Atomic Structure of Material

Dr.A.K.Das
Mechanical Engineering
BML Munjal University

Content of this Chapter

Review of Atomic Structure
Electrons, Protons, Neutrons, Quantum mechanics, Electron states,
The Periodic Table
Atomic Bonding in Solids
Energies vs. Forces
Periodic Table
Primary Interatomic Bonds
Ionic
Covalent
Metallic
Secondary Bonding (Van der Waals)
Molecules and Molecular Solids

The Structure of Metals

All matter is made up of atoms containing a nucleus of protons

and neutrons and surrounding clouds, or orbits, of electrons.
Atomic bonds are created by transferring or sharing of
electrons; in doing so, multiple atoms combine to form
molecules. Molecules are held together by attractive forces
called bonds. There are different types of bonds like:-

History of Atomic Theory Development

Electrons form a cloud around the

nucleus
Radius ~ 0.05 1nm.
Picture looks like a mini planetary
system. But Quantum Mechanics
says this analogy is not correct

Invention of Electron
A simple cathode-ray tube consists of two electrodes
sealed in a glass tube. A glow discharge appears in the
gas between the electrodes as the tube is evacuated. With further
evacuation, the discharge disappears, and a glow appears on the
end of the tube opposite the cathode.

If the north pole of a magnet is brought down toward

the top of a cathode-ray tube, the spot of light is
deflected to the left across the face of the tube.

Review of Atomic Structure

Atoms = nucleus (protons and neutrons) + electrons
Charges:
Electrons (-): protons(+) 1.6 10-19 Coulombs.
Neutrons are electrically neutral.
Masses:
Protons and Neutrons ~1.67 10-27 kg.
Electron 9.11 10-31 kg
Atomic mass = # protons + # neutrons
Atomic number (Z) = # protons
chemical identification of element
Isotope number # neutrons

Atomic mass units. Atomic weight.

Atomic mass unit (amu)
1 amu = 1/12 of mass of most common isotope of C
6 protons (Z=6) and six neutrons (N=6).
The atomic mass of

12C

atom is 12 amu.

Atomic weight: A
Weighted average of atomic masses of naturally
occurring isotopes.
Atomic weight of carbon is 12.011 amu.
Atomic weight is often in mass per mole.
A mole
Amount of matter with mass in grams equal to the atomic mass in amu
(A mole of carbon has a mass of 12 grams).

One Mole contains Avogadros number of atoms,

Nav = 6.023 1023.
Nav = 1 gram/1 amu.
Example:
Atomic weight of iron = 55.85 amu/atom = 55.85 g/mol

Atomic Mass
The Atomic Mass of an atom is the total number of protons and neutrons which
are present in the nucleus of the atom. The reference atomic mass unit is onetwelfth of the mass of the Carbon-12 isotope of carbon. The mass of Carbon12 is defined as 12.000000 atomic mass units (amu). One amu. is 1.66*10 -27
kg.
An Atom is the smallest part of an element which can take part in a chemical
reaction. The atom consists of three fundamental particles, The Proton which has
mass of approximately 1 atomic mass unit and a positive charge,
The Neutron which has a mass of approximately 1 atomic mass unit and no charge,
and
The Electron which has a mass 1/1840 of the proton and a negative charge.
Each Elements is made up of one kind of atom only.

Atomic Mass Number

The Atomic Mass Number of an atom is the total number of protons and
neutrons in the nucleus of the atom.
Atomic Mass of Chlorine
Chlorine consists of a mixture of two Isotopes. The first isotope has a mass
number of 35, and its nucleus contains 17 protons and 18 neutrons and
The second isotope has a mass number of 37, , and its nucleus contains 17
protons and 20 neutrons.
The observed atomic weight of chlorine is 35.46. This indicates that chlorine is
a mixture of these two isotopes, and that the isotope with mass number 35 is
the more abundant atom present.
Indeed, the isotope of mass number 35 is approximately three times more
abundant than the isotope of mass number 37.

Typical Parameters

The Structure of Atoms

Periodic Table of Elements

Quiz
Choose the best answer:
A beam of electrons can be deflected by
1. A constant electric field
2. Constant magnetic fields
3. Gravity
4. Variable electric or magnetic fields or both
5. All of the above.

Thomson used both electric and magnetic fields to deflect

the cathode-ray beam in a tube specially designed to
measure the mass of the cathode-ray particles.

Quiz
Choose the best answer:
A beam of electrons can be deflected by
1. A constant electric field
2. Constant magnetic fields
3. Gravity
4. Variable electric or magnetic fields or both
5. All of the above.

Important Definitions

Bohr Atomic Model

Bohr Atomic Model

Electrons are assumed to be revolving around the atomic nucleus at discrete
orbitals.
The position of any particular electron is more or less well defined in terms of
its orbitals.
The Bohr model represents an early attempt to describe electrons in atom, in
terms of both position (orbital) & energy (quantized energy level). This model had
several limitations.

Schematic representation of the

Bohr atom.

Wave Mechanical Model of Atom

Wave Mechanical Model

Electrons are considered to exhibit both wave like &
particle like characteristics.
With this model, electron is no longer treated as a
particle moving in discrete orbital, rather it is the
probability of an electron being in a discrete orbital.
Position described by a probability distribution of
electron cloud.

Quantum Numbers

Quantum number
Every electron in an atom is characterized by four parameters called Quantum
Numbers.
The size, shape, spatial orientation of an electrons probability density (orbitals),
are specified by three of these quantum numbers.
Shells are specified by Principal Quantum Number, n.
This n have integral values, 1,2,3,4..
These are also designated by letters K, L, M, N, O
The second (Azimuthal) quantum number, l, designates the subshell.
Values of I is restricted by value of n, ranges from l=0 to l=(n-1)
Designated by lower case letter s, p, d, f.

Electron Orbitals

Electron orbital shapes depends on l

First s orbital is spherical & centred on the
nucleus.
There are three orbitals for p subshell, each
has a nodal surface in the shape of a
dumbbell, the axes of three orbitals are
mutually perpendicular & are designated as
px, py, pz

Orientation shape
of s orbital

Orientation shape
of p orbitals

Schematic representation of relative energies of

electrons for various shells & subshells
Summary:

Smaller the principal quantum

number, lower is the energy level.

Within each shell, the energy of

sub-shell level increases with the
value of l quantum number.

There may be overlap in energy of

a state in one shell with states in
the adjacent shell (refer d & f
state).

Quiz

Atomic Bonding
Forces & Energies

How two atoms behave as they are brought closer from infinite distance.
Two types of forces
Attractive, FA and Repulsive, FR
The magnitudes of which depends on separation distance, r
The net force between two atoms is algebraic sum of these two forces, i.e.
FN = FA + FR
Plot of Attractive,
Repulsive & Net forces
between two atoms,
when they are brought
from infinite distance

In equilibrium condition, net force is zero,

FA + FR = 0
In the equilibrium state, the two atoms are separated by the equilibrium spacing r0 as
shown in above figure.
Order of r0 is 0.3nm for many atoms.
The energy E & force F are related as,

For atomic system,

Plot of Attractive, Repulsive & Net Energies between two

atoms, when they are brought from infinite distance
E0 = the bonding energy at minimum point.

Energy and Packing

Atomic Structure & Interatomic Bonding

Bonds can Stretch and Bend

Because bonds are formed from the attraction between the nucleus of an atom and the
electrons of another atom the bond is not a rigid structure but rather a flexible spring-like
attraction.
The electrons are in constant motion causing the forces of attraction and repulsion to
constantly change, resulting in the distance between two bonded atoms to constantly
change.
Three different types of Primary or Chemical bonds are found in solids.
Ionic
Covalent
Metallic
Each of these bonding arises from the tendency of the atoms to assume stable electron
structure.

Ionic Bond

Formed between ions of opposite charges.

The nucleus of one ion attracts the electrons of the other ion.
Ionic bonds are usually formed by the transfer of electrons from a metal to a nonmetal.
Cations must free up electrons for the anions to accept.
The elements are situated at the horizontal extremities of Periodic Table.
Neon configuration
Argon configuration

Ionic compounds

Ionic compounds are a network of ions and not molecules.

The simplest ratio of ions that combine to form an ionic compound is called a formula unit
The ratio of ions in an ionic compound depends on the charges of the ions

Characteristics of Ionic Compounds

Ionic Compounds:
Are always solids at room temperature
Conduct electricity when dissolved in water or in the molten state
Have high melting and boiling points
Are brittle
Are usually white and crystalline
Are termed non-directional, i.e. the magnitude of the bond is same in all directions
around an atom.
Bonding energies ranges from 600 to 1500 kJ/mol, are showing high melting
temperature, as shown in next table.

Covalent Bonding

Covalent Bonds:
Often form between two nonmetals
Formed by the sharing of electrons
Polar covalent bonds are formed when atoms do not share electrons equally like in a
water molecule oxygen attracts the electrons more strongly than hydrogen.
Nonpolar covalent bonds the atoms share the electrons equally two identical atoms
have nonpolar covalent bonds
Atoms can share more than one pair of electrons. These multiple bonds usually occur
between carbon, oxygen, sulfur, or nitrogen atoms.
The more bonds two atoms share the stronger the bond is and the more energy that is
required to break it.
Longer bonds are weaker than shorter bonds.
Covalent bonds are directional, i.e. it is between two specific atoms.
Covalent bond may be very strong, e.g. Diamond
Hard
High melting point
Or it may be weak e.g. Bismuth has low melting point.

It is difficult to predict their mechanical properties for covalently bonded

materials based on their bond strength, as;
Some of them may fail in brittle manner whereas other may undergo large
deformation before failure.
They are generally insulator to electricity but in some cases they are
semiconductors.
They lie near one another in periodic table.
Bonding of
Polymers

Bonding of Hydrogen molecule

Metallic Bonding
Metallic bonds:
only exist between atoms of two different metals or atoms of the
same metal element.
Are formed by delocalized valence electrons, (electrons that do not
belong to only one nucleus but are free to move from nucleus to
nucleus)
Metals atoms also have an arrangement called close packed
stacking in which atoms stack in layers with the atoms on the top
layer sitting between atoms on the lower layer.
Characteristics of metallic bonds
Properties of Metals:
Malleable ( can be hammered into a thin sheet)
Ductile (can be drawn into a wire)
Can conduct heat and electricity easily
Shiny
All these properties can be attributed to the delocalized
electrons and the close stacking of atoms

Metallic bonding in sodium

Sodium has the electronic structure 1s22s22p63s1. When sodium atoms come together, the
electron in the 3s atomic orbital of one sodium atom shares space with the corresponding
electron on a neighbouring atom to form a molecular orbital - in much the same sort of way
that a covalent bond is formed.
The difference, however, is that each sodium atom is being touched by eight other sodium
atoms - and the sharing occurs between the central atom and the 3s orbitals on all of the
eight other atoms. And each of these eight is in turn being touched by eight sodium atoms,
which in turn are touched by eight atoms - and so on and so on, until you have taken in all
the atoms in that lump of sodium.
All of the 3s orbitals on all of the atoms overlap to
give a vast number of molecular orbitals which
extend over the whole piece of metal. There have
to be huge numbers of molecular orbitals, of
course, because any orbital can only hold two
electrons.
The electrons can move freely within these
molecular orbitals, and so each electron becomes
detached from its parent atom. The electrons are
said to be delocalised. The metal is held together
by the strong forces of attraction between the
positive nuclei and the delocalised electrons.