Chapter 1

ATOMIC STRUCTURE & INTERATOMIC

BONDING

Tri 3, 2017/18

Atomic Structure
• Each atom consists of a very small nucleus composed of protons
and neutrons, which is encircled by moving electrons.
• Electron - a negatively charged particles. (mass = 9.11 × 10−31 kg)
• Proton - a positively charged particles in the nucleus. Nucleus is a
dense central core within the atom. (mass = 1.67 × 10−27 kg)
• Neutron - an electrically neutral particles having a mass slightly
greater than that of protons.

Protons and neutrons of an atom are packed in

an extremely small nucleus. Electrons are
shown as “clouds” around the nucleus.
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 Atomic Number, Mass Number, and Isotopes

Atomic number (Z) = number of protons in nucleus

Mass number (A) = number of protons + number of neutrons
= atomic number (Z) + number of neutrons
Isotopes are atoms of the same element (X) with different
numbers of neutrons in their nuclei

Mass Number A
ZX
Element Symbol
Atomic Number

Example: consider two common isotopes of uranium with mass

numbers of 235 and 238, respectively:

235 238
92 U 92 U
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Atomic Mass
The atomic mass (A) - the sum of the masses of protons and neutrons
within the nucleus.
The atomic weight of an element corresponds to the weighted average
of the atomic masses of the atom’s naturally occurring isotopes.
The atomic mass unit (amu) may be used for computations of atomic
weight.
A scale has been established whereby 1 amu is defined as 1/12 of the
atomic mass of the most common isotope of carbon, carbon 12 (12C)
(A = 12.00000).

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 Atomic Mass
Setting the atomic mass of carbon-12 at 12 amu provides the standard
for measuring the atomic mass of the other elements.
For example:
• Experiments have shown that, on average, a hydrogen atom is only
8.400 percent as massive as the carbon-12 atom if the mass of one
carbon-12 atom is exactly 12 amu, the atomic mass of hydrogen must
be 0.084 × 12.00 amu or 1.008 amu.
• Similar calculations show that the atomic mass of oxygen is 16.00 amu
and that of iron is 55.85 amu.
Thus, although we do not know just how much an average iron atom’s
mass is, we know that it is approximately 56 times as massive as a
hydrogen atom.

• Referring to the periodic table, the atomic mass for a carbon is not
12.00 amu but 12.01 amu.
• Reason for the difference: carbon has more than one isotope.
• When measuring the atomic mass of an element, the average mass of
the naturally occurring mixture of isotopes must be considered.

The average atomic mass is the weighted

average of all of the naturally occurring isotopes
of the element.

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 The Mole
• The atomic weight of an element or the molecular weight of a
compound may be specified on the basis of amu per atom
(molecule) or mass per mole of material.

• In one mole of a substance there are 6.022 X 1023 (Avogadro’s

number) atoms or molecules.

• These two atomic weight schemes are related through the

following equation:

Bohr Atomic Model

• Quantum mechanics - a set of principles and laws that govern
systems of atomic and subatomic entities.

• 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.

Schematic representation of the

Bohr atom.
An understanding of the behavior of electrons in atoms and crystalline solids necessarily involves the discussion of quantum-
mechanical concepts. 8
 Bohr Atomic Model
Bohr model - an early attempt to describe electrons
in atoms, in terms of both position (electron
orbitals) and energy (quantized energy levels).
Energies of electrons are quantized (permitted to
have only specific values of energy).
An electron may change energy, but in doing so it
must make a quantum jump either to an allowed
higher energy (with absorption of energy) or to a
lower energy (with emission of energy).
Adjacent states are separated by finite energies.
(a) The first three These energies are taken to be negative, whereas
electron energy the zero reference is the unbound or free electron.
states for the
Bohr hydrogen The single electron associated with the hydrogen
atom. atom will fill only one of these states.

Wave-Mechanical Model
An electron is no longer treated as a
particle moving in a discrete orbital.
Position is described by a probability
distribution or electron cloud.

Comparison of the (a) Bohr and (b) The first three electron
(b) wave-mechanical atom models energy states for the
in terms of electron distribution. Bohr hydrogen atom. 10
 Quantum Numbers of an Atomic Orbital
Three quantum numbers are required to describe the
distribution of electrons in hydrogen and other atoms.
They are called the principle quantum number, the angular
momentum quantum number, and the magnetic quantum
number.
These quantum numbers will be used to describe atomic
orbitals and to label electrons that reside in them.
A fourth quantum number – the spin quantum number –
describes the behavior of a specific electron and
completes the description of electron in atoms.

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Schrodinger Wave(n,Equation
Quantum Numbers l, ml, ms)
Principal Quantum Number, n
n = 1, 2, 3, 4, …. (n can have integral values 1, 2, 3, and so forth)

The principle quantum number relates to the average distance of the

electron from the nucleus in a particular orbital.

The larger n is, the greater the average distance of an electron in the
orbital from the nucleus and therefore the larger the orbital.

n=1 n=2 n=3

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 Quantum numbers: (n, l, ml, ms)
Angular Momentum Quantum Number, l
for a given value of n, l = 0, 1, 2, 3, … n–1

l=0 s orbital
n = 1, l = 0
l=1 p orbital
n = 2, l = 0 or 1
l=2 d orbital
n = 3, l = 0, 1, or 2
l=3 f orbital

The angular momentum quantum number (l) tells us the “shape” of the
orbitals.

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Quantum numbers: (n, l, ml, ms)

Magnetic Quantum Number, ml
For a given value of l
ml = −l, (−l + 1), …., 0, …. (+l − 1), +l
if l = 0 (s orbital), ml = 0
if l = 1 (p orbital), ml = -1, 0, or 1
if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2
The magnetic quantum number (ml) describes the orientation of the
orbital in space.

Within a subshell, the value of ml depends on the value of the angular

momentum quantum number, l.
For a certain value of l, there are (2l + 1) integral values of ml.
The number of ml values indicates the number of orbitals in a subshell
with a particular l value.
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 Schrodinger Wave(n,Equation
Quantum numbers: l, ml, ms)
Spin Quantum Number, ms
ms = +½ or -½
There are two possible spinning
motions of an electron: (a) clockwise
and (b) counterclockwise.

To take the electron spin into account, a

fourth quantum number is introduced,
called the electron spin quantum
number (ms).
The magnetic fields generated by these two
spinning motions are analogous to those
from the two magnets.
The upward and downward arrows are used
to denote the direction of spin. (a) ms = +½ (b) ms = -½

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Quantum numbers: (n, l, ml, ms)

A collection of orbitals with the same value of n is

frequently called a shell.
One or more orbitals with the same n and l values are
referred to as a subshell.
For example, the shell with n = 2 is composed of two
subshells, l = 0 and 1 (the allowed values for n = 2).
These subshells are called the 2s and 2p subshells
where 2 denotes the value of n , and s and p denote the
values of l.

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 Quantum Numbers of an Atomic Orbital

Summary of the Relationships among the Quantum Numbers and

Numbers of Orbitals and Electrons

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Electron Energy States

Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.

4d
4p N-shell n = 4

3d
4s

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1
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 Electron Configuration
• For many-electron atoms, we must know the electron configuration
of the atom, that is, how the electrons are distributed among the
various atomic orbitals, in order to understand electronic behavior.
• For this discussion, recall that the number of electrons in an atom is
equal to its atomic number Z.
• The electron in a ground-state hydrogen atom must be in the 1s
orbital, so its electron configuration is 1s1 :

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.
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Electron Configuration
• The electron configuration can also be represented by an orbital
diagram that shows the spin of the electron:
The upward arrow denotes one of the two possible
spinning motions of the electron.
Alternatively, we could have represented the electron
with a downward arrow.
The box represents an atomic orbital.

Remember that the direction of electron spin has no effect on the

energy of the electron.

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 The Pauli Exclusion Principle
For many-electron atoms we use the Pauli exclusion principle to
determine electron configurations.
This principle states that no two electrons in an atom can have the
same set of four quantum numbers.
If two electrons in an atom should have the same n, l, and ml values
(that is, these two electrons are in the same atomic orbital), then
they must have different values of ms.
Only two electrons may occupy the same atomic orbital, and these
electrons must have opposite spins.

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The Pauli Exclusion Principle

• Consider the helium atom, which has two electrons. The three
possible ways of placing two electrons in the 1s orbital are as follows:

Note that 1s2 is read “one s two,”

not “one s squared.”

• Diagrams (a) and (b) are ruled out by the Pauli exclusion principle.
• In (a), both electrons have the same upward spin and would have the
quantum numbers (1, 0, 0, +½).
• In (b), both electrons have downward spins and would have the
quantum numbers (1, 0, 0, –½).
• Only the configuration in (c) is physically acceptable, because one
electron has the quantum numbers (1, 0, 0, +½) and the other has (1,
0, 0, –½).
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 Hund’s Rule

To minimize electron-electron repulsions,

the last added (sixth) electron of
carbon enters one of the unoccupied 2p
orbitals

• None of the three arrangements violates the Pauli exclusion principle,

so we must determine which one will give the greatest stability.
• The answer is provided by Hund’s rule, which states that the most
stable arrangement of electrons in subshells is the one with the
greatest number of parallel spins.
• The arrangement shown in (c) satisfies this condition. In both (a) and
(b) the two spins cancel each other.
• Thus, the orbital diagram for carbon is

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Electron Configurations
• Valence electrons – those that occupy the outermost shell, they
participate in the bonding between atoms to form atomic and
molecular aggregates.
• 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

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 Electronic Configurations
Example: Fe (Z = 26) 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

4d
4p N-shell n = 4 valence
electrons
3d
4s

Energy 3p M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p L-shell n = 2
2s

1s K-shell n = 1

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SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.
Element Atomic # Electron configuration
Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
Lithium 3 1s 2 2s 1
Beryllium 4 1s 2 2s 2
Boron 5 1s 2 2s 2 2p 1
Carbon 6 1s 2 2s 2 2p 2
... ...
Neon 10 1s 2 2s 2 2p 6 (stable)
Sodium 11 1s 2 2s 2 2p 6 3s 1
Magnesium 12 1s 2 2s 2 2p 6 3s 2
Aluminum 13 1s 2 2s 2 2p 6 3s 2 3p 1
... ...
Argon 18 1s 2 2s 2 2p 6 3s 2 3p 6 (stable)
... ... ...
Krypton 36 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)

Stable electron configurations - the outermost or valence electron shell

are completely filled. Example: noble gases.
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 The Periodic Table
All the elements have been classified according to electron configuration.
The elements are situated, with increasing atomic number, in seven
horizontal rows called periods.
All elements arrayed in a given column or group have similar valence
electron structures, as well as chemical and physical properties.

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The Periodic Table

• Columns: Similar Valence Structure
inert gases
give up 1e-
give up 2e-

accept 2e-
accept 1e-
give up 3e-

H He
Li Be O F Ne
Adapted from
Na Mg S Cl Ar Fig. 2.6,
Callister &
K Ca Sc Se Br Kr
Rethwisch 8e.
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

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

At large distances, interactions
are negligible because the
atoms are too far apart to have
an influence on each other.

At small separation distances,

each atom exerts forces on the
others.

These forces are of two types,

attractive (FA) and repulsive
(FR), and the magnitude of each
depends on the separation or
interatomic distance (r).

The dependence of repulsive, attractive, and net

forces/energies on interatomic separation for two
isolated atoms. 30
Bonding Forces and Energies
The net force FN between the
two atoms is just the sum of
both attractive and repulsive
components:

When FA and FR are equal in

magnitude but opposite in sign,
there is no net force, and a state
of equilibrium exists. The
centers of the two atoms remain
separated by the equilibrium
spacing r0.

The dependence of repulsive, attractive, and net

forces/energies on interatomic separation for two
isolated atoms. 31

Bonding Forces and Energies

The net curve of potential

energy is the sum of the
attractive and repulsive curves.
The minimum in the net energy
curve corresponds to the
equilibrium spacing, r0.
The dependence of repulsive, attractive, and net
forces/energies on interatomic separation for two
isolated atoms. 32
 Bonding Forces and Energies
The bonding energy for these
two atoms, E0, corresponds to
the energy at this minimum
point; it represents the energy
required to separate these two
atoms to an infinite separation.
A similar yet more complex
condition exists for solid
materials because force and
energy interactions among
atoms must be considered.
The magnitude of E0 and the
shape of the curve vary from
material to material (depend on
the type of atomic bonding).
The dependence of repulsive, attractive, and net
forces/energies on interatomic separation for two
isolated atoms. 33

Ionic Bonding
Ionic bond – metal + nonmetal

donates accepts
electrons electrons

Dissimilar electronegativities
Example: MgO
Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4
[Ne] 3s2

Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6

[Ne] [Ne]
34
 Ionic Bonding
• Occurs between positive and negative ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl

Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable Coulombic stable
Attraction

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Ionic Bonding
• Energy – minimum energy most stable
– Energy balance of attractive and repulsive terms

−
A +
B
EN = EA + ER =
r rn
Repulsive energy ER

Interatomic separation r

Net energy EN

Attractive energy EA

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 Ionic Bonding
Ionic bonding is termed
nondirectional - the magnitude of
the bond is equal in all directions
around an ion.
For ionic materials to be stable, all
positive ions must have as nearest
neighbors negatively charged ions
in a three-dimensional scheme, and
vice versa.
Bonding energies is large and
generally range between 600 and
1500 kJ/mol.
Ionic solids have high melting
temperatures.
Hard, rigid, strong and brittle.
Excellent Insulators.
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Examples: Ionic Bonding

• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

38
 Covalent Bonding
• Similar electronegativity ∴ share electrons
• Stable electron configurations are assumed by the sharing
of electrons between adjacent atoms.
• 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

• Covalent bond is directional. It is between specific atoms

and may exist only in the direction between one atom and
another that participates in the electron sharing.
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Covalent Bonding - Examples

• 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

• Oxygen (Outer orbital - 2s2 2p4) atoms share two p electrons

O + O O O O=O

• Nitrogen (Outer orbital - 2s2 2p3) atoms share three p electrons

N + N N N N N
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 Metallic Bonding
• Found in metals and their alloys.
• Atoms in metals are closely packed in crystal structure.
• Loosely bounded valence electrons are attracted towards
nucleus of other atoms.
• Electrons spread out among atoms forming electron clouds.
• These free electrons are reason for electric conductivity and
ductility.
• Since outer electrons are shared by many atoms, metallic
bonds are Non-directional.

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Metallic Bonding
• Pure metals are significantly more malleable than ionic or
covalent networked materials.
• At room temperature, most metals and their alloys fail in a
ductile manner (fracture occurs after the materials have
experienced significant degrees of permanent deformation).
• Strength of a pure metal can be significantly increased
through alloying.
• Pure metals are excellent conductors of heat and electricity.

42 42
 SECONDARY BONDING
• Secondary bond or van der Waals (physical) bond is weak in
comparison to the primary (chemical) bonds, with lower bonding
energy.
• Secondary (or intermolecular) bonds are possible between atoms or
groups of atoms, which themselves are joined together by primary (or
intramolecular) ionic or covalent bonds.
• Secondary bonding forces arise from atomic or molecular dipoles.
• An electric dipole exists whenever there is some separation of positive
and negative portions of an atom or molecule.
• The bonding results from the coulombic attraction between the
positive end of one dipole and the negative region of an adjacent one.
• Dipole interactions occur between induced dipoles, between induced
dipoles and polar molecules (which have permanent dipoles), and
between polar molecules.

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Fluctuating Induced Dipole Bonds

An electrically symmetric atom.
All atoms experience constant vibrational
motion that can cause instantaneous and
short-lived distortions of this electrical
symmetry for some of the atoms or
molecules and the creation of small electric
dipoles.

An electric dipole induces an

electrically symmetric
atom/molecule to become a
dipole.

The van der Waals bond between

the dipoles.
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 Polar Molecule–Induced Dipole Bonds
A hydrogen chloride molecule
(dipole).
Permanent dipole moments exist in some
molecules by virtue of an asymmetrical
arrangement of positively and negatively
charged regions; such molecules are
termed polar molecules.

How an HCl molecule induces an

electrically symmetric
atom/molecule to become a
dipole.

The van der Waals bond

between these dipoles.
45

Permanent Dipole Bonds

The strongest secondary bonding type, the hydrogen bond, is 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), or nitrogen (as in
NH3).
For each H−F, H−O, or H−N bond, the single hydrogen electron is
shared with the other atom.
The hydrogen end of the bond is essentially a positively charged
bare proton unscreened by any electrons.
This highly positively charged end of the molecule is capable of a
strong attractive force with the negative end of an adjacent
molecule.

Hydrogen bonding in
hydrogen fluoride (HF).
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 Mixed Bonding
• Mixed bonding are found for many real materials, the atomic
bonds are mixtures of two or more bonding types.
Ionic-Covalent Mixed Bonding
• The degree of either bond type depends on the relative
positions of the constituent atoms in the periodic table or the
difference in their electronegativities.
• The greater the difference in electronegativity, the more ionic is
the bond.
• Percent ionic character (% IC) of a bond between elements A
and B (A being the most electronegative) can be approximated:

47

Mixed Bonding
Example: MgO XMg = 1.2
XO = 3.5

 −
( 3.5 −1.2 )2 
 
% ionic character = 1 − e 4
 x (100%) = 73.4% ionic

 

48
 Mixed Bonding
• Mixed bonding are found for many real materials, the atomic
bonds are mixtures of two or more bonding types.
Metallic-Covalent Mixed Bonding
• Commonly found for some elements in Groups IIIA, IVA, and VA
of the periodic table (viz., B, Si, Ge, As, Sb, Te, Po, and At).
• These materials are called the metalloids or semi-metals, and
their properties are intermediate between the metals and
nonmetals.
• For Group IV elements, there is a gradual transition from
covalent to metallic bonding as one moves vertically down this
column (bonding in carbon (diamond) is purely covalent,
whereas for tin and lead, bonding is predominantly metallic).

49

Mixed Bonding
• Mixed bonding are found for many real materials, the atomic
bonds are mixtures of two or more bonding types.
Metallic-ionic Mixed Bonding
• Usually for compounds composed of two metals when there is
a significant difference between their electronegativities.
• Some electron transfer is associated with the bond inasmuch as
it has an ionic component.
• The larger this electronegativity difference, the greater the
degree of ionicity.
• For example, there is little ionic character to the titanium–
aluminum bond for the intermetallic compound TiAl3 because
electronegativities of both Al and Ti are the same (1.5).
• A much greater degree of ionic character is present for AuCu3;
the electronegativity difference for copper and gold is 0.5.
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