Boiling point
Solubility
Basicity

(i) Boiling Point


Amines have higher boiling points than
alkanes or haloalkanes of similar relative
molecular mass due to intermolecular
hydrogen bonding Example
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
molecular mass

Boliling
points/oC

CH3CH2CH2CH3
butane
CH3CH2Cl
chloroethane
CH3CH2CH2NH2
1-propanamine

Alkane

58

-0.5

Haloalkane

64.5

12.5

Amine

59

48.6

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3
Boiling point
Solubility
Basicity

(i) Boiling Point


Amines have higher boiling points than
alkanes or haloalkanes of similar relative
molecular mass due to intermolecular
hydrogen bonding Example
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
molecular mass

Boiling
points/oC

CH3CH2CH2CH3
butane
CH3CH2Cl
chloroethane
CH33CH
CH22CH22NH
CH
NH22
1-propanamine
CH3CH2CH2OH
1-propanol

Alkane

58

-0.5

Haloalkane

64.5

12.5

Amine

59

48.6

Alcohol

60

97.2

Carboxylic
acid

60

118

CH3COOH
ethanoic acid

Boiling Point : Carboxylic acid > Alcohol > Amine >


Haloalkane > Alkane

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3
Boiling point
Solubility
Basicity

(ii) Solubility
All amines including tertiary amines,
are capable of forming hydrogen
bonds with water molecules. Thus
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 3amine

R N
R : N3H< 2 < 1R N R
TheHsolubility
H
R
R

Increasing2osolubility

1
O

3o

H
R

H
O

N
R

3 hydrogen bonds
per a 1 amine
molecule

: hydrogen bonds
2 hydrogen bonds
per a 2 amine
molecule

1 hydrogen bond
per a 3 amine
molecule

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3
Boiling point
Solubility

Basicity
An amine is a nucleophile (a Lewis base)
base
because its lone pair of non-bonding
electrons on nitrogen

Basicity

+ H OH

H
Ammonia

H + OH

H
Ammonium ion

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3
Boiling point
Solubility
Basicity

Basicity (i) Inductive effect


An alkyl group is electron donating
group, and it stabilises the
alkylammonium ion by dispersing its
positive charge
H
H
R

+ H OH

1 Amine
Stabilised by the
alkyl group

H + OH

alkylammonium ion
Stronger base

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

Boiling point

19.3
R

+ H OH

1 Amine

Basicity

R
R

N
H

H + OH

H
alkylammonium ion

Solubility

+ H OH

2 Amine

OH

H
alkylammonium ion

Strength as a base : Methyl, 1, 2

Increasing

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3
Boiling point
Solubility
Basicity

Basicity (ii) Resonance effect


Aromatic amines (e.g., aniline) are
weaker bases than the corresponding
aliphatic and cyclic amines
Example:

NH2

Cyclohexylamine
pKb = 3.36

NH2

Aniline
pKb = 9.42

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3
Boiling point
Solubility
Basicity

Basicity (ii) Resonance effect


Aromatic amines are less basic
The lone pair electrons of nitrogen atom
are delocalised and overlapped with the
aromatic ring electrons system make it
less available for bonding to H+
NH2

NH2

NH2

arylamines are stabilised due to the 4


resonance structures

NH2

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.4
Reduction of
nitro compound

Reduction of nitro compounds


Aromatic amines can be prepared by
reduction of nitro compounds using
Zn/H+ or SnCl2/H+

Reduction of
nitriles
Reduction of
amides
Hoffmanns
degradation of
amides

Zn/H+ or
NO2
nitrobenzene

SnCl2/H+

NH2
Aniline
anline

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.4
Reduction of
nitro compound
Reduction of
nitriles
Reduction of
amides
Hoffmanns
degradation of
amides

Reduction of nitriles
Nitriles are reduced to primary amines
by H2 / catalyst, LiAlH4 / H+ or
NaBH4 / H+.
H2

R C N

catalyst (Pt, Ni, Pd)

RCH2NH2

Example :
OH
CN

1. LiAlH 4
2. H

OH
CH 2 NH 2

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.4
Reduction of
nitro compound
Reduction of
nitriles
Reduction of
amides
Hoffmanns
degradation of
amides

Reduction of amides
Reduction of an amide using LiAlH4 / H+
or NaBH4 / H+ can yield a primary,
secondary, or tertiary amine
depending on the type of amide used
O

1. LiAlH 4

R C NH 2 2. H +

H
R C NH 2
H

H 2O

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.4
Reduction of
nitro compound

Example :
O

i.
CH3

Reduction of
nitriles
Reduction of
amides
Hoffmanns
degradation of
amides

C NH 2

H
1. LiAlH 4
2. H

CH3

Ethanamide
(2o amide)

ii.

Ethanamine
(1o amine)

O CH3 1. NaBH4
CH3

C NH

N-methylethanamide
(2o amide)

C NH 2 + H2O

2. H

CH3

H CH
3
C NH + H2O
H

N-methylethanamine
(2o amine)

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.4
Reduction of
nitro compound
Reduction of
nitriles
Reduction of
amides
Hoffmanns
degradation of
amides

Hoffmanns degradation of amides


On warming a primary amide with bromine
in solution of NaOH, a primary amine is
formed.
This reaction is used to synthesise
primary alkyl and aryl amines.
O
R C NH2
amide

Br2 , NaOH
H2O

RNH2

2CO3

amine

The elimination of carbonyl group is


shortening the length of carbon chain by
one carbon atom.
atom

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.4
Reduction of
nitro compound
Reduction of
nitriles
Reduction of
amides
Hoffmanns
degradation of
amides

Example :
CONH2

NH2
Br2, OH-

+
H2O

CO32-

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5
Reaction with :
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride

Nitrous acid
Bromine water
Formation of dye

Reaction with acyl chlorides


1 and 2 amines are acylated to form
N-substituted amides
O

H
2 R N H

Cl C CH 3

2 R N H + Cl C CH3
2o amine

R N C CH3

RNH3 Cl -

2o amide

1o amine

H O

R O
R N C CH3

R2NH+2 Cl

3o amide

3 amines are not acylated because they


do not have a H atom attached to N atom.

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5
Reaction with :
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride

Nitrous acid

Reaction with acid anhydride


1 and 2 amines are acylated to form
N-substituted amides

1o amine

H O

R N H + CH3 C O C CH 3

R N

R
2o amine

CH3COO H
R O

CH 3 C O C CH 3

R N C CH3

acid anhydride

3o amide
+

Formation of dye

C CH 3

2o amide

acid anhydride
+

R N H

Bromine water

CH3COO H

3 amines are not acylated because they


do not have a H atom attached to N atom.

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5
Reaction with :
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride

Nitrous acid
Bromine water
Formation of dye

Reaction with benzenesulphonyl chloride


Hinsbergs test
This reaction is used to differentiate
between 1, 2 and 3 amines.

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5
Reaction with :
Acyl chloride

1 amines
Benzenesulphonyl chloride reacts with a
1 amine to form a white precipitate
(N-substituted sulphonamides)Acidic hydrogen

Acid anhydride

Benzenesulphonyl
chloride

R-N-H

Nitrous acid
Bromine water
Formation of dye

1o amine

O
+

Cl-S-

OH

H O
R-N -S-

(-HCl)

Na O
R-N -S-

O
N-substituted
benzenesulphonamides
(precipitate)

N-substituted sulphonamides have an


O
acidic hydrogen, N-H.NaOH
wateritsoluble
salt in aqueous NaOH.
Therefore,
dissolve
(clear solution)

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5
Reaction with :
Acyl chloride

2 amines
Benzenesulphonyl chloride reacts with a
2 amines to form a white precipitate
(N,N-disubstituted sulphonamide)

Acid anhydride

R'

Benzenesulphonyl
chloride

R-N-H

Nitrous acid
Bromine water
Formation of dye

2 amine

O
+

Cl-S-

OH

(-HCl)
O

R' O
R-N -SO
N,N-disubstituted
benzenesulphonamides
(precipitate)

N,N-disubstituted sulphonamides do not


No reaction
NaOH
have an acidic hydrogen, N-H.
Therefore, it dissolve in aqueous NaOH.

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5
Reaction with :

3 amines
3 amine do not gives visible reaction
with benzenesulphonyl chloride

Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride

Nitrous acid
Bromine water
Formation of dye

Summary of Hinsbergs test:


NaOH

1 amines white precipitate


solution

clear

NaOH

2 amines white precipitate


dissolved

3 amines do not give any visible


change

do not

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5
Reaction with :
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride

Nitrous acid
Bromine water
Formation of dye

Reaction with nitrous acid (NaNO2 + HCl)


Nitrous acid (HNO2) is a weak and
unstable acid.
It is always prepared in situ, by treating
cold sodium nitrite (NaNO2) with an
aqueous solution of a cold dilute
hydrochloride acid (-5C).
Nitrous acid reacts with all classes of
amines
Nitrous acid test can be used to distinguish:
1 aliphatic and 1 aromatic amines
1 and 2 aliphatic amines

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5

1 amines (Aliphatic)
Primary aliphatic amines react with
nitrous acid to yield highly unstable
aliphatic diazonium salts

Reaction with :
Acyl chloride

Acid anhydride
Benzenesulphonyl
chloride

R-N-H

NaNO2, HX
o

-5 to 0 C

1 amine

Nitrous acid

[ R-N

NX ]

-N2

aliphatic
diazonium salt
(unstable)

Bromine water

Observation :

Formation of dye

Formation of gas bubbles


(N2)

C=C

carbocation

ROH

RX

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5
Reaction with :

1 amines (Aromatic)
Primary arylamines react with nitrous
acid to give arenediazonium salts

Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride

Nitrous acid
Bromine water
Formation of dye

N2+Cl

NH2
NaNO2, HCl

cold

+ NaCl + H2O

arenediazonium salt

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5
Reaction with :
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride

Nitrous acid
Bromine water
Formation of dye

1 aliphatic amines and 2 aliphatic amines


Primary
aliphatic
amines
Secondary
aliphatic
amines

Form a mixture of alkenes,


alcohols, alkyl halides and
nitrogen gas.
Form secondary Nnitrosamines as yellow oil,
which is stable under the
reaction conditions.

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5
Reaction with :
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride

Nitrous acid

Identification
test
Aniline reacts with aqueous bromine to
yield white precipitates
NH2 group is an activating and orthopara directors group

Reaction with bromine water

NH2

NH2
3Br2(aq)

Br

Br

room temperature

Bromine water
Br

Formation of dye

(2,4,6-tribromoaniline)
Observation: White precipitate formed

3HBr

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5
Reaction with :
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride

Nitrous acid
Bromine water
Formation of dye

Formation of dye
Primary arylamines react with nitrous acid
to give arenediazonium salts which are
stable at 0 C
Arenediazonium salts also undergo coupling
reaction with aromatic compounds with
strong electron donating group, such as OH
and NR2 at the para position to yield azo
compounds
Azo compounds are usually intensely
coloured and relatively inexpensive
compounds, they are used as dyes

Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature


19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5
Reaction with :
OH

Acyl chloride

N=N

Acid anhydride

OH

(orange)
+

Benzenesulphonyl
chloride

N N: X

Nitrous acid
Bromine water
Formation of dye

CH3

CH3
CH3

N=N
(yellow)

CH3

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction

20.2 : Chemical Properties

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.1
-amino acid
20 amino acids
Naming

Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI

20.2 : Chemical Properties

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.1
-amino acid

20.2 : Chemical Properties

Amino acid:
acid a compound that contains
both an amino group, -NH2 and a
carboxyl group, -COOH
H

20 amino acids
Naming

CH 3 CH 2

Zwitterion
Isoelectric point
Structures in:

NH 2

-amino acid: an amino acid in which


the amino group is on the carbon
adjacent to the carboxyl group
H

Acidic
Basic
pI

COOH

NH 2

COOH

CH 2 CH 3

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.1
-amino acid
20 amino acids
Naming

Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI

Name
Glycine
Gly
Alanine
Ala
Valine
Val

20.2 : Chemical Properties

Structure
H

CH

COOH

NH2
H3C

CH

COOH

NH2
CH 3
HC

CH

CH 3 NH 2

COOH

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.1
-amino acid
20 amino acids
Naming

20.2 : Chemical Properties

Name
Leucine
Leu

Structure
C H

C H C H
C H

Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI

Isoleucine
Ile
Phenylalanine
Phe

3
2

C H
N H

CH 3CH 2CH

C O O H
2

CH

CH 3

COOH

NH2

CH2

CH COOH
NH2

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.1
-amino acid
20 amino acids
Naming

Zwitterion
Isoelectric point

20.2 : Chemical Properties

Name
Threonine
Thr
Cysteine
Cys

Structures in:
Acidic
Basic
pI

Methionine
Met

Structure
OH
CH

CH 2

CH

NH

COOH
2

CH 2

COOH
C

CH 2

HO

NH

CH2 CH
NH2

COOH

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.1
-amino acid
20 amino acids
Naming

Zwitterion
Isoelectric point

Name

Basic
pI

Structure
O

Tryptophan
Trp
Proline
Pro

Structures in:
Acidic

20.2 : Chemical Properties

Serine
Ser

OH
NH2

NH

CH 2

CH 2

COOH
C

CH 2

HO

NH

CH2 CH
NH2

COOH

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.1
-amino acid
20 amino acids
Naming

Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI

20.2 : Chemical Properties

Name
Structure
OH
Threonine
CH3 C
Thr
H

Cysteine
Cys

HS

CH2

CH
NH

COOH
2

CH

COOH

NH2

Methionine CH S CH CH CH COOH
3
2
2

Met

NH2

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.1
-amino acid
20 amino acids
Naming

Zwitterion
Isoelectric point

Name

Structure

Tyrosine
Tyr

HO

Asparagine
Asn

Structures in:
Acidic
Basic
pI

20.2 : Chemical Properties

Glutamine
Gln

CH2

CH

COOH

NH2

NH2CCH2CH COOH

O
NH2
NH2CCH2CH2CHCOOH

O
NH2

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.1
-amino acid
20 amino acids
Naming

Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI

20.2 : Chemical Properties

Name
Structure
Aspartic
HOOCCH2CHCOOH

acid
NH2
Asp
Glutamic HOOCCH2CH2CHCOOH

acid
NH2
Glu
Lysine
H2NCH2CH2CH2CH2CH COOH

Lys
NH2

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.1
-amino acid
20 amino acids
Naming

Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI

20.2 : Chemical Properties

Name
Structure
H2NCNH(CH2)3CHCOOH
Arginine

NH
NH2
Arg
Histidine
His

HCC=CH2CH COOH

N NH
NH2
CH

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.1
-amino acid

20.2 : Chemical Properties

IUPAC Name

i)
H

20 amino acids

pI

COOH 2-amino propanoic acid

NH2

Structures in:

Basic

CH3

ii)

Isoelectric point

Acidic

COOH 2-amino ethanoic acid

NH2

Naming

Zwitterion

CH2OH

iii)

NH2

COOH

2-amino-3-hydroxy
propanoic acid

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.1
-amino acid

20.2 : Chemical Properties

IUPAC Name
CH2CH2CH2NH2

iv)

20 amino acids

COOH

Naming

NH2

2,5-diamino pentanoic acid

Zwitterion
Isoelectric point

v)

CH2CH2CH2COOH

Structures in:
H

Acidic
Basic
pI

NH2

COOH

2-amino hexanedioic acid

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.1

Zwitterion
Amino acids can undergo an
internal acid-base reaction, in which a
proton is transferred from the
carboxyl (-COOH) to the amino group
(-NH2) to form dipolar ion called
zwitterion.

-amino acid
20 amino acids
Naming

Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI

20.2 : Chemical Properties

CH2CH2CH3
H

COOH

NH2

(neutral)

CH2CH2CH3
H

COO

NH3

(dipolar ion @
zwitterion)

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction

20.2 : Chemical Properties

20.1

Isoelectric Point (pI)

-amino acid

In general, zwitterion is electrically


neutral and exists at specific pH

20 amino acids
Naming

Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI

This particular pH is called isoelectric


points
Each amino acid has its specific pI
H2N(CH2)4CH COOH 9.7
Lysine
Example:

(Lys)

Amino Acid

NH2
Structure

Aspartic
Glycine
acid
(Gly)
(Asp)

HOOCCH
CHCOOH
H
CH 2 COOH

N H 2 NH2

pI
2.9
6.1

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction

20.2 : Chemical Properties

In Acidic
The cation, H3N+ CH2 COOH
predominates (Amino acids as base)
c
In Basi
The anion, H2N CH2 COOpredominates (Amino acids as acid)
I n pI
The zwitterion, H3N+CH2COOpredominates (Amino acids as
amphoteric)

20.1
-amino acid
20 amino acids
Naming

Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI

NH2CH2COOH

Gly (pI = 6.1)


NH3CH2COOH NH3CH2COO NH2CH2COO
+

at pH < 6.1

at pH = 6.1

at pH > 6.1

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.2
Reactions of
NH2 group:
HCl
HNO2
Reactions of
-COOH group:
NaOH
ROH
Peptide bond
Importance

20.2 : Chemical Properties

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.2
Reactions of
NH2 group:
HCl
HNO2
Reactions of
-COOH group:
NaOH
ROH
Peptide bond
Importance

20.2 : Chemical Properties

a) Reaction with HCl


R'
R C NH2

HCl

R'
_
+
R C NH3Cl
COOH

COOH
Example:

CH2CH3
H C NH2
COOH

CH2CH3
+

HCl

H C NH3Cl
COOH

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.2
Reactions of
NH2 group:
HCl

20.2 : Chemical Properties

b) With Nitrous Acid (HNO2)


R'

R'

R C NH2
COOH

NaNO2 / HCl
o

-5 to 0 C

HNO2
Reactions of
-COOH group:

R C

COOH
diazonium ion
elimination of N2(g)

Observation: Bubbling
of gas (N2)

R'
R C+
COOH
carbocation

NaOH
ROH

H 2O

Peptide bond

2-hydroxy

Importance

carboxylic acid

+ Cl

halocarboxylic
acid

-H

+
Alkenoic
acid

Chapter 20 : Amino Acids and Proteins


Example:

CH3

H C NH2

NaNO2 / HCl

COOH

CH3
H C

COOH
diazonium ion
elimination of N2(g)
CH3
H C+
COOH
carbocation
H 2O

CH3
H C OH
COOH

+ Cl

-H

CH3
H C

Cl

COOH

CH2
H C
COOH

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.2
Reactions of
NH2 group:
HCl
HNO2
Reactions of
-COOH group:
NaOH
ROH
Peptide bond
Importance

20.2 : Chemical Properties

c) Reaction with NaOH


R'
R C NH2

NaOH

R'
R C NH2
_

COO Na+

COOH
Example:

CH2CH3

CH2CH3
H C NH2
COOH

NaOH

H C NH2
_

COO Na+

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.2
Reactions of
NH2 group:
HCl
HNO2
Reactions of
-COOH group:
NaOH
ROH
Peptide bond
Importance

20.2 : Chemical Properties

d) Reaction with ROH + HCl (catalyst)


R'
R C NH2

R''OH

COOH

R'
R C NH2

+ H 2O

COOR''

Example:
CH2CH3
H C NH2
COOH

HCl

CH3OH

R'
R C NH2
COOR''

+ H 2O

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.2
Reactions of
NH2 group:
HCl
HNO2
Reactions of
-COOH group:
NaOH
ROH
Peptide bond
Importance

20.2 : Chemical Properties

Peptide Bond
2 amino acids react together, H2O
is eliminated.
This is condensation reaction.
Peptides are amino acid polymers
in which the individual amino acid
units, are linked together by amide
bonds, or peptide bonds
2 amino acids form dipeptide
3 amino acids form tripeptide
15 30 amino acids form oligopeptide
> 30 amino acids form polypeptide

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.2
Reactions of
NH2 group:
HCl
HNO2
Reactions of
-COOH group:
NaOH
ROH
Peptide bond
Importance

20.2 : Chemical Properties

Formation of dipeptide bond:


O

H
H2N CH2 C OH + H N C COOH
H CH3
O

Notes:

H2N CH2 C

N C COOH + H O
N-terminal (with free NH2) 2is
H CH3

always written on the left and


C-terminal
(with
amide bond
/ free COOH) at
thepeptide
right side
bond
A dipeptide

Chapter 20 : Amino Acids and Proteins


Formation of tripeptide bond:
O
H2N CH2 C OH

H
H N C COOH
H

Gly

CH2

OH

H N C COOH

CH3

H
Tyr

Ala

Write the structural formula of tripeptide with the following


sequence Gly-Ala-Tyr :
O

H O

H2N CH2 C N C C
H CH3

CH2
N C COOH
H

A tripeptide

OH

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.2
Reactions of
NH2 group:
HCl
HNO2
Reactions of
-COOH group:
NaOH
ROH
Peptide bond
Importance

20.2 : Chemical Properties

Importance of amino acids :


Human beings can synthesize about half
of the amino acids needed to make
proteins.
Other amino acids, called the essential
amino acids,
acids must be provided in the
diet.
The ten essential amino acids are :
arginine (Arg) valine (val)
methionine (Met)
threonine (Thr) leucine (Leu) phenylalanine (Phe)
histidine (His) isoleucine (Ile) lysine (Lys)
trypthophan (Trp)

Chapter 20 : Amino Acids and Proteins


20.1 : Introduction
20.2
Reactions of
NH2 group:
HCl
HNO2
Reactions of
-COOH group:
NaOH

20.2 : Chemical Properties

Importance of proteins :
Proteins are the most abundant organic
molecules in animals, playing important
roles in all aspects of cell structure and
function.
Examples of protein functions :
Class of protein
structural protein

Examples
collagen, keratin

Importance

tendons, skin
hair, nails

ROH
Peptide bond

Functions

enzymes

DNA polymerase

repair DNA

transport protein

hemoglobin

transport O2

CHAPTER 21
POLYMERS
FJ/Chemistry Unit, KMPk/Mac 2006

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.

Homopolymer
-

a polymer formed from only one types monomer units.

nA

-A-n

Example :

nCH2 CH2
ethene
(ethylene)

-CH2CH2-n
polyethene
(polyethylene)

Copolymer
-

a polymer formed from two or more different monomers.

nA + nB

-A-B-n

Example :

nCH2 CCl2 + nCH2 CHCl


1,1-dichloroethene 1-chloroethene

-CH2-CCl2-CH2-CHCl-n
Saran

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

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-AX

-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.

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-CH2S

-CHC CH-CH2-CHC CH-CH2CH3

CH3

After vulcanization rubber becomes more stable over wide


ranges of temperature and far more durable than natural
rubber.

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

ii. Carbohydrates
Carbohydrates such as starch is also a polymer.
i.

Starch (amylose)

H
O

CH2OH
O
HH
H
OH H
O

CH2OH
O
H
H
OH H
O

OH

OH

-(1,4)-glycosidic linkages

ii. Starch (amylopectin)


-

contains
linkages.

-(1,4)-glycosidic

and

-(1,6)-glycosidic

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

isoprene

cis-polyisoprene

Another name for natural rubber is cis-1,4-polyisoprene.


All the double
configuration.

bond

in

natural

rubber

are

cis-

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.

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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

ethene

-CH
( 2-CH2)n
polyethene

ii. Formation of polyvinyl chloride

n HC CH2
Cl

chloroethene

ROOR

(
-HC-CH
)n
2Cl

polychloroethene
(polyvinyl chloride or PVC)

12

iii. Formation of polystyrene

n HC CH2

ROOR

phenylethene
(styrene)

(
-HC-CH
)n
2-

Polyphenylethene
(polystyrene)

iv. Formation of polyisopropene

n CH 2 =C-CH=CH 2

-CH 2 -C=CHCH 2-

CH 3

CH 3

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

n H2N-(CH2)6-NH2 + n HO-C-(CH2)4-C-OH
hexane-1,6-diamine

hexane-1,6-dioic acid

O
H
H O
(
-N-(CH
)n + n H2O
2)6-N-C-(CH2)4-CNylon 6,6
ii. Formation of Nylon 6

O
n H2N-(CH2)5-C-OH
6-aminohexanoic acid

O
(
-NH-(CH
)n + n H2O
2)5-CNylon 6

15

iii. Formation of Kevlar

H
n H-N-

-N-H + n Cl-C-

1,4-diaminobenzene

H
N-

O
-C-Cl

terephthalic acid

H O

-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
n CH3O-C-

O
-C-OCH3 + n HO-CH2CH2-OH
1,2-ethanediol
(ethylene glycol)

dimethyl terephthalate

O
(
-O-CH
2CH2-O-C-

O
-C)n + n CH3OH

Dacron or poly(ethylene terephthalate)

metanol

17

ii. Formation of Terylene

O
n HO-CH 2CH 2-OH

+ n HO-C-

ethane-1,2-diol

O
-C-OH

benzene-1,4-dicarboxylic acid

O
(
-O-CH
2CH 2-O-CTerylene

O
-C)n + n H 2O
water

18

21.4 : Uses of Synthetic Polymers


No.

Polymer

Uses

Polyethene

plastics, drinking bottles, toys

Polyvinyl chloride

Polystyrene

Nylon 6

Textile

Nylon 6,6

Sweater

Kevlar

Bullet proof vest

Dacron

Fabric

Terylene

piping, floor tiles, clothing, toys,


wire covering
containers, thermal insulation-ice buckets

Fiber-optic material

19