1

CHAPTER 2
ATOMIC STRUCTURE AND BONDING INSOLIDS
Learning objectives:
After careful study of this chapter you should be able to do the following:
1. Name the two atomic models cited and note the difference between them
2. Describe the important quantum-mechanical principle that relates to electron
energies
3. a) schematically plot attractive, repulsive and net energies versus interatomic
separation for two atoms or ions
( (b) note on this plot the equilibrium separation and the bonding energy

4. a) briefly describe ionic, covalent, metallic , hydrogen and van der Waals bonds
b ) note with materials exhibit each of these bonding types

THE STRUCTURE OF MATERIAL: TECHNOLOGY RELEVANCE
In todays world, information technology (IT), biotechnology, energy technology,
environmental technology and many other areas require smaller, lighter faster, portable,
more efficient, reliable, durable and inexpensive devices. We want batteries that are
smaller, lighter and last longer. We need cars that are relatively affordable, light-weight,
safe, highly fuel efficient, and loaded with many advanced features, ranging from
global positioning systems (GPS) to sophisticated sensors fro airbag deployment.
We will examine atomic structure in order to lay a foundation for understanding how it
affects the properties, behaviors, and resulting applications of engineering materials.
The structure of atoms affects the types of bonds that hold materials together. These
different types of bonds directly affect suitability of materials for real world engineering
applications.
Both the composition and the structure of a material have a profound influence on its
properties and behavior. Engineers and scientist who study and develop materials must
understand their atomic structure. The properties of materials are controllable and can
actually be tailored to the needs of a given application by controlling their structure and
composition.
Structure of materials can be examine and describe at five different levels:
1. Macrostructure
2. Microstructure
3. Nanostructure
4. Short and long range atomic arrangement
5. Atomic structure

2

Engineers and scientist concerned with development and practical applications of
advanced materials need to understand the microstructure and macrostructure of
various materials and ways of controlling them.
Microstructure is the structure of material at a length-scale of ~10 to 1000 nm.
Microstructure typically includes such features as average grain size, grain-size
distribution, grain orientation and other features related to defects in material.
Macrostructure is the structure of a material at a macroscopic level where the length-
scale is ~ 1000 100,000. Features that constitute macrostructure include porosity,
surface coatings and such features as internal or external cracks.
Atomic structure it is also important to understand atomic structure and how the
atomic bonds lead to different atomic or ionic arrangements in materials. The atomic
structure includes all atoms and their arrangements, which constitute the building of
blocks of matter.
It is from this building blocks that all the nano, micro and macrolevels of structures
emerge.
A close examination of atomic arrangement allows us to distinguish between materials
that are amorphous or crystalline. Amorphous materials have only short range atomic
arrangement while crystalline materials have short and long range arrangements.
In short range arrangement the atoms or ions shows a particular order only over
relatively short distances. For crystalline materials, the long range atomic order is in the
form of atoms or ions arranged in a three dimensional pattern that repeats over much
larger distances (from ~100 nm to few cm).
Properties and behavior of materials at micro levels can vary greatly when compared to
those in their macro or bulk state. As a result, understanding the structure at nano-scale
or nanostructure ( length-scale 1 100 nm) and microstructure are areas that have
received considerable attention. The term nanotechnology is used to describe a set of
technologies that are based on physical, chemical and biological phenomena occurring
at nanoscale.

ATOMIC STRUCTURE

Atoms consist primarily of three basic subatomic particles: protons, neutrons and
electrons

The current simple model of an atom envisions a very small nucleus of about 10
-14
m
in diameter surrounded by a relatively thinly dispersed electron cloud of varying density
so that the diameter of the atom is of the order of 10
-10
m.
The nucleus accounts for almost all the mass of the atom and contains protons and
neutrons.


3

Mass (gram) Charge ( C )
Proton 1.673 x 10
-24
+1.602 x 10
-19

Neutron 1.675 x 10
-24
0
Electron 9.109 x 10
-28
-1.602 x 10
-19


The electron charge cloud thus constitutes almost all the volume of the atoms but
accounts only for a very small part of its mass. The electrons, particularly the outer
ones, determine most of the electrical, mechanical, chemical and thermal properties of
the atoms, thus a basic knowledge of atomic structure is important in the study of
engineering materials.
ATOMIC NUMBERS AND ATOMIC MASSES
ATOMIC NUMBERS

The atomic number of an atom indicates the number of protons (positively charged
particles) that are in its nucleus, and in a neutral atom the atomic number is also equal
to the number of electrons in its charge cloud. Each element has its own characteristic
atomic number, and thus the atomic number identifies the element.






ATOMIC MASSES

The relative atomic mass of an element is the mass in grams of 6.023 x 10
23
atoms (
Avogadros number N
A
) of that element. The carbon atom with 6 protons and 6
neutrons is the carbon 12 atom and is the reference mass for atomic masses.
One atomic mass unit ( u ) is defined as exactly one-twelfth of the mass of the mass of
carbon atom, which has a mass of 12u. One molar relative atomic mass of carbon 12
has a mass of 12g on this scale.

H
1
1.00794

Li
3
6.941

Be
4
9.0121

C
6

12.011

Na
11
22.9898

Mg
12
24.305

Al
13
26.981
5
Atomic number

Atomic mass

4

One gram-mole of mole (mol) of an element is defined as having the mass in grams of
the relative molar atomic mass of that element. For example: 1 gram-mole of aluminum
has a mass of 26.98g and contains 6.023 x 10
23
atoms.
Mole and molecular (Relative) mass
Assume that the molecular mass of a substance/material is M and the mass is m gram.
M gram of substance has a quantity of 1 mol
So m gram of substance has a quantity of n mol where n = mol m x
M
|
.
|

\
| 1

Mole and number of molecules
Assume that m gram of a gas has N number of molecules. The molecular mass of the
gas is M, that is one mole of gas has a mass of M gram.
M gram contains N
A
number of molecules. So:
A
A
N
N
n so n
M
m
N
N
M
m
= =
=

Where n = N/N
A


is the ratio of the number of molecules N with respect to Avogadros
number N
A
or alternatively n = m/M is the ratio of the mass of the gas m to the relative
molecular mass M.
Example
1. What is the mass in grams of one atom of copper?
2. How many copper atoms are in 1g of copper

Solution:
1. the atomic mass of copper is 63.54 g/mol. Since in 63.54 g of copper there are
6.022 x10
23
atoms, the number of grams in one atom of copper is


g x
atom x
mol atoms x
mol g
atom
Cu g x
mol atoms x
Cu mol g
N
M
m
A
22
23
23
10 05 . 1
1
/ 10 022 . 6
/ 54 . 63
1 / 10 022 . 6
/ 54 . 63

=
=
= = =

2. number of copper atoms in 1 g of copper

5


( )
atoms x
mol g
mol atoms x g
M
mN
N atoms copper of number
A
21
23
10 48 . 9
/ 54 . 63
) / 10 022 . 6 )( 1 (
=
= =


ELECTRONS IN ATOMS
Atomic models
An understanding and of the behavior of electrons in atoms and crystalline solids
necessarily involves the discussion of quantum-mechanical concepts which will not be
discussed in this chapter.
Bohr atomic model, in which electrons are assumed to revolve around the atomic
nucleus in discrete orbitals and the position of any particular electron is more or less
well defined in terms of its orbital. This model of the atom is represented in Figure 1.
Electrons occupy discrete energy levels within the atom. Each electron possesses a
particular energy, with no more than two electrons in each atom having the same
energy. This also implies that there is a discrete energy difference between any two
energy levels

QUANTUM NUMBER

The energy level to which each electron belongs is determined by four quantum
numbers. The number of possible energy levels is determined by the first three quantum
numbers.

1. the principal quantum number n is assigned integral values 1,2,3,4, that refer
to the quantum shell to which the electron belongs ( figure). Quantum shells are
also assigned a letter: the shell for n = 1 is designated K, for n=2 is designated L,
for n=3 is M and so on.










6















Figure 1: Schematic representation of the Bohr atom

Maximum number of electrons for each principal atomic shell
Shell number, n
(principal quantum
number)
Maximum number of
electrons in each shell
(2n
2
)
Maximum number of
electrons in orbitals

1 2(1
2
) = 2 s
2

2 2(2
2
)=8 s
2
p
6

3 2(3
2
)=18 s
2
p
6
d
10
-
4 2(4
2
)=32 s
2
p
6
d
10
f
14
5 2(5
2
)=50 s
2
p
6
d
10
f
14

6 2(6
2
)=72 s
2
..
7 2(7
2
)=98 s
2
.


11 proton
12 neutrons
K shell ( n=1)
L shell ( n=2)
M shell ( n=3)

7

2. the number of energy levels in each quantum shell is determined by the
azimuthal quantum number l and the magnetic quantum number m
l
.

The azimuthal quantum numbers are also assigned numbers: l = 0. 1. 2, .n-1.
If n =2,then there are also two azimuthal quantum numbers, l = 0 and l = 1. The
azimuthal quantum numbers are designated by lowercase letters.
s for l = 0 d for l = 2
p for l = 1 f for l =3
The magnetic quantum numbers m
l
gives the number of energy levels, or
orbitals, for each azimuthal quantum number. The total number of magnetic
quantum number for each l is 2l + 1. The values for m
l
are given by whole
numbers between l and +l. For l =2, there are 2(2) + 1 = 5 magnetic quantum
numbers, with values 2, -1, 0, +1, +2
3. The Pauli exclusion principle specifies that no more than two electrons with
opposing electronic spins, may be present in each orbital.

The shorthand notation frequently used to denote the electronic structure of an
atom combines the numerical value of the principal quantum number, the
lowercase letter notation for the azimuthal quantum number, and a superscript
showing the number of electrons in each orbital. The shorthand notation for
germanium which has an atomic number of 32 is:
1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
2

The pattern used to assign electrons to energy levels
l=0
(s)
l=1
(p)
l=2
(d)
l=3
(f)
l=4
(g)
l=5
(h)
n=1 (K) 2
n=2 (L) 2 6
n=3 (M) 2 6 10
n=4 (N) 2 6 10 14
n=5 (O) 2 6 10 14 18
n=6 (P) 2 6 10 14 18 22
Note: 2, 6, 10, 14, refer to the electrons in the energy level





8







9

INTERATOMIC FORCES FOR AN ION PAIR

Consider a pair of oppositely charged ions ( for example a Na
++
Cl
-
ion pair) approaching
each other from a large distance of separation a.

As the ions comes closer together, they will be attracted to each other by coulombic
forces. That is, the nucleus of one ion will attract the electrons charge cloud of the other,
and vice versa. When the ions come still closer together, eventually their two electron
charge clouds will interact and repulsive forces will arise.


When the attractive forces equal the repulsive forces, there will be no net force between
the ions and they will remain at an equilibrium separation distance, the interionic
distance a
o
as shown in figure 2 below.

















Figure 2:

F
A
B
r
o
C
D
r
F
attractive
F
repulsive
F
resultant
r
1
a
o

R r
r = cation
R = anion
a
o
= r + R

10

The net force between a pair of oppositely charged ions is equal to the sum of the
attractive and repulsive forces. Thus:
F
net
= F
attractive
+ F
repulsive
2
2
2 1
2
2 1
4 4
) )( (
a
e Z Z
a
e Z e Z
F
o o
att
tc tc
= =
where
Z
1
, Z
2
= number of electrons removed or added from the atoms during the ion formation
E = electron charge
a = interatomic separation distance
1 +
=
n
repul
a
nb
F
where
a = interatomic separation distance
b and n = are constants

1 2
2
2 1
4
+
=
n
o
net
a
nb
a
e Z Z
F
tc


BINDING ENERGY AND INTERATOMIC SPACING
Interatomic spacing the equilibrium distance between atoms is caused by a balance
between repulsive and attractive forces. In the metallic bond, for example, the attraction
between the electrons and the ion cores is balanced by the repulsion between iron core.
Equilibrium separation occurs when the total interatomic energy (IAE) of the pair of
atoms is at a minimum, or when no net force is acting to either attract or repel the
atoms (figure 3)

11


Figure 3: Atoms or ions are separated by an equilibrium spacing that corresponds to the
minimum interatomic energy for a pair of atoms or ions (or when zero force is acting to
repel or attract the atoms or ions)
The interatomic spacing in a solid metal is approximately equal to the atomic diameter,
or twice the atomic radius r. We cannot use this approach for ionically bonded materials,
however, since the spacing is the sum of the two different ionic radii.
The minimum energy in figure is the binding energy , or the energy required to create or
break the bond. Consequently, material having high binding energy also have a high
strength and a high melting temperature.
Ionically bonded materials have a particularly large binding energy because of the large
difference in electronegativities between the ions. Metals have lower binding energies
because the electronegativities of the atoms are similar.





12

ATOMIC BONDING
TYPES OF ATOMIC AND MOLECULAR BONDS
Chemical bonding between atoms occurs since there is a net decrease in the potential
energy of atoms in the bonded state. That is, atoms in the bonded state are in a more
stable energy condition than when they are unbonded. In general, chemical bonds
between atoms can be divided into two groups: PRIMARY (or strong bonds) and
SECONDARY ( or weaker bonds).
PRIMARY ATOMIC BONDS
Primary atomic bonds in which relatively large interatomic forces develop can be
subdivided into the following three classes:
1. Metallic bond
2. Covalent bond
3. Ionic bond
SECONDARY ATOMIC AND MOLECULAR BONDS
1. Permanent dipole bonds
2. Fluctuating dipole bonds

PRIMARY BONDING:
METALLIC BONDING:
Metallic bonding occurs in solid metals. In metals in the solid state, atoms are packed
relatively close together in a systematic pattern or crystal structure.
The metallic elements have more electropositive atoms that donate their valence
electrons to form a sea of electrons surrounding the atoms (figure 4)










13



Figure 4: The metallic bond forms when atoms give up their valence electrons, which
then form an electron sea. The positively charged atoms core are bonded by mutual
attraction to the negatively charged electrons.

Aluminum for example gives up its three valence electrons, leaving behind a core
consisting of the nucleus and inner electrons. Since three negatively charged electrons
are missing from this core, it has a positive charge of three. The valence electrons
moves freely within the electron sea and become associated with several atom cores.
The positively charges atom cores are held together by mutual attraction to the electron,
thus producing a strong metallic bond.

COVALENT BOND

Materials with a covalent bond share electrons among two or more atoms. For example,
a silicon atom, which has a valence of four, obtains eight electrons in its outer energy
shell by sharing its electrons with four surrounding silicon atoms as shown in figure 5
below. Each instance of sharing represents one covalent bond; thus each silicon atom
is bonded to four neighboring atoms by four covalent bonds.




14


Figure 5: a) covalent bonding requires that electrons be shared between atoms in such
a way that each atom has its outer sp orbital filled. (b) in silicon, with a valance of four,
four covalent bonds must be formed
In order for the covalent bonds to be formed, the silicon atoms must be arrange so the
bonds have a fixed directional relationship with one another. In the case of silicon, this
arrangement produces a tetrahedron, with angles of 109.5
o
between the covalent bonds
as shown in figure 6 below.

Figure 6: The tetrahedral structure ofsilica (Si
2
O
3
) which contains covalent bonds
between silicon and oxygen atoms.
Although covalent bonds are very strong, materials bonded in this manner typically has
poor ductility and poor electrical and thermal conductivity.
For an electron to move and carry a current, the covalent bond must be broken,
requiring high temperatures and voltages. Many ceramic, semiconductor, and polymer
materials are fully or partly bonded by covalent bonds, explaining why glass shatters
when dropped and why bricks are good insulating materials.


15


IONIC BOND

The ionic bond arises from electrostatic attraction between the oppositely charged ions.
These ions result from transfer of one or more electrons from an electropositive atom to
an electronegative atom, so that positive and negative ions are formed.

In chemical combination, atoms tend to attain the electronic configuration of an inert
gas, or eight electrons in their outer shell. Thus the atoms of metallic elements that have
only up to three valence electrons in their outer shell will lose their electrons and
become positive ions, whereas electronegative elements tend to acquire additional
electrons to complete their octet and become negative ions, or anions.

Figure 7: An ionic bond is created between two unlike atoms with different
electronegativies. When sodium donates its valence electron to chlorine, each becomes
anion; attraction occurs, and the ionic bond is formed.
SECONDARY BONDING ( VAN DER WAALS BONDING)
It has been discussed that primary bonding between atoms depends on the interaction
of their valence electrons. The driving force for primary atomic bonding is the lowering
of energy of the bonding electrons.
Secondary bonds are relatively weak in contrast to the primary bonds and have
energies for only about 4 to 42 kJ/mol. The driving force for secondary bonding is the
attraction of the electric dipoles contained in atoms or molecules.
The electric dipole moment is created when two equal and opposite charges are
separated, as shown in Figure 5a. Electric dipoles are created in atoms or molecules
when positive and negative charge centers exist (figure 8b).


16


Figure 8: (a) An electric dipole. The dipole moment is qd (b) An electric dipole moment
in a covalently bonded molecule. Note the separation of the positive and negative
charge centers.
Dipoles in atoms or molecules create dipole moments. A dipole moment is defined as,
the charge value multiplied by the separation distance between positive and negative
charges, or
qd =
Unit: Coulomb-meter or Debye
Where:
= dipole moment
q = magnitude of electric charge
d = separation distance between the charge centers
In general, there are two main kinds of secondary bonds between atoms or molecules
involving electric dipoles; fluctuating dipoles and permanent dipoles. Collectively, these
secondary dipole bonds are sometimes called van der Waals bonds.

FLUCTUATING DIPOLES:

Very weak secondary bonding forces can develop between atoms of noble-gas
elements that have complete outer-valence-electron shells (s
2
for helium and s
2
p
6
for
Ne, Ar, Kr, Xe and Rn).

These bonding forces arise because the asymmetrical distribution of electron charges in
these atoms creates electric dipoles. At any instant there is a high probability that there
will be more electron charge on one side of an atom than on the other (figure 9). Thus,
in particular atom, the electron charge cloud will change with time, creating a fluctuating
dipoles.

17


Figure 9: Electron charge cloud distribution in a noble-gas atom (a) idealized
symmetrical electron charge cloud distribution (b) real case with asymmetrical electron
charge cloud distribution that changes with time, creating a fluctuating electric dipole.
PERMANENT DIPOLES
Weak bonding forces among covalently bonded molecules can be created if the
molecules contain permanent dipoles. For example, the methane molecule, CH
4
, with
its four C-H bonds arranged in a tetrahedral structure (Figure 10), has a zero dipole
moment because of its symmetrical arrangement of four C-H bonds.






Figure 10: Permanent dipole nature of water molecule
The bonding between molecules that have a permanent dipole moment, is known as the
Keesom force, is often referred to as the hydrogen bond, where hydrogen atoms
represent one of the polarized regions.
Note that van der Waals bonds are secondary bonds, but the atoms within the
molecules or group of atoms are joined by strong covalent or ionic bonds. Heating water
to boiling point breaks the Van der Waals bonds and changes water to steam, but much
higher temperature are required to break the covalent bonds joining oxygen and
hydrogen atoms.
Van de Waals bonds can dramatically change the properties of materials. Since
polymers normally have covalent bonds, we would expect polyvinyl chloride (PVC
plastic) to be very brittle, but this material contains many long, chain-like molecules (as
shown in figure 8). Within each chain, bonding is covalent, but individual chains are

18

bonded to one another by Van der Waals bonds. Polyvinyl chloride can be deformed by
breaking the Van der Waals bonds, permitting the chains to slide past one another.


Figure 11: (a) In polyvinyl chloride (PVC) the chlorine atoms attached to the polymer
chain have a negative charge and the hydrogen atoms are positively charged. The
chains are weakly bonded by van der Waals bond. This additional bonding makes PVC
stiffer (b) when a force is applied to the polymer, the van der Waals bonds are broken
and the chains slide past one another.

MIXED BONDING

In most materials, bonding between atoms is a mixture of two or more types. Iron, for
example is bonded by a combination of metallic and covalent bonding which prevents
atoms from packing as efficiently as we might expect.

Compounds formed from two or more metals (intermetallic compounds ) may be
bonded by a mixture of metallic and ionic bonds, particularly when there is a large
difference in electronegativity between the elements. Because lithium has an
electronegativity of 1.0 and aluminum has an electronegativity of 1.5, we would expect
AlLi to have a combination of metallic and ionic bonding. On the other hand, because
both aluminum and vanadium have electronegativities of 1.5, we would expect Al
3
V to
be bonded primarily by metallic bonds.
Many ceramic and semiconducting compounds, which are combinations of metallic and
nonmetallic elements, have mixture of covalent and ionic bonding. As the
electronegativity difference between the atoms increases, the bonding become more
ionic.