4.

2 : VARIATION OF
PHYSICAL AND
CHEMICAL PROPERTIES
 Periodic Trends
• In this chapter, we will rationalize observed
trends in
– Sizes of atoms and ions.
– Ionization energy.
– Electron affinity.
– Electronegativity.
 Periodic Trends
1) Sizes of atoms and ions
- Across the period, sizes of atoms and ions decrease.
- Down the group, sizes of atoms and ions increase.
2) Ionization energy
- Across the period, IE increase.
- Down the group, IE decrease.
3) Electronegativity
- Across the period, electronegativity increase.
- Down the group, electronegativity decrease.
4) Electron affinity
- Across the period, EA increase.
- Down the group, EA decrease.
Effective Nuclear Charge
• In a many-electron
atom, electrons are
both attracted to the
nucleus and repelled
by other electrons.
• The nuclear charge
that an electron
experiences depends
on both factors.
Effective Nuclear Charge
The effective nuclear
charge, Zeff, is found
this way:
Zeff = Z − S
where Z is the atomic
number and S is a
screening constant,
usually close to the
number of inner
electrons.
Sizes of Atoms
The bonding atomic
radius (size of atom)
tends to
- Decrease from left to
right across a row (due
to increasing Zeff).
- Increase from top to
bottom of a column
(due to the increasing
value of n).
Sizes of Ions
• Ionic size depends
upon
– The nuclear
charge
– The number of
electrons
– The orbitals in
which electrons
reside
Sizes of Ions
• Cations are
smaller than their
parent atoms:
– The outermost
electron is
removed and
repulsions
between
electrons are
reduced.
Sizes of Ions
• Anions are larger
than their parent
atoms
– Electrons are
added and
repulsions
between
electrons are
increased.
 Sizes of Ions
• Ions increase in size
as you go down a
column:
– This increase in
size is due to the
increasing value
of n and
screening effect)
 Sizes of Ions

• In an isoelectronic series, ions have the

same number of electrons.
• Ionic size decreases with an increasing
nuclear charge.
Exercise
1)Arrange the following atoms and ions in
order of increasing atomic and ionic radii.
(a) B, N, O
(b) F-, Be2+, Li+
(c) Al3+, O2-, F-
(d) O, Al, Mg, Br
 Ionization Energy
• The ionization energy is the amount of
energy required to remove 1 mole of
electron from the ground state of a
gaseous atom or ion.
– The first ionization energy is that energy
required to remove the first electron.
– The second ionization energy is that
energy required to remove the second
electron, etc.
 Ionization Energy
• It requires more energy to remove each
successive electron.
Trends in First Ionization Energies
• As one goes down a
column, less energy is
required to remove the
first electron.
– For atoms in the
same group, Zeff is
essentially the same,
but the valence
electrons are farther
from the nucleus.
 Trends in First Ionization Energies
• Generally, as one
goes across a row, it
gets harder to
remove an electron.
– As you go from
left to right, Zeff
increases.
Variation of first IE (kJ/mol) across period 2 :

1 2 13 14 15 16 17 18
Group

Elemen Li Be B C N O F Ne
ts
IE 520 900 801 1086 1402 1314 1681 2081

• In general the IE increase across the Period 2, however

there is exception. There are slight decrease in IE between
a) Be and B b) N and O

17
18
 Anomalous IE in Period 2
• Electronic configuration for Be and B :

2 2
2 2 1

•2p electron is at higher energy than the 2s

electrons.
• The 2p electron in Boron is more easily
removed compared to 2s orbital in beryllium.
•As a result, IE is smaller for B than Be.

•
• The irregularity between Group 15 and 16 can be explained by
the repulsion between electrons.

• O contains 4 electrons in the 2p orbital while N contains 3

electrons in the 2p orbital.
• The electron-electron repulsion in O is stronger than N makes it
easier to remove 1 of the paired electrons in the same 2p orbital
than the unpaired electron from a half-filled 2p orbital of
nitrogen.
• As a result, IE is smaller for O than N.
Exercise
1)The proton numbers of the elements P, Q
and R and the ions formed from these
elements are shown below:
ELEMENT P Q R

PROTON 9 11 15
NUMBER

Arrange P, Q and R in order of

increasing ionization energies. Explain.
 Successive Ionization Energies

• The successive ionization energies increase

because the ions produced become
increasingly more positive as each
electron is removed.
• Eg:
Ca (g) Ca+ + e- ∆IE1= + 590kJmol-1
Ca+ (g) Ca 2+ + e- ∆IE2= + 1150kJmol-1
A large increase in successive
ionization energies occurs
between the removal of the
last valence electron and the
removal of the first core
(inner) electron.
 Therefore, we can determine the
electronic configuration of the valence
electron for an element M using
following methods:
 Method 1:-

By determining the IE ratios

 Method 2:-
By determining the differences in
ionization energy:
 Be: 1s2 2s2
IE 1 2 3 4
(kJmol-1) 899 1757 14845 21000
Method 1:-
By determining the IE ratios:
IE2 = 1757 = 1.95
IE1 899
IE3 = 14845 = 8.45
IE2 1757
IE4 = 21000 = 1.41
IE3 14845
 The first and second electron are removed
from the same energy subshell (2s).

 The third electron is removed from an inner

subshell that is 1s, hence it requires a
higher IE3 (8.45 times) than IE2.
 Since IE3 / IE2 have the highest
ratio, 2 valence electrons are
present.

 Electron configuration: ns2

 This element is Be: Group 2

By determining the differences in ionization
energy:

IE2-IE1= 858 kJ mol-1

IE3-IE2= 13088 kJ mol-1
IE4-IE3= 6155 kJ mol-1
 The first and second electron are
removed from the same energy subshell
(2s).

 The third electron is removed from an

inner subshell that is 1s, hence it
requires a higher IE3 than IE2 (a
difference of 13088 kJmol-1).
 Since IE3 - IE2 have the highest
difference, 2 valence electrons are
present.

 Electron configuration: ns2

 This element is Be: Group 2

Five successive ionization energies (kJmol-1) for
atom M is shown below:
IE1 IE2 IE3 IE4 IE5
800 1580 3230 4360 16000

Determine
i) electron configuration of the valence electron
for M
ii) group number of M in the periodic table
 By determining the IE ratios:

IE2 = 1580 = 1.98

IE1 800

IE3 = 3230 = 2.04

IE2 1580

IE4 = 4360 = 1.35

IE3 3230

IE5 = 16000 = 3.67 ( the highest ratio)

IE4 4360
 Since the ratio IE5/IE4 is the highest, this
shows that there are 4 valence electrons in
the valence shell.
 The fifth electron is removed from an inner
shell with octet configuaration.
 Electron configuration of valence electron
for M is ns2np2
 M is in Group 14 at the periodic table
 Exercise:
The first five ionisation energies (kJ/mol) for three
elements are given below:

Element First Second Third Fourth Five

A 786 1580 3230 4360 16000
B 418 3070 4600 5860 7990
C 590 1150 4940 6480 8120

Determine the groups in the periodic table to which they are

belong
2) A period 3 element has the following
successive ionisation energies (in kJ/mol).

IE1 IE2 IE3 IE4 IE5 IE6 IE7

1012 1900 2920 4960 6280 21 200 25 900
(a) Locate the group in which the element is
placed in the periodic table
(b) Name the element
(c) Write the electronic configuration of the
elecrtrons in the outermost sgell
 ELECTRONEGATIVITY
• Electronegativity is the relative tendency of
an atom to attract electrons to itself when
chemically combined with another atom.
 ELECTRONEGATIVITY
• Atoms with strong attraction for the bonding
electrons have high electronegativity.

• The most widely used scale – developed by

Linus Pauling. He assigned the most
electronegative element, flourine a value 4.0
and work out the the others relative to
flourine.
 ELECTRONEGATIVITY
(a) Across Period 2 and 3
• Going across a period from left to right, the
atomic size decreases, while the Zeff
increases. Hence, the attraction for
electrons increases and the
electronegativity increases.
 ELECTRONEGATIVITY

(b) Down a group

• Going down a group, the atomic size
increase because the shielding effect
(principal quantum number) increases.
Hence, the attraction for electrons
decrease and the electronegativity
decreases.
 Chart 1:
electronegativities of
elements

Linus Pauling
 Electron Affinity
Electron affinity is the energy change
when 1 mol of gaseous atom receive
electron to form anion under standard
condition:

Cl (g) + e−  Cl− (g)

 Trends in Electron Affinity
o Across the period, the ability to accept
electron increase, so the electron affinity
also increases.
o For most atoms, energy is released when an
electron is added.
o The greater the attraction between an atom
and an added electron, the more –ve the
electron affinity.
Trends in Electron Affinity
There are
again,
however, 2
discontinuities
(interruption) in
this trend.
Trends in Electron Affinity
• 1st discontinuty:
occurs between
Groups 2 and 13.
– The added electron
must go in a p orbital,
not an s orbital.
– The electron is farther
from the nucleus and
feels repulsion from
the s electrons.
 Trends in Electron Affinity
2nd discontinuity: occurs between
Groups I5 and 16.
• Group 15 has no
empty orbitals.
• The extra
electron must go
into an already
occupied orbital,
creating
repulsion.
 MELTING AND BOILING
POINTS : GROUP 1

• All elements in group 1 are reactive

metals
• Melting and boiling points of group 1:

47
MELTING AND BOILING POINTS
: GROUP 1
• Going down the group, the melting
and boiling points of the elements
decrease.

-As we go down the group, the size

of atoms increases; which caused
the electron to be less attracted to
the nucleus. Therefore the metallic
bond is weaker as we go down the
group. 48
MELTING AND BOILING POINTS :
GROUP 17

• All the halogens exist as diatom, X2.

• They have valence electrons with the

configuration of ns2np5.

• This allows them to form covalent bond

between atoms in order to achieve noble
gas configuration.
49
 MELTING AND BOILING POINTS :
GROUP 17

• Their physical properties change gradually

as we go down the group.
• Descending a group, the melting and boiling
points increase. 50
 MELTING AND BOILING
POINTS : GROUP 17
• This is related to the increasing strength of van
der Waals forces with increasing size or relative
molecular mass.

• Thus, F2 and Cl2 are gases, Br2 is a liquid and I2

is a solid

51
i) The melting / boiling point
• The melting / boiling point of a substance depends
greatly on the types of intermolecular forces or
bondings involved.
Element Na Mg Al Si P S Cl Ar

MP,ºC 97.8 651 660 1410 44 119 -101 -189

BP,ºC 892 1107 2467 2680 280 445 -34.5 -186

52
 Variation of melting and boiling point of elements in
period 3 can be discussed in 3 parts:

a) Metallic structure (Na to Al)

Metallic crystals have positive metal ions
attracted by electrons in a cloud - metallic
bonding.
Strength of metallic bonding is proportional to
the number of valence electrons.
• Na-1 valence electron The more valence electrons,
• Mg- 2 valence electrons the stronger the metallic
bonding and the higher
• Al- 3 valence electrons
melting / boiling point
53
b) Gigantic covalent structure (Si)

• Silicon is made up of atoms that are

tetrahedrally covalently bonded to other S
atoms at neighboring lattice sites.

• The result is a crystal that is essentially

one gigantic covalent structure.

54
• Melting and boiling point of Si is very high
because of the strong attractions
between covalently bonded atoms.

• High energy is needed to break the

strong covalent bonding in melting or
boiling.

55
c) Simple molecular structure ( P to Ar)

• These are mainly the nonmetal that exist

as molecules of P4, S8, Cl2 and Ar
(monoatom).

• The covalent bond between the atoms is

very strong but the intermolecular force,
that is, Van der Waals, is very weak.

56
• Van der Waals force is proportional to
molecular size (relative molecular
mass).

• Molecular size: Ar < Cl2 < P4 < S8

therefore melting / boiling point increase
from Ar < Cl2 < P4 < S8

57
 Reactivity of Elements Period 3 towards
Oxygen
• All the Period 3 elements (except Cl and Ar) burn in
oxygen when heated to form their respective oxides.

Element Na Mg Al Si P S Cl
Oxide Na2O MgO Al2O3 SiO2 P4O6 SO2 Cl2O
P4O10 SO3 Cl2O7
Oxidation +1 +2 +3 +4 +3 +4 +1
state +5 +6 +7
Physical Solid Solid Solid Solid Liquid Gas Gas
state Solid Gas Liquid
Reactivity of Elements Period 3 towards
Water
ELEME REACTION WITH WATER
NT
Na Vigorous at room temperature to form NaOH
Mg Reacts with steam to form Mg(OH)2
Al Vigorous at room temperature if the surface
oxide layer is removed to form Al(OH)3
Si Very slow with steam even at elevated
temperature
P No reaction
S No reaction
Cl Slight reaction to form acidic solution
 Reactivity of Elements towards Oxygen
and Water
Group Assignment
 Explain reaction of elements in Period 3
with oxygen.
 Explain reaction of elements in Period 3
with water.
 Acid-base character of oxides of
Period 3
Na2O MgO Al2O3 SiO2 P4O10 SO2 Cl2O7

Acid – Basic Basic Amph Acidic Acidic Acidic Acidic

base oteric
nature

61
• Na reacts with oxygen to form basic oxide. The
oxide will produce base when react with water.

4Na (s) + O2 (g) 2Na2O (s)

Na2O (s) + H2O (l) 2NaOH (aq)

• Mg burns in oxygen to form basic oxide, MgO.

2Mg (s) + O2 (g) 2MgO (s)
MgO (s) + 2HCl (aq) MgCl2 (aq) + H2O (l)

62
• Al forms amphoteric oxide, oxide that can react with
either an acid or a base.
Al2O3 (s) + 6HCl (aq) 2AlCl3 (aq) + 3 H2O (l)
base acid

Al2O3(s) + 2NaOH(aq) + 3H2O(l) 2NaAl(OH)4(aq)

acid base sodium aluminate

63
Sulphur burns in oxygen to form acidic oxide.
S (s) + O2 (g) SO2 (g)

SO2 (g) + H2O (l) H2SO4 (aq)

SO2 (g) + 2NaOH (aq) Na2SO3(aq) + H2O(l)

acid base

Dichlorine heptaoxide
Cl2O7 (g) + H2O (l) 2HClO4 (aq)
hypochloric acid

64
 Acid-base behavior of oxides of Period 3
P4O10 (or SO3(or
Na2O MgO Al2O3 SiO2 Cl2O7
P4O6) SO2)
P4O10 + SO3 + Cl2O7 +
Na2O + MgO +
Add H2 O  6H2O H2 O H2 O
H2 O H2 O  Insoluble Insoluble
Mg(OH)2   
2NaOH 4H3PO4 H2SO4 HClO4

P4O6 + SO2 +
Add
- - - - 6H2O  H2O  -
H2 O
4H3PO3 H2SO3

Na2O + MgO + Al2O3 +

Add 2H+  2H+  6H+  No No No No
HCl 2Na+ + Mg2+ + 2Al3+ + reaction reaction reaction reaction
H2 O H2 O 3H2O
65
 Acid-base behavior of oxides of Period 3

P4O10 (or SO3(or

Na2O MgO Al2O3 SiO2 Cl2O7
P4O6) SO2)
Al2O3 + P4O10 + SO3 + Cl2O7 +
SiO2 +
2OH +
-
12OH- 2OH-  OH-
Adding No No 2OH- 
3H2O   SO42- + 
NaOH reaction reaction SiO32- +
2Al(OH) 4PO43- + H2 O 2ClO4- +
H2 O
4
6H2O H2 O
P4O6 + SO2 +
12OH- 2OH- 
Adding  SO32- +
- - - - 4PO33- + -
NaOH H2 O
6H2O

Basic Basic Amphote Acidic Acidic Acidic Acidic

66
Nature
Oxide Oxide ric Oxide Oxide Oxide Oxide Oxide
 Exercise
(a)In terms of structure and bonding, explain
the variation in the boiling points of the
Period 3 elements shown below:
ELEMENTS BOILING POINTS (°C)
Na 800
Mg 1120
Si 2600
Cl -34
Ar -186
 Exercise
Element Na Al P S Cl
Formula of Al2O3 SO3
oxide

(b) The table shows some of the oxides of

Period 3 elements.
(i) Write the formula of the oxides of Na,
P and Cl.
(ii) Write the chemical equation for the reaction
between SO3 and water.
(iii) Predict the properties of oxides for the
elements above.