METB113 Oct 2015
CHAPTER 2
Atomic Structure and Bonding
CO2
Able to describe primary and
secondary atomic bondings of
materials and classify the
fundamental physical properties
of the materials.
Lecture 2-1
METB113 Oct 2015
Why study atomic structure?
2
• What promotes bonding?
• What types of bonds are there?
• What properties are inferred from bonding?
Understanding of interatomic bonding allow us to
explain a material’s properties.
Lecture 2-2
METB113 Oct 2015
Why study atomic structure?
3
Some of solid materials important properties depend on the
geometrical atomic arrangement and the types of
interatomic bonding
atom – electrons – 9.11 x 10-31 kg
protons
neutrons } 1.67 x 10-27 kg
Valence electrons govern the following properties :
1) Chemical
2) Electrical
3) Thermal
4) Optical
Lecture 2-3
METB113 Oct 2015
Electron Configurations
4
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
METB113 Oct 2015
Atomic Bonding in Solids
5
Primary Bond (Strong Bond)
Each atom seeks to be in the most stable state – by bonding.
Potential energy is lowered. Large interatomic forces.
Ionic bonds :- Strong non-directional atomic bonds due to
transfer of electrons.
Covalent bonds :- Large interactive force due to sharing of
electrons and directional.
Metallic bonds :- Non-directional bonds formed by sharing of
electrons in solid metals.
METB113 Oct 2015
Atomic Bonding in Solids
6
Secondary Bond (Weak Bond) or Van Der Waals Bond
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.
METB113 Oct 2015
Ionic Bonding
7
The attractive bonding forces are Coulombic by virtue (due to)
of their net electrical charge, attract one another.
• Occurs between positive and negative ions.
• Requires electron transfer.
• Large difference in electronegativity is required.
• Example: NaCl
Na (metal) Cl (nonmetal)
unstable unstable
electron
Na+ (cation)
stable
+ - Cl- (anion)
Coulombic stable
Attraction
METB113 Oct 2015
Ionic bond – metal + nonmetal
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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]
METB113 Oct 2015
Ionic Bonding
Energy – minimum energy most stable
Energy balance of attractive and repulsive terms
A B
ENet = EA + ER =- -
r rn
Repulsive energy ER
Interatomic separation r
Net energy EN
Adapted from Fig. 2.8(b),
Callister & Rethwisch 3e.
Attractive energy EA
9
9
METB113 Oct 2015
Ionic Force for Ion Pair
Nucleus of one ion attracts electron of another ion.
Attractive bonding forces are Coulombic forces.
The electron clouds of each ion repulse each other when they
are sufficiently close.
Fnet = Fattractive + Frepulsive
METB113 Oct 2015
Ion Arrangements in Ionic Solids
Ionic bonds are Non Directional. Ionic solids will pack in 3-d
Geometric arrangements are present in solids so that the
charge are electrically neutral. 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.
METB113 Oct 2015
Bonding Energies
Lattice energies and melting temperature of ionically bonded
solids are high.
Lattice energy decreases when size of ion increases.
Because electron are farther away to be attracted to the
neucleus of the cation.
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
METB113 Oct 2015
Examples: Ionic Bonding
• Predominant bonding in Ceramics
13
NaCl
MgO
CaF 2
CsCl
Give up electrons Acquire electrons
Adapted from Fig. 2.7, Callister & Rethwisch 3e. (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.
METB113 Oct 2015
Ionic Bonding and Material Properties
14
Lattice energies and melting temperature of ionically bonded
solids are high.
MgO has highest 3932 kJ and 2800 C.
Ionic solids are hard (do not dent)
rigid (do not bend or stretch)
strong (hard to break)
brittle (deform little before fracture)
due to strong electrostatic force that holds the
ions together
METB113 Oct 2015
Ionic Bonding and Material Properties
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METB113 Oct 2015
Covalent Bonding
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• 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 & Rethwisch 3e.
METB113 Oct 2015
Electronegativity
17 • Ranges from 0.7 to 4.0
• Large values: tendency to acquire electrons.
Smaller electronegativity Larger electronegativity
Adapted from Fig. 2.7, Callister & Rethwisch 3e. (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.
METB113 Oct 2015
Covalent Bonding - Examples
18
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 = 28 kJ/mol
Nitrogen (Outer orbital - 2s2 2p3) atoms share three p electrons
N + N N N N N
Bond Energy = 54 kJ/mol
METB113 Oct 2015
Bond Length, Bond order and Bond Energy
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For a given pair of atoms, with higher bond order, the bond
length will decrease; as bond length decreases, bond energy
will increase (H2, F2, N2)
Nonpolar bonds: sharing of the
bonding electrons is equal
between the atoms and the bonds.
Polar covalent bond: Sharing of
the bonding electrons is unequal
(HF, NaF).
METB113 Oct 2015
Covalent Bonding in Carbon
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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
orbital. Result four sp3 orbitals. Indicates
four covalent
1s
bonds are
2p
Four ½ filled sp3 orbitals formed
METB113 Oct 2015
Structure of Diamond
21
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
METB113 Oct 2015
Carbon Containing Molecules
22
In Methane, Carbon forms four covalent bonds with
Hydrogen.
Molecules are very weekly
bonded together resulting Methane
in low melting temperature molecule
(-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
METB113 Oct 2015
Covalent Bonding in Benzene
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Chemical composition of Benzene is C6H6.
The Carbon atoms are arranged in hexagonal ring.
Single and double
H bonds alternate between the atoms.
H C H
C C
C C H
H
C
H
Structure of Benzene Simplified Notations
METB113 Oct 2015
Covalent Bonding and Material Properties
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The covalent bond between atom is strong however the bond
between molecules are weak.
Low melting temperature and breaks easily.
3-D Network Covalent Solids (no molecules) such as diamond
and quartz (SiO2).
Hard and high melting temperature.
METB113 Oct 2015
Metallic Bonding
Atoms in metals are closely packed in crystal structure.
Loosely bounded valence electrons are attracted towards
nucleus of other atoms. (metal cation has 1 to 3 electron the most)
Electrons spread out among atoms forming electron clouds and free
to drift throughout the entire metal.
Positive Ion Cores
These free electrons are reason for
electrical conductivity and ductility.
Non-valence electron and nuclei
form positive ion cores.
Since outer electrons are
shared by many atoms,
metallic bonds are Valence electron
Non-directional cloud
METB113 Oct 2015
Metallic Bonds (Cont..)
26
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 97.7oC
Higher the number of valence electrons involved, higher is the
bonding energy.
Example:- Ca Bonding energy 177 kJ/mol
Melting temperature 851oC
METB113 Oct 2015
Metallic Bonds and Bond Energies
27
The bond energies and the melting point of metals vary
greatly depending on the number of valence electrons and
the percent metallic bonding.
METB113 Oct 2015
Metallic Bonds and Material Properties
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Pure metals are significantly more malleable than ionic or
covalent networked materials.
Strength of a pure metal can be significantly increased through
alloying.
Pure metals are excellent conductors of heat and electricity.
METB113 Oct 2015
Secondary Bonding (van der Waals)
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Weak bond : around 10 kJ/mol
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= Electric charge
+q -q d = separation distance
There two types of polar bonds permanent and fluctuating.
METB113 Oct 2015
Permanent Dipoles
30
Dipoles that do not fluctuate with time are
called Permanent dipoles.
Symmetrical No Dipole
CH4 Arrangement moment
Of 4 C-H bonds
Asymmetrical
Creates
CH3Cl Tetrahedral
Dipole
arrangement
METB113 Oct 2015
Fluctuating Dipoles
31
Weak secondary bonds in noble gasses.
Dipoles are created due to asymmetrical distribution of
electron charges.
Electron cloud charge changes with time.
+ -
Asymmetrical
Symmetrical distribution
distribution of electron charge cloud
of electron charge cloud
(changes with time) creating a
“fluctuating electric dipole”
METB113 Oct 2015
Secondary Bonding (van der Waals)
Arises from interaction between dipoles
32
• Fluctuating dipoles
asymmetric electron ex: liquid H 2
clouds H2 H2
+ - + - H H H H
secondary secondary
bonding bonding
• Permanent dipoles-molecule induced
-general case: + - secondary + -
bonding
-ex: liquid HCl H Cl secondary H Cl
bonding
-ex: polymer
METB113 Oct 2015
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.
H
O 1050
Hydrogen
H Bond
METB113 Oct 2015
Mixed Bonding - Ionic-Covalent Mixed Bonding
34
Most molecules have mixtures of ionic bonding and covalent
bonding.
- X A-XB
1 2
1 - e 4 100%
% ionic character
XA and XB = electronegativities of atoms A and B in the
compounds.
The ionic character increase as the electronegativities
between the atoms increased.
METB113 Oct 2015
Summary: Bonding
35
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
METB113 Oct 2015
Properties From Bonding: Tm
36
• 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”
METB113 Oct 2015
Properties From Bonding : a
• Coefficient of thermal expansion, a
37
length, L o coeff. thermal expansion
unheated, T1
DL DL
= a (T2 -T1)
heated, T 2 Lo
• a ~ symmetric at ro
Energy
unstretched length
ro
r a is larger if Eo is smaller.
E
smaller a
o
E larger a
o
METB113 Oct 2015
Summary: Primary Bonds
38
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
