P – Block Group-I

Group-I5 ns2np3 Anamolous Behavior of Nitrogen

N P As Sb Bi ▪ Small size
▪ High I.E , High E.N
metal ▪ Absence of d-orbital
Non-metal metalloid
NCl5 does not exist
Metallic Character PCl5 does exist (empty d-orbital)
N P As Sb Bi
Metallic character increases N2 (N N) Very high Bond Energy unreactive(inert)
Atomic Radius Bond Enthalpy
N < P < As < Sb < Bi N-N < P-P
I.E O-O < S-S
N > P > As > Sb > Bi F-F < Cl-Cl
E.N Reactivity with Hydrides
E + H2 → EH3
N > P > As > Sb > Bi
Bond association Enthalpy
B.P NH > PH > AsH > SbH > BiH
N < P < As < Sb < Bi Stability
M.P NH > PH > AsH > SbH > BiH
N < P < As > Sb > Bi Reducing Character
Oxidation State ns2np3 NH < PH < AsH < SbH < BiH
Basic Nature
Tendency to form -3 O.S
NH > PH > AsH > SbH > BiH
N > P > As > Sb > Bi M.p
Tendency to form +3 O.S NH > SbH > AsH > PH
B.P
N < P < As < Sb < Bi
BiH > SbH > NH > AsH > PH
Tendency to form +5 O.S
N > P > As > Sb > Bi Reactivity with oxygen
E + O2 → E2O3
E + O2 → E2O5
: Nitrogen does not show allotropy
 More the % of oxygen, the more is acidic character N2O3 (Dinitrogen oxide)
acidic character: E2O3 < E2O5
N2O3 P2O3 As2O3 Sb2O3 Bi2O3 NO2 (nitrogen dioxide)
Basic
acidic amphoteric
2NO2 → N2O4 (Dinitrogen tetroxide)
Reactivity of Halogens
E + X2 → EX3
E + X2 → EX5
N2O5 (Dinitrogen Pentoxide)
NX does not exist, nitrogen cannot form five bonds
Covalent Character: EX5 > EX3

Dinitrogen N2
Nitric Acid HNO3
Dinitrogen is produced commercially by the On a large scale it is prepared mainly by
liquefication and fractional distillation of air Ostwald’s process
: Dinitrogen is colourless, odourless ,tasteless and
non-toxic gas.
: It is inert at room temperature
Catalyst used in Haber’s Process is Fe sp2
: In the gaseous state, HNO exist as a
Ammonia NH3 planar molecule as shown above
: Conc HNO is a strong oxidising agent
Trigonal pyramidal
Brown Ring Test
This test is carried by adding dilute ferrous sulphate
: Ammonia is colourless gas with a pungent odour solution to an aqueous solution containing
: Ammonia gas is highly soluble in water Nitrate ion and then adding concentrated sulphuric
acid along the side of test tube
: Ammonia is a lewis base
NO3- + 3Fe+2 +4H+ → NO + 3Fe+3 + 2H2O
[Fe(H2O)6]2++NO→[Fe(H2O)5(NO)]2++ H2O
N 2O (Dinitrogen oxide ) brown
NO (Nitrogen monoxide) A brown ring indicates the presence of nitrate
ion in solution
 Phosphorous Phosphine PH3

Phosphorous is found in many allotropic forms, the
important ones being white, red And black
White Phosphorous
• White phosphorous is translucent white waxy
solid
• It is poisonous and insoluble in water but
soluble in CS
• White phosphorus is less stable and more
reactive 3 It is also used in smoke screens
sp (angular strain)
• Phosphine is prepared by the reaction
calcium phosphide with water or dilute
acid
• It is a colorless gas with rotten fish
smell and is highly poisonous
NOTE:
The spontaneous combustion of phosphine
is used in Holme’s Signal.

P4O10 P4O6

Red Phosphorous
• Red phosphorus is obtained by heating white
phosphorus at 573 K in an inert atmosphere
Phosphorus Trichloride PCl3
• It is odourless, non poisonous, and insoluble in
water as well as carbon disulphide It is obtained by passing dry chlorine over
• Chemically red phosphorus is much less reactive heated white phosphorus
than white phosphorus sp3

Pyramidal shape

Phosphorus Pentachloride PCl5

Black Phosphorous
• Black phosphorus has two forms -black
phosphorus and -black phosphorus.
• When red phosphorus is heated under pressure,
A series of black phosphorus is formed
It is obtained by passing dry chlorine over
heated white phosphorus
With excess of dry chlorine
 PCl5 →In gaseous and liquid H4P2O5 Pyrophosphorous acid
phases,it has trigonal
bipyramidal structure
→The three equatorial
P-Cl bonds are
equivalent while the two
Short,strong axial bonds are longer
than equatorial bonds

H4P2O7 Pyrophosphoric acid

PCl5 (s) → [PCl4]+ [PCl6]-

sp d , octahedral
sp ,tetrahedral

Oxoacids
H4P2O6 Hypophosphoric acid
H3PO4 Ortho phosphoric acid

Acidic hydrogen

H3PO3 Ortho phosphorous acid

Reducing Nature
H3PO2 Hypophorous acid
 P–Block Group-I
Group-I6 ns2 np4 (Chalcogen) M.P
O < S < Se < Po < Te
O S Se Te Po
B.P
(metal) O < S < Se < Po < Te
(Radioactive) Oxidation State ns2 np4
(metalloids)
(non-metals)
Tendency to form -2 O.S
CaSO4.2H2O (Gypsum) O > S > Se > Te > Po

CaSO4.1/2H2O (Plaster of Paris) Tendency to form +4 O.S

O < S < Se < Te < Po
MgSO4.7H2O (Epsom salt) Tendency to form +6 O.S
PbS (Galena) O > S > Se > Te > Po
ZnS (Zinc Blende) Anomalous behavior of oxygen
CuFeS2 (Copper Pyrites) Small size
High I.E , High E.N
Atomic Size
Absence of d-orbital
O < S < Se < Te < Po Hydrogen bonding
I.E Reactivity with Hydrides
Bond dissociation Enthalpy:
O > S > Se > Te > Po H2O > H2S > H2Se > H2Te > H2Po
E.N Thermal stability:
O > S > Se > Te > Po H2O > H2S > H2Se > H2Te > H2Po

Electron gain Enthalpy Acidic Character:

H2O < H2S < H2Se < H2Te < H2Po
S > Se > Te > Po > O Reducing Character:
H2O < H2S < H2Se < H2Te < H2Po
All group-I element show allotropy
Reactivity with Oxygen Ozone O3
E + O2 → EO2 →Ozone is an allotropic form of oxygen
E + O2 → EO3 → Ozone layer protects the earth surface from U.V
radiation
Acidic Nature: EO2 < EO3 Properties
Reducing nature: SO > SeO > TeO → Ozone is a pale blue gas, dark blue liquid and violet-
black solid
Reactivity with Halogens
E + X2 → EX2
E + X2 → EX4
E + X2 → EX6
Stability of halides: F- > Cl- > Br- > I- Suplhur allotropic forms
: Among hexahalides, only hexafluorides
Are stable Yellow rhombic
Among tetraflourides ,SF is gas , monoclinic
SeF a liquid and TeF solid
Rhombic Sulphur ( - sulphur)
Oxygen →it is soluble in water but dissolves to some extent in
→ On a large scale it can be benzene , alcohol and ether
prepared from water or air. →it is readily soluble in CS
Electrolysis of water leads to Monoclinic sulphur ( -sulphur)
the release of hydrogen at the
cathode and oxygen at the anode. →It is soluble in CS
→ Dioxygen is a colorless and Note:
odorless gas →At 369 K both the forms are stable. This temperature
→ O2 is paramagnetic is called transition temperature
Acidic oxide If
T> →Monoclinic ( - sulphur)
→Generally non-metals are acidic
T< →Rhombic ( -sulphur)
→ Oxide of some metal in high
oxidation state have acidic character
Crown shape
Basic oxide Chair form

In general metallic oxides are basic

 SO2
Sulphur Dioxide H2SO5 Caro’s Acid
→Sulphur dioxide is formed with a little( )
Sulphur trioxide when sulphur is burnt in air or
oxygen
→Sulphur dioxide is a colorless with pungent H2S2O3 Thiosulphuric Acid
smell and highly soluble in water

Angular H2S2O4 Dithionous Acid

Oxoacids
H2SO3 Sulphurous Acid

H2S2O5 Disulphurous Acid

H2SO4 Sulphuric Acid

Sulphuric Acid H2SO4

→ Sulphuric acid is manufactured by the
H2S2O8 Peroxodisuplhuric Acid contact process
→ The sulphuric acid obtained by contact
process is % pure
→Sulphuric acid is a colorless
→ It’s strong oxidizing agent
H2S2O7 Pyrosulphuric Acid → It’s a dibasic acid