INTRODUCTION TO

ENGINEERING CHEMISTRY

SYLLABUS
B. Tech I / II Semester
(Common to all branches)
AS103/AS203

Engineering Chemistry

a. Lecture (L ) 3 hrs / week

Total Lectures hrs per Sem - 42

b. Practical ( P ) 2hrs / week

c. Total Credits : - L + P

Total Lab hrs per Sem - 24

4

UNIT 1
Atoms
INTRODUCTION OF ENGINEERING
CHEMISTRY
to molecules

to materials for Engineers.

Atoms combines to give molecules and how molecules aggregate o give

materials
Recapitulation of salient feature of valence bond theory, Hybridization,
sigma and pi bonds shape of the simple inorganic compounds based upon concepts
of hybridization and to illustrate planar, tetrahedral, square planer, and
octahedral geometries.
Molecular orbital theory and its application to form homo
(H2 N2 &O2) and hetero (HF, NO) diatomic
molecules.

Structure

and stereo structure of molecules

Representing three dimensional structure of organic molecules including
Conformations, Newman, Saw horse, Fischer, projections wedge and dash
structural representation, equivalence of structural representations
Chirality, optical activity and isomerism , compounds containing one and two
chiral carbons , enantiomers, di stereo isomers, meso compounds, no. of chiral
atoms and optical isomers, Dynamic stereochemistry , concepts of regiochemistry,
stereo selectivity, Stereo specificity
and enantiomeric excess R&S nomenclature.
Geometrical isomerism in simple acyclic and cyclic molecules, E & Z
nomenclature.

UNIT 2
MATERIALS AND THEIR CHARACTERIZATION

Micro
and
macroscopic
properties
of
molecules,
Intermolecular forces, Molecular aggregation micelles,
Examples of inorganic and organic functional materials,
core concepts of nanotechnology.
Purification;
Physical
(crystallization,
fractional
crystallization , distillation , fractional distillation,
steam distillation) and chemical methods of purification.
General
chromatographic(Adsorption
and
partition)
techniques (column thin layer and paper chromatography)
and their application.
Criteria of purity ; Melting and Boiling point,
chromatography , particle size measurement and surface
area
Characterization; Surface tension, Viscosity , Conductivity
, and Absorption Spectroscopy (IR, UV Visible , NMR)

UNIT 3

STABILITY AND REACTIVITY OF MOLECULES : UNIT

PROCESSES IN ORGANIC CHEMISTRY
Reactivity of Molecules : Electron displacement effects
inductive, electromeric, resonance and hyper conjugation,
Reactive sites in molecules - functional groups.

Reactions Dynamics:
Chemical kinetics,
Order and
molecularity, zero, first and second order reactions, pseudo
first order reaction , temperature dependence of reaction rates,
Catalysis and some industrially important catalytic reactions.

Reaction Mechanism: Fission of a covalent Bond, types of

reactions nucleophilic ( SN1 & SN2, SNi, SNAr) and
electrophilic substitution reactions ( Nitration, Sulphonation,
Halogenation, and Friedel Crafts reaction ) and their
mechanism , regio and Stereochemistry of involved reactions

UNIT 4
WATER AND ITS TREATMENT

Alkalinity of water, estimation of alkalinity, Hard and

soft water, hardness- units, determination of hardness
by complexometric Titration, Removal of hardness
of water- Zeolite , ion exchange process, Boiler Feed
water, descaling of boilers desalination of brackish
water, Reverse osmosis, potable water,

UNIT 5
SOME MATERIALS OF INDUSTRIAL IMPORTANCE:

Polymers and Polymerization ( ionic, anionic and free

radical induced), Properties of polymers , Number
average and Weight average
molecular weighs,
characterization of polymer samples , polymer blends,
Stereo structures of polymers, Dendrimers, Some
examples of common polymers used in Industry, Natural
and Synthetic rubber, Silicones, Composites, Adhesives,
Conducting polymers, Biodegradable polymers.
Metallic corrosion and its prevention, electrolysis ,
Industrial electrolytic processes-( aluminium). Fuel cells
and batteries.
Control of friction Oils,
Soaps and detergents

fats and

lubricants ,

RECOMMENDED REFERENCE BOOKS:

Students are encouraged to use available library resources, electronic

media and internet information for further understanding of the subject.
The following books are suggested as reference works for teachers/students

1. Organic Chemistry, P.Y. Bruice , Ninth Impression, 2011,

Pearson
India

2. Chemistry 3 , A. Burrows, john Holman, A, Parsons, G. Pilling, G.Price,

Oxford University Press, 2009

3. Engineering Chemistry, A Text book of Chemistry for Engineers

published by John Wiley and Sons,India 2011

4. Unit processes in Organic Synthesis by Groggins, Tata McGraw Hill,

2001

5. Spectroscopic Methods in Organic Chemistry, D H Williams and I.

Fleming, Tata McGraw Hill, 1991

UNIT 1
INTRODUCTION OF ENGINEERING CHEMISTRY

What is an Atom ?

Theatomis a basic unit ofmatterthat consists of a dense

centralnucleussurrounded
bycloudofnegatively
charged electrons.

WHY ATOMS FORM MOLECULES ?

Under normal conditions no other element exists as

an independent atom in nature, except noble gases.
Ionic Bond - NaCl

&

Covalent bond CH 4

Since the formation of chemical compounds takes

place as a result of combination of atoms of various
elements in different ways, it raises many questions.
Why do atom combine with each other ?

Why bonds are formed ?

Why are only certain combination possible ?

Why do molecules possess definite shape ?

To answer such questions , different theories have come

time to time.
Lewis theory octet rule
Valence Shell Electron Pair Repulsion (VSEPR)
Valence Bond (VB) Theory
Molecular Orbital (MO) Theory

VALENCE BOND THEORY

VSEPR Theory had some drawbacks. It only tells us

about the geometry of the molecules. Therefore, a new
theory VB Theory came into existence.

FORCE = 0

(i) Nucleus of one atom and its own electron that is NA eA and NB eB.

(ii) Nucleus of one atom and electron of other atom i.e., NA eB, NB eA.

Similarly repulsive forces arise between

(i) electrons of two atoms like eA eB,
(ii) nuclei of two atoms NA NB.

The potential energy curve for the formation of H2

molecule as a function of internuclear distance of the
H atoms. The minimum in the curve corresponds to
the most stable state of H2.

OVERLAPPING OF ATOMIC ORBITALS

This partial merging of atomic orbitals is called overlapping

of atomic orbitals which results in the pairing of electrons.
This causes the formation of a covalent bond.

Therefore, the formation of a covalent bond between two

atoms results by pairing of electrons present in the valence
shell having opposite spins.

The bond strength depends upon extent of overlapping .

Axial overlapping Sigma Bond

Sidewise overlapping Pi bond.

HYBRIDIZATION

Overlapping of atomic orbitals ----- Covalent bond.

Example formation of H2.
In case of polyatomic molecules CH4, NH3 and
H2O Formation of bond & Geometry both are
important.

Simply overlap does

(directional properties).

Why is the shape of CH4 tetrahedral ?

not

explain

geometry

According to Pauling the atomic orbitals combine

to form new set of equivalent orbitals known as
hybrid orbitals.

In place of pure orbitals, the hybrid orbitals are

used in bond formation. The phenomenon is
known as Hybridisation.

SALIENT FEATURES OF
HYBRIDISATION:

The number of hybrid orbitals is equal to the

number of the atomic orbitals that get hybridized.

The hybridized orbitals are always equivalent in

energy and shape.

These hybrid orbitals are directed in space in

some preferred direction to have minimum
repulsion between electron pairs and thus a stable
arrangement. Therefore, the type of hybridisation
indicates the geometry of the molecules.

TYPES OF HYBRIDISATION
1 . SP hybridisation
Example :- BeCl2
2. SP2 hybridisation
Example :- BCl3
3.

SP3 hybridisation
Example : - CH4

AMMONIA (NH3)

WATER (H2O)

ETHENE

QUIZ
1.

An atom may be defines as

a) combination of molecules
b) basic unit of matter
c) a fundamental particle
d) None of these

QU 2
Which of the following is obtained in nature in Atomic
form ?
a) Lithium
b) Aluminium
c) Argon
d) All

QU . 3
Atoms combine together to
a) To increase their energy
b) To become unstable
c) To attain stability
d) Both a & c

QU. 4
Overlapping of atomic orbitals leads to
a) Formation of Ionic bond
b) Formation of covalent bond
c) May be ionic & covalent
d) None of these

QU. 5
According to pauling, In hybridisation, Atomic
orbitals combine together to form a set of
equivalent energy orbitals known as .
A) P orbitals
B) Hybrid orbitals
C) SP3 orbitals
D) All of these are possible

QU. 6
Hybrid orbitals are
a) Equal in energy
b) Equal in shape
c) Equal in size
d) All of these

QU. 7

The phenomenon of intermixing of dissimilar

orbitals of the same atom but having
SLIGHTLY different energies to form same
number of new orbitals of equal energies and
identical shapes is known as
a) Resonance
b) Mesomeric effect
c) Hybridisation
d) Molecular orbital theory

QU. 8

Predict the hybridisation by

A) combination of 2s and 2p orbitals of Carbon
atom
B) combination of 3s and two 3p orbitals
C) combination of 4s and 2p orbitals

QU. 9
Which of the following orbitals can be involved in
hybridisation
a) Fully filled orbitals
b) Half filled orbitals
c) Both a & b
d) None of these

FIND THE HYBRIDISATION OF THE FOLLOWING

MOLECULES AND EXPLAIN THEIR GEOMETRY

1. Boron trifluoride

FORMULA FOR HYBRIDISATION

How to determine type of hybridization: The

structure of any molecule can be predicted on the basis
of hybridization which in turn can be known by the
following general formulation,
H = 1/2 (V + M C + A)

Where H = Number of orbitals involved in hybridization

viz. 2, 3, 4, 5, 6 and 7, hence nature of hybridization will
be sp, sp2, sp3, sp3d, sp3d2, sp3d3 respectively.
V = Number electrons in valence shell of the central atom,
M = Number of monovalent atom
C = Charge on cation,
A = Charge on anion

QU. ON HYBRIDISATION
Which molecule is not linear
(a) BeF2 (b) 1. BeH2
(c) CO2 (d) H2O
The bond angle in water molecule is nearly or Directed bonds in water forms an angle of
(a) 120o
(b) 180o
(c) 109o 28'
(d) 104o 30'
Ans: (d)
3. The central atom in a molecule is in hybrid state. The shape of molecule will be
(a) Pyramidal (b) Tetrahedral
(c) Octahedral (d) Trigonal planar
Ans: (d)
4. Which molecule is linear
(a) NO2 (b) ClO2
(c) CO2 (d) H2S
Ans: (c)

5. Which of the following molecules has trigonal planer geometry

(a) IF3 (b) PCl3
(c) NH3 (d) BF3
Ans: (d

SP3d HYBRIDISATION
Examples :- PF5 , PCl5

SP3d2 Hybridisation
Example :SF6

ASSISGNMENT
1.
a)

What is the shape and hybridization of the following

molecules ?
SF4, XeF4, PCl5 , PF5 , SF5

1.

A) What is valence bond theory?

B) Describe the formation of H2 molecule through Valence
Bond theory it.
C) What is hybridization? Write its Salient features.
D) Explain the formation of CH4 molecules through Valence
Bond theory.

2.

What is Molecular orbital Theory? Draw Molecular orbital

diagram of following molecules H2 , N2 ,F2 ,Cl2 ,NO.

PROBLEMS WITH VALENCE BOND THEORY

VB theory predicts many properties better than

Lewis Theory

bond strengths, bond lengths, hybridisation, shape

However, there are still many properties of molecules

it doesnt predict perfectly

magnetic behavior of O2

The need to explain the magnetic behavior seen for O2 led

to the development of another bonding theory called the
Molecular Orbital (MO) Theory.

47

MOLECULAR ORBITAL THEORY

The electrons in a molecule are present in the various
molecular orbitals as the electrons of atoms are present in the
various atomic orbitals.

The atomic orbitals of comparable energies

symmetry combine to form molecular orbitals.

and

proper

The number of molecular orbital formed is equal to the

number of combining atomic orbitals. When two atomic orbitals
combine, two molecular orbitals are formed. One is known as
bonding molecular orbital while the other is called antibonding
molecular orbital.

While an electron in an atomic orbital is influenced by one

nucleus, in a molecular orbital it is influenced by two or more nuclei
depending upon the number of atoms in the molecule. Thus, an
atomic orbital is monocentric while a molecular orbital is
polycentric.

The bonding molecular orbital has lower energy and hence

greater stability than the corresponding antibonding
molecular orbital.

The molecular orbitals like atomic orbitals are filled in

accordance with the aufbau principle obeying the Paulis
exclusion principle and the Hunds rule.

Just as the electron probability distribution around a

nucleus in an atom is given by an atomic orbital, the
electron probability distribution around a group of nuclei in a
molecule is given by a molecular orbital.

Hydrogen
Atomic
Orbital

Dihydrogen,H2
Molecular
Orbitals

1s

Hydrogen
Atomic
Orbital

1s

50

Bond order
Bond order (B.O.) is defined as one half the difference between
the number of electrons present in the bonding and the
antibonding orbitals i.e.,
Bond Order = (Nb Na)

Bond-length
The bond order between two atoms in a molecule may be taken as an
approximate measure of the bond length. The bond length decreases as
bond order increases.
Magnetic nature
If all the molecular orbitals in a molecule are doubly occupied, the
substance is diamagnetic (repelled by magnetic field). However if one or
more molecular orbitals are singly occupied it is paramagnetic (attracted
by magnetic field), e.g., O2 molecule.
Nature of the bond
Integral bond order values of 1, 2 or 3 correspond to single, double or
triple bonds respectively as studied in the classical concept.

BONDING MOLECULAR ORBITAL

The constructive interference of wave functions results

into Bonding Molecular Orbital having less energy.
,

most of the electron density between the nuclei

53

ANTIBONDING MOLECULAR
ORBITALS

The destructive interference of the wave functions

results into Antibonding Molecular Orbital of higher
energy than the original atomic orbitals.
*, *
most of the electron density outside the nuclei
nodes between nuclei

54

Lithium
Atomic
Orbitals

Dilithium,Li2
Molecular
Orbitals

2s

Lithium
Atomic
Orbitals

2s

BO=(42)=1

1s

1s

55

Helium
Atomic
Orbital

Dihelium,He2
Molecular
Orbitals

1s

Helium
Atomic
Orbital

1s

56

TYPES OF MOLECULAR ORBITAL

Sigma () MO
Pi () MO
Sigma () molecular orbitals are symmetrical
around the bond-axis while pi () molecular
orbitals are not symmetrical.

ELECTRONIC CONFIGURATION

For B2 ,C2 ,N2

MO DIAGRAM OF C2

ELECTRONIC CONFIGURATION

For O2 ,F2

MO DIAGRAM O2