CHAPTER

Atomic Structure
And
Bonding
2-1

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Structure of Atoms
ATOM

Basic Unit of an Element

Diameter : 10 10 m.
Neutrally Charged

Nucleus

Electron Cloud

Diameter : 10
m
Accounts for almost all mass
Positive Charge
14

Proton

Mass : 1.673 x 10 24 g
Charge : 1.602 x 10 19 C
2-2

Mass : 9.109 x 10 28 g
Charge : -1.602 x 10 9 C
Accounts for all volume

Neutron

Mass : 1.675 x 10 24 g
Neutral Charge

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Atomic Number and Atomic Mass

Atomic Number = Number of Protons in the nucleus

Unique to an element
Example :- Hydrogen = 1, Uranium = 92

Relative atomic mass = Mass in grams of 6.203 x 1023

( Avagadro Number) Atoms.
Example :- Carbon has 6 Protons and 6 Neutrons. Atomic Mass
= 12.

One Atomic Mass unit is 1/12th of mass of carbon

atom.
One gram mole = Gram atomic mass of an element.

Example :-

One gram
Mole of
Carbon
2-3

12 Grams
Of Carbon

6.023 x 1023
Carbon
Atoms

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Periodic Table

2-4

Source: Davis, M. and Davis, R., Fundamentals of Chemical Reaction Engineering, McGraw-Hill, 2003.

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Electron Structure of Atoms

Electron rotates at definite energy levels.

Energy is absorbed to move to higher energy level.

Energy is emitted during transition to lower level.
Energy change due to transition = E = hc

h=Planks Constant
Absorb
Energy
(Photon)

Emit
Energy
(Photon)

Energy levels
Photon = Electromagnetic radiation

2-6

= 6.63 x 10-34 J.s

c= Speed of light
= Wavelength of light

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Quantum Numbers of Electrons of Atoms

Principal Quantum
Number (n)
Represents main energy
levels.
Range 1 to 7.
Larger the n higher
the energy.

Subsidiary Quantum
Number l
Represents sub energy

levels (orbital).
Range 0n-1.
Represented by letters
s,p,d and f.

n=1
n=2
n=3

2-8

n=1

n=2

s orbital
(l = 0)
p Orbital
(l =1)

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Electron Structure of Multielectron Atom

Maximum number of electrons in each atomic shell is
given by 2n2.
Atomic size (radius) increases with addition of shells.
Electron Configuration lists the arrangement of electrons
in orbitals.
Example :-

Orbital letters

Number of Electrons

1s2 2s2 2p6 3s2

Principal Quantum Numbers
For Iron, (Z=26), Electronic configuration is
1s2 2s2 sp6 3s2 3p6 3d6 4s2
Z = atomic no. = no. of proton
2-10

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Electron Structure and Chemical Activity

Except Helium, most noble gasses (Ne, Ar, Kr, Xe, Rn)
are chemically very stable

All have s2 p6 configuration for outermost shell.

Helium has 1s2 configuration

Electropositive elements give electrons during

chemical reactions to form cations.
Cations are indicated by positive oxidation numbers
Example:Fe : 1s2 2s2 sp6 3s2 3p6 3d6 4s2
Fe2+ : 1s2 2s2 sp6 3s2 3p6 3d6
Fe3+ : 1s2 2s2 sp6 3s2 3p6 3d5

2-11

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Electron Structure and Chemical Activity (Cont..)

Electronegative elements accept electrons during

chemical reaction.
Some elements behave as both electronegative and
electropositive.
Electronegativity is the degree to which the atom
attracts electrons to itself
Measured on a scale of 0 to 4.1
Example :- Electronegativity of Fluorine is 4.1
Electronegativity of Sodium is 1.
Te

Na

Electropositive 0
2-12

K 1

2H

N
Se

Fl

Electronegative

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Atomic and Molecular Bonds

-Atoms in bonded state are in a more stable energy condition compared to unbonded
condition. Net decrease of potential energy after bonding.

2-12

Ionic bonds :- Strong atomic bonds due to transfer of

electrons non-directional
Covalent bonds :- Large interactive force due to
sharing of electrons - directional
Metallic bonds :- Non-directional bonds formed by
sharing of electrons
Permanent Dipole bonds :- Weak intermolecular
bonds due to attraction between the ends of permanent
dipoles.
Fluctuating Dipole bonds :- Very weak electric dipole
bonds due to asymmetric distribution of electron
densities.

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Ionic Bonding
Ionic bonding is due to electrostatic force of attraction
between cations and anions.
It can form between metallic and nonmetallic
elements.
Electrons are transferred from electropositive to
electronegative atoms

Electropositive
Electronegative
Electron
Element
Atom
Transfer
Electrostatic (coulombic)
Attraction
Cation
Anion

+ve charge

-ve charge

IONIC BOND
2-14

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Ionic Bonding - Example

To achieve inert gas configuration

Ionic bonding in NaCl

Atomic no= 11

3s1

3p7

Sodium
Atom
Na

Sodium Ion
Na+

I
O
N
I
C
B
O
N
D

2-15

Atomic no= 17
Chlorine
Atom
Cl

Chlorine Ion
Cl -

Figure 2.10

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Ionic Force for Ion Pair

(Proton + neutron)

Nucleus of one ion attracts electron of another ion.

The electron clouds of ion repulse each other when
they are sufficiently close.

Force versus separation

Distance for a pair of
oppositely charged ions
Figure 2.11

2-16

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Ion Force for Ion Pair (Cont..)

( e)(Z e) Z Z e
= Z
=
(4 a ) (4 a )
2

attractive

Z1,Z2 = Number of electrons removed or

added during ion formation
e = Electron Charge
a = Interionic seperation distance
= Permeability of free space (8.85 x 10-12c2/Nm2)

repulsive

nb

(n and b are constants)

n +1

net

Z Z e nb
(4 a ) a
1

2-17

n +1

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Interionic Force - Example

Force of attraction between Na+ and Cl- ions

Z1 = +1 for Na+, Z2 = -1 for Cle = 1.60 x 10-19 C , 0 = 8.85 x 10-12 C2/Nm2

a0 = Sum of Radii of Na+ and Cl- ions
= 0.095 nm + 0.181 nm = 2.76 x 10-10 m
Cl-

Na+
a0
2

( +1)( 1)(1.60 10 C )
e
Z
Z
=
=
(4 a ) 4 (8.85 x 10 C /Nm2)(2.76 x 10
1

attraction

= +3.02 10 9 N

2-18

19

-12

-10

m)

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Ion Arrangements in Ionic Solids

Ionic bonds are Non Directional

Geometric arrangements are present in solids to
maintain electric neutrality.
Example:- in NaCl, six Cl- ions pack around central Na+ Ions

Ionic packing
In NaCl
and CsCl
Figure 2.13
CsCl

NaCl

As the ratio of cation to anion radius decreases, fewer

anion surround central cation.
2-20

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Bonding Energies
(Measure of bonding strength)

Lattice energies and melting points of ionically

bonded solids are high.
Lattice energy decreases when size of ion
increases (because bonding electrons in larger ions are farther away from

the attractive influence of the +ve nucleus).

Multiple bonding electrons increase lattice energy.

Example :NaCl
CsCl
BaO

2-21

Lattice energy = 766 KJ/mol

Melting point = 801oC
Lattice energy = 649 KJ/mol
Melting Point = 646oC
Lattice energy = 3127 KJ/mol
Melting point = 1923oC

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Covalent Bonding
In Covalent bonding, outer s and p electrons are
shared between two atoms to obtain noble gas
configuration.
Takes place between elements
with small differences in
electronegativity and close by
in periodic table.
In Hydrogen, a bond is formed between 2 atoms by
sharing their 1s1 electrons Electron
Overlapping Electron Clouds

Pair

H + H
2-22

1s1
Electrons

H H
Hydrogen
Molecule

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Covalent Bonding - Examples

In case of F2, O2 and N2, covalent bonding is formed by

sharing p electrons

Fluorine gas (Outer orbital 2s2 2p5) share one p electron to

attain noble gas configuration.

F + F

F F

F F

Bond Energy=160KJ/mol

Oxygen (Outer orbital - 2s2 2p4) atoms share two p electrons

O + O

O=O
Bond Energy=28KJ/mol

Nitrogen (Outer orbital - 2s2 2p3) atoms share three p electrons

HH
2-23

N + N

Bond Energy=54KJ/mol

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Covalent Bonding in Carbon

Carbon has electronic configuration 1s2 2s2 2p2

Ground State arrangement

1s

2s

2p

Two filed 2p orbitals

Hybridization causes one of the 2s orbitals promoted to

2p orbital. Result
four sp3 orbitals.

1s
2-24

Indicates
carbon
Forms two
Covalent
bonds

2p

Four filled sp3 orbitals

Indicates
four covalent
bonds are
formed

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Covalent Bonding in Benzene

Chemical composition of Benzene is C6H6.

The Carbon atoms are arranged in hexagonal ring.
Single and double bonds alternate between the atoms.
H
H

C
C

C
C

H
Structure of Benzene
2-27

Figure 2.23

Simplified Notations

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Metallic Bonding

Atoms in metals are closely packed in crystal

structure.
Loosely bounded valence electrons are attracted
towards nucleus of other atoms.
Electrons spread out among atoms forming electron
clouds.
Positive Ion
These free electrons are
reason for electric
conductivity and ductility*
Since outer electrons are
shared by many atoms,
metallic bonds are
Non-directional

*a mechanical property used to describe the extent to which materials can be deformed plastically without
fracture

2-28

Valence electron charge cloud

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Metallic Bonds (Cont..)

Overall energy of individual atoms are lowered by
metallic bonds (i.e. from unstable atoms to stable bonding).
Minimum energy between atoms exist at equilibrium
distance a0
Fewer the number of valence electrons involved, more
metallic the bond is (i.e. valence electrons are freer to move).
Example:- Na
Bonding energy 108KJ/mol,

Melting temperature 97.7oC

Higher the number of valence electrons involved,

higher is the bonding energy.
Example:- Ca
Bonding energy 177KJ/mol,
Melting temperature 851oC

2-29

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Secondary Bonding
Secondary bonds are due to attractions of electric
dipoles in atoms or molecules.
Dipoles are created when positive and negative charge
centers exist.

nucleus

Dipole moment=
-q

+q

q= Electric charge
d = separation distance

d
There two types of bonds
fluctuating.
2-30

=q.d

permanent and

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Fluctuating Dipoles
They have complete outervalence-electron shells

Weak secondary bonds in noble gasses.

Dipoles are created due to asymmetrical distribution of
electron charges.
Electron cloud charge changes with time.

nucleus

+
Symmetrical
distribution
of electron charge
2-31

Figure 2.27 Asymmetrical

Distribution
(Changes with time)

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Permanent Dipoles

Dipoles that do not fluctuate with time are

called Permanent dipoles (weak bonding forces among covalently
bonded molecules can be created if molecules contain permanent dipoles) .

Examples:-

CH4

(Methane)

CH3Cl

(Chloromethane)

2-32

Symmetrical
Arrangement
Of 4 C-H bonds

Asymmetrical
Tetrahedral
arrangement

No Dipole
moment

Creates
Dipole

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Hydrogen Bonds
(special case of permanent dipole-dipole interaction betw. polar molecules)

Hydrogen bonds are Dipole-Dipole interaction

between polar bonds containing hydrogen
atom.
Example :In water, dipole is created due to asymmetrical
arrangement of hydrogen atoms.
Attraction between positive oxygen pole and
negative hydrogen pole.

105 0
Figure 2.28

H
2-33

Hydrogen
Bond