LECTURE 1

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The periodic table
ü The work of 19th century chemists such as Newland,
Lother and most especially Mendelev, led to what is
today known as the Periodic Table.

ü The periodic table is a tabular arrangement of elements

in the order of increasing atomic number (number of
protons)

ü The occurrence of similar properties at regular intervals,

with increasing atomic number is known as Periodicity.

ü The periodic law states that the properties of elements

are a periodic function of their atomic numbers. 2
 Period
s-block d-block p-block
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Group

f-block

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Periodic trends of physical properties
ü Major periodic trends include:

v Atomic radius
v Ionic radius
v Ionization energy
v Electron affinity
v Electronegativity
v Metallic character
v Melting point and Boiling point.
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 Atomic Radii

Radius

Atomic Radius = half the distance between 2

nuclei of a homo-nuclear diatomic molecule.
 Group trends
• As we go down a group... H 1s
Li 2s
• Each succeeding atom is
Na 3s
in a higher energy level
K 4s
• so the atoms get bigger.

• Atomic radius increases Rb 5s

down the group
 Periodic Trends
Across a period,
• Valence electrons are in same energy level.
• nuclear charge increases
• Therefore outermost electrons are closer.
• THE RADIUS GETS SMALLER

Na Mg Al Si P S Cl Ar
• The radius decreases across a period owing to increase in
the positive charge from the protons.

• Each added electron feels a greater and positive charge

because the protons are pulling in the same direction.

.
 Trends in Atomic Radii
ØThis is Influenced by three factors:

1. Energy Level of the valence electron

üThe higher the energy level the further the
distance from the nucleus.
üDistance from nucleus is in order of energy
level
1<2<3<4<5<6<7
2. Nuclear charge - this is related to the number of protons in the
nucleus

üThe higher the charge the closer the electrons to the nucleus.

Nuclear charge = atomic number

üThe higher the atomic number, the smaller the size

3. Shielding or screening effect by inner electrons -this is the

screening of outermost electrons from the nucleus by the
inner electrons (electron repulsion)

üThe greater the shielding or screening effect, the larger the

size
 IONIC RADIUS
ØIons are not the same size as the atoms they come
from.
ØThere are two types of ions; positive and negative ions
Positive ions
ØPositive ions are smaller than the atoms they come from.
Sodium (Na) is 2,8,1; Na+ is 2,8.

ØA whole layer of electrons is lost, and the remaining 10

electrons are being pulled in by the full force of 11 protons.
 Negative ions

ØNegative ions are bigger than the atoms they

come from.

Ø Addition of an electron increases int er-

electronic repulsion causing the atom to
expand.
Ø For chlorine ion, there are still 17 protons, but
they are now having to hold 18 electrons.
 Ionization Energy

Ionization energy (IE) is defined as the energy

(in kJ/mole) required to remove the most
loosely bound electron from an isolated
gaseous atom to form a positive gaseous ion
 First Ionization Energy
First Ionization energy is the minimum energy
(kJ/mol) required to remove an electron from a
gaseous atom in its ground state to form a
gaseous ion.
X(g) X+(g) + e- I1 first ionization energy
X+(g) X2+(g)+ e- I2 second ionization energy

X2+(g) X3+(g) + e- I3 third ionization energy

I1 < I2 < I3
Factors Affecting Ionization Energy

The larger the nuclear charge, the greater the ionization energy.

The greater the shielding effect, the less the ionization energy.

The greater the distance between the nucleus and the outer
electrons of an atom, the less the ionization energy.
Ionization energy and atomic radius are inversely proportional

An electron from a full or half-full sublevel requires additional

energy to be removed.
Group trends in Ionization Energy (IE)
ØGroup trends is based on first, second, third, fourth etc IE

ØDown a group, first IE decreases because

üAtomic radius of the atoms increases

üShielding effect increases.

 First Ionization Energies
(in kilojoules per mole)

H He
1312.1 2372.5

Li Be B C N O F Ne
520.3 899.5 800.7 1086.5 1402.4 1314.0 1681.1 2080.8

Na Mg Al Si P S Cl Ar
495.9 737.8 577.6 786.5 1011.8 999.7 1251.2 1520.6

K Ca Ga Ge As Se Br Kr
418.9 589.9 578.6 761.2 946.5 940.7 1142.7 1350.8

Rb Sr In Sn Sb Te I Xe
402.9 549.2 558.2 708.4 833.8 869.0 1008.7 1170.3
 Periodic Trends in IE
• Atoms in the same period have valence electrons in the

same energy level.

• Same shielding.

• nuclear charge increases across the period

• So IE generally increases from left to right.

• Exceptions at full and 1/2 full orbitals.

Full and half full orbitals in IE
ØFull and half full orbitals are stable.

Øfilled ns and np orbitals i.e. ns2 and np6

Øhalf filled np3 orbitals

üThey have higher ionization energy than is expected

due to reluctance of orbital to lose its stability

Electron Affinity
• Electron affinity is defined as the change in energy (in
kJ/mole) when an electron is added to a neutral atom (in
the gaseous phase) to form a negative gaseous ion

X(g) + e− → X− + energy first electron affinity

X−(g) + e → X2−(g) + energy second electron affinity

üA more negative electron affinity corresponds to a
greater attraction for an electron
üElectron affinity becomes less negative down the group
Reason: increase in atomic size/decrease in effective
nuclear charge
üElectron affinity becomes more negative across the
period
üReason: decrease in atomic size/increase in effective
nuclear charge.

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• Electron affinity is exothermic, that is energy is given off when
an electron is added to the atom

• Lithium (Li): 60 KJ mol-1 Fluorine (F) -328 kJ mol-1

• Sodium (Na): 53 KJ mol-1 Chlorine (Cl) -349 kJ mol-1
• Potassium (K): 48 KJ mol-1 Bromine (Br) -324 kJ mol-1
• Rubidium (Rb): 47 KJ mol-1 Iodine (I) -295 kJ mol-1
• Cesium (Cs): 46 KJ mol-1

• ELECTRON AFFINITY DECREASES DOWN THE GROUP

AND INCREASES FROM LEFT TO RIGHT ACROSS THE
PERIOD. .22 22
 Electronegativity
Electronegativity is the ability of an atom to attract
toward itself the electrons in a covalent bond

A . B

Metals: Low tendency to attract electrons, high

tendency to release electrons.

Non-metals: High tendency to attract electrons, low

tendency to release electrons.
 Group Trends in Electronegativity
• Down a group in the periodic table, the size of the atom
increases therefore valence electrons are further away from
the nucleus and better shielded from the nuclear charge .

• This results in less attraction of nucleus for the valence

electrons.

• For that reason the electronegativity decreases as you go

down the group

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 Periodic Trends in Electronegativity
• The atoms have same energy levels but size decreases

across the period.

• Attraction of nucleus for valence electrons increases.

• Hence, Electronegativity increases from left to right across

a period

• F is highest or most electronegative element

ü Metallic character of an element gives the extent or
level of reactivity of a metal.
Metallic character decreases across the period
Reason: outermost electrons are not shielded from
the effective nuclear charge.

Metallic character increases down the group.

Reason: outermost electrons are shielded from the
effective nuclear charge due to the addition of new
shells. 26
 The melting and boiling points
üThe m.pt and b.pt of an element is the temperature at
which the solid–liquid phase and liquid–gaseous phase
changes occur.
üIt tells us something about how strongly their atoms are
stuck together.
üMelting and boiling points vary and do not generally form a
distinguishable trend across the periodic table. However,
certain conclusions can be drawn.
v Metals (especially transition metals) generally
possess a high melting and boiling point.
v Most non-metals possess low melting and
boiling points.
v The non-metal carbon possesses the highest
melting and boiling point of all the elements. 27