PERIODICITY

The Periodic Table

• from left to right, in order of increasing proton
number (atomic number)
• horizontal rows or periods

1 1H 2He

2 3Li 4Be 5B 6C 7N 8O 9F 10
Ne

3 11Na 12Mg 13Al 14Si 15P 16S 17Cl 18Ar

4
5
6
7
 The Periodic Table
• vertical groups
• blocks:
s-block,
block p-block,
block d-block and f-block
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
1 1H 2He

2 3Li 4Be 5B 6C 7N 8O 9F 10
Ne

3 11Na 12Mg 13Al 14Si 15P 16S 17Cl 18Ar

4
5
6
7
 The Periodic Table
• arrangement is such that elements show
periodicity in physical and chemical properties
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

1 1H 2He

2 3Li 4Be 5B 6C 7N 8O 9F 10
Ne

3 11Na 12Mg 13Al 14Si 15P 16S 17Cl 18Ar

4
5
6
7
 periodicity
the repeating pattern of
physical and chemical
properties
 Atomic Radii
• Atomic radii describes the relative sizes of
atoms.
• Atomic radii increase within a column going
from the top to the bottom of the periodic
table.
• Atomic radii decrease within a row going
from left to right on the periodic table.
– This last fact seems contrary to intuition.
– How does nature make the elements smaller
even though the electron number is increasing?
Periodic Trends in Atomic Radius

Li F

Na Mg Al Si Cl Ar
P S

K Br

Rb I

Cs
Atomic Radii
 Atomic Radii
• The reason the atomic radii decrease across a
period is due to shielding or screening effect.
– Effective nuclear charge, Zeff, experienced by an electron
is less than the actual nuclear charge, Z.
– The inner electrons block the nuclear charge’s effect on
the outer electrons.
• Moving across a period, each element has an
increased nuclear charge and the electrons are
going into the same shell (2s and 2p or 3s and 3p,
etc.).
– Consequently, the outer electrons feel a stronger effective
nuclear charge.
– For Li, Zeff ~ +1 For Be, Zeff ~ +2
 Atomic Radius Trend across Period 3

Na Mg Al Si P S Cl Ar
Atomic
radius/nm 0.190 0.145 0.118 0.111 0.098 0.088 0.079 0.071
Nuclear
charge +11 +12 +13 +14 +15 +16 +17 +18

decreases from left to right

Factors determining size
• Nuclear charge
– the greater the nuclear charge, the
smaller the size
• Shielding effect by inner electrons
– the greater the shielding effect, the
greater the size

• Number of shells
+11
– the greater the +17

number of shells,
the greater the
size
Reasons for trend across the Period
• Nuclear charge increases across the Period

• Shielding effect is relatively constant

• Number of shells remains constant

Hence, overall atomic radius decreases across

the Period.
Atomic Radius Trend down Group 1

Element Atomic Radius/nm Nuclear Charge Electronic

Structure
Li 0.123 +3 2.1
Na 0.157 +11 2.8.1
K 0.203 +19 2.8.8.1
Rb 0.216 +37 2.8.18.8.1
Cs 0.235 +55 2.8.18.18.8.1
 Atomic Radius vs Proton Number (Group 1)
0.25

0.2

Atomic 0.15
Radius/nm
0.1

0.05
3 11 19 37 55
Proton Number

Reasons for trend down a Group

• The number of shells increases
• The increase in nuclear charge is nullified by the
shielding effect of inner electrons
 Atomic Radii
• Example 6-1: Arrange these elements
based on their atomic radii.
– Se, S, O, Te
You do it!
O < S < Se < Te
 Atomic Radii
• Example 6-2: Arrange these elements
based on their atomic radii.
– P, Cl, S, Si
You do it!
Cl < S < P < Si
 Atomic Radii
• Example 6-3: Arrange these elements
based on their atomic radii.
– Ga, F, S, As
You do it!
F < S < As < Ga
 Ionic Radii
• Anions (negative ions) are always larger
than their neutral atoms.
Element N O F

Atomic 0.75 0.73 0.72

Radius(Å
)
Ion N3- O2- F1-

Ionic 1.71 1.26 1.19

Radius(Å
 Ionic Radii
• Cations (positive ions) are always smaller
than their respective neutral atoms.
Element Na Mg Al
Element Li Be
Atomic 1.86 1.60 1.43
Radius
Atomic 1.52 1.12
(Å)
Radius (Å)
Ion Na + Mg 2+ Al 3+
Ion Li + Be 2+

Ionic 1.16 0.85 0.68

Ionic
Radius 0.90 0.59
Radius
(Å) (Å)
 Ionic Radii
Li+ F-

Na+ Mg2+ Al3+

P3- S2- Cl-

K+ Br-

Rb+ I-

Cs+

A neutral atom is larger than its cation.

A neutral atom is smaller than its anion.

 Ionic Radii
• Cation (positive ions) radii decrease from left
to right across a period.
– Increasing nuclear charge attracts the electrons
and decreases the radius.
Ion Rb+ Sr2+ In3+

Ionic 1.66 1.32 0.94

Radii(Å)
 Ionic Radii
• Anion (negative ions) radii decrease from left
to right across a period.
– Increasing electron numbers in highly charged
ions cause the electrons to repel and increase the
ionic radius.

Ion N3- O2- F1-

Ionic 1.71 1.26 1.19

Radii(Å)
 Ionic Radii
• Cation (positive ions) radii decrease from left
to right across a period.
– Increasing nuclear charge attracts the electrons
and decreases the radius.
Ion Rb+ Sr2+ In3+

Ionic 1.66 1.32 0.94

Radii(Å)
 Ionic Radii
• Anion (negative ions) radii decrease from left
to right across a period.
– Increasing electron numbers in highly charged
ions cause the electrons to repel and increase the
ionic radius.

Ion N3- O2- F1-

Ionic 1.71 1.26 1.19

Radii(Å)
A neutral atom is larger than its cation.

Na Na+

Electronic
Structure 2.8.1 2.8

Nuclear +11 +11

Charge

• Nuclear charge attracting 1 less electron

• Loss of 1 shell
A neutral atom is smaller than its anion.

Cl Cl−

Electronic
Structure
2.8.7 2.8.8

Nuclear
Charge
+17 +17

Nuclear charge attracting 1 more electron

 Ionic Radius vs Proton Number for Periods 2 and 3
Ionic radius/nm
0.25

0.2

0.15

0.1

0.05

0
3 4 5 6 7 8 9 11 12 13 14 15 16 17
Proton Number
 Period 3 (Na+ Cl−)

Ion Na+ Mg2+ Al3+ Si4+ P3−− S2−− Cl−

Electronic
Structure
2.8 2.8 2.8 2.8 2.8.8 2.8.8 2.8.8
Nuclear
+11 +12 +13 +14 +15 +16 +17
Charge

Ionic radius decreases from Na+ to Si4+ because

Na+, Mg2+, Al3+, Si4+ are isoelectronic but the

nuclear charge increases from +11 to +14.
Hence, the electrons are pulled closer to the
nucleus.
 Ion Na+ Mg2+ Al3+ Si4+ P3−− S2−− Cl−
Electronic
Structure 2.8 2.8 2.8 2.8 2.8.8 2.8.8 2.8.8
Nuclear
Charge
+11 +12 +13 +14 +15 +16 +17

Ionic radius decreases from P3− to Cl− because

P3−, S2−, Cl− are isoelectronic but the nuclear

charge increases from +15 to +17

sharp rise in ionic radius from Si4+ to P3−

 Electronegativity

Electronegativity is a
measure of how strongly an
atom of an element attracts
valence electrons in a
chemical bond.
Electronegativity
 Periodic Trends in Electronegativity

Li F
0.98 3.98
Na Mg Si Cl Ar
Al P S
0.93 1.31 1.61 1.90 2.19 2.58 3.16

K Br

0.83 2.96

Rb I

2.66
0.82

Cs

0.79

Going down a Group, Electronegativity decreases because atomic radius increases.

Across a Period, Electronegativity increases because atomic radius decreases.

 Electronegativity

• Example 6-11: Arrange these elements

based on their electronegativity.
– Se, Ge, Br, As
You do it!
Ge < As < Se < Br
 Electronegativity

• Example 6-12: Arrange these elements

based on their electronegativity.
– Be, Mg, Ca, Ba
You do it!
Ba < Ca < Mg < Be
 Ionisation Energy

The energy required to remove one mole of

electrons from one mole of atoms of the
element in the gaseous state to form one
mole of positively charged gaseous ions.

e.g. H(g) → H+(g) + e- ∆H = +1310 kJ mol-1

Na(g) → Na+(g) + e- ∆H = +494 kJ mol-1
First Ionization Energies
of Some Elements
Factors affecting ionisation energies
• Nuclear charge
– the greater the nuclear charge, the
greater the I.E.

• Atomic/ ionic size

– the greater the atomic/ ionic size, the
lower the I.E.
• Shielding effect by inner electrons
– the greater the
shielding effect, the +3 +9
lower the I.E.
 Ionization Energy
• First, second, third, etc. ionization
energies exhibit periodicity as well.
• Look at the following table of ionization
energies versus third row elements.
– Notice that the energy increases enormously
when an electron is removed from a
completed electron shell.
 Ionization Energy
Group IA IIA IIIA IVA
and Na Mg Al Si
element
IE1 496 738 578 786
(kJ/mol)
IE2 4562 1451 1817 1577
(kJ/mol)
IE3 6912 7733 2745 3232
(kJ/mol)
IE4 9540 10,550 11,580 4356
(kJ/mol)
 Ionization Energy
• The reason Na forms Na+ and not Na2+ is
that the energy difference between IE1 and
IE2 is so large.
– Requires more than 9 times more energy to
remove the second electron than the first one.
• The same trend is persistent throughout
the series.
– Thus Mg forms Mg2+ and not Mg3+.
– Al forms Al3+.
 Ionization Energy

• Example 6-7: What charge ion would be

expected for an element that has these
ionization energies?
IE1 (kJ/mol) 1680
You do3370
IE2 (kJ/mol) it!
IE3 (kJ/mol) 6050
IE4 (kJ/mol) 8410
IE5 (kJ/mol) 11020
IE6 (kJ/mol) 15160
Notice that the largest IE
increase in ionization
(kJ/mol) 17870 energies occurs
7
between IE7 and IE8. Thus this element
IE (kJ/mol)
would form a 1- ion.
92040
8
 Periodic Trend in First Ionization Energy of Period 3

1600
1400
1200
1000
800 3rd period
600
400
200
0
Na Mg Al Si P S Cl Ar
 Ionization Energy
• Example 6-4: Arrange these elements
based on their first ionization energies.
– Sr, Be, Ca, Mg
You do it!
Sr < Ca < Mg < Be
 Ionization Energy
• Example 6-5: Arrange these elements
based on their first ionization energies.
– Al, Cl, Na, P
You do it!
Na < Al < P < Cl
 Ionization Energy
• Example 6-6: Arrange these elements
based on their first ionization energies.
– B, O, Be, N
You do it!
B < Be < O < N
 Periodic Trend in First Ionization Energy of Group 7

2000

1500

1000 Group 7

500

0
F Cl Br I
 Periodic Trend in First Ionization Energy of Group 1

600
500
400
300 Group 1
200
100
0
Li Na K Rb Cs
 Periodic Trend in Melting Points of Period 3

2000

1500

1000 3rd period

500

0
Na Mg Al Si P S Cl Ar

melting point depends both on the structure of the

element and on the type of attractive forces holding the
atoms together
 Group 1 Li Na K Rb Cs

M.pt/K 454 371 336 312 302

Melting point decreases down the group as the

atoms become larger and the strength of the
metallic bond decreases.
 Group 17 F2 Cl2 Br2 I2

M.pt/K 53 172 266 387

The melting points increase as the van der Waals’

forces of attraction between the diatomic molecules
increases down the group.
ALKALI METALS

Alkali Li Na K Rb Cs
metals
Electronic 2,1 2,8,1 2,8,8,1 2,8,8,18,1 2,8,8,18,18,1
structure

increasing atomic and ionic radius

decreasing ionization energy

increasing reactivity

decreasing electronegativity
HALOGENS

Halogens F Cl Br I
Electronic 2,7 2,8,7 2,8,8,7 2,8,8,18,7
structure

Colour pale yellow yellowish reddish- black

green brown

State at r.t.p. gas gas liquid solid

increasing atomic and ionic radius

decreasing ionization energy

increasing reactivity

increasing electronegativity

decreasing oxidising strength

reagent F- Cl- Br- I-

Aqueous No reaction White Cream Pale yellow

Ag+ precipitate precipitate precipitate
(rapidly
darkens to
black in
sunlight)
Chlorine No reaction No reaction Solution turns Solution turns
yellow, then yellow, then
brown brown, then
black
precipitate
Bromine No reaction No reaction No reaction Solution turns
yellow, then
brown, then
black
precipitate
Iodine No reaction No reaction No reaction No reaction

summary of reactions of the halide ions

 Anomalous Behaviour
Bond Dissociation
Energy of halogens
F2: 155 300

250
Cl2: 242
200
Br2: 193
150
I2: 151 100

50

0
Fluorine Chlorine Bromine Iodine
 Anomalous Behaviour
Reduction Potentials of alkali metal ions
Li+: -3.05
Na+: -2.71
K+: -2.92
Rb+:-2.93
Cs+: -2.92
PERIOD 3

Period 3 Na Mg Al Si P S Cl Ar

Electronic 2,8,1 2,8,2 2,8,3 2,8,4 2,8,5 2,8,6 2,8,7 2,8,8

structure

Boiling 1156 1380 2740 2528 553 718 238 87

point /K

decreasing atomic radius

increasing ionization energy

increasing electronegativity

decreasing metallic character

increasing hydrolysis of chlorides

increasingly acidic oxides

Chlorides of Period 3

formula NaCl MgCl2 Al2Cl6 SiCl4 PCl3 S2Cl2 Cl2

(PCl5)
State at 25oC solid solid solid liquid liquid liquid gas
(solid)
Melting pt/ oC 801 714 178 -70 -112 -80 -101
(sublimes)

boiling pt/ oC 1413 1412 - 58 76 136 -35

Electrical good good poor none none none none

conductivity
in
molten state

Structure ionic ionic simple molecular

Reaction dissolve easily fumes of HCl produced dissolve

with water

Nature of neutral weakly acidic

solution acidic
Oxides of Period 3

formula Na2O MgO Al2O3 SiO2 P4O10 SO3 Cl2O7

(P4O6) (SO2) (Cl2O)
State at 25oC solid solid solid solid solid liquid liquid
(solid) (gas) (gas)

Melting pt/ oC 1275 2852 2027 1610 24 17 -92

boiling pt/ oC - 3600 2980 2230 175 45 80

Electrical good good good very none none none

conductivity in poor
molten state

Structure ionic ionic ionic giant simple molecular

covalent

Reaction with Forms Forms Does not Does not P4O10 SO3 forms Cl2O7
NaOH(aq) Mg(OH)2(aq) react react forms H2SO4 a forms
water weakly
an H3PO4 an strong acid HClO4 an
alkaline alkaline acidic acidic
solution solution solution

Nature basic basic amphoteric acidic acidic acidic acidic

of oxide
• exhibit variable oxidation states
• ability to form complex ions
• ability to form coloured compounds
• catalytic property
 Variable oxidation states

1st row of
d-block
Sc Ti V Cr Mn Fe Co Ni Cu Zn

Electronic [Ar]3d14s2 [Ar]3d24s2 [Ar]3d34s2 [Ar]3d54s1 [Ar]3d54s2 [Ar]3d64s2 [Ar]3d74s2 [Ar]3d84s2 [Ar]3d104s1 [Ar]3d104s2
structure

Common +3 +2,+3, +2,+3, +2,+3, +2,+4, +2,+3 +2 +2 +1,+2 +2

oxidation +4 +4,+5 +6 +6,+7
states

decreasing stability of maximum oxidation state

increasing stability of +2 oxidation state

Formation of Complex Ions

Low energy unfilled d-orbitals or p-orbitals can

accept a lone pair of electrons from LIGANDS to
form a dative bond.

Result: complex ion

Ligands : species that can donate a pair of non-

bonding electrons to the central metal ion eg water,
ammonia, chloride ion.
 ↑↓ ↑ ↑↓ ↑↓
white light Reflected light is
Energy is absorbed as complementary
∆E colour to
electron is promoted.
absorbed light.
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑

Energy corresponds to
particular frequency in
visible spectrum
Formation of Complex Ions

•Stabilises certain oxidation states

•Affects the solubility of compounds

•Major effect on the colour of the solution

of a metal ion
Stereochemistry of Complex Ions

NH3 2+
H2O
2+ 2-

H2O H2O Cl Cl
Cu Cu
Cu H2O Cl
NH3 H2O Cl

H3N
NH3 H2O

tetrahedral octahedral Square planar

Coordination Number: the number of particles around the central metal

Complex ions are capable of exhibiting cis-trans & optical isomerism

Stereochemistry:cis-trans
Stereochemistry:cis-trans
Stereochemistry: Chirality
Stereochemistry: Chirality
Catalytic properties of Transition Elements