CH205 course on

Chemistry For Civil Engineers

Professor Surendra Prasad
School of Biological and Chemical Sciences
Faculty of Science, Technology & Environment
The University of the South Pacific
Suva, Fiji
prasad_su@usp.ac.fj

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International Year of Chemistry 2011
(IYC 2011)
United Nations sessions at its 63rd
General Assembly held in
December 2008 declared the year
2011 the International Year of
Chemistry (IYC 2011).

The theme for the IYC 2011 was

“Chemistry – Our Life, Our
Future”. ???

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 Chemistry is part of everyone's life

• Chemistry is part of everyone's life, from

cooking and cleaning to the latest computer
chip technology and vaccine development.

• It doesn't have to be frightening and it

doesn't have to be hard to understand.

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Aryabhatta: Invented the Zero

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Who invented atom?

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 Classical Dance forms

Dumbell shape

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What is an Orbital?

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 Atomic Structure
By
Professor Surendra Prasad
 ATOM: A Greek word: meaning can not be cut
further, not divisible. Democritus (450 BC)

• Law of conservation of mass: No detectable gain

or loss in mass occurs in chemical reactions. Mass
is conserved. H2 + ½ O2 → H2O

• Law of definite proportions: In a chemical

reaction, the elements are always combined in the
same proportion by mass.

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 Dalton’s Atomic Theory
and Its Failure
• Matter consists of definite particles called atoms.
• Atoms are indestructible.
• The atoms of one particular element are all same.
• When atoms of different elements combine, they
always maintain a definite proportion.
• Two of his theories, 2 & 3 failed as:
– Atoms can now be destructed (Nuclear fission).
– Atoms have different masses (isotopes).

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 What atoms are made up of?
& Discoveries

 composed of smaller particles (sub-atomic

particles). These are protons (p+), neutrons (n) and
electrons (e-) .
 J.J. Thomson (1897) – discovered the electrons
and the protons using the cathode rays tube.
• Proposed the idea of “plum-pudding” model of the
atom.
• Milikan – determined the charge of an electron
using the oil drop experiment.

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 Thompson’s Plum-Pudding” Model of the
Atom

• Atom is breakable
• Atom has structure
• Electrons suspended in a positively charged
electric field: must have +ve charge to balance -ve
charge of electrons and make the atom neutral.
• Mass of the atom is due to electrons (but wrong)
• Atom mostly have “empty space”.

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The Plum pudding model (PPM) of the atom was
made after the discovery of the electron but before
the discovery of the proton or neutron.

The PPM (also known as

Thomson's PPM) is a historical
scientific models of an atom.

The PPM is defined by e-s

surrounded by a volume of
positive charge, like negatively-
charged “plums” embedded in a
positively-charged “pudding”
(hence the name)
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 Discoveries
Rutherford (1911), Thomson’s student–
Introduced the idea of a solar system type
atom. (using  particles);

awarded Nobel prize for his discovery.

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Rutherford's Experiment

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Rutherford's Nuclear Model of Atom
• 1. The atom contains a tiny dense center called the nucleus.
the volume of nucleus is about 1/10 trillionth the
volume of the atom.
• 2. The nucleus is essentially the entire mass of the atom.
• 3. The nucleus is positively charged.
the amount of positive charge of the nucleus balances
the negative charge of the electrons.
• 4. The electrons move around in the empty space of the
atom surrounding the nucleus.

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Chadwick (1932) – discovered the neutrons
which accounts for the atom’s mass.

Total number of protons in an atom- atomic

number.

Total number of protons + the number of

neutrons – atomic mass or mass number of
an atom. 16
Nucleus:
The central part of the atom, is made from
protons and neutrons called as ---.

All of your atom's p & ns go in the nucleus.

N nucleus

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 Representation of an Atom

• is represented by its symbol, with atomic

number (as subscript on left hand side) and
atomic mass (superscript on LHS).
• AZX, eg.,
• 11H, 42He, 63Li, 94Be, 105B, 126C,

• 14 N, 16 O, 18 F, 20 Ne,
7 8 9 10 etc.
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 Isotopes
• the mass of the atom is taken relative to Carbon 12
as the reference point – atomic weight.
• elements with same number of protons and different
number of neutrons – isotopes.

• eg., Protium 1H1, Deuterium 1H2 and Tritium 1H3.

• carbon 12: 6C12, carbon 13: 6C13 and carbon 14: 6C14.
(Qu. Name & write the isotopes of H and C.)

• Useful in the study of radioactivity.

• Used in the study of the biosynthetic pathway of
organic compounds.
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Isotopes of Carbon: carbon 12, carbon 13 and
carbon 14.

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 Allotropes

• elements which exist in more than one physical form

(chemically same) are known as - allotropes

• Various allotropes of elements:

• Carbon- graphite, diamond & fullerene.

• Sulphur – rhombic, monoclinic
• Oxygen – O2 and O3
• Phosphorous – Red (P), Yellow (P) & White (P4).

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 Structure of graphite, at p.180

The distance between the layers is about 2.5 times the distance
between the atoms within each layer.
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Structure of graphite (Layer str.), p. 181

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Carbon possesses the strongest tendency to form long C-C
chains amongst all elements.
Some examples of catenations compounds are shown:

Buckminster fullerene, C70, C60's big

C60 molecule brother

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 Model of an Atom

 Neils Bhor (1913), Rutherford’s student. Introduced

the idea that;

• e’s circles the nucleus without loss of energy.

• e’s could only move in certain fixed orbits.
• e’s could shift from one orbit to another by absorbing
or releasing energy.
• energy released in small packets known as quanta. Acts
like a particle.
• quantum of energy emitted is called photon.

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Bohr's Model of the Hydrogen Atom

e
e

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(Delta) ΔE = hν

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e e
e

K L M N
e
n =1

n=2

n=3

n=4

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Closure the orbit to the nucleus lower is the energy
of the orbit.

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 Limitations of Bohr’s Theory:
• Bohr’s Theory can only be applied to atoms or ions
containing only one electron. It does not explain the
spectral lines for an atom having a large number of
electrons.
• Bohr assumed that an electron in an atom is located at a
definite distance from the nucleus and is revolving round
it with a definite velocity i.e. associated with fixed value
of momentum. (against Heisenberg’s U.P.)
• According to Bohr’s theory, the radiation results when
an electron jumps from one energy level i.e. orbit to
another energy orbit, but how this radiation occurs is not
explained by Bohr.
• Qu. Give three limitations of Bhor’s theory.
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 How to improve Bohr model of atom?
by
Wave Nature of Electron

• Louis de Broglie: improved Bohr’s theory by

proposing e’s behaved like waves.
• stated that e’s has both particle and wave
characteristics i.e. e- has duel nature.
• Heisenberg’s (Werner Heisenberg) Uncertainty
Principle: (the U.P.) states that it is impossible to
find the exact position and the momentum of the
electron at the same time.
Therefore, probability of finding an electron in an
atom is used (2).
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 SchrÖdinger (1926) Equation (not in detail)

• used de Broglie’s idea of matter & waves to

develop the SchrÖdinger’s equation.
• The solutions of SchrÖdinger's equation are used
to describe arrangement of electrons in the atom
(Quantum Nos.)
• The arrangement of electrons around the nucleus is
called the atom’s electronic/electron structure.
• The electronic/electron structure of different
elements comes from the study of light emitted by
atoms.
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 Orbit (Shell)/Orbitals
• e’s have different wave forms ().
• each of these wave forms are called Orbitals.
• The volume of space in an atom where the probability
of finding an e- is maximum is called orbital.
• An atomic orbital is a picture of the electron cloud
that surrounds the nucleus of an atom.
• Orbital is the region around the nucleus of an atom
(or, in a molecule, around several nuclei) in which an
electron is likely to be found i.e. the volume of space
in an atom where the probability of finding an e- is
maximum is called orbital.
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 Orbitals
• each orbital has characteristic energy and any
change in the energy changes the wave pattern.
• the orbital in which the e- is in the most stable
state is called the ground state.
• Each orbital/sub-orbital (box) can be occupied by
one or two electrons (if their spins are aligned in
opposite directions).
• Location of e- in an atom? by quantum numbers.

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 Quantum Numbers
Four types:

• Principal Quantum Number (n) – size; shell no.

• Azimuthal Quantum Number (l) – shape
• Magnetic Quantum Number (ml) -orientation
• Spin Quantum Number (s) – number of electrons
and their direction

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 Principal Quantum Number (n)

 describes the size of the atomic orbital.

 is the energy level (orbit or shell).
 PQN have values of 1, 2, 3, 4,……
 If n =1 2 3 4 ……….
1st 2nd 3rd 4th ---energy level (orbit/shell)
K L M N
 shell which is closer to the nucleus is lower in energy
(see energy values in next slide).

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As the distance of shell/orbit from the nucleus increases
energy of the shell/orbit increases.

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 Azimuthal Quantum Number (l)

• describes the shape of the orbital; have

values of 0 to (n-1)
• eg., When n = 1, l = 0 (one value)
• n=2 l = 0, 1 (two values)
• n=3 l = 0, 1, 2 (three values)
• If l = 0 1 2 3 4
• s p d f g orbital
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 Shape of orbitals

• s-orbital is spherical in shape.

• p-orbital has dumbell shape.
• d-orbital has double dumbell shape.
• f-orbital’s shape is not well defined.
• Qu. Draw the shapes of s, p and d orbitals.

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Shape of s and p and d-orbitals

dxy

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s-orbital is spherical in shape

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p-orbital is lobed (dumb-bell shaped)

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 Magnetic Quantum Number(ml)

• gives information about the orientation of the

orbital in space.
• orbitals splits the subshell into individual sub-
orbitals – (like box diagram) orientation
• each sub-orbital (box) can have a maximum of two
e’s. (Pauli exclusion principle: states that no two
electron in the same atom can have the same four
quantum numbers.)
• ml has values from –l…0…+l
• This total ml values = (2l+1)

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• l values Orbitals No of sub-orbitals
• l=0 s Then ml = 0 (1 type)
• l= 1 p then ml = -1, 0, +1 (3 types)
• l=2 d then ml = -2, -1, 0, 1, 2 (5 types)
• Note:
• When l = 0 there is one orbital of the s-type.
• When l = 1 there are three orbitals of the p-type.
• When l = 2 there are five orbitals of the d-type.

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 Orientation of orbitals

px py pz

d z2 dx2 -y2 dxy dyz dzx

Write + ve and –ve sign in various lobes of the orbitals as shown.

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 Spin Quantum Number (s or ms)

• in orbitals of identical energy, e’s remain

unpaired. (Hund’s rule)
• each sub-orbital can accommodate two e’s with
opposite spin The directions of the e’s are
represented as
•  then s =+ ½  then s= - ½
• s or ms is independent of other three Q. Nos.

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 Pauli Exclusion Principle
• states that no two electron in an atom can have all
the four quantum numbers same.
• eg. He 1s 2 
2
• e1 e2
• n 1 1
• l 0 0
• m 0 0
• s +1/2 -1/2
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 Example to explain Pauli’s Exclusion
Principle

• 4Be 1s2 2s2  

• e1 e2 e3 e4
• n= 1 1 2 2
• l= 0 0 0 0
• m=0 0 0 0
• s = +1/2 -1/2 +1/2 -1/2

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 Hund’s rule

• states that e’s in orbitals/sub-orbitals (box) of

identical energy remain unpaired and pairing starts
only when all the orbitals/sub-orbitals (box) are
half filled.
• 2p2  

• 2p3   

• 2p4    49
 Rules for filling the orbitals:
Max capacity of an orbital
• The maxm number of electrons in a main shell is
equal to 2n2, n is the Pr. Qum. No.
• Orbit no 1 contains (1s ) 2x12 = 2 electrons.
• Orbit no 2 i.e. contains (2s, 2p) 2x22= 8 electrons.
• Orbit no 3 i.e. contains (3s, 3p, 3d) 2x32= 18e-
• Orbit no 4 i.e. contains (4s, 4p, 4d, 4f) 2x42= 32e-
• The s, p, d, f orbitals can have a maxm of 2, 6, 10
and 14 electrons respectively.

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 Rules for filling the orbitals
(The electronic configuration)

- Aufbau (pronounced as of bau) Principle.

German expression meaning building up or
construction. According to this principle the
orbitals of lower energy are filled first, then the
next higher energy orbital is filled and so on.
• The order of increasing energy of orbitals may be
summarised up as below:
• 1s2s2p3s3p4s3d4p5s4d5p6s4f5d
6p7s5f6d7p.
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 Electronic Configuration
• 1H 1s1
• 2He 1s2
• 3Li 1s22s1
• 4Be 1s22s2
• 5B 1s22s22p1
• 6C 1s22s22p2
• 7N 1s22s22p3
• 8O 1s22s22p4
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 Electronic Configuration
• 9F 1s22s22p5
• 10Ne 1s22s22p6
• 11Na 1s22s22p63s1
• 12Mg 1s22s22p63s2
• 13Al 1s22s22p63s2 3p1
• 14Si 1s22s22p63s23p2
• 15P 1s22s22p63s23p3
• 16S 1s22s22p63s23p4
• 17Cl 1s22s22p63s23p5
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• 18Ar 1s22s22p63s23p6
• 19K 1s22s22p63s23p64s1
• 20Ca 1s22s22p63s23p64s2
• 21Sc 1s22s22p63s23p64s23d1
• 22Ti 1s22s22p63s23p64s23d2
• 23V 1s22s22p63s23p64s23d3
• 24Cr 1s22s22p63s23p64s23d4 ×
• 24Cr 1s2 2s22p63s23p64s13d5 √
• This is because two half filled orbitals has a more
stable arrangement than one partially filled and one
completely filled.

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• 25Mn 1s22s22p6 3s2 3p64s23d5
• 26Fe 1s22s22p63s23p64s23d6
• 27Co 1s22s22p63s2 3p64s23d7
• 28Ni 1s22s22p63s23p64s23d8
• 29Cu 1s22s22p63s23p64s23d9 ×
• 29Cu 1s22s22p63s23p64s13d10 √
• This is because one half filled and one fully
filled orbitals are more stable arrangement
than one completely filled one partially filled.

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 Electronic Configuration of Ions
• In cation the no. of e- as equal to + ve charge
are removed e.g.
• 3Li 1s22s1
• 3Li+ 1s2
• 11Na 1s22s22p63s1
• 11Na + 1s22s22p6
• 13Al 1s22s22p63s23p1
• 13Al 3+ 1s22s22p6
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 Electronic Configuration of Anions

• In anions the no. of e- as equal to - ve charge

are added e.g.
• 7N 1s22s22p3
• 7N3- 1s22s22p6
• 8O 1s22s22p4
• 8O2- 1s22s22p6
• 9F 1s22s22p5
• 9F - 1s22s22p6
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 Covalent Bonding

• In a covalent bond, electrons are shared among the

atoms. The simplest case occurs when two atoms
are bonded together using two electrons. This is a
two-center two-electron bond i.e. a single bond.

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• Certain constraints apply to the formation of
a covalent bond:
• there must be orbitals;
• they must be proximal enough to overlap;
• they must be oriented properly to overlap;
• they must have the correct phase to form a
bond.
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• The orbitals considered for overlap are
those of the valence shell.
• The shared pair of electrons can be thought
of as 2 overlapping orbitals with
• the maximum probability of finding the
electron pair in the middle.

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 Formation of sigma () bond
is formed by the end on or head on overlap of
two orbitals

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 Formation of pi () bond
is formed by side wise overlap of two
orbirals

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 Characteristics of sigma and pi bonds

• Sigma bonds: Are stronger than  bonds

• allows free rotation about the bond axis. Formed
by the "head on overlap" of the orbitals.
• Pi bonds: weak
• restricts rotation about the bond axis
• formed by the "side ways" overlap of the p
orbitals.

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