CHAPTER 2:

BONDING AND PROPERTIES

ISSUES TO ADDRESS...
• What promotes bonding?

• What types of bonds are there?

• What is the bonding type present in different

types of materials?

• What properties are inferred from bonding?

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 Introduction
• Properties of materials depend on the ATOMIC STRUCTURE
and INTERATOMIC BONDING (interactions existing
between constituent atoms or molecules)
• GRAPHITE Vs DIAMOND:
– Both are forms of CARBON
– Graphite: Soft and Greasy whereas Diamond: Hardest known Material
– Different behavior is due to different bonding characteristics
• Atomic Structure:

Subatomic Particles:
Electrons: -vely Charged
Protons: +vely Charged
Neutrons: Electrically Neutral
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 Definitions
• Atomic Number Z: Number of protons in nucleus
• Atomic Mass A: Sum of masses of protons and neutrons
within nucleus
• Isotopes: Number of neutrons N may be different forming
different isotopes
• Atomic Mass Unit amu:
– 1 amu = 1/12 atomic mass of the most common isotope of Carbon
– 1 amu/atom (or molecule) = 1 g/mole
– In one mole of a substance we have 6.023 x 1023 atoms
• ELECTRONS IN ATOMS:
– Bohr Atomic model based on the principle of quantum mechanics
– Electrons revolve in discrete orbitals with specific value of energy
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 BOHR ATOM
orbital electrons:
n = principal
quantum number 1
n=3 2

Nucleus: Z = # protons
= 1 for hydrogen to 94 for plutonium
N = # neutrons
Atomic mass A ≈ Z + N

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 Quantum Numbers
• Size, Shape and Spatial Orientation of an Electron probability
density are specified by FOUR Quantum Numbers
1. Principal Quantum Number n: Specifies distance from Nucleus
• K, L, M, N, O or 1, 2, 3, 4
2. Sub-shell Quantum Number 
: Specifies shape of electron sub-
shell
• s, p, d, f
3. Number of Energy States ml: Each electron state cannot hold
more than two electrons with s=1, p=3, d=5 and f=7 energy
states
4. Spin Moment Quantum Number ms : Oriented either up or
down
• ms =1/2 or -1/2
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 ELECTRON ENERGY STATES
Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.

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• VALENCE ELECTRONS:
– Electrons occupying the outermost filled shell
– Very important since they participate in the bonding between atoms to
form atomic and molecular aggregates

• STABLE ELECTRONIC CONFIGURATIONS:

– Outermost or valence electron shell are completely filled

s and p states for the outermost shell

are occupied by 8 electrons

– Atoms with unfilled valence shell assume stable electronic

configurations by gaining or losing electrons (IONIC BONDS) or by
sharing electrons with other atoms (COVALENT BONDS)

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STABLE ELECTRON CONFIGURATIONS
Stable electron configurations...
• have complete s and p subshells
• tend to be unreactive.

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 SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.
Electron configuration
1s1
1s2 (stable)
1s22s1
1s22s2
1s22s22p1
1s22s22p2
...
1s22s22p6 (stable)
1s22s22p63s1
1s22s22p63s2
1s22s22p63s23p1
...
1s22s22p63s23p6 (stable)
...
1s22s22p63s23p63d104s246 (stable)

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

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 The Periodic Table
• Elements are classified according to electron configuration in the
Periodic Table
• Periods  Horizontal Rows: Elements situated with increasing atomic
numbers
• Groups or Columns  Vertical columns: Elements in each column
have similar valence electrons structure, as well as chemical and
physical properties
– Group 0: Inert
– Group VII: One electron deficient
– Group IA and IIA: Alkali metals with one electron in excess
– Group IIIA, IVA, and VA: Intermediate between metals and non-metals
– Group IIIB through IIB: Transition metals
• Most elements in Periodic table are Metals
• Metals are electropositive: Capable of giving up their few valence electrons to
become +vely charged ion
• Elements on right hand side are electronegative: Ready to accept electrons
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 THE PERIODIC TABLE
• Columns: Similar Valence Structure

Electropositive elements: Electronegative elements:

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

Smaller electronegativity Larger electronegativity

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 Bonding Forces and Energies
• As two isolated atoms are brought closer from an infinite
separation following effects will be observed:
– At large distance no interaction
– As they come closer two forces are experienced
– (1) Attractive Forces FA and (2) Repulsive Forces FR
– In beginning Attractive Forces are important, however, Repulsive
Forces become significant when outer electron shells of two atoms
overlap
• Net Force FN =FA + FR
• When FA+FR = 0  No Net Force  State of equilibrium; the
two atoms are separated by an equilibrium spacing ro (ro 3A)
• Distance less than ro Repulsive forces will dominate, distance
more than ro attractive forces will dominate
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Bonding Forces and Energies

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 Bonding Energies
• In terms of Potential energy instead of Forces:
E N   FN dr
r r
E N   FAdr   FR dr  E A  E R
 

• Bonding Energy Eo:

– Energy at the minimum point
– Energy required to separate two atoms to an infinite separation
• The situation for real solid materials although complex but
analogous
• Physical Properties of materials depend on Bonding Energy:
– Higher the bonding energy higher the melting points
– Modulus or stiffness of the material also depend on the curve

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 Properties from Bonding: TM
• Bond length, r • Melting Temperature, Tm
F
F

• Bond energy, Eo

Tm is larger if Eo is larger.

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 Properties from Bonding: E
• Elastic modulus, E
Elastic modulus
F L
=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

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 PROPERTIES FROM BONDING: a
• Coefficient of thermal expansion, a
coeff. thermal expansion
L
= a(T2-T1)
Lo

• a ~ symmetry at ro

a is larger if Eo is smaller.

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 Types of Bonds
• PRIMARY OR CHEMICAL BONDS:
– Ionic
– Covalent
– Metallic
(Based on the atoms assuming stable electronic structure by filling
outer most electron shell; Strong Bonds)

• SECONDRY OR PHYSICAL BONDS:

– Van der Waals Bonds
– Hydrogen Bonds

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 IONIC BONDING
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl

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 Ionic Bonding
• Present in compounds between metallic and non-metallic
elements
• Metals gives up electrons and non-metal gains electrons

To acquire stable or inert gas configurations

• Attractive force are Coulombic  Based on Charge

• EA = -A/r ER = B/rn
• Eo  600-1500 kJ/mol are large as reflected by their high
melting temperatures
• Ionic bonds are non-directional same on all sides
• Ceramics have ionic bonding
• Hard & Brittle and Electrical & Thermal Insulator
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 Examples: Ionic Bonding
• Predominant bonding in Ceramics
NaCl
MgO
H He
2.1 CaF2 -
Li Be O F Ne
1.0 1.5 CsCl 3.5 4.0 -
Na Mg Cl Ar
0.9 1.2 3.0 -
K Ca Ti Cr Fe Ni Zn As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 2.0 2.8 -
Rb Sr I Xe
0.8 1.0 2.5 -
Cs Ba At Rn
0.7 0.9 2.2 -
Fr Ra
0.7 0.9

Give up electrons Acquire electrons

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 COVALENT BONDING
• Requires shared electrons
• Example: CH4
C: has 4 valence e,
needs 4 more
H: has 1 valence e,
needs 1 more
Electronegativities
are comparable.

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 Covalent Bonding
• Stable Electron Configuration assumed by sharing of electrons
between adjacent atoms
• The bonded atoms will share at least one electron and shared
electron may be considered to belong to both atoms
• Covalent bonds are directional
• Present in dissimilar molecules such as CH4 and elemental
solids such as Diamond (Carbon) and Silicon, and in Semi-
conductor Materials
• Number of covalent bonds present depend on number of
valence electrons
• Covalent bonds can be very strong and weak depending on
atomic arrangements
• Polymer have covalent bonds in their main chain
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 Examples: Covalent Bonding
H2O

column IVA
H2 F2
C(diamond)
H He
2.1
SiC - Cl2
Li Be C O F Ne
1.0 1.5 2.5 2.0 4.0 -
Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -
K Ca Ti Cr Fe Ni Zn Ga Ge As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 1.6 1.8 2.0 2.8 -
Rb Sr Sn I Xe
0.8 1.0 1.8 2.5 -
Cs Ba Pb At Rn
0.7 0.9 1.8 2.2 -
Fr Ra
0.7 0.9 GaAs

• Molecules with nonmetals

• Molecules with metals and nonmetals
• Elemental solids (RHS of Periodic Table)
• Compound solids (about column IVA) 27
 METALLIC BONDING
• Arises from a sea of donated valence electrons
(1, 2, or 3 from each atom).

• Primary bond for metals and their alloys

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 Metallic Bonding
• All metals and their alloys have this bonding
• Valence electrons are not bound to any particular atom in solid
and belong to the metal as a whole
• Can be imagined to form "Sea of Electrons” or an “Electron
Cloud”
• Non-Valence electrons and atomic nuclei form “ion cores” with
valence electron acting as “glue” to hold them together
• Net positive charge equal in magnitude to the total valence
electron charge per atom
• Bonding energy can be weak or strong
• Metals conduct heat and electricity due to these electrons
• Metallic Bonding are non-directional
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Secondary or van Der Waals Bonding or Physical Bonds
• Weak in comparison to the primary or chemical bonds
(bonding energies ~ 10 kJ/mol)
• Provides forces between different molecules e.g: H20
• Present due to dipoles  Separation of +ve and –ve portions of
an atom or molecule.
The two types are:
• FLUCTUATING DIPOLES:
– Dipole present due to electronic vibrations  Induced Dipoles
– E.g: Liquid H2, Inert gases

• PERMANENT DIPOLES:
– Due to unsymmetrical arrangements of positive and negatively charged
regions
– Bonding energies are greater than Fluctuating Dipoles. E.g: HCl
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 Van Der Waals BONDING
Arises from interaction between dipoles
• Fluctuating dipoles

• Permanent dipoles-molecule induced

-general case:

-ex: liquid HCl

-ex: polymer

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• HYDROGEN BONDS:
– A special case of secondary polar molecule bonding
– E.g: HF, H2O, NH3

• Normally bonds within atoms or molecules are COVALENT

and bonds between molecules are weak SECONDRY
• Same is true for Polymers:
– Bonds within a Polymer chain  Covalent
– Bonds between different Polymer molecules  Secondary

• Ceramics and Metals:

– Large Bond Energy  Large Tm and E
• Polymers:
– Secondary Bonding Dominates  Small Tm and E

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• Intramolecular bonds within a polymer chains are covalent (e.g:C-C and C-H)

• Intermolecular bonds betweens two polymer chains are weak hydrogen and
van der Waals 33
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 SUMMARY: BONDING
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Variable Directional
Covalent large-Diamond semiconductors, ceramics
small-Bismuth polymer chains)

Variable
Metallic large-Tungsten Nondirectional (metals)
small-Mercury
Directional
Secondary smallest inter-chain (polymer)
inter-molecular

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 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 T
small E
large a

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