Chemistry of Materials

TMS 1122
Faculty of Technology, University of Ruhuna

Mrs. D.N. Liyanage

Department of Engineering Technology

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Learning Outcomes of Lecture -1
• At the end of this lecture, you should be able to

• Identify basic structure of atom

• Describe subatomic particles & Isotopes
• Define dual nature of electrons
• Define Atomic Models (Bohr Model & Quantum model)
• Explain Pauli Exclusion Principle, Hund’s Rule and Aufbau
Principle
• Describe the properties of Periodic Table

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Why we need Chemistry ?
• Chemistry is everywhere in the world around you!
• Chemistry sometimes is called the "central science" because it connects
other sciences to each other, such as biology, physics, geology, and
environmental science.
• Example :

Iron rusts but

gold does not
?

Iron, though widely used Gold, one of the most

as a structural material, valuable of elements
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 Matter

In science, matter is the term for any type of material. Matter is anything that has mass and takes
up space. At a minimum, matter requires at least one subatomic particle, although most matter
consists of atoms.

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 An atom
An atom is the smallest building block of matter. Atoms are made of neutrons,
protons and electrons.

Subatomic Particles

Std
Particle Charge Mass (kg) Location
Notation
0
e Electron
Electron -1 9.109 x 10-31
-1
cloud

1
Proton
+1
1.673 x 10-27 P Nucleus
1

1
Neutron
0
1.675 x 10-27 n Nucleus
0
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 History of the concept of Atom

1. A plum pudding model of the atom -In 1897, J.J.

Thomson 2. Ernest Rutherford - a planetary model

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Atomic Structure and the Nucleus
• 1911 by the New Zealand physicist Ernest Rutherford.
• The protons and neutrons are grouped together in the center of the atoms. The
center of atom is called nucleus.

• Negatively charged electrons are in a cloud (10-10 m) around nucleus.

• The nucleus has an overall positive charge and electron cloud has a negative charge.
• The density of a nucleus is about 2.4 x 1014 g cm-3
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• The electrons are held in their shells by the attraction of
protons in the nucleus. This is called the nuclear attraction.

• The number of protons or electrons in the atom is called the atomic

number (Z)

• The number of protons and neutrons is called the mass number

(A)

Mass number A
Element X
Atomic number Z
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 Examples :

Number of neutrons = Mass number – Atomic number

n = (A-Z)
Q1:
Using the given data below , write the atomic symbol for each

Element Hydrogen (H) Lithium (Li ) Beryllium (Be)

Atomic number 1 3 4
# of neutrons 0 4 5

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 Isotopes
◼ Isotopes are atoms of the same element having different masses, due to varying
numbers of neutrons.
eg: 12 C 13
C 14
C
6 6 6

◼ There are three naturally occurring isotopes of uranium:

234 235 238
92
U 92
U 92
U

- Chemical properties of isotopes are identical

(because it depends on # of protons and # of electrons).
- Physical properties of isotopes are different (because it depends
on mass number)
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 Dual nature of electron
In 1924, de Brogie postulated that the dual character existed with electrons.
Sometimes the electrons are considered as particles, and at other times it is
more convenient to consider them as waves.
Atom is described as a central nucleus surrounded by electrons in certain orbits.
Thus, the electron is considered as a particle.
It was shown that moving particles, such as electron, behaved in some
ways as waves.

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 Atomic models - Bohr Model
Bohr Model of the Atom- In 1914, Niels Bohr proposed the Bohr model, which states
that electrons only orbit the nucleus at specific distances from the nucleus. According
to his model, electrons couldn't spiral into the nucleus but could make quantum leaps
between energy levels.
- He described the hydrogen atom as a nucleus with an electron circling around
it, much in the same way as planet orbits the sun. Furthermore, said Bohr, only
certain specific orbits corresponding to certain specific energy levels for the
electron are available.
- The model fails for atoms with more than one electron.

-The Bohr model was later proven to be incorrect. 12

 Heisenberg Uncertainty Principle
Calculation on the Bohr model of an atom require precise information about the
position of an electron and its velocity.

It is difficult to measure both quantities accurately at the same time.

Heisenberg states that the more precisely we can define the position of an electron,
the less certainly we are able to define its velocity, and vice versa.

Mathematically, the uncertainty principle may be expressed

as: h Planck’s
Δx.Δυ  constant
This implies that it is

Uncertainty
4π impossible to know
Uncertainty in both the position and
in defining
the position the velocity the velocity. 13
 Quantum model
The "accepted" model is the quantum model.
-It states that the electron cannot be found precisely, but we can
predict the probability, or likelihood, of an electron being at some
location in the atom.

As Heisenberg showed, we can never be completely certain about an electron’s

position. A wave function, however, tells where the electron will most probably be
found.

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• It describes with quantum numbers, a series of numbers used
to describe the location of an electron in 3D space:
• n - Principal quantum number
• l - Azimuthal quantum number or orbital angular momentum
quantum number
• ml - Magnetic quantum number
• s - Spin quantum number

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Quantum Numbers
n: Principle quantum number:
-An integer value (1, 2, 3...) that is used to describe the quantum level,
or shell, in which an electron resides.
-The principle quantum number is the primary number used to determine
the amount of energy in an atom.

n increases, the number of allowed orbitals increase and the size of those
orbitals become larger, thus allowing an electron to be farther from the
nucleus. increased distance between the electron and the nucleus.
As result the energy of the electron in the orbital increases as the quantum
number n increases.

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l: Azimuthal quantum number/ orbital angular momentum quantum number
A number that specifies a sublevel, or subshell, in an orbital and defines the three-
dimensional shape of the orbital.
The value of l is always one less than the principle quantum number n (l = 0, 1, 2,
…n-1).
e.g., if n=1, then “l"=0.
If n = 2, then “l" = 0 or 1
If n = 3, then “l" = 0, 1, or 2 l can have three values: 0,1, and 2.

Value of l Subshell designation

The values of l are used to define sub shells 0 s

1 p
2 d
3 f 17
 Magnetic quantum number (ml = −l, ... 0 ... l).
This is the projection of the orbital angular momentum along a specified axis.
Each sub shell is composed of one or more orbitals.
The magnetic quantum number has values between -l to +l.
When l=1, ml can have three values: -1, 0, and +1.
When l=1, the sub shell designation is "p", it has three
components, px, py, and pz.

Spin quantum number (ms = −½ or + ½),

the intrinsic angular momentum of the electron. This is the projection of the
spin s=½ along the specified axis.
A spin of is usually represented by an up arrow ( ) and a spin of is
represented by a down arrow ( ) 18
 Principal Azimuthal Number of
Subshell Magnetic Quantum
Quantum Quantum orbitals in
Designation Number (ml)
Number (n) Number (l) subshell
1 0 1s 0 1
0 2s 0 1
2
1 2p -1 0 +1 3
0 3s 0 1
3 1 3p -1 0 +1 3
2 3d -2 -1 0 +1 +2 5
0 4s 0 1
1 4p -1 0 +1 3
4
2 4d -2 -1 0 +1 +2 5
3 4f -3 -2 -1 0 +1 +2 +3 7

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Q. 2

• Identify the shell and subshell of an orbital with the quantum

numbers n= 3, l =1, ml = 1

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 Pauli exclusion principle
The Pauli exclusion principle is a quantum mechanical principle formulated
by Wolfgang Pauli in 1925.
It states that “no two electrons can have the same four quantum numbers”.
If n, l, and ml are the same, ms must be different such that the electrons have
opposite spins.

Hund’s Rule
Every orbital in a sub shell is singly occupied with one electron before any one
orbital is doubly occupied.

All electrons in singly occupied orbitals have the same spin.

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 Aufbau principle
-The Aufbau principle is used to determine the electron configuration of an
atom, molecule or ion.

-According to the principle, electrons fill orbitals starting at the lowest possible
energy states before filling higher states (e.g.1s before 2s).

-Orbitals are generally filled according to the n+l rule where orbitals with a lower n+l
value are filled before those with higher n+l values. E.g. 4s before 3d

-In case of equal n+l values, the orbital with a lower n value is filled first. E.g. 3d
before 4p

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Sequence of filling up orbitals with electrons

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d-block elements or transition
Group 3 to 12 elements are called d-block or transition elements. The filling of
electrons into the d-levels creates the d-block.
These elements are present between p-block and s- block elements in the
periodic table.
General electronic configuration of d-block
elements is :(n+1)s2 ndm or (n+1)s1ndm
Learning Objectives of Lecture -2
• At the end of this lecture, you should be able to

• Define what is an atomic orbital

• Identify shapes of s-, p-, d- atomic orbitals Atomic properties &
their variations:
• Describe periodic table of the elements and their properties.

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 Atomic Orbitals
◼ Orbital is the volume in space where there is a high
probability of finding the electron.
◼ Four different kinds of orbitals for electrons based on those
derived for a hydrogen atom.

Subsidiary Quantum number l, describes the shape of the orbital.

When l = 0, ➔ an s-orbital
l = 1, ➔ a p-orbital
l = 2, ➔ a d-orbital
l = 3, ➔ a f-orbital

The letters s, p, d, and f come from the spectroscopic terms: sharp,

principal, diffuse, and fundamental
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 Shapes of Atomic Orbitals
◼ Four different kinds of orbitals for electrons based
on those derived for a hydrogen atom
◼ Denoted as s, p, d, and f

◼ s and p orbitals most important in organic chemistry

◼ s orbitals: spherical, nucleus at center
◼ p orbitals: dumbbell-shaped, nucleus at middle
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 p- Orbitals

◼ In each shell there are

three perpendicular p
orbitals, px, py, and pz, of
equal energy

◼ Lobes of a p orbital are

separated by region of
zero electron density, a
node

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 d- Orbitals

t2g eg
Two sets of d-orbitals, t2g and eg
t2g- lobes of the orbital lying in between the axes
eg – lobes of the orbital lying along the axes

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• What is the total number of orbitals associated with the principal
quantum number n =3?

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 The Organization of the Elements
• Dmitri Mendeleev, a Siberian-born Russian chemist, was the first scientist to
make a periodic table much like the one we use today.
• Mendeleev organized the elements in order of increasing atomic mass and in
groups of similar chemical behavior.

Modern Periodic Table

• The modern periodic table now arranges elements in order of
increasing atomic number. Additionally, more groups
and elements have been added as they have been discovered

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Periodic Table of the Elements

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 Periodic Table
● Periodicity: ( “PERIODIC LAW”)
The periodic law states that when the elements are arranged by atomic number,
their physical and chemical properties vary periodically.

● Group: vertical column of elements (“family”)

● Period: horizontal row of elements

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Representative Elements: “Group A” elements; columns 1A-8A; they include:
-metals
-nonmetals
-metalloids

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Characteristics :metal , nonmetal metalloids
Metal
• high electrical conductivity
• high luster
• ductile & malleable
• on the left side of the periodic table (except hydrogen)
Nonmetal
• in the upper-right corner of the periodic table
• nonlustrous
• poor conductors of electricity
• some (O, Cl) are gases at room temp.
• others (S) are brittle solids

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Metalloids
• On the stair-step line that divides the metals from the nonmetals
• Exhibit properties that are intermediate between those of metals and
nonmetals
• Important metalloids: silicon, germanium

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Learning Objectives of Lecture -3
At the end of this lecture, you should be able to

• Define Atomic/ ionic radius

• Describe Ionization energy, Ionic size / radius, Electronegativity

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PERIODIC PROPERTIES:

● Atomic radius
● Ionization energy
● Ionic size / radius
● Electronegativity

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Atomic Radius
The atomic radius of a chemical element is a measure
of the size of its atoms, usually the mean or typical
distance from the center of the nucleus to the boundary
of the surrounding cloud of electrons.
200 pm

Cl Cl
◼ Estimate of atomic size
 ½(homonuclear bond length)
 Cl =100 pm (Cl2 bond = 200 pm) 100 pm
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 Atomic radius
Two factors determine the size of an atom:

➢ n - the principal quantum number.

The larger “n”, the larger the size of the orbital.

➢ Zeff - the effective nuclear charge.

The larger Zeff, the smaller the size of the orbital.

Zeff = Z actual – Electron shielding

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Zeff - the effective nuclear charge

Zeff = Z actual – Electron shielding

The idea that electrons in different orbitals are shielded differently and feel different
values of is a very useful one that we’ll return to on several occasions to explain various
chemical phenomena.
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 ATOMIC RADIUS:
● GROUP TREND: increases as you move down a group
● WHY???
-electrons are added to higher energy levels (farther away from the
nucleus).
• PERIODIC TREND: decreases as you move L to R across a
period
● WHY???
-an increase in effective nuclear charge for the valence-shell
electrons
-As the # of protons in the nucleus increases, the positive charge
increases and as a result, the “pull” on the electrons increases. 46
ATOMIC RADIUS:

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 Atomic Radius

BIG increase from noble gas

to next row element.

Transition metals – little change

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 IONS:
● ION: an atom or group or atoms that has a positive or negative charge
● An atom is electrically neutral because it has equal # of protons (+) & # of
electrons (-)
● Positive & negative ions form when electrons are transferred between atoms!.

● Atoms of METALS tend to form positive ions by losing 1 or more e- from their
valence (outermost) shell.
● An ion with a positive charge is called a CATION.
● Example: Sodium (Na Na+)

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● Atoms of NONMETALS tend to form negative ions by gaining 1 or
more e- (& thus filling their outermost energy level).
● An ion with a negative charge is called an ANION.
● example:
CHLORINE (Cl Cl-)

• Electron configurations for ions:

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 IONIC RADIUS:
● ANIONS (negative ions) have full valence shells: they are LARGER
than their neutral ATOM.
● CATIONS (positive ions) have empty valence shells: they are SMALLER
than their neutral ATOM.
● BUT, the size of one ion compared to the next is the same pattern as
ATOMIC RADIUS.
Eg:
● Na Na +
1s2 2s2 2p6 3s1 1s2 2s2 2p6

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 Ionic radii – Main Group Elements
Anions are always larger than
atoms from which they are
derived.
More en/en repulsion (more en)
so the shell swells.

In general, the size of anions

decrease going across a
period. 3 52
 Ionic radii –Main Group Elements
Cations are always smaller than the
atoms from which they are derived.
The outer shell (main block) is
completely removed and e-/e-
repulsions reduced (fewer
e- ).

In general, the size of the

cation decreases going across
a period. 4 53
Periodic Trends: Ionic Radii
The following anions and cations are isoelectronic with Ne.
(The electron configuration is the same.)

Isoelectronic Ions O2- F- Na+ Mg2+

Ionic radius (pm) 140 133 102 66
Number of protons 8 9 11 12
Number of electrons 10 10 10 10
Increasing nuclear charge
decreasing size

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 IONIZATION ENERGY:
● Definition : The amount of energy necessary to remove
the highest-energy electron from an isolated neutral
atom in the gaseous state is called the atom’s ionization
energy
The first ionization energy is the energy required to
remove an electron from the gaseous neutral atom.
Examples:

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Factors affecting on I.E.
- Principle quantum number (n)
- When n increases I.E. decreases

- Effective nuclear charge

- When ENC is high I.E. is high

- Stable electron configuration

- I.E. is high for completely filled or half filled
electron configurations

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Ionization Energy
Second Ionization energy (IE2)
Energy required to remove a 2nd e- (from A+(g)).

Mg+(g) Mg2+(g) + e- IE2 = 1450 kJ/mol

Third Ionization energy (IE3)

Energy required to remove a 3rd e- (from A2+ (g)).
Mg2+(g) Mg3+(g) + e- IE3 = 7734 kJ/mol

Mg2+ is a noble gas configuration

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 Periodic Trends: Ionization Energies

◼ IE3>IE2 > IE1

◼ Mg+ holds the 2nd e- more
tightly.
[Ne]
◼ Mg2+ holds the 3rd e- even more
tightly.
◼ Huge increase if e- removal breaks a
complete shell (the core).

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 Ionization Energy

Core Electrons

A big jump in IE occurs when you try to remove more

than the valence electrons. (i.e. from a core or noble
gas configuration) 15 60
 IONIZATION ENERGY:

● GROUP TREND: decreases as you

move down a group

● WHY???
-Electrons are in higher energy levels as
you move down a group; they are farther
away from the positive “pull” of the
nucleus and therefore easier to remove.
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 IONIZATION ENERGY:

● PERIODIC TREND: increases as you move from L

to R across a period

● WHY???
-The increasing charge in the nucleus as you move
across a period exerts greater “pull” on the electrons;
it requires more energy to remove an electron.

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Ionization Energy
Why is the ionization energy of Be higher than B?

Be 1s22s2
1s 2s

B 1s22s22p1 1s 2s 2px 2py 2pz

2s sub-shell of Be is more stable than the partially filled 2p

shell of B.
Therefore it takes more energy to remove the outer electron.
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Ionization Energy
Why is the ionization energy of nitrogen higher than the
ionization energy of oxygen?

N 1s22s22p3
1s 2s 2px 2py 2pz

O 1s22s22p4
1s 2s 2px 2py 2pz

N is more stable (half-filled p-shell), therefore the

outer electron is lower energy or…it takes more
energy to remove (n=∞) the outer electron.
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 Electron Affinity

The electron affinity is the energy change for the process of adding
an electron to a neutral atom in the gaseous state to form a
negative ion.
Cl(g) +e − →Cl (g)

Electron Affinity = -349 kJ/mol

The electron affinities depend on the size and effective

nuclear charge.
They cannot be determined directly, but are obtained indirectly
from the Born-Harber cycle.
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 Periodic Trends: Electron Affinities

F(g) + e- F-(g) ΔE = -328 kJ/mol

◼ Usually exothermic (E.A. is negative)

◼ Metals have low E.A.; nonmetals have high E.A.
◼ Some tables list positive numbers.
(a sign-convention choice)

Q1. )Why does nitrogen have a less favorable (more positive) than
its neighbors on either side, C and O?
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 ELECTRONEGATIVITY:

● Definition: The tendency of an atom to attract electrons of another atom.

● GROUP TREND: decreases as you move down a group

-higher energy levels means the electrons are farther away from the nucleus;
-greater distance = decreased attraction

• PERIODIC TREND: increases as you move across a period (noble gases

excluded!)

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 Electronegativity
• Electronegativity, χ, is a chemical property that measures the tendency of an
atom to attract a bonding pair of electrons. Electronegativity is almost the exact
reverse of ionization energy.
It is not an atomic property, but rather a property of an atom in a molecule:

• The Pauling scale is the most commonly used. F (the most electronegative
element) is assigned a value of 4.0, and values range down to Cs and Fr which
are the least electronegative at 0.7.

• The rare gases (He, Ne, Ar, Kr, Xe, Rn) have zero Electronegativities, i.e.,
they only form covalent bonds, and have no tendency to attract electrons of
that bond.
 Factors affecting Electronegativity
EN depends on number of factors:
- Size of the atoms:
When size decreases tendency to attract shared electron pair
increases. e.g. F
- Nearly filled shells:
Atoms with nearly filled shells of electrons have higher ENs, e.g.
F(ns2,np5)
- The oxidation number of the atom:
Large oxidation numbers will have large EN e.g. Fe(1.80) <
Fe2+(1.83) < Fe3+(1.96)
- Effective nuclear charge of the element when Zeff increases
EN also increases
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Electronegativity generally decreases going down a group and generally
increases going from left to right in a row.

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