CHAPTER

2
Atomic Structure
And
Bonding
Structure of Atoms
ATOM
Basic Unit of an Element
Diameter : 10 –10 m.
Neutrally Charged

Nucleus Electron Cloud

Diameter : 10 –14 m Mass : 9.109 x 10 –28 g
Accounts for almost all mass Charge : -1.602 x 10 –19 C
Positive Charge Accounts for all volume

Proton Neutron
Mass : 1.673 x 10 –24 g Mass : 1.675 x 10 –24 g
Charge : 1.602 x 10 –19 C Neutral Charge
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
( Avogadro 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 6.023 x 1023

12 Grams
Mole of Carbon
Of Carbon
Carbon Atoms
Periodic Table

Source: Davis, M. and Davis, R., Fundamentals of Chemical Reaction Engineering, McGraw-Hill, 2003 .
Example Problem
• A 100 gram alloy of nickel and copper consists of 75 wt%
Cu and 25 wt% Ni. What are percentage of Cu and Ni
Atoms in this alloy?
Given:- 75g Cu Atomic Weight 63.54
25g Ni Atomic Weight 58.69

• Number of gram moles of Cu = 75 g

 1.1803mol
63.54 g/mol
• Number of gram moles of Ni = 25g
 0.4260mol
58.69 g/mol
• Atomic Percentage of Cu = 1.1803
 100  73.5%
(1.1803  0.4260)
• Atomic Percentage of Ni = 0.4260
 100  26.5%
(1.1803  0.4260)
 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 = ΔE = hc
h=Planks Constant

= 6.63 x 10 J.s
-34

Absorb c= Speed of light

Emit
Energy Energy = 3 x 108 m/s
(Photon) (Photon)λ=Wavelength of light

Energy levels
Energy
•
in Hydrogen Atom
Hydrogen atom has one proton and one electron
• Energy of hydrogen atoms for different energy levels is
given by 13.6 (n=1,2…..) principal quantum
E   2 ev
numbers
n
• Example:- If an electron undergoes transition from n=3
state to n=2 state, the energy of photon emitted is

13.6 13.6
E   2
 2
 1.89ev
3 2remove an electron from
• Energy required to completely
hydrogen atom is known as ionization energy
Quantum Numbers of Electrons of Atoms

Principal Quantum Number (n) Subsidiary Quantum

• Represents main energy Number (l)
levels.
• Represents sub energy
• Range 1 to 7. levels (orbital).
• Larger the ‘n’ higher the • Range 0…n-1.
energy.
• Represented by letters s, p,
n=1 d and f. s orbital
n=2 (l=0)
n=2
n=1
n=3 p Orbital
(l=1)
Quantum Numbers of Electrons of Atoms
(Cont..)
Magnetic Quantum Electron spin quantum
Number ml. number ms.
• Represents spatial • Specifies two directions of
orientation of single atomic electron spin.
orbital. • Directions are clockwise or
• Permissible values are –l to anticlockwise.
+l. • Values are +1/2 or –1/2.
• Example:- if l=1, • Two electrons on same
ml = -1,0,+1. orbital have opposite spins.
I.e. 2l+1 allowed values. • No effect on energy.
• No effect on energy.
 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 :-
Number of Electrons
Orbital letters

1s2 2s2 2p6 3s2

Principal Quantum Numbers

 For Iron, (Z=26), Electronic configuration is
1s2 2s2 2p6 3s2 3p6 3d6 4s2

0
 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

1
 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.

Na Te N O Fl
Electro- Electro-
positive 0 K 1 W
negative
2H Se 3 4

2
 Atomic and Molecular Bonds

• Ionic bonds :- Strong atomic bonds due to transfer of

electrons
• Covalent bonds :- Large interactive force due to sharing of
electrons
• 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.

3
 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
Cation Attraction Anion
+ve charge -ve charge

IONIC BOND
4
 Ionic Bonding - Example

• Ionic bonding in NaCl 3s1

3p5 Chlorine
Sodium Atom
Atom Cl
Na

I
O
N
I Chlorine Ion
Sodium Ion Cl -
C
Na+
B
O
Figure 2.10
N
D
5
 Ionic Force for Ion Pair

• 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

6
 Ion Force for Ion Pair (Cont..)
 e Z e Z Z e 2

F  Z 1
 2 1 2
attractive
4  a  4  a 
0
2
0
2

Z1,Z2 = Number of electrons removed or

added during ion formation
e = Electron Charge
a = Interionic seperation distance

ε0 = Permeability of free space (8.85 x 10-12c2/Nm2)

(n and b are constants)

nb
F repulsive

n 1
a
2
Z Z e  nb
F  1 2
net
4  a  a
0
2 n 1

7
 Interionic Force - Example

• Force of attraction between Na+ and Cl- ions

Z1 = +1 for Na+, Z2 = -1 for Cl-

e = 1.60 x 10-19 C , ε0 = 8.85 x 10-12 C2/Nm2
a = Sum of Radii of Na+ and Cl- ions
= 0.095 nm + 0.181 Na
nm
+
= 2.76
Cl - x 10-10 m

a
2 19
Z Z e ( 1)( 1)(1.60  10 C )
2

F  1 2
  3.02  10 9 N
attraction
4  a  4 (8.85 x 10 C /Nm2)(2.76 x 10
0
2 -12 2 -10
m)

8
 Interionic Energies for Ion Pairs

• Net potential energy for a pair

2
ofb oppositely
Z 1Z2e
charged ionsE=net  

4  0 a
2
 a
n

Attraction Repulsion
Energy Energy

Energy Energy
Released Absorbed

• Enet is minimum when ions are at equilibrium seperation distance

a0

9
 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.

0
 Bonding
•
Energies
Lattice energies and melting points of ionically
bonded solids are high.
• Lattice energy decreases when size of ion increases.
• Multiple bonding electrons increase lattice energy.

 Example :-
NaCl Lattice energy = 766 KJ/mol
Melting point = 801oC
CsCl Lattice energy = 649 KJ/mol
Melting Point = 646oC
BaO Lattice energy = 3127 KJ/mol
Melting point = 1923oC

1
 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
Electron 1 Overlapping Electron Clouds
between 2 atoms by sharing theirPair
1s electrons
H H
H + H H H
1s1 Hydrogen
Electrons Molecule
2
 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
H Bond Energy=160KJ/mol
• Oxygen (Outer orbital - 2s2 2p4) atoms share two p electrons

O + O O O O=O
Bond Energy=28KJ/mol
• Nitrogen (Outer orbital - 2s2 2p3) atoms share three p electrons

HH

N + N N N N N
Bond Energy=54KJ/mol
3
 Covalent Bonding in Carbon

• Carbon has electronicGround

configuration 1s2 2s2 2p2
State arrangement Indicates
carbon
Forms two
Covalent
1s 2s 2p bonds
Two ½ filed 2p orbitals

Indicates
four covalent
• Hybridization causes one of the 2s orbitals promoted to 2p orbital.
Result four sp3 orbitals. bonds are
formed
1s 2p
Four ½ filled sp3 orbitals

4
 Structure of Diamond

• Four sp3 orbitals are directed symmetrically toward corners

of regular tetrahedron.
• This structure gives high hardness, high bonding strength
(711KJ/mol) and high melting temperature (3550oC).

Carbon Atom Tetrahedral arrangement in diamond

Figure 2.18 Figure 2.19

5
 Carbon Containing Molecules
Methane
• In Methane, Carbon forms four covalent bonds withmolecule
Hydrogen.
Figure 2.20
• Molecules are very weekly
bonded together resulting
in low melting temperature
(-183oC).
• Carbon also forms bonds with itself.
• Molecules with multiple
H
carbon
H
bonds are more reactive.
 Examples:-
C C H
C C H

H H Acetylene

Ethylene

6
 Covalent Bonding in Benzene

• Chemical composition of Benzene is C6H6.

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

C C

C C H
H
C
Figure 2.23
H
Structure of Benzene Simplified Notations

7
 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

Valence electron charge cloud Figure 2.24

8
 Metallic Bonds (Cont..)

• Overall energy of individual atoms are lowered by metallic

bonds
• Minimum energy between atoms exist at equilibrium
distance a0
• Fewer the number of valence electrons involved, more
metallic the bond is.
 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

9
 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.

Dipole moment= μ =q.d

+q -q
q= Electric charge
d = separation distance

Figure 2.26 d

• There two types of bonds permanent and fluctuating.

0
 Fluctuating Dipoles

• Weak secondary bonds in noble gasses.

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

Symmetrical Figure 2.27 Asymmetrical

distribution Distribution
of electron charge (Changes with time)

1
 Permanent
•
Dipoles
Dipoles that do not fluctuate with time are called
Permanent dipoles.

 Examples:-

Symmetrical No Dipole
CH4 Arrangement moment
Of 4 C-H bonds

Asymmetrical
Creates
CH3Cl Tetrahedral
Dipole
arrangement

2
 Hydrogen Bonds

• 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
O
Figure 2.28 Hydrogen
H Bond