CHAPTER 2

ATOMIC STRUCTURE AND INTERATOMIC

BONDING

Fundamentals of Materials Science and

Engineering
William D. Callister Jr.

ENS167

Assoc. Prof. Maria Cristina P. Vegafria, PhD

 Atomic Structure and Interatomic
Bonding
• Atomic Structure
• Atomic Bonding in Solids
▪ Bonding Energies and Forces
• Periodic Table
• Interatomic Bonds
▪ Primary Interatomic Bonds
⮚Ionic, Covalent, Metallic
▪ Secondary Bonding (Van der Waals)
⮚Three types of Dipole Bonds
Atomic Structure

Electrons
charge: - 1.60 x 10-19 C
mass: 9.11 x 10-31 kg
Protons
charge: 1.60 x 10-19 C
mass: 1.67 x 10-27 kg
Neutrons
charge: neutral
mass: 1.67 x 10-27 kg
Atomic Number (Z) = number of protons

⮚ gives the chemical identification of the element

⮚ ranges from 1 for hydrogen to 92 for uranium, the
highest of the naturally occurring elements.
The Atomic Mass (A)
= number of protons + number of neutrons
Note:
⮚ number of protons is the same for all atoms of a given
element but the number of neutrons (N) may vary
⮚ atoms of some elements have two or more different atomic
masses, which are called isotopes
atomic weight
⮚ corresponds to the weighted average of the atomic masses of the of the
atom’s naturally occurring isotopes
⮚ often specified as mass per mole.

atomic mass unit (amu)

⮚ may be used for computations of atomic weight
⮚ used for indicating mass on an atomic or molecular scale
⮚ defined as one twelfth of the rest mass of an unbound neutral atom
of carbon-12 in its nuclear and electronic ground state
⮚ has a value of 1.66 ×10−24 g
one mole of a substance
⮚ 6.023x1023 (Avogadro’s number) atoms or molecules

1 amu/atom (or molecule) = 1 g/mol

Example:
the atomic weight of iron is 55.85 amu/atom, or 55.85 g/mol.
 Electrons in Atoms

Electrons form a cloud around

the nucleus, of radius of 0.05
– 2 nm.

This picture looks like a mini

planetary system. But
quantum mechanics tells us
that this analogy is not
correct.
The Bohr Atom
 The Bohr Atomic Model

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.
 The Wave-Mechanical Model

The electron is considered to exhibit both wavelike and particle-like

characteristics

With this model, an electron is no longer treated as a particle moving

in a discrete orbital; but rather, position is considered to be the
probability of an electron’s being at various locations around the
nucleus.

Position is described by a probability distribution or electron cloud.

THE CONCEPTS OF QUANTUM MECHANICS

Electrons move not in circular orbits, but in ‘fuzzy’ orbits.

We cannot tell how electrons move, but can we can only say
what is the probability of finding it at some distance from
the nucleus.

Only certain “orbits” or shells of electron probability densities

are allowed.
THE PRINCIPAL QUANTUM NUMBER, n

⮚ describes the electron shell or energy of an atom

⮚ can be related to the size of the shell,
n = 1 is the smallest; n = 2, 3 .. are larger

THE AZIMUTHAL QUANTUM NUMBER, l

⮚ defines subshells within each shell, denoted by s, p, d, or f.

⮚ also known as the angular quantum number or orbital
quantum number
⮚ values of l range from 0 to n-1
Schematic representation of the relative energies of the
electrons for the various shells and subshells
THE MAGNETIC QUANTUM NUMBER , mℓ
⮚ determines the number of energy states for each subshell

⮚ describes the specific orbital (or "cloud") within that subshell,

and yields the projection of the orbital angular momentum
along a specified axis
⮚ the values of mℓ range from −ℓ to ℓ, with integer steps
between them:
mℓ = −ℓ, −ℓ + 1, −ℓ + 2,...,ℓ − 2, ℓ − 1, ℓ.

⮚ For an s subshell, there is a single energy state, whereas for p,

d, and f subshells, three, five, and seven states exist,
respectively.
THE SPIN QUANTUM NUMBER, ms

⮚ describes the spin of an electron for which two

values are possible ( +1/2 and -1/2), one for each of
the spin orientations

spin up spin down

 The Number of Available Electron States in Some of the
Electron Shells and Subshells

For l = 1, then ml = -1, 0, 1

For l = 2, then ml = -2, -1, 0, 1, 2
For l = 3, then ml = -3, -2, -1, 0, 1, 2, 3
 Electron Configurations
Pauli Exclusion Principle – this principle stipulates that each
electron state can hold no more than two electrons, which
must have opposite spins.

Thus, s, p, d, and f subshells may each accommodate 2, 6, 10,

and 14 electrons respectively.

When all the electrons occupy the lowest possible energies in

accord with the foregoing restrictions, an atom is said to be
in its ground state.

The electron configuration or structure of an atom represents

the manner in which these states are occupied.
Electrons fill up the lowest possible energy states in the
electron shells and subshells, two electrons (having
opposite spins) per state.

Schematic representation
of the filled energy states
for a sodium atom.
Valence electrons
⮚ those that occupy the outermost filled shell
⮚ these electrons participate in the bonding between atoms

Stable electron configurations

⮚ the states within the outermost or valence electron shell are
completely filled

Elements that have unfilled valence shells assume stable

electron configurations by gaining or losing electrons to form
charged ions, or by sharing electrons with other atoms
 Electron
Configuration
 Electron Configuration

Assignment: What causes the anomalies in the

electron configuration of some of the elements?
 The Periodic Table
-the most important tool in Chemistry
The Periods/Series
-the rows of the periodic table

The Families/Groups
-the columns of the periodic table
 The Periodic Law
The properties and characteristics of the elements are periodic
functions of the atomic masses
-DMITRI MENDELEEV
 The Modern Periodic Law
The properties and characteristics of the elements are periodic
functions of the atomic numbers
-HENRY MOSELEY
 Trends in the Periodic Table

Metallicity
Electronegativity
Electron Affinity
Atomic Radii
Ionization Energy
 Trends in the Periodic
Metallicity Table
⮚ defined as the tendency of an atom to donate electrons to
metallic or ionic bonds

increases from top to bottom and from right to left

 Trends in the Periodic
Atomic Size (Atomic Radius)
Table
CATIONS (positive ions) are smaller than neutral atoms, while ANIONS (negative ions) are
larger.

increases from top to bottom and from right to left

Ions always shrink with increasing positive charge and expand with increasing
negative charge.
 Trends in the Periodic
Atomic Mass Table

Increases with increasing atomic number

 Trends in the Periodic
Periodic trends are not absolute.Table

The fact that the mass of tellurium (Te) is actually greater than the mass of iodine (I)
illustrates that even the masses are not perfectly ordered.
 Trends in the Periodic
Electronegativity Table
⮚ the tendency of an atom to attract an electron

increases from bottom to top and from left to right

 Trends in the Periodic
Table
Electronegativity
⮚ the tendency of an atom to attract an electron

Electropositive Elements – capable of giving up their few valence

electrons to become positively charged ions.

Electronegative Elements – readily accept electrons to form

negatively charged ions, or sometimes they share electrons with
other atoms.
 Trends in the Periodic
Table
Pauling’s Electronegativities

Pauling graded electronegativities on a 0 to 4.0 scale, with fluorine having the highest
electronegativity of 4.0 and cesium and francium having the lowest with 0.7
 Trends in the Periodic
Table
Periodic trends are not absolute.

For example, when moving from left to right, the electronegativity does not increase
continuously for every element.
 Trends in the Periodic
Periodic trends are not absolute.Table

The electronegativity actually decreases to the immediate right of the noble metals
(group IB).
 Trends in the Periodic Table
Ionization Energy- the minimum amount of energy required to remove an
electron from an atom

increases from bottom to top and from left to right

 Trends in the Periodic Table
What is the electronegativity of the noble gases?
ZERO

Noble gases have filled octets.

 Trends in the Periodic Table
What element has the highest electronegativity ? FLOURINE

Flourine has an electronegativity of 4.0

 Trends in the Periodic Table
What element has the lowest electronegativity (ex. noble gases)?
CESIUM and FRANCIUM

Cesium and Francium have an electronegativity of 0.7.

 Trends in the Periodic Table
Which has the highest electronegativity ? OXYGEN
K, O, Fe, Cl, Ne

Oxygen has the second highest electronegativity (3.5) among the elements, third is
Chlorine (3.0)
 Trends in the Periodic Table
Which has the lowest electronegativity ? NEON
K, O, Fe, Cl, Ne

Noble gases have an electronegativity of zero.

 Trends in the Periodic Table
Which has the lowest ionization energy ? SODIUM
Na, O, Fe, Cl, Ne
 Trends in the Periodic Table
Which has the highest ionization energy ? NEON

Na, O, Fe, Cl, Ne

 Trends in the Periodic Table
Which ion or atom is the smallest? MAGNESIUM
Na, Mg, Ca, K,Sr
 Trends in the Periodic Table
Which ion or atom is smaller? Fe3+
Fe, Fe3+

CATIONS (positive ions) are smaller than neutral atoms, excess electrons cause them to
shrink.
 Bonding Forces and Energies

• Consider the interaction between two isolated atoms as

they are brought into close proximity from an infinite
separation.
⮚ At large distances, interactions are negligible
⮚ As atoms approach, each exerts forces on the other

Two Types of Bonding Forces

• Attractive Force
• Repulsive Force
Attractive Force, FA
⮚ depends on the particular type of bonding that exists between
the two atoms
⮚ magnitude varies with the distance.

Repulsive Force, FR
⮚ exists when the outer electron shells of the two atoms begin to
overlap

Net Force, FN is the sum of both attractive and repulsive

components. FN = FA + FR
 Assignment
a) Explain the dependence of
repulsive, attractive, and net
forces on interatomic
separation for two isolated
atoms.
(b) Explain the dependence of
repulsive, attractive, and net
potential energies on
interatomic separation for two
isolated atoms.
Three types of primary or chemical bond:
• Ionic
• Covalent
• Metallic

Secondary bonds or Van der Waals Bonding

Ionic Bonding (Heteropolar Bond)
⮚ Involves transfer of electrons
⮚ Always found in compounds that are composed of both
metallic and nonmetallic elements, elements that are situated
at the extremities of the periodic table
 Schematic representation
of ionic bonding in sodium chloride (NaCl)
Covalent Bonding (Homopolar Bond)
⮚ makes use of sharing of electrons between adjacent atoms to
assume stable configurations

Schematic representation of
covalent bonding in a molecule
of methane (CH4).

Number of covalent bonds that is available for a particular atom is 8 – N,

where N is the number of valence electrons.
Metallic Bonding
⮚ found in metals and their alloys
⮚ electrons are not bound to any particular atom (delocalized)
and are free to move throughout the entire metal as a “sea
of electrons “

Proposed Model
⮚ Metallic materials have one, two, or at most, three valence
electrons.
⮚ With this model, these valence electrons are not bound to
any particular atom in the solid and are more or less free to
drift throughout the entire metal.
⮚ The remaining nonvalence electrons and atomic nuclei form
what are called ion cores.
Schematic illustration of metallic bonding
Secondary bonding forces arise from atomic or
molecular dipoles. In essence, an electric dipole
exists whenever there is some separation of
positive and negative portions of an atom or
molecule.

Fig. 2.12 Schematic illustration of van der Waals bonding between two
dipoles.
 Induced Dipole Bonds

A dipole may be induced in an atom or

molecule that is normally electrically
symmetric.

All atoms are experiencing constant

vibrational motion that can cause short-
lived distortions of this electrical
symmetry.
 Induced Dipole Bonds
The liquefaction or solidification of the inert gases and other
electrically neutral and symmetry molecules such as H2 and
Cl2 are realized because of this type of bonding.

Melting and boiling temperatures are extremely low in

materials for which induced dipole bonding predominates; of
all possible intermolecular bonds, these are the weakest.
 Polar Molecule-Induced Dipole Bonds
Polar molecules
⮚ molecules that have permanent dipole
moments by virtue of an asymmetrical
arrangement of positively and negatively
charged regions
⮚ can also induce dipoles in adjacent nonpolar
molecules, and a bond will form as a result of
attractive forces between the two molecules.
 Permanent Dipole Bonds
• Permanent dipole bonds exist between adjacent polar
molecules.

Hydrogen Bonding
⮚ a special case of polar molecule bonding
⮚ it occurs between molecules in which hydrogen is covalently
bonded to fluorine (as in HF), oxygen (as in H2O), and nitrogen (as
in NH3).
 Concept of a Molecule
Molecule
⮚ a group of atoms that are bonded together by strong primary bonds.

Within this context, the entirety of ionic and metallically bonded solid
specimens may be considered as a single molecule.

However, this is not the case for many substances in which covalent bonding
predominates; these include elemental diatomic molecules (F2, O2, H2 , etc.)
as well as a host of compounds (H2O, CO2 , HNO3, C6H6, CH4 , etc.).