TKT2023 noorshida mohd ali

 Uniqueness principle
Diagonal effect
Inert-pair effect
 TKT2023 noorshida mohd ali
PERIODIC TRENDS OF THE ELEMENTS
The way certain properties (chemical and physical) of elements vary
according to their location on the periodic table
Some variations in:
Electronegativity increases

Electron affinity increases

Ionization energy increases
Effective nuclear charge decreases

Effective nuclear charge increases

Electronegativity decreases

Ionization energy decrease

Electron affinity decreases

Atomic radius increase

Ionic radius increase

Atomic radius decreases

Ionic radius decreases

 TKT2023 noorshida mohd ali

Uniqueness principle

Li Be B C N O F Ne

The chemistry of the second-period elements

(Li, Be, B, C, N, O, F, Ne) are significantly different from
other elements in their respective groups
 TKT2023 noorshida mohd ali

Uniqueness principle

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar

Second element in each group

(Na, Mg, Al, Si, P, S, Cl, Ar) are more representative
 TKT2023 noorshida mohd ali

Uniqueness principle

Li Be B C N O F Ne

Why the first elements of the groups are different from

their congeners (elements of the same group)?

a) The small size of the elements leading to a high polarizing power

and a high degree of covalent character in their compounds
b) The greater probability of π bonds (pπ -pπ )
c) The lack of availability of the d orbitals
 TKT2023 noorshida mohd ali

 small size of the first elements

• Size effect leads to :

1) Smaller electron affinities - ability to accept one or more electrons

Electron affinity is the energy change that occurs when an electron

is accepted by an atom in the gaseous state to form an anion
X (g) + ē X-(g)

Electrons added to these small atom,

experience more electron repulsions

2) Larger charge densities

3) Enhanced degrees of covalent character in their compounds

 TKT2023 noorshida mohd ali

The first electron affinities

of the halogens
 TKT2023 noorshida mohd ali

What about fluorine?

> It is a very small atom.
> Incoming electron quite close to the nucleus.
> The existing electron density is very high.
> The extra repulsion is particularly great and
lessens the attraction from the nucleus
enough to lower the electron affinity below that
of chlorine.
 TKT2023 noorshida mohd ali

GROUP 1 (ALKALINE METALS) : Li, Na, K, Rb, Cs, Fr

 lithium behaves differently than others

 small size
 high charge density of cation allow it to polarize nearby
anion – allows a large degree of covalency in its bond and
less ionic
less soluble in water and more soluble in polar organic
solvents
 TKT2023 noorshida mohd ali

1) Small lithium cation get very close to larger, more diffuse or

filled electron cloud of chloride ion.

2) Electron cloud of chloride ion is distorted or polarized by lithium ion

3) This distortion makes overlap between two ions. Orbital overlap and
sharing electron between two species – characteristic of a covalent bond

overlap between the valence orbitals in Li+ (empty 2s) and Cl- (filled 3p)
is increased
 TKT2023 noorshida mohd ali

Bond energies increase

Weakness of the fluorine – fluorine bond

-owing to the small atomic size – closeness/ nearness in F2 compared to Cl2

-lone pairs of electrons on adjacent fluorine atoms repel each other (increase
repulsion )

-weakening the F-F bond in F2 molecule

 TKT2023 noorshida mohd ali

 increased π bonding in the first element

Due to small size, increase π bond formation among themselves and with
other elements (capable of forming strong double and triple bond)

∀ π bonds involve parallel overlap between for example two p orbitals

(π bonding can occur using d orbitals and antibonding molecular orbitals
of some molecules)

Utilizing π bond than σ bond :

C C C O N N C C O O C OC C

Parallel orbital overlap or π bonding is more effective in smaller first

elements for example carbon than larger congeners, silicon
 TKT2023 noorshida mohd ali

 lack of availability of d orbitals in the first elements

• The lighter elements lack availability of d orbitals and therefore

cannot form compounds with expanded octets

ClF3
CF4

SiF62-
 TKT2023 noorshida mohd ali

Diagonal effect
DIAGONAL RELATIONSHIPS exists between the chemistry of the
first member of a group and the second member of the next group

• Similarities between pairs of 1 2 13 14

elements in different groups
and periods of the periodic
table
Phenomenon happens :
1) small ionic size
Li Be B
2) closeness of the charge
densities of their cations
(charge density = charge of
an ion divided by its radius : Mg Al Si
charge nm-1 )
3) electronegativity
 TKT2023 noorshida mohd ali

Diagonal effect
1 2 13 14

Li Be B C
Charge of ion +1 +2 +3 +4
Ionic radius, Å 0.73 0.41 0.25 0.29
Charge density 1.4 4.9 12 14
Electronegativity 1.0 1.5 2.0 2.5
Na Mg Al Si
Charge of ion +1 +2 +3 +4
Ionic radius, Å 1.13 0.71 0.53 0.40
Charge density 0.88 2.8 5.7 10
Electronegativity 0.9 1.2 1.5 1.8
 TKT2023 noorshida mohd ali

Diagonal effect
•Ionic radius of Be2+ (0.41Å) is
more similar to Al3+ (0.53Å) than
Mg2+ (0.71Å)
•High charge density of Al3+ ion 1 2 13 14
(5.7) and Be2+ ion (4.9)
•Same electronegativity (1.5)
•Be-X and Al-X : covalent character
•Its small size & high charge density
Li Be B
of cation Be2+ and Al3+ allow them to 0.41Å
polarize the electron cloud of anion 4.9
(X atom in M-X bond) to give
additional covalent character Mg Al Si
AlH3 resembles BeH2 in its 0.71Å 0.53Å
2.8 5.7
properties (example of the
diagonal relationship)
 TKT2023 noorshida mohd ali

Inert-pair effect
C
Si
Oxidation state : +4
Ge +4
CCl4, CO2, SiCl4, SiO2, SnO2
Sn
CO easily oxidized to CO2 (+2 to +4) Pb

Convert tin(II) to tin(IV) – more stable. Sn2+ ions in solution

suitable as reducing agents

Reversed situation for lead C

Moving down a group, there are more Si
and Ge +2
more examples oxidation state +2 : Sn
CO, SnCl2, PbO, Pb2+
Pb
 TKT2023 noorshida mohd ali

Inert-pair effect

Ionization energy increases

Ionization energy decrease

ATOMIC RADIUS
The increase in size of atom is accompanied by a decrease of ionization energy

-going down a group, size of the atom increases

-the outer electrons lie farther away from the nucleus
-attractive pull from the nucleus on the outer electrons
decreases
-easier to pull out an electron from the outer shell of the atom
 TKT2023 noorshida mohd ali

IONIZATION ENERGY

Slight increase between

tin and lead

Large increase between

tin and lead
 TKT2023 noorshida mohd ali

Inert-pair effect
As an example in group 13 the +1 oxidation state of Tl
is the most stable and TlIII compounds comparatively
rare. The stability increases in the following sequence:
AlI < GaI < InI < TlI

• All four elements (Al, Ga, In, Tl) give trivalent compounds but the
univalent state becomes increasingly important for Ga, In and Tl

• Valence ns2 electrons of metallic elements : In, Tl, Sn, Pb, Sb, Bi and
Po
are less reactive than expected.

• Inert ns2 pairs mean oxidation state is 2 less than the expected
group valence for the heavier elements of groups 13, 14, 15 and 16.
 TKT2023 noorshida mohd ali

Inert-pair effect
• Get closer to the bottom of the group (heavier elements –
increasing tendency s2 pair not to be used in the bonding
(left unchanged / inert pair)

• Valence electrons in an s orbital are more tightly bound

are of higher energy than electrons in p orbitals
and therefore less likely to be involved in bonding.

• Electrons closer to the nucleus – difficult to remove

the heavier the element the greater this effect
 TKT2023 noorshida mohd ali

Inert-pair effect

• Two major reasons for this effect:

a) larger than normal effective nuclear charges (higher than expected

ionization energies for Ga, In, Tl)

4s, 5s and 6s electrons experience larger effective nuclear charge

than expected – they are more difficult to ionize

b) lower bond energies (as expected)

due to increase in atomic size and bond distance