CHAPTER

2
Atomic Structure
And
Bonding

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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 –14
Mass : 9.109 x 10 –28 g
Accounts for almost all mass Charge : -1.602 x 10 –9 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

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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 6.023 x 1023

12 Grams
Mole of Carbon
Of Carbon
Carbon Atoms
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Periodic Table

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 = ΔE =
hc

h=Planks Constant
Absorb Emit = 6.63 x 10-34 J.s
Energy Energy c= Speed of light
(Photon) (Photon) λ = Wavelength of
light

Energy levels
Photon = Electromagnetic radiation
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Quantum Numbers of Electrons of Atoms

Principal Quantum Subsidiary Quantum

Number (n) Number l
• Represents main energy • Represents sub energy
levels. levels (orbital).
• Range 1 to 7. • Range 0…n-1.
• Larger the ‘n’ higher • Represented by letters
the energy. s,p,d and f.
n=1 s orbital
n=2 (l = 0)
n=2
n=1
n=3 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 :- Number of Electrons
Orbital letters

1s2 2s2 2p6 3s2

Principal Quantum Numbers

 For Iron, (Z=26), Electronic configuration is

Z = atomic no. = no. of proton 1s2 2s2 sp6 3s2 3p6 3d6 4s2
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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

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

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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.

• 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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Atomic and Molecular Bonds

Directional (2D bonding)

That is, it is between specific atoms and may exist only
in the direction between one atom and another that
participates in the electron sharing (in the case of covalent
bond)

Non-Directional (3D bonding)

That is, the magnitude of the bond is equal in all
directions around an ion (in the case of ionic & metallic bond)

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Atomic and Molecular Bonds

-Ionic bonds are non directional because the number of

anions surrounded a cation is limited by the efficiency
of its lattice packing therefore it is not directional
afterall.

-However in covalent bonds (directional), notice how

the orbitals overlap, side-ways or head-on which
defines the bond angle. The orbitals need to overlap in
a specific direction in covalent bonding unlike in ionic
bonding.

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Atomic and Molecular Bonds

Metal (Non-Directional)

That is, an atom's nearest neighbors surround it in every direction,

rather than in a few particular directions. Because the bonding in
metals is non-directional and coordination numbers are high, it is
relatively easy to deform the coordination sphere (i.e., break or
stretch bonds) than it is in the case of a nonmetal. This is why
elements like lead are much more malleable than C, Si, or Ge.

Nonmetals (insulators and semiconductors), on the other hand,

have directional bonding.

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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)
Cation Attraction Anion
+ve charge -ve charge

IONIC BOND
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Ionic Bonding - Example

To achieve inert gas configuration
• Ionic bonding in NaCl
Atomic no= 17
Atomic no= 11 3s 1

3p7 Chlorine
Sodium Atom
Atom Cl
Na

I
O
N
I Chlorine Ion
Sodium Ion Cl -
C
Na+
B
O
Figure 2.10
N
D
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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

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Ion Force for Ion Pair (Cont..)

 e Z e Z Z e 2

F  Z 1
 2 1 2
attractive
4  a  4  a 
Z1,Z2 = Number of electrons removed or
added during ion formation 0
2
0
2

e = Electron Charge
a = Inter-ionic separation distance
ε = 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

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

Na+ Cl-

a0
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)

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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.

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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 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

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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
H + H H H
1s1 Hydrogen
Electrons 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
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 - 2s 2p ) atoms share three p electrons
2 3

HH

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

• Carbon has electronic configuration 1s2 2s2 2p2

Ground State arrangement Indicates

carbon
Forms two
1s 2s 2p Covalent
Two ½ filed 2p orbitals bonds

• Hybridization causes one of the 2s orbitals promoted to 2p

Indicates
orbital. Result four sp3 orbitals. four covalent
1s
bonds are
2p
Four ½ filled sp3 orbitals 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 H
C C

C C H
H
C
Figure 2.23
H
Structure of Benzene 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.
• These free electrons are
reason for electric
Positive Ion
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

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

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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=μ =q.d
+q -q q= Electric charge
d = separation distance
d
• There two types of bonds permanent and
fluctuating.

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Fluctuating Dipoles
They have complete outer-
• Weak secondary bonds in noble gasses. valence-electron shells

• Dipoles are created due to asymmetrical distribution

of electron charges.
• Electron cloud charge changes with time.

nucleus

_
+

Symmetrical Figure 2.27 Asymmetrical

distribution Distribution
of electron charge (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:-
Symmetrical No Dipole
CH4 Arrangement moment
Of 4 C-H bonds
(Methane)

Asymmetrical
Creates
CH3Cl Tetrahedral
Dipole
arrangement
(Chloromethane)

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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.
H

105 0
O
Figure 2.28
Hydrogen
H Bond
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Last Semester’s Questions

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