Group 15 Elements .

Atomic radius(pm)

N 70

Large increase in atomic radius due to strong

shielding effect of s & p electrons

P 110

As 120

Small increase in atomic radius due to poor

shielding effect of d / f electrons
Sb 140

Bi 150
Group 15 Elements Ionisation enthalpy

(k J / mol)

N 1402
Large decrease in ionisation enthalpy due to large increase in atomic size and strong
shielding effect of s & p electrons in P

P 1012

As 947

Small increase in atomic size and poor

shielding effect of d / f electrons
Sb 834

Bi 703
Group 15 Elements Electronegativity

N 3

P 2.1

Electronegativity decreases
As 2 down the group due to
increase in atomic size

Sb 1.9

Bi 1.9
 Metallic character &
Group 15 Elements non metallic character

P Non metals On moving down the group,

the atomic size increases, the
screening effect increases.
As Therefore tendency to lose
Metalloids electron increases i.e metallic
character increases
Sb

Bi Metal
Group 15 Elements

Melting point(K) Boiling point(K)

The m.p increases down

N 63 the group due to increase 77.2
in atomic size. The
unexpected decrease in
m.p of Sb and from Sb to Boilling
Bi is because of their point
P 317.1(white P) tendency to form three 554(white P) increases
covalent bonds instead of down the
five covalent bonds due group from
to inert pair effect N to Bi
As 1087.5(Grey α form) 883(Grey α form) because of
increase in
their
atomic size

Sb 904 1653

Bi 544 1813
Group 15 Elements
Density(g/ml)

Density increases down the group. This is due to

N 0.879 less increase of size with reference to atomic mass
on moving down the group. It increases the
magnitude of van der Waals forces of attraction
acting between the molecules and consequently
P 1.823 the lattice become more compact.

As 5.778

Sb 6.58

Bi 9.808
OXIDATION STATE

The element have five electrons in the valence shell. Therefore they exhibit various oxidation state from -3 to +5.

Negative Oxidation state

Oxidation state -3
N being smallest and most electronegative gains three electrons to attain nearest noble gas configuration forming

nitride ion with highly electropositive metals. Example Mg3 N2, Ca3 N2. Thus N shows -3 oxidation state.

Other elements show -3 oxidation state by forming covalent bond with metals e.g. Ca3 P2 , Na3As

Down the group due to decreasing electronegativity, decreasing ionization enthalpy, increase in atomic size and increase in metallic
character, the tendency of the elements to exhibit -3 oxidation state decreases.

Oxidation state -2

N and P show oxidation state of -2 in hydrazne (NH2 NH2) and diphosphine(P2H4) respectively.

Oxidation state -1

Nitrogen also shows an oxidation state of -1 in hydroxyl amine (NH2 OH)

P does not show an oxidation state of -1
Positive oxidation state

Oxidation state +5

On moving down the group, the stability of +5 oxidation state decreases while that of +3 oxidation state increases

due to inert pair effect.

They do not form M+5 ion showing +5 Oxidation state since element can not lose all the five electrons which requires very high energy.

They show +5 oxidation state in covalent compounds like PF5, PCl5, SbF5 AsF5etc.

N does not form pentahalide(NF5, NCl5 etc) because N do not have vacant d orbitals in their valence shell.

N show +5 oxidation state in N2 O5 (Nitrogen pentoxide)

Oxidation state +4

N and P also +4 oxidation state because of the ability to lose lone pair of electron to bond with Lewis acids.

Oxidation state +3

All the elements of group 15 show +3 oxidation state in both covalent compound(NCl3, PCl3, AsCl3, SbCl3)

and ionic compounds (BiF3, SbF3 etc)

As we go down the group the +3 Oxidation state becomes more and more stable.
VARIOUS OXIDATION STATES OF NITROGEN

NH3 N2H4 NH2OH N2 N2O NO N2O3 N2O4 N2O5

Nitric Nitrogen Nitrogen Nitrogen
Ammonia Hydrazine Hydroxyl Nitrogen Nitrous Oxide trioxide tetraoxide pentaoxi
amine oxide & & NO2 de
HNO2 &
HNO3

Oxidation -2 -1 0 +1 +2 +3 +4 +5
state
 ALLOTROPY IN GROUP 15 ELEMENTS
Except bismuth all elements show allotropy

Element Allotropic forms

N α - nitrogen having β - nitrogen having
cubic crystal hexagonal crystalline
structure structure

P White phosphorus red phosphorus has black phosphorus is most

is P4 tetrahedra complex chain thermodynamically stable
structure has layer structure

As grey arsenic yellow arsenic black arsenic

Sb metallic form yellow antimony explosive antimony

 PROPERTIES OF HYDRIDES OF GROUP 15 ELEMENTS

Property NH3 PH3 AsH3 SbH3 BiH3

E-H distance (pm) 102 142 152 171

Boiling Point(K) 240 186 211 256 290

Melting Point(K) 195 140 157 185

H-E-H Angle 108 94 92 91

∆diss (E-H) / KJ per mol 389 322 297 255

∆H f / KJ per mol -46 13 66 145 278

 OXIDES OF NITROGEN
Name Formula Oxidatio Common method of preparation Physical
n state appearance and
of chemical nature
Nitroge
n
Nitrous oxide or N2O +1 NH4NO3 → N2O + 2H2O Colourless gas,
Dinitrogen oxide Heat neutral

Nitrogen NO +2 2NaNO2 + FeSO4 + 3H2SO4 → Colourless gas,

monoxide or Fe2(SO4)3 + 2NaHSO4 + 2H2O + neutral, reactive
Nitric oxide 2NO
Dinitrogen N2O3 +3 250K Blue, solid,
trioxide 2N0 + N2O4 → 2N2O3 acidic
Nitrogen dioxide NO2 +4 673K Brown gas,
2Pb(NO3)2 → 4NO2 + 2PbO + acidic, reactive
O2
Dinitrogen N2O4 +4 Colourless solid
tetraoxide 2NO2 → N2O4 / liquid, acidic

Dinitrogen N2O5 +5 4HNO3 + P4O10 → 4HPO3 + Colourless ionic

pentoxide 2N2O5 solid, unstable
acidic
 ALLOTROPIC FORMS OF PHOSPHORUS
PROPERTIES WHITE PHOSPHORUS RED PHOSPHORUS BLACK PHOSPHORUS
Colour Yellowish white Reddish violet Black metallic lustre
Internal P4 Units. The four P atoms lie at Polymeric consisting of P4 Highly polymeric layered
Structure the corners of regular tetrahedra linked together by structure
tetrahedron covalent bonds
Preparation Heating phosphorite with silica By heating white phosphorus α-black P is obtained by heating
and coke at 1775 K in an inert atmosphere at 573 red P in a sealed tube at 803 K.
2Ca3(PO4)2 + 6SiO2 →6CaSiO3 + K for several days β-black P is obtained by heating
P4O10 white P at 473 K under very high
P4O10 + 10C → 10CO +P4 pressure (4000-12000atm) in an
inert atmosphere.

State Waxy solid Brittle powder Crystalline

Action of air Chemiluminescence(glow in No chemiluminescence No chemiluminescence
dark due to oxidation)
P4 + 5O2 → P4O10

Density 1.84 g / cm3 2.1 g / cm3 2.69 g / cm3

Solubiity in Soluble Insoluble Insoluble
CS2
M.P 317 K Above 773 K 860 K
Stability Less stable at ordinary temp. More stable at ordinary temp. Most stable
Reactivity Very reactive Less reactive Least reactive
 OXYACIDS OF PHOSPHORUS
Sr. Name of oxyacid Formula Oxidatio Number of – Preparation
No. n state OH
of P group(Basicity)

1 Hypophosphorus H3P02 +1 One –OH When yellow P is boiled with BaOH2 solution,
acid (Monobasic barium hypophosphite is formed. The salt is treated
acid) with sulphuric acid.
3Ba(OH)2 + 8P + 6H2O → 3Ba(H2PO2)2 + 2PH3
Ba(H2PO2)2 + H2SO4 → BaSO4 + 2H3PO2
2 Orthophosphorus H3P03 +3 Two–OH It is obtained by dissolving phosphorus trioxide in
acid (Dibasic acid) water.
P4O6 + 6H2O → 4 H3P03
3 Pyrophosphorus H4P205 +3 Two –OH By the action of PCl3 on H3P03
acid (Dibasic acid) 5H3P03 + PCl3→ 3 H4P205 + 3HCl
4 Hypophosphoric H4P206 +4 Four –OH Reaction between red P and alkali gives this acid.
acid (Tetrabasic 2P + 4NaOCl + 2H2O → H4P2O6 + 4NaCl
acid)
5 Orthophosphoric H3P04 +5 Three –OH It is formed when phosphorus pentoxide is boiled
acid (Tribasic acid) with hot water.
P4O10 + 6H2O → 4H3P04
6 Pyrophosphoric acid H4P207 +5 Four –OH It is obtained by simply heating orthophosphoric
(Tetrabasic acid at 523-533 K.
acid) 2H3P04 → H4P207 + H2O
7 Polymetaphosphoric (HP03)n +5 Three –OH It is prepared by heating a mixture of phosphorus
acid (Tribasic acid) acid and Br2in a sealed tube.
 Comparison of Ammonia and Phosphine
Sr.N Property Ammonia Phosphine
1 Molecular NH3 PH3
Formula
2 Structure Trigonal pyramidal Trigonal pyramidal
H-N-H bond angle is 107.8o H-N-H bond angle is 93.6o
N atom is sp3 hybridised. N atom is sp3 hybridised.
It has three bond pairs and one lone pair of It has three bond pairs and one lone pair of
electrons. electrons.
N-H distance is 101.7pm P-H distance is 141.9pm

3 Laboratory Heat Heat

Preparation NH4Cl + Ca(OH)2 → CaCl2 + 2 NH3 +2H2O P4 + 3NaOH + 3 H2O → PH3 + 3NaH2PO2
White P Sodium hypophosphite

4 Manufacturing Haber’s Process Ca3P2 + 6H2O → 3Ca(OH)2 + 2 PH3

method 700 K, 200 atm Calcium phosphide
N2 + 3H2 → 2NH3
Fe, Al2O3 Ca3P2 + 6HCl → 3CaCl2 + 2 PH3

2AlP + 3H2SO4 → Al2(SO4)3 + 2PH3

Heat
CaCN2 + 3H2O → CaCO3 + 2NH3 PH4I + KOH → KI + PH3 + H2O
Calcium cyanamide
Sr.No Property Ammonia Phosphine
.
5 Physical
property

a) Physical Colourless gas Colourless gas

state
b) Odour Characteristics pungent smell Unpleasant odour of rotten fish

c) Solubility Highly soluble in water Sparingly soluble in water

d) Density Lighter than air Heavier than air

e) Boiling 239.6 K 185.5 K Lower than ammonia

point due to absence of H
g) Melting 195.3 K 139.5 K bonding
point
h) Physiologic Non poisonous Poisonous
al action
Sr.No Property Ammonia Phosphine
.
5 Physical
property

a) Physical Colourless gas Colourless gas

state
b) Odour Characteristics pungent smell Unpleasant odour of rotten fish

c) Solubility Highly soluble in water Sparingly soluble in water

d) Density Lighter than air Heavier than air

e) Boiling 239.6 K 185.5 K Lower than

point ammonia due to
g) Melting 195.3 K 139.5 K absence of H
point bonding
h) Physiologic Non poisonous Poisonous
al action
Sr.No. Property Ammonia Phosphine
6 Chemical
property
a) Combustibili It burns in oxygen It burns with white bright flame
ty 4NH3 + 502 →4NO + 6H2O 2PH3 + 402 →P2O5 + 3 H2O
b) Basic nature Basic in nature. Forms ammonium salts Weakly basic. Forms ammonium
with acids salts with acids
NH3 + HCl → NH4Cl PH3 + HCl → PH4Cl
c) Action of 8NH3 + Cl2 → 6NH4Cl + N2 It explodes
chlorine PH3 + 4Cl2 → PCl5 + 3HCl
With excess of Cl2
NH3 + Cl2 → NCl3 + 3HCl

d) Action of Forms soluble complex Ag(NH3)2NO3 Forms black precipitate Ag3P

AgNO3 AgNO3 + NH3 → Ag(NH3)2NO3 3 AgNO3 + PH3→ Ag3P + 3HNO3
e) Action of Forms soluble complex of blue colour Forms black precipitate of copper
CuSO4 Cu(NH3)4SO4 tetra amine copper phosphide Cu3P2
sulphate 3CuSO4 + 2 PH3→ Cu3P2 + 3H2SO4
CuSO4 +2NH4OH→ Cu(NH3)4SO4 +
4H2O
f) Action of hot Forms sodamide Forms phosphide
sodium 2Na + 2NH3 → 2NaNH2 + H2 6Na + 2PH3 → 2Na3P + 3H2