Group Chemistry

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 Metal
They are hard but not brittle
Conduct heat and electricity
Metallic Luster
They are sonorous
Metals can lose electron easily
Metals cannot gain electron easily
Metals generally form ionic
compounds
Metals oxides are basic in nature
Metals have low ionization enthalpy
Metals are electropositive elements
Metals have a high reducing power
Non-metal
They are soft and brittle.
In general, they don’t conduct heat and
electricity
No lustrous property
No such property
Non-Metals cannot lose electron easily
Non-Metals can gain electron easily
Non-Metals generally form covalent
compounds
Non-Metallic oxides are acidic in nature
Non-Metals have high ionization enthalpy
Non-Metals are electronegative elements
Non-Metals have a low reducing
power/high oxidizing power
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 Periodic Table and Periodic Properties

Periodic Table

Inner
Representative Transition
Transition
elements elements
elements

s+p block d-block f-block

Group 1-2, 13-14 Group 3-12 Lanthanides-4f
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Actinides-5f 02/07/2024
 Periodic Table and Periodic Properties

Vertical columns or groups

Group 1 Alkali Metals

Group 2 Alkaline earth Metals
Group 15 Pnictogens
Group 16 Chalcogens
Group 17 Halogens
Group 18 Noble Gases
Group 3+ Lanthanides Rare Earth elements

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 Periodic Table and Periodic Properties

Lanthanides or Lanthanoids or Rare Elements from Ce (58) to Lu (71)

earths
Actinides or Actinoids: Elements from Th (90) to Lr (103)

Coinage metals Cu, Ag and Au

Noble metals (very low reactivity) Ag, Au, Pt and Hg

Trans uranium metals Elements beyond U (92)

Bridging elements
Diagonal relationship
Elements of third period
Set of elements, that is, (Li, Mg),
(Be, AI) and (B, Si), which, though,
placed in different groups, show
some similarities in their properties
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 Properties of S-block Elements

●S-block elements constitute two groups present on the

extreme left of periodic table. The last electron is filled in the
valence s-orbital in these elements.
(nS1, nS2)

●The first group contains Li, Na, K, Rb, Cs and Fr elements,

having general electronic configuration of [inert gas] ns1. They
are also called alkali metals.

●The second group contains Be, Mg, Ca, Sr, Ba and Ra

elements, having general electronic configuration of [inert gas]
ns2.They are also called alkaline earth metals.
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 Properties of S-block Elements

Atomic and Ionic Radii

● The alkali metal atoms have the largest sizes in a particular period of
the periodic table.

● With increase in atomic number, the atom becomes larger. The

monovalent ions (M+) are smaller than the parent atom.

● The atomic and ionic radii of alkali metals increase on moving down
the group i.e., they increase in size while going from Li to Cs.

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Physical Properties

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Physical Properties

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 Physical Properties

Properties Alkali metals Alkaline earth metals

Ionization enthalpy Sharply decreases down Sharply decreases upto

(1st) the group. It is less than Ba and then increases
the corresponding alkaline slightly
earth metals and also the from Ba to Ra.
least in the corresponding
period.
Hydration enthalpy Sharply decreases down Sharply decreases
the group (due to increase down the group (due to
in ionic radius). increase in ionic
radius).
Density Irregular Irregular (but higher
than the corresponding
alkali metal).

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 Physical Properties

Properties Alkali metals Alkaline earth metals

Melting and boiling Decrease sharply down the Irregular (but higher than
points group the corresponding alkali
metal).

Colour to oxidizing Li-crimson red, Na-yellow, K- Ca-brick red, Sr-crimson

flame violet, Rb-red violet, Cs-blue. red, Ba-apple green (Be and
Mg do not impart any
colour).

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 Chemical Properties
Properties Alkali metals
Reactivity Highly reactive
Reaction with air Li forms oxide (Li2O), Na
forms peroxide
(Na2O2) and other metals
form superoxides (MO2 ).
Only lithium reacts with
N2 to form nitride.
Li + N2 ⟶Li3N
Na forms oxide in presence of limited amount of Oxygen
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Alkaline earth metals
Reactive (but less than the
corresponding alkali
metal)
React with O2 and N2 to
form oxides and nitrides
respectively. Be and Mg
are quite inert to O2 due
to the formation of oxide
layer.
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 Chemical Properties

Properties Alkali metals Alkaline earth metals

Reaction with H2O Form hydroxide and H2 gas Form hydroxides and H2 gas
M + H2O → MOH + ½ H2 ( Be and Mg are less
reactive due to the
formation of oxide layer)

Reaction with H2 Form ionic hydrides with high All except Be form ionic
melting point. hydrides (MH2), BeH2 can
be prepared by the reaction
of BeCl2 with LiAIH4.

Reaction with halogens All form ionic halides except LiX All form ionic halides (MX2)
wich is covalent. except BeX2which is
covalent.
Reducing nature These are strong reducing Their reducing power is less
agents (Li is the strongest one than the corresponding
due to high hydration enthalpy). alkali metal.

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 Chemical Properties

Properties Alkali metals Alkaline earth metals

Solution in liquid NH3 M + (x + y ) NH3 M + (x + y ) NH3

↓ ↓
[M(NH3)x]+ + [e(NH3)y]- [M(NH3)x]2+ + 2[e(NH3)y]-
(blue colour solution, (deep blue-black solution,
paramagnetic) On long standing, paramagnetic)
the solution slowly converts to (M = alkaline earth metals)
MNH2 liberating H2 gas. (M =
alkali metal)

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 Compounds of S Block elements

Metal compounds Alkali metals Alkaline earth metals

Oxides Stability of peroxides and BeO is amphoteric, while

superoxides increases the rest are ionic. All
down the group (due to except BeO are basic and
stabilization of larger react with water to form
anion by larger cation). hydroxides
All react with water to
form hydroxides.

Hydroxides Solubility, thermal Solubility, thermal stability

stability and basic and basic character of
character increases down hydroxides increase down
the group. the group (less basic and
stable than the
corresponding alkali metal
hydroxide).
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 Compounds of S Block elements

Metal compounds Alkali metals Alkaline earth metals

Halides All halides have negative All are ionic except

ΔfH°value and the order of the beryllium halides which are
magnitude of ΔfH°is covalent. The tendency of
LiF > NaF > KF > RbF > CsF formation of halide
M + 1/2X2= MX,
The order of ΔfH°for chlorides, hydrates decreases down
ΔHf0= -Ve the group. The fluorides
bromides and iodides is
FrX>CsX>RbX>KX>NaX>LiX are less soluble than the
(X = Cl-, Br-, I-) corresponding chlorides
Order of melting and boiling due to high lattice
points is MF > MCl > MBr > MI. enthalpies.

MX2.nH2O

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Small cation have high polarizing power so increase hydrates formation tendency
 Compounds of S Block elements

Metal compounds Alkali metals Alkaline earth metals

Salts of oxoacids Their stability increases down These are very less soluble
the group. These are soluble and their solubility
I.Carbonates and in water. decreases down the group.
Thermal stability increases
hydrogen carbonates
down the group.

M+O+H = Oxoacids
Ex. H2CO3
Due to stabilization of larger anion
by larger cation (CO32-, HCO3-)

Latice energy & Hydration enthalpy

both are decrease down the group but
their difference decided the solubility.
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Easy broken easy dissolve
 Compounds of S Block elements

Metal compounds Alkali metals Alkaline earth metals

Salts of oxoacids The stability (thermal) of Sulphates of Be and Mg are

II.Sulphates sulphates increases down readily soluble in water due
the group. These are to higher hydration enthalpy.
soluble in water. However, solubility decreases
from CaSO4 to BaSO4.

Carbonates, Sulphates, Bicarbonates of Group 2

solublilty in water decreases down the group

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 Compounds of S Block elements

Metal Alkali metals Alkaline earth metals

compounds
Salts of oxoacids The stability of nitrates The tendency of nitrates to
III.Nitrates increases down the group. form hydrates decreases
These are all soluble in down the group (due to
water. LiNO3 on heating decrease in hydration
gives Li2O, NO2 and O2, enthalpy). They decompose
whereas other alkali metal to give corresponding oxide,
nitrates give corresponding NO2and O2gas. Thermal
nitrite on heating. stability increases down the
group.

4 Li NO3 → 2Li2O + 4NO2 + O2

M(NO3)2 → MO + NO2 + O2
2 NaNO3 → 2NaNO2 + O2

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 Anomalous Behaviour of Li /
Difference between Lithium and other Alkali Metals

Due to small size, high polarizing power and absence of d-orbitals, Li shows
the following anomalous properties:
• It is much harder having higher melting and boiling points.
• Compounds of Li are covalent and hence, soluble in organic solvents.
• It is the strongest reducing agent among alkali metals and unlike other
alkali metals, it forms Li2O and Li3N with oxygen and nitrogen respectively.
• It does not form acetylide on reaction with CH ☰ CH.
• Only LiCl forms LiCl.2H2O with water.
• LiHCO3 is not obtained in solid form, whereas other alkali metals form solid
metal hydrogen carbonates.

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 Anomalous Behaviour of Li /
Difference between Lithium and other Alkali Metals

Due to small size, high polarizing power and absence of d-orbitals, Li shows
the following anomalous properties:
• LiOH is weak base but other alkali metal from strong hydroxides.
• Li2CO3 → Li2O + CO2
other alkali metal carbonates do not evolve carbon dioxide.

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 Diagonal Relationship of Li with Mg/
Similarities between Li and Mg
Diagonal Relationship is said to exist between certain pairs of diagonally
adjacent elements in the SECOND and THIRD periods of the periodic table.

Li and Mg show diagonal relationship with each other due to their small
size (atomic & ionic radii), and high polarising power.

Similarity between Li Mg
Li & Mg
Atomic Radii 152 pm 160 pm
Ionic Radii 76 pm 62 pm
Polarizsing power 1.7 3.9
Electronegativity 1.00 1.2

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 Diagonal Relationship of Li with Mg/
Similarities between Li and Mg

Both have the following common properties:

• Both form covalent compounds that are soluble in organic solvents like
ethanol.
• Both LiCl and MgCl2 crystallise in aqueous solution to form LiCl2.2H2O
and MgCl2.8H2O, respectively.
• Both Li and Mg do not form solid hydrogen carbonates and their
carbonates decompose easily on heating.
• Their oxides do not combine with excess oxygen to give any
superoxides.
• Their oxides and hydroxides are very less soluble in water.
• Both react with N2 to form Li3N and Mg3N2 .
• Both are lighter and harder than other elements in their respective
groups.

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 Anomalous Behaviour of Be

Be shows anomalous behaviour due to its small size (atomic &

ionic radii), high ionisation energy and absence of d-orbitals

• Be is hard metal whereas other alkaline earth metals are

soft.
• Its mp, bp, I.E are the highest of all alkaline earth metals.
• It forms covalent compounds. Its oxides and hydroxides are
amphoteric in nature rather than basic.
• Be does not liberate H2 from HCl, H2SO4 but other alkaline
metals liberate H2
• It does not exhibit coordination number more than 4 due to
the absence of vacant d-orbitals.

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 Diagonal Relationship between Be & Al /
Similarities between Be & Al
• It shows diagonal relationship with Al having the following common
properties:
(i) Both are not easily attacked by acids due to the formation of oxide
layer.
(ii) Beryllium and aluminium hydroxides dissolve in excess of alkali give
a beryllate ion, [Be(OH)4]2- and aluminate ion, [Al(OH)4]-,
respectively.
(iii) Both have bridged chloride structure in vapour phase. Chlorides of
both can be used in Friedel-Crafts reaction, as both act as strong
Lewis acid and are soluble in organic solvents.

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 P-Block elements

The elements in which last electron enters into "p" subshell

is called "p Block"elements

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 P-Block elements

P BLOCK
G13 →ns2np1
G14 →ns2np2
G15 →ns2np3
G16 →ns2np4
G17 →ns2np5
G18 →ns2np6

p-block contains : -
(i) Metals
(ii) Non-metals
(iii) Metalloids
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P-Block elements

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 P-Block elements

Boron family

B 2nd period 2s2 2p1

Al 3rd period 3s2 3p1
Ga 4th period 4s2 4p1
In 5th period 5s2 5p1
Tl 6th period 6s2 6p1

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 Diagonal Relationship between B & Si /
Similarities between B & Si
6. Both the elements exhibit allotropy.
(7) Both possess closer electronegativity values (B=2.0; Si=1.8).
(8) Both form numerous large no. of volatile hydrides which
spontaneously catch fire on exposure to air and are easily
hydrolysed.
(9) The chlorides of both these are liquid, fume in most air and
readily hydrolysed by water.
BCl3 + 3H2O → B(OH)3 + 3HCl
SiCl4 + H2O → Si(OH)4 + 4HCl
(10) Both form weak acids like H3BO3 and H2SiO3.
(11) Both form binary compounds with several metals to give borides
and silicide. These borides and silicide react with H3PO4 to give
mixture of boranes and silanes.
3Mg+2B → Mg3B2; Mg3B2+H3PO4 → Mixture of boranes
(Magnesium boride)
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2Mg + Si → Mg2Si ; Mg2Si + H3PO4 → Mixture of silanes

 Diagonal Relationship between B & Si /
Similarities between B & Si
(12) The carbides of Boron and silicon (B4C and SiC) are very hard and used
as abrasive.
(13) Oxides of both are acidic and can be reduced by limited amount of Mg
In excess of Mg boride and silicide are formed.
B2O3+3Mg → 3MgO+2B ; SiO2+2Mg →2MgO+Si
(14) The both metals and their oxides are readily soluble in alkalies.
2B + 6NaOH → 2Na3BO3 + 3H2 ­
(borate)

Si + 2NaOH + H2O → Na2SiO3 + 2H2 ­

(Formula for silicate)

B2O3 + 6NaOH → 2Na3BO3 + 3H2O

SiO2 + 2NaOH → Na2SiO3 + H2O
Both borates and silicates have tetrahedral structural units and
respectively. The boro silicates are known in which the boron replaces
silicon in the three dimensional lattice. Boron can however form planar BO3
units.
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(15) Acids of both these elements form volatile esters on heating with
alcohol in presence of concentrated H SO .
 Diagonal Relationship between C & P /
Similarities between C & P
Some of the similarities between carbon and phosphorus are as
follows:
• Both carbon and phosphorus exhibit allotropes.
• Both carbon and phosphorus show almost the same
electronegativities.
• Both form strong pi and sigma bonds.
• Like carbon, phosphors can also form triple bonds.

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 P-Block elements

Boron family

B Al Ga In Tl

Extremely hard Most abundant metal. M.P.= 303K

• H3BO3 3rd most abundant B.P.= 2676K
• Na2B4O7.10H2O element in earth’s • High temp.
• Na2B4O7.4H2O crust thermometer
(Kernite) • Al2O3.2H2O,
NaAlF6

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P-Block elements

Boron family

Poor shielding effect

D-Block Contraction

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 P-Block elements

Ionization Energy

B >Tl > Ga > Al > In

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 P-Block elements

Boron family
D-Block Contraction
When we move from 3rd to 4th period, the electrons start filling
in "d" sub shell.
Electrons in 'd' sub shell shows poor shielding effect.
•
Nucleus attracts outer electrons that is why element of 4th
period has less size than 3rd period element.

D-Block Contraction
D sub shell electrons function?
• strong shielding between Nucleus and outer electrons
• But d & f Sub shell electrons do not show strong shielding
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P-Block elements

D-Block Contraction

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 P-Block elements

Lanthanide Contraction
Due to poor shielding of f sub shell electrons, the size
becomes smaller (almost comparable)

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P-Block elements

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 P-Block elements

Down the group

20 faced
Icosahedron

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P-Block elements

As we move down the group Because of poor

bonding/poor overlap of s electron,
they refuse to participate bonding

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 P-Block elements

Because of small size

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 P-Block elements

O.S. and Trends in reactivity

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 P-Block elements

O.S. and Trends in reactivity

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P-Block elements

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Carbon Family

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Carbon Family

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Carbon Family

Mp = 16000C

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Carbon Family

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Carbon Family

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 Carbon Family

Size

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Carbon Family

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Carbon Family

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Carbon Family

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 Carbon Family

C60

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SiO2

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SiO2

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Silicates

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Silicates

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Silicates

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Silicates

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Silicates

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Silicates

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Silicones

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Silicones

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Silicones

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Silicones

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G-15: Nitrogen Family

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 Electronic Configuration

Atomic Size Ionization

Energy
Down the group atomic size increases
N < P < As < Sb < Bi N > P > As > Sb >
Bi

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 Allotropes of Nitrogen Family

N→X
P → White, Red, Black, Scarlet, α Black,β Βlack, Violet
As →Grey, Yellow, Black
Sb →Yellow, Black, Explosive
Bi → X

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 Covalency of Nitrogen Family

•N →3
•P →5
•As →5
•Sb →5
•Bi →3

General electronic configuration : ns2np3

General Oxidation State : +3, +5
N → 1S22S22P3
P → 1S22S22P6 3S23P3
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Max. Covalency of Nitrogen Family

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 Max. Covalency of Nitrogen Family

PCl5 →Covalency 5 (due to excited state

configuration)
PCl6– →Covalency 6 (due to "d" orbital)

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 Boiling Point

N (non‐metal) NH3
P (non‐metal) PH3
As (metalloid) AsH3
Sb (metalloid) SbH3
Bi (metal) BiH3

BiH3 > SbH3 > NH3 > AsH3 > PH3

↓
metal So,
highest boiling
point

due to Hydrogen bonding

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Thermal Stability

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Reducing character

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Basic nature

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Bond angle

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Reaction of Nitrogen family with Oxygen

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Reaction of Nitrogen family with Halogen

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G-15: Nitrogen Family

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Anomalous properties of N

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Dπ-pπ bond in Phosphorus compounds

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Nitrogen vs Phosphorus Chemistry

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 Oxidation States

The common oxidation states of these elements are -3, +3 and+5.

Tendency to exhibit -3 decreases down the group: increase inmetallic

character.

In the case of N, all oxidation states from +1 to +4 tend to

disproportionate in acid solution
3HNO2→HNO3 + H2O + 2NO

Similarly, in case of P nearly all intermediate oxidation states

disproportionate into +5and–3 both in alkali and acid.

Whereas considering the case of As, Sb and Bi the +3 state is stable with
respect to disproportionation.

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 Inert pair effect

The stability of +5oxidation state decreases down the group (only

BiF5exists) whereas stability of +3increases

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Oxides of Group 15

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Halides of Group 15

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 Compounds of Group 15 with Metals

All these elements react with metals to form their binary compounds
exhibiting –3 oxidation state, such as, Ca3N2(calcium nitride)
Ca3P2(calcium phosphide), Na3As2(sodium arsenide), Zn3Sb2(zinc
antimonide) and Mg3Bi2(magnesium bismuthide).

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 Properties of Nitrogen

➔Colourless, odourless, tasteless, non-toxic gas

➔Very low solubility in water
➔Inert at low temperature
➔Two stable isotopes: 14N and 15N

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Phosphorous

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 White Phosphorous

●Translucent white waxy solid

●Poisonous -Caused “Phossy Jaw” in matchstick industry workers

●Insoluble in water but soluble in carbon disulphide

●Catches fire in air to give dense white fumes of P4O10

●Glows in dark (chemiluminescence and not phosphorescence).

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Allotropes of Phosphorus

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Allotropes of Phosphorus

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Phosphorus allotropes interconversion

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G-16: Oxygen Family

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G-16: Oxygen Family

Atomic Radius

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 G-16: Oxygen Family

Group 16 of the periodic table has the elements: Oxygen, sulphur,

selenium, tellurium and polonium. This is also known as group of
chalcogens.

Oxygen and sulphur are non-metals, selenium and tellurium metalloids,

whereas polonium is a metal. All these elements exhibit allotropy.

Oxygen is the most abundant of all the elements on earth. Oxygen forms
about 46.6% by mass of earth’s crust. Dry air contains 20.946% oxygen by
volume.

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 Sulphur

The abundance of Sulphur in the earth’s crust is only 0.03-0.1%.

Combined sulphur exists primarily as sulphates such as:

●Gypsum CaSO4.2H2O,
●Epsom salt MgSO4.7H2O,
●Baryte BaSO4
●Sulphides such as galena PbS, zinc blende ZnS, copper pyrites
CuFeS2

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 Oxygen vs Sulphur Chemistry

●The O ＝ O double bondis much stronger than the O ― Osingle bond.

●This is in contrast to sulfur and the other members of the group,

where the energy of two single bondsis greater than that of one
double bond.

For this reason, multiple bonding is only common for oxygen.

Oxygen Bonds Bond Energy Sulphur Bond Energy

(kJ.mol-1) Bonds (kJ.mol-1)
O―O 142 S―S 268

O＝O 494 S＝S 425

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 Oxygen vs Sulphur Chemistry

●Compounds containing two oxygen atoms singly bonded together

are usually strong oxidizing agents. Such behavior can be explained
by the weakness of the oxygen-oxygen single bond compared to its
bonds to other elements.

●Oxygen endeavors to bond to other elements rather than to itself.

In particular, the covalent bondto hydrogen is very strong.

Oxygen Bonds Bond Energy Sulphur Bond Energy

(kJ.mol-1) Bonds (kJ.mol-1)
O―O 142 S―S 268
O ― Cl 218 S ― Cl 271

O―H 459 S―H 363

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General Trends

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G-16: Oxygen Family

Basic Character Decreases

Thermal Stability Decreases
Reducing Character
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Compound of G 16 -Oxides

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Anomalous behaviour of Oxygen

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Oxygen: Small Scale Preparation

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 G-17: Halogen Family

●Members of G-17: Fluorine, chlorine, bromine, iodine and astatine.

●Known as the halogens(salt producers)
●F and Cl are much more abundant compared to Br and I in following forms:

1. Fluorspar CaF2
2. Cryolite Na3AlF6
3. Fluoroapatite 3Ca3(PO4)2.CaF2)
4. Sodium Chloride NaCl
5. Carnallite, KCl.MgCl2.6H2O

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Properties of Halogens

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 Physical Properties of Halogens

Solubility
Fluorine and chlorine react with water
Bromine and iodine are only sparingly soluble in water but are soluble
in various organic solvents.

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Chemical Properties

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Chemical Properties

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 Chemical Properties

Reaction with water

Cl2(g) + H2O (l) →HCl (aq) + HOCl (aq)

Br2(g) + H2O (l) →HBr (aq) + HOBr (aq)

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Chemistry of Fluorine vs Chlorine

Reason: Repulsions
between the nonbonded
electrons of the two atoms
of the molecule. It also
accounts for the high
reactivity of fluorine gas.

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 Chemistry of Fluorine vs Chlorine

Ionic Bonding: More energy is released with fluorides than with the other
halides since fluorides have a high lattice energy of formation due to the
small, high-charge-density fluoride ion.

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Anomalous behaviour of fluorine

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 G-18: Nobel gas

Helium
●Filling balloons for meteorological observations.
●It is also used in gas-cooled nuclear reactors.
●As cryogenic agent for carrying out various experiments at low
temperatures.
●To produce and sustain powerful superconducting magnets which form an
essential part of modern NMR spectrometers and MRI
●As a diluent for oxygen in modern diving apparatus because of its very
low solubility in blood.

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 G-18: Nobel gas

Argon
●Argon is used mainly to provide an inert atmosphere in high
temperature metallurgical processes (arc welding of metals or alloys)
and for filling electric bulbs. It is also used in the laboratory for handling
substances that are air-sensitive.
●There are no significant uses of Xenon and Krypton. They are used in
light bulbs designed for special purposes.

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 G-18: Nobel gas

●Group 18 consists of six elements: helium, neon, argon, krypton,

xenon and radon.
●Except radon all occur in the atmosphere in which argon is the major
constituent.
●Xenon and radon are the rarest elements of the group.
●Radon is obtained as a decay product of 226Ra.

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 G-18: Nobel gas

Abundance
Helium and sometimes neon are found in minerals of radioactiveorigin
e.g., pitchblende, monazite, cleveite. The main commercial source of
helium is natural gas.

Properties

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 G-18: Nobel gas

Physical properties
●Colourless, odourless and tasteless.

●Sparingly soluble in water.

●Very low melting and boiling points because the only type of interatomic
interaction in these elements is weak dispersion forces.

●Helium has the lowest boiling point (4.2 K) of any known substance. It
has an unusual property of diffusing through most commonly used
laboratory materials such as rubber, glass or plastics.

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 G-18: Nobel gas

Chemical Reactivity
●Noble gases are least reactive due to:
○Completely filled ns2and np6configuration.
○High ionisation enthalpy and more positive electron gain
enthalpy.

●Compounds of He, Ne or Ar are yet known

●Under extreme conditions, krypton reacts with fluorine to form KrF2

●First laboratory compound of Noble gases to be prepared was Xe+PtF6-.

Thereafter a number of xenon compounds mainly with most
electronegative elements like fluorine and oxygen, have been synthesised
like XeF4 and XeOF4
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Compounds of Xenon with Fluorine

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 Compounds of Xenon with Fluorine

●Colourless crystalline solids

●Sublime readily at 298 K
●Powerful fluorinating agents. React with fluoride ion acceptors
to form cationic species and fluoride ion donors to form
fluoroanions.

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Hydrolysis of Xenon Fluorides

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Effective nuclear charge

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 Screening Effect

The decrease in the force of attraction exerted by the nucleus on the

valence electrons due to the inner electrons is called shielding or
screening effect.
Zeff = Z-σ
Where σ is screening constant.

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 Variation of effective nuclear charge

2nd Li Be B C N O F Ne
period

Z 3 4 5 6 7 8 9 10
Zeff 1.28 1.91 2.42 3.14 3.83 4.45 5.10 5.76

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 Metallic Radius
It is defined as half of the internuclear distance separating
two adjacent metal atoms in a metallic lattice.

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 Van der Waals Radius

The sum of the van der Waals radii of two atoms is the shortest
distance between two immediately adjacent atoms (either of same or
different elements) in the structure of the solid compound in which
they are not bonded to each other.

Covalent radius
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rVdw > rMetallic > rcovalent
 Variation of atomic size

Atomic size decreases across a period.

Zeff increases across a period.

Element Li Be B C N O F
Size(pm) 152 111 88 77 74 66 64
Element Na Mg Al Si P S Cl
Size(pm) 186 160 143 117 110 104 99

For d-block elements, the atomic radius initially

decreases, then remains constant and finally
increases again
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 Variation of atomic size

Atomic Size increases down the group.

Atom Atomic Atom Atomic
(Group I) Radius (Group 17) Radius

Li 152 F 722
Na 186 Cl 99
K 231 Br 114
Rb 244 I 133
Cs 262 At 140

Inert gases have the largest atomic size in their period

because we define V.D.W. radii for them.

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02/07/2024
 Ionic radius

Formation of positive and negative ions from an atom is shown

below. The order of radius is: A−> A > A+

A3-> A2-> A-> A > A+> A2+> A3+

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02/07/2024
Na Na+
186 102
Mg Mg2+
160 72
Al Al3+
143 54
N N3-
75 146
O O2-
73 140
F F-
72 133
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 Exceptions

Exceptions
●In every and each period, noble gases have largest in size (largest
radius) due to electronic repulsion dominating. i.e. completely
electron filled.

●For transition element (d-block element)We are not observing

regular trends.

●B < Ga < Al < In ≈ Tl

88 < 135 < 143 < 167 ≈ 170 pm
●Lanthanide contraction:-
Due to the very poor shielding effect of f-electrons the
corresponding proton inside the nucleus attracts the outermost shell
electrons strongly by which radius of the element gets contracted
which is known as “Lanthanide contraction”.
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 Ionization energy (Enthalpy)

It is the energy required to remove an electron from an

isolated gaseous atom in its ground state.

Factors Affecting Ionization Energy

1. Effective Atomic Number Zeff

2. Size of atom/ion
3. Charge on ion
4. Half-filled & fully-filled Electronic configuration
5. Type of subshell (s, p, d or f ) of the electron being removed
6. Shielding Effect
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 Ionization energy (Enthalpy)

It is the energy required to remove an electron from an

isolated gaseous atom in its ground state.

Li
Na e
K z E
i
Rb
I
S
Cs

IE (alkali): Li > Na > K > Rb > Cs

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 Trend in Periodic table

Across group Ionisation energy, in general, decreases down the group with the
following exceptions.

(a) In group 13, the 1st IE decreases from B to Al as expected, but the trend
becomes irregular for rest elements (Ga, In, Tl) due to the addition of extra
electrons by d and f-block elements.

B Al Ga In Tl Group 13
(IE)1 801 577 579 558 589 (kJ mol-1)

(Irregular)
(b)Transition elements do not follow any regular trend in ionization energy.

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 Trend in Periodic table

Across period Ionization enthalpy in general increases across a period, with the
exception of those with either half-filled or fully-filled electronic configuration as
discussed.

●It also follow an irregular trend in case of transition elements.

●Ionization energy of noble gases (except Xe) is highest in their respective

period due to stable fully-filled configuration.

●Ionization enthalpy of alkali metals is the lowest in their respective period

because on the removal of one electron, nearest stable noble gas configuration is
attained.

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140 02/07/2024
Electron Affinity or Electron Gain Enthalpy

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 Electron Affinity or Electron Gain Enthalpy

It is the energy released when one mole of electron is added to one mole of an
element in its isolated gaseous state (ground state). It is also called electron gain (eg)
enthalpy, ΔHeg
A + e- → A - x kj/mol

(E.A.)2 is always +ve, because of electrostatic repulsion between anion and

electron (having same charge).

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Electron Affinity or Electron Gain Enthalpy

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Electron Affinity or Electron Gain Enthalpy

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 Electron Affinity or Electron Gain Enthalpy

Electron affinity depends upon the following factors:

It decreases when radius increases. However, this is having the

following exceptions.

ΔegH of Cl > ΔegH of F, ΔegH of S > ΔegH of O ΔegH of P > ΔegH of N

• It increases across a period when Zeff increases.

• EA of half-filled and full-filled electronic configuration is less (mostly
endothermic).
• EA order for addition of electron in different orbitals having the same

principal quantum number is: s > p > d > f.

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Electronegativity

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 Electronegativity

It is the tendency of the atom to attract electrons (bond pair) towards itself
when combined in a compound.

● Electronegativity for an individual atom in a non-bonded state doesn’t

have any meaning.
● Electronegativity depends on bonding conditions.
● Electronegativity of any given element is not constant; it varies
depending on the element to which it is bound.

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 Electronegativity

Pauling scale: Linus Pauling developed a method for calculating

relative electronegativities of most elements. According to
Pauling:

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Electronegativity

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 Electronegativity

Mulliken’s scale :Electronegativity χ (chi) can be regarded as the

average of the ionization energy (IE) and the electron affinity (EA) of
an atom (both expressed in electron volts).

Mulliken’s values were about 2.8 times larger than the Pauling’s
values.
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 Electronegativity
Electron Gain Enthalpy
It is the tendency of an atom to
attract outside electrons
It is the property of an isolated
atom
It is the absolute electron
attracting tendency of an atom
It has units like kJ/mol and
Ev/atom
151
Electronegativity
It is the tendency of an atom to
attract shared pair of electrons.
It is the property of bonded atom
It is the relative electron
attracting tendency of an atom
It has no units
02/07/2024
 Electronegativity

● Charge on cationic species increases, Electronegativity increases.

● Charge on anionic species increases, Electronegativity decreases.

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