Materials Science

Lecture #2

Atomic Structure
and
Interatomic Bonding

2-1
ISSUES TO ADDRESS...

• What promotes bonding?

• What types of bonds are there?

• What properties are inferred from bonding?

2
Structure of Atoms

ATOM
Basic Unit of an Element
Diameter : 10 –10 m.
Neutrally Charged

Nucleus Electron Cloud

Diameter : 10 –14m 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 QUARKS??
Charge : 1.602 x 10 –19 C Neutral Charge
https://www.fizzics.org/quarks-and-
2-2 leptons-notes-and-video/
Atomic Structure (Freshman Chemistry)

• atom – electrons – 9.11 x 10-31 kg

protons
neutrons } 1.67 x 10-27 kg

• atomic number = # of protons in nucleus of atom

= # of electrons of neutral species

• A [=] atomic mass unit = amu = 1/12 mass of 12C

Atomic wt = wt of 6.023 x 1023 molecules or atoms

1 amu/atom = 1g/mol
C 12.011
H 1.008 etc.

4
ELECTRONIC STRUCTURE OF
ELEMENTS

Electrons of an
atom can have only Energy
very distinct energy levels
values. Therefore,
the electrons are
restricted to
specific “energy
levels” or
“stationary states” 5
Electrons in these energy levels rotate
about the nucleus in fixed orbits, without
radiating or absorbing any energy

H atom He atom

6
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

2-6
When an electron receives energy it moves from a
lower to a higher energy level

energy

8
Movement of the electrons from a higher level to a
lower level of energy results in emission of radiant
energy (electromagnetic radiation)

X – ray

9
Electron Configurations

• Valence electrons – those in unfilled shells

• Filled shells more stable
• Valence electrons are most available for bonding
and tend to control the chemical properties

– example: C (atomic number = 6)

1s2 2s2 2p2

valence electrons

10
Atomic Structure vs Properties

• Valence electrons determine all of the

following properties

1) Chemical
2) Electrical
3) Thermal
4) Optical

11
SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.
Element Atomic # Electron configuration
Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
Lithium 3 1s 2 2s 1
Beryllium 4 1s 2 2s 2
Boron 5 1s 2 2s 2 2p 1 Adapted from Table 2.2,
Callister 7e.
Carbon 6 1s 2 2s 2 2p 2
... ...
Neon 10 1s 2 2s 2 2p 6 (stable)
Sodium 11 1s 2 2s 2 2p 6 3s 1
Magnesium 12 1s 2 2s 2 2p 6 3s 2
Aluminum 13 1s 2 2s 2 2p 6 3s 2 3p 1
... ...
Argon 18 1s 2 2s 2 2p 6 3s 2 3p 6 (stable)
... ... ...
Krypton 36 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)

• Why? Valence (outer) shell usually not filled completely.

12
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

2-10
Sub-levels with the lowest energy are
filled before those with higher energy
1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f 5g

Using the above principle, electronic

configuration of elements can be decided
Consequently the elements can be tabulated
according to their electronic structure
Such a table is called the periodic table
14
• Periodic table is arranged in the order of the atomic
number.
• Rows are called periods. Columns are called groups.
• The elements in a row, have the same number of main
energy levels 16
• All the elements in the periodic table can be divided into three
categories:
– Metals
– Non – metals
– Metalloids (elements that exhibit the properties of both
metals and non – metals) – B, Si, Ge, As, Sb, Te, Po.
• About 80 % of the elements are metals
17
• In metals, electrons
move freely from one
atom to another giving
high electrical and
thermal conductivity,
chemical reactivity etc.
• All the metals except
mercury (Hg) are solid
at room temperature.
• The light metals (IA &
IIA) are soft and
chemically reactive

18
The noble gases (He, Ne,
Ar, etc.,) have the last
orbital fully filled and
they are chemically inert
or inactive.
The (groups IIIA - VIIA)
have atoms in which the
outermost p-orbital is
filling.
Most non-metals are
gaseous but bromine
(Br) is a liquid.
19
• The (groups IB - VIIIB) are the elements in which
the d-orbit is filling
• From these, the elements in which the d-orbit is
not fully occupied are called the “transition
metals” (groups IIIB – VIIIB)
• They are stronger and harder than the other metals
20
Interatomic Bonds
• Primary bonds form when valence
electrons are present (outer shell not
completely filled)
• Secondary bonds form when there
are no valence electrons (outer shell
filled completely)
Interatomic Bonds

BONDING

PRIMARY SECONDARY
[STRONG] [WEAK]

VAN DER
IONIC COVALENT METALLIC HYDROGEN
WALL’S

V. SIVAHAR / IESL / PART 1 / 2008 23

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.

2-12
The Periodic Table
Columns: Similar Valence Structure

inert gases
give up 1e
give up 2e

accept 2e
accept 1e
give up 3e

H He
Li Be O F Ne
Adapted from
Na Mg S Cl Ar Fig. 2.6,
Callister 7e.
K Ca Sc Se Br Kr
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
25
Electronegativity
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

Adapted from Fig. 2.7, Callister 7e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd
edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

26
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
2-14
Ionic Bonding
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl

28
Ionic Bonding - Example

Na Cl

Na+ Cl-

29
30
Atomic arrangement – crystal structure

31
Ionic bond – metal + nonmetal

donates accepts
electrons electrons

Dissimilar electronegativities

ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

[Ne] 3s2

Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6

[Ne] [Ne]

32
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. Energy – minimum energy most stable
Energy balance of attractive and
repulsive terms

Force versus separation

Distance for a pair of
oppositely charged ions

Figure 2.11

Interatomic distance Density

2-16
Ionic Bonding
Nucleus of one ion attracts electron of another ion.
The electron clouds of ion repulse each other when they are sufficiently close

• Energy – minimum energy most stable

– Energy balance of attractive and repulsive terms

Repulsive energy ER

Interatomic separation r

Net energy EN

Adapted from Fig. 2.8(b),

Callister 7e.

Attractive energy EA

34
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
Examples: Ionic Bonding
• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister 7e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd
edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

36
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 = 801 oC
CsCl Lattice energy = 649 kJ/mol
Melting Point = 646 oC
BaO Lattice energy = 3127 kJ/mol
Melting point = 1923 oC

2-21
METALLIC BOND
Metallic bond forms in metals
It is an arrangement of positive ion cores
in a ‘sea’ of electrons
Electrons that form this electron sea are
‘free’ to move within the structure and thus
known as free electrons
These free electrons make the metals
good conductors of electricity and heat

38
Metallic Bonding
• Atoms in metals are closely packed in crystal structure.
• Loosely bonded valence electrons are attracted towards
nucleus of other atoms.
• Electrons spread out among atoms forming electron
clouds.
• These free electrons are Positive Ion
reason for electric
conductivity and ductility
• Since outer electrons are
shared by many atoms,
metallic bonds are
Non-directional

Figure 2.24
Valence electron charge cloud
2-28
+
Na+ Na

+
Na Na+ SEA OF ELECTRONS

+ +
Na Na

40
41
42
Na+ Na+

Na+ Na+ SEA OF ELECTRONS

KERNELS

Na+ Na+

43
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 108 kJ/mol,
Melting temperature 97.7 oC
• Higher the number of valence electrons involved, higher
is the bonding energy.
➢ Example:- Ca Bonding energy 177 kJ/mol,
Melting temperature 851 oC

2-29
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
2-22
Covalent Bonding

Cl Cl

46
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=160 kJ/mol

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

O + O O O O=O
Bond Energy=28 kJ/mol

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

HH N + N N N N N
Bond Energy=54 kJ/mol
2-23
Covalent Bonding
• similar electronegativity  share electrons
• bonds determined by valence – s & p orbitals
dominate bonding
• Example: CH4
shared electrons
H
C: has 4 valence e-, CH 4
from carbon atom
needs 4 more
H: has 1 valence e-, H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
are comparable. atoms

Adapted from Fig. 2.10, Callister 7e.

48
H2

H2O

49
Structure of Diamond

• Four sp3 orbitals are directed symmetrically toward

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

Carbon Atom Tetrahedral arrangement in diamond

Figure 2.18 Figure 2.19

2-25
Carbon Containing Molecules
• In Methane, Carbon forms four covalent bonds with
Hydrogen.
Methane
• Molecules are very weakly molecule
bonded together resulting Figure 2.20
in low melting temperature
(-183oC).
• Carbon also forms bonds with itself.
• Molecules with multiple carbon bonds are more reactive.
➢ Examples:-

H H
C C H C C H
H H Acetylene
Ethylene
2-26
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
2-27
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.

2-30
SECONDARY BONDING
Arises from interaction between dipoles
• Fluctuating dipoles
asymmetric electron ex: liquid H2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding Adapted from Fig. 2.13, Callister 7e. bonding

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -
Adapted from Fig. 2.14,
Callister 7e.
secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer secondary bonding

54
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)

2-31
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

2-32
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
2-33
Summary: Bonding

Type Bond Energy Comments

Ionic Large! Nondirectional (ceramics)

Covalent Variable Directional

large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
inter-molecular
58
Properties From Bonding: Tm
• Bond length, r • Melting Temperature, Tm
Energy
r

• Bond energy, Eo ro
r
Energy smaller Tm

unstretched length
ro larger Tm
r
Eo = Tm is larger if Eo is larger.
“bond energy”

59
Properties From Bonding : a
• Coefficient of thermal expansion, a
length, L o coeff. thermal expansion
unheated, T 1
DL DL
= a (T2 -T1 )
heated, T 2 Lo

• a ~ symmetry at ro a is larger if Eo is smaller.

Energy
unstretched length
ro
r
Eo
smaller a

Eo larger a
60
PROPERTIES FROM BONDING: E
• Elastic modulus, E
Elastic modulus

F DL
=E
Ao Lo

• E ~ curvature at ro
Energy

unstretched length
ro E is larger if Eo is larger.
r
smaller Elastic Modulus

larger Elastic Modulus 16

Summary: Primary Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small a

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate a

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
small E
large a

62