15TH GROUP ELEMENTS

15TH GROUP ELEMENTS

15TH GROUP ELEMENTS

INTRODUCTION
15TH GROUP ELEMENTS

H He

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar

K s Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge
p
As Se Br Kr

d
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Rf Db Sg Bh Hs Mt Ds Rg

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Ac Th Pa U Np Pu Am Cm
f Bk Cf Es Fm Md No Lr
15TH GROUP ELEMENTS

Group 15 Atomic number

N Nitrogen 7
P Phosphorus 15 Nitrogen family members
are also called Pnicogens
As Arsenic 33

Sb Antimony 51 Because compounds of these

elements are poisonous in nature
Bi Bismuth 83 or form suffocating compounds
15TH GROUP ELEMENTS

Occurrence

Elements NITROGEN

Atmosphere (78%)(free state ),

Nitrates (combined)
Occurrence Example –
Chile salt petre (NaNO3)
Indian salt petre (KNO3)
15TH GROUP ELEMENTS

Occurance

PHOSPHOROUS
Elements
occurs in apatite family

Ca9 [PO4]6.CaX2 (3Ca3(PO4)2 .CaX2 )

(X = F, Cl, OR, OH)
Occurence 3Ca3 (PO4)2.CaF2
(FLUORAPATITE)Present in
bones as well as living cells.
15TH GROUP ELEMENTS

Occurrence

Elements BISMUTH, ARSENIC,

ANTIMONY

Oxide–BISMUTHITE (Bi2O3)
Occurrence sulphide-
BISMUTHGLANCE(Bi2S3)
15TH GROUP ELEMENTS

ELECTRONIC CONFIGURATION
PHYSICAL PROPERTIES OF 15 TH
GROUP ELEMENTS
15TH GROUP ELEMENTS

1s

2s 2
According to Aufbau Principle
p
an atom is "built up" by
3s 3 3
p d progressively adding electrons
4s 4 4 4f
p d
5s 5 5 5f
p d
6s 6 6
p d
15TH GROUP ELEMENTS

Elements Symbol & Brief rep of

Atomic Electronic Configuration electronic
Number configuration
Nitrogen N 7 1s2 2s2 2p3 [He] 2s2 2p3

Phosphorous P 15 1s2 2s2 2p6 3s2 3p3 [Ne] 3s2 3p3

Arsenic As 33 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p3 [Ar] 3d10 4s2 4p3

Antimony Sb 51 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 [Kr]4d10 5s2 5p3
4d10 5s2 5p3

Bismuth Bi 83 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 [Xe]4f14 5d10 6s2
4f14 5s2 5p6 5d10 6s2 6p3 6p3
15TH GROUP ELEMENTS

 GEC  ns2 np3

15TH GROUP ELEMENTS

Atomic size
Elements Elec. Config. Diagram
2-Energy levels
N [He] 2s2 2p3
3-Energy levels
P [Ne] 3s2 3p3

As [Ar] 3d10 4s2 4p3 4-Energy levels

Sb [Kr] 4d10 5s2 5p3 5-Energy levels

Bi [Xe] 4f145d10 6s2 6p3 6-Energy levels

15TH GROUP ELEMENTS

Down the group

New shells are added

Atomic size increases

Nuclear charge decreases

15TH GROUP ELEMENTS

Ionization Energy
What is
It is the minimum amount of energy Ionization
required to remove the most loosely energy ?
bound e– from the outer most shell of
an isolated atom in the gaseous state

Ionization energy decreases down the group from Nitrogen to

Bismuth due to the increase in atomic size.
15TH GROUP ELEMENTS

METALLIC CHARACTER

ELEMENT METALLIC CHARACTER

N Non-metal
P Non-metal
As Metalloid

Sb Metalloid

Bi Metal
15TH GROUP ELEMENTS

OXIDATION STATES
Oxidation
Compound NAME
State of N
NH3 AMMONIA –3

N 2 H4 HYDRAZINE –2

NH2OH HYDROXYL AMINE –1

-
N3H HYDRAZOIC ACID
N2 DINITROGEN 0
DINITROGEN MONOXIDE
N2O (LAUGHING GAS) +1
15TH GROUP ELEMENTS

OXIDATION STATES
Oxidation
Compound NAME
State of N
NO Nitrogen monoxide +2
nitrous acid or
HNO2 or N2O3 dinitrogen trioxide +3
NO2 or N2O4 nitrogen dioxide or
Dinitrogen tetroxide +4
nitric acid or
HNO3 or N2O5 dinitrogen pentoxide +5
15TH GROUP ELEMENTS

OXIDATION STATES
Characteristic electronic configuration : ns2 np3
This suggests common oxidation states :- +3, +5, and –3
N Stability of + 3 oxidation state
increases and that of + 5
P oxidation state decreases
As
Reason : - Inert Pair effect
Sb
N cannot form compounds like NF5 or NCl5 while P can form
Bi
compounds like PCl5
15TH GROUP ELEMENTS

Explain : P (Ground state)

3s 3p 3d

P (Excited state)

This cannot happen in Nitrogen due to lack of d orbitals

15TH GROUP ELEMENTS

CHEMICAL PROPERTIES
OF
15TH GROUP ELEMENTS
15TH GROUP ELEMENTS

Chemical properties
Reactivity towards
Oxygen:
• These elements react with Oxygen to form two types of oxides
• Trioxides - M2O3 • Pentoxides - M2O5

• The Oxides in the higher oxidation state of the element is more acidic
than that of lower oxidation state.
• Acidic character decreases down the group

• The trioxides of Nitrogen and Phosphorus are purely acidic, that of

Arsenic and Antimony are amphoteric and that of Bismuth is
predominantly basic .
15TH GROUP ELEMENTS

• All Pentoxides are acidic.

• Except Bi other elements form pentoxides represented by M 4O10.

• Tri-oxides dissolve in water giving – Ous acids

• Pentoxides dissolve in water giving – ic acids

15TH GROUP ELEMENTS

Reactivity towards metals :

These elements react with metals to form binary compounds

in which VA group element exhibits – 3 oxidization state.

Example:

6Mg + N2 2Mg3N2
Magnesium nitride
6Ca + P4 2Ca3P2
Calcium phosphide
15TH GROUP ELEMENTS
Reactivity towards halogens:
• These elements form two types of halides
• Trihalides - MX3 • Pentahalides - MX5
• Nitrogen does not form petahalides due to non availability of the
d-orbitals in it’s valence shell.
15TH GROUP ELEMENTS

DINITROGEN
(N2)
15TH GROUP ELEMENTS
PREPARATION:-
1. Laboratory method:
• In the laboratory Dinitrogen prepared by treating an aqueous
solution of Ammonium chloride with Sodium nitrite

NH4Cl + NaNO2 N2­ + 2H2O + NaCl
ammonium Sodium Dinitrogen
chloride nitrite

Make a note
Small amounts of NO and HNO3 formed, removed by
passing the gas through aq. H2SO4 + K2Cr2O7.
15TH GROUP ELEMENTS

2. Commercial method :

Liquification Fractional distillation

Air Liquid Air Dinitrogen
15TH GROUP ELEMENTS

3. By thermal decomposition of ammonium dichromate :

• N2 can also be obtained by the thermal decomposition of

ammonium dichoromate.

(D)
(NH4)2Cr2O7 N2­ + Cr2O3 + 4H2O
Ammonium Dinitrogen
dichromate
15TH GROUP ELEMENTS

4. From suspension of bleaching powder and ammonia

3CaOCl2 + 2 NH3 N 2­ + 3CaCl2 + 3H2O

Calcium Ammonia Dinitrogen
oxychloride
15TH GROUP ELEMENTS

5. Thermal decomposition of metal azides :

• Very pure nitrogen can be obtained by the thermal
decomposition of sodium or barium azide
Note :
()
2NaN3 2Na + 3N2­ – +≡

:
N- N N

:
:
Dinitrogen

:
Sodium azide (or)
() –
Ba(N3)2 Ba + 3N2­ N3
Barium azide Dinitrogen Azide ion

Highly pure form of dinitrogen is obtained by this method.

15TH GROUP ELEMENTS

CHEMICAL PROPERTIES
OF NITROGEN
15TH GROUP ELEMENTS

Chemical reactions
1. Action on metals : At high temperature N2 directly combines with Li
and Mg metals to form nitrides
(heat)
6Li + N2 2Li3N Lithium nitride
(heat)
3Mg + N2 Mg3N2 Magnesium nitride
(heat)
2Al + N2 2AlN Aluminium nitride
2. Action of dioxygen :
( or heat)
N 2 + O2 2NO
2000 K
Nitric oxide
15TH GROUP ELEMENTS

Chemical reactions
3. Action of calcium carbide :
Ca 10000C –
–

:
:
+ N2 Ca+2 :
N=C=N
: + C
CºC (D)
or Dinitrogen or Carbon(graphite)
CaC2 CaCN2
Calcium
Calcium
carbide
cyanamide
15TH GROUP ELEMENTS

Chemical reactions

4. Action of dihydrogen:
N2 773 K
+ 3H2 (g) 2NH3 (g)
(g)

Uses : ammonia
 Di nitrogen is mainly used in the manufacture of Ammonia and
other industrial chemical containing nitrogen (Eg ; CaCN 2)
 It is used to maintain the inert atmosphere (Eg: In iron and steel
industry)
 Liquid dinitrogen is used as a refrigerant to pressure biological
materially food items and in cryo surgery
15TH GROUP ELEMENTS

ANOMALOUS PROPERTIES
OF NITROGEN
15TH GROUP ELEMENTS

Anomalous properties of nitrogen

Nitrogen differs from the rest of the members of this group due to its
small size, high electronegativity, high ionisation enthalpy and non-
availability of d orbitals.

Nitrogen has unique ability to form p - p multiple bonds with itself

and with other elements having small size and high electronegativity
(Eg: C, O). Heavier elements of this group do not form p - p bonds as
their atomic orbitals are so large and diffuse that they can not have
effective overlapping.
15TH GROUP ELEMENTS

PREPARATION OF AMMONIA
15TH GROUP ELEMENTS

Preparation of Ammonia
1. Laboratory method :
()
2NH4Cl + Ca(OH)2 2NH3 + CaCl2 + 2H2O
Ammonium Calcium
Ammonia
chloride hydroxide
15TH GROUP ELEMENTS

Preparation of Ammonia
2. Commercial method (Haber’s process):
Fe-catalyst
Mo-Promoter
N2 + 3H2 2NH3(g) (ΔH = −92.4 kJ·mol−1)
(g) (g)
773K, 200atm
Dihydrogen Ammonia
Dinitrogen
15TH GROUP ELEMENTS

Note : Dehydrating agents cannot be used

H2SO4 P2 O5 anhy. CaCl2

Acidic Acidic Forms a complex
 reacts with NH3  reacts with NH3 CaCl2. 8NH3

Therefore, moist NH3 is dried over quicklime i.e., CaO

 15TH GROUP ELEMENTS
Preparation of Ammonia

3. Action of calcium carbide (Cynamide process):

10000C
(I) CaC2 + N2 CaCN2 + C
(D)
Calcium Calcium cyanamide + Carbon(graphite)
carbide Dinitrogen

NITROLIM

(II) CaCN2 + 3H2O NH3­ + CaCO3

Calcium Super Calcium
Ammonia
Cyanamide heated Steam carbonate
15TH GROUP ELEMENTS

CHEMICAL PROPERTIES
OF AMMONIA
15TH GROUP ELEMENTS

Action of halogens :
1. Chlorine :
8 NH3 + 3Cl2 6NH4Cl + N2­
(excess) Ammonium
chloride

NH3 + 3Cl2 NCl3 + 3HCl

(excess) Nitrogen
trichloride
15TH GROUP ELEMENTS

Action of halogens :
2. Bromine :
8 NH3 + 3Br2 6 NH4Br + N2­
Ammonium bromide
3. Iodine :
2NH3 + 3l2 NH3NI3 + 3Hl
Nitrogen triodide ammonia

8NH3NI3 5N2 + 9I2 + 6NH4I

Ammonium iodide
15TH GROUP ELEMENTS
 Ammonia precipitates the hydroxides of many metals from
their salt solutions

ZnSO4(aq) + 2NH4OH(aq) Zn(OH)2(S) + (NH4)2 SO4(aq)

(White
ppt)
FeCl3 (aq) + NH4OH(aq) Fe2O3 . xH2O(S) + NH4Cl(aq)
(brown ppt)
15TH GROUP ELEMENTS
 Due to the presence of lone pair in ammonia, ammonia is used in
detection of metal ions such as Cu+2 , Ag+
Examples
AgCl(s) + 2NH3(aq) [Ag(NH3)2] Cl(aq) Colourless
White ppt 2+
Cu+2 (aq) + 4 NH3(aq) Cu(NH3)4 Deep Blue Colour
Reaction of ammonia with Nessler’s reagent:

Hgl2(aq) + 2KI(aq) K2HgI4(aq) (formation of Nessler’s reagent)

2K2HgI4 + NH3 + 3KOH H2N – Hg – O – Hg – I +7KI+ H2O
(Nessler’s reagent) (Iodide of Millon’s base)
15TH GROUP ELEMENTS

STRUCTURE
&
USES OF AMMONIA
15TH GROUP ELEMENTS

Structure of Ammonia
 Ammonia is expected to have a tetrahedral
geometry
 The central nitrogen atom invloves sp3 mN
p
hybridisation. 0 1 .7
1
H 107.80 H
 one position is occupied by a lone pair.
H
 Three bond pairs and one lone pair of electrons as shown in the
structure.
 15TH GROUP ELEMENTS

Protophilic and non aqueous solvent.

Ammonium nitrate
Urea
NH3 is used Ammonium Phosphate
Cooling agent in the
Uses of
or refrigerant. preparation of Ammonium sulphate
Ammonia
Other fertilizers
HNO3 by Ostwald’s process.
15TH GROUP ELEMENTS

OXIDES OF NITROGEN
15TH GROUP ELEMENTS
Oxides of Nitrogen
Physical
Oxidation state Common methods
Name Formula appearance and
of nitrogen of preparation
chemical nature
Dinitrogen Monoxide
or nitrous oxide NH4NO3 Heat Colourless gas,
(Nitrogen (I) oxide) N2O +1 neutral
(laughing gas) N O + 2H O
2 2

2NaNO2 + 2FeSO4
Nitrogen monoxide
+ 3H2SO4  Colourless gas,
or Nitric oxide NO +2
Fe2(SO4)3 + 2NaHSO4 neutral
(Nitrogen (II) oxide) + 2H2O + 2NO
2NO + N2O4 250 K
Dinitrogen trioxide 2N2O3 Blue solid ,
NO +3
(Nitrogen (III) oxide) 2 3 NO + NO2 N2O3 acidic
15TH GROUP ELEMENTS
Oxides of Nitrogen
Physical
Oxidation state Common methods
Name Formula appearance and
of nitrogen of preparation
chemical nature
Nitrogen dioxide 2Pb(NO3)2 673 K Brown gas,
NO2 +4
(Nitrogen (IV) oxide) 4NO2 + 2PbO+O2 acidic

Colourless
Dinitrogen tetroxide Cool
N2O4 +4 2NO2 N2O4 solid/ liquid,
(Nitrogen (IV) oxide) Heat
acidic

Dinitrogen pentoxide 4 HNO3 + P4O10 Colourless

N2O5 +5
(Nitrogen (V) oxide)  4HPO3 + 2N2O5 solid ,acidic
15TH GROUP ELEMENTS

NITRIC ACID
15TH GROUP ELEMENTS

Nitric Acid

Preparation of Nitric acid

Laboratory method to prepare nitric acid.

NaNO3 + H2SO4 NaHSO4 + HNO3

Sodium Nitric acid
nitrate
15TH GROUP ELEMENTS

Preparation of nitric acid on a large scale by Ostwald’s process.

Pt/ Rh gauze catalyst

Step 1 4NH3(g) + 5O2 4NO(g) + 6H2O(g)
500 K 9 bar
Nitric oxide
Step 2 2NO(g) + O2(g) 2NO2(g)
Nitrogen Dioxide

Step 3 NO2 + H2O(l) 2HNO3(l) + NO(g)

Nitric acid
15TH GROUP ELEMENTS

Structure of Nitric Acid

m O
H 1 p
96 102° 12
pm
O N 130°
140.6 pm
O
 HNO3 is a planar molecule.
 Bond length between H–O is 96 pm
 O–N is 140.6 pm
 Bond angle between H–O–N is 1020
 Bond angle between O–N–O is 1300.
15TH GROUP ELEMENTS

REACTIONS OF
NITRIC ACID
15TH GROUP ELEMENTS

Reactions of NITRIC ACID

With copper Metal + acid Metal salt

3Cu+ 8HNO3(dil) 3Cu(NO3)2 + 2NO + 4H2O

Copper nitrate Nitric oxide

Cu + 4HNO3(conc.) Cu(NO3)2 + 2NO2 + 2H2O

Copper nitrate Nitrogen
dioxide
15TH GROUP ELEMENTS
Reactions of NITRIC ACID

With Zinc Metal + acid Metal salt

4Zn + 10HNO3(dil) 4Zn(NO3)2 + N2O + 5H2O

Zinc nitrate nitrous oxide

Zn + 4HNO3(conc.) Zn(NO3)2 + 2NO2 + 2H2O

Zinc nitrate Nitrogen

dioxide
15TH GROUP ELEMENTS

Reactions of NITRIC ACID

With Phosphorous
Non metal + acid Acid
P4 + 20HNO3 4H3PO4 + 20NO2 + 4H2O

Phosphoric acid
With Iodine

I2 + 10HNO3 2HIO3 + 10NO2 + 4H2O

Iodic acid.
15TH GROUP ELEMENTS

Reactions of NITRIC ACID

With Sulphur

S8 + 48HNO3 8H2SO4 + 48NO2 + 16H2O

Sulphuric acid
With Carbon

C + 4HNO3 CO2 + 2H2O + 4NO2

(hot, conc.)
Carbon dioxide
15TH GROUP ELEMENTS

The brown ring test.

N + 3Fe2+ + 4H+ NO + 3Fe3+ + 2H2O

[Fe(H2O)6]2+ + NO [Fe(H2O)5(NO)]2+ + H2O

(Brown ring)
15TH GROUP ELEMENTS

Action of HNO3 on Gold and Platinum

HNO3 + 3HCl NOCl + 2H2O + 2[Cl]
Nitrosyl
chloride

Au + 3[Cl] + 3HCl 4AuCl4

Tetrachloroaurate

Pt + 4[Cl] + 2HCl H2PtCl6

Chloroplatinic acid
15TH GROUP ELEMENTS
Mixture of conc. H2SO4 + conc. HNO3
Action of concentrated HNO3 is called nitration mixture
With Benzene
NO2
conc. H2SO4
+ HNO3 + H2 O
< 600C
(benzene)(conc) Nitrobenzene
With Toluene
Reaction is called “Nitration”
CH3
conc. H2SO4 NO2 NO2
C6H5CH3 + 3HNO3 + 3H2O
> 600C
Toluene (conc)
NO2
2, 4, 6 – trinitrotoluene
15TH GROUP ELEMENTS

Action of concentrated HNO3

With phenol NO2
conc. H2SO4 OH
C6H5OH + 3HNO3 + 3H2O
Phenol (conc) O2 N NO2
2, 4, 6 – trinitrophenol

 2,4,6-trinitrophenol is called Picric acid ( explosive in nature)

15TH GROUP ELEMENTS

Action of concentrated HNO3

With Cane sugar

conc. H2SO4 COOH + 5H2O

C12H22O11 + 18(O) 6
HNO3 COOH
Cane Sugar
Oxalic acid
15TH GROUP ELEMENTS

TYPES OF
NITROGEN OXIDE
15TH GROUP ELEMENTS

Dinitrogen oxide, N2O (Laughing Gas)

 It is also called nitrous oxide.
 It is stable and colorless gas.
 It has all electrons paired.
 Diamagnetic.
:

:
:N ≡ N  O  = N = O
:
N
:

:
15TH GROUP ELEMENTS

Nitric oxide (Nitrogen monoxide), NO :

 It is most stable oxide of nitrogen.
 ‘N’ and ‘O’ together have 11 valence electrons.
 An odd electron molecule.
 Paramagnetic.
15TH GROUP ELEMENTS

Nitric oxide (Nitrogen monoxide), NO :

 It acts as an oxidising and reducing agent.

– +


:
:


:N = O:  :N = O:
(Ionic structure) (Covalent structure)

N O
Dimeric structure of NO
O N
15TH GROUP ELEMENTS

Nitrogen dioxide, NO2 1

N 20 pm
 It is an acidic oxide
134°
 It is a reddish brown gas O O
 It is paramagnetic
 It is dimerizes to N2O4

2NO2 N 2 O4




N N
:O: :O: :O: :O:
:

:
15TH GROUP ELEMENTS

Dinitrogen trioxide N2O3 105° O

O 114 pm N 186 pm N 130°
 It is an acidic oxide
117° 121 pm O
 It is also known as nitrogen sesquioxide
 It is diamagnetic
 It’s a planar molecule
:O:
:

:O:

:
:O
:

:O
N N
:O :
: N O: N
:
15TH GROUP ELEMENTS
O O
Dinitrogen tetroxide N2O4
 It is an acidic oxide 176 pm
N N 135°
 It has no unpaired electron on N atom. 118 pm
  It is diamagnetic
 It is a planar molecule O O
:
:

:O: :O:

:
:O: :O:

N N N N
: :
: :

O O

: :
O
: :
O
:
15TH GROUP ELEMENTS

Dinitrogen pentoxide N2O5 O O O

 It is an unstable acidic oxide. N 120° N 134°
O O
 It is an excellent oxidizing agent.

:O:

: :

:
: O: :O:

: :
:O:
: :

O O

N N N N
: :

O: :O: :O:
:O:
15TH GROUP ELEMENTS

Symbol Atomic Number

P 15
Phosphorus
15TH GROUP ELEMENTS

:
Allotropic forms of phosphorus P
60°
White phosphorus :P P:
 Common variety of
phosphorus.
 Consists of P P

:
4

 Four P-atoms lie at the corners of the regular tetrahedron

 Each phosphorus bonded to each of the three P-atom by covalent

bonds.
 It is poisonous.
15TH GROUP ELEMENTS

Allotropic forms of phosphorus

White phosphorus
 White phosphorus is a white waxy solid.
 It is poisonous, insoluble in water but soluble in carbon disulphide

and glows in dark ( chemiluminescence).

 It dissolves in boiling NaOH solution in an inert atmosphere giving

P4 + 3NaOH + 3H2O → PH3 +3NaH2PO2

PH3

(Sodium hypophosphite)
 and it is less stable
15TH GROUP ELEMENTS

Allotropic forms of phosphorus

White phosphorus

 It readily catches fire in air to give dense white fumes of P 4O10.

P4+ 5O2 → P4O10

 It consists of discrete tetrahedral P4 molecules are held by

Vander Waal’s forces.
15TH GROUP ELEMENTS

Allotropic forms of phosphorus

Red phosphorus
 It is polymeric.

P P P

P P P P P P

P P P

 It is non poisonous.
15TH GROUP ELEMENTS

Allotropic forms of phosphorus

Red phosphorus
 It is obtained by heating white “P” at 573 K in an inert atmosphere
for several days.
 It Possesses iron grey lustre.
 It is odourless.
 non-poisonous and insoluble in water as well as in carbon disulphide.
 Chemically, red phosphorus is much less reactive than white phosphorus.
 It is polymeric, consisting of chains of P4 tetrahedral linked together
through covalent bonds.
15TH GROUP ELEMENTS

Allotropic forms of phosphorus

Black phosphorus
 It is thermodynamically most stable form
 It has a layered structure
 It has mainly two forms  - Black and  - Black
 Red phosphorus gives  - Black phosphorus
 White phosphorus gives  - Black phosphorus
 It does not get oxidized easily with air
 It can be sublimed in air and has opaque monoclinic or rhombohedral

 It does not oxide in air. 𝛃- black phosphorus is prepared by

crystals.

heating white phosphorus at 473K under high pressure.

15TH GROUP ELEMENTS

Allotropy
Arsenic  Allotropic forms are
Grey metallic Yellow Black
Antimony  Allotropic forms are
Metallic Yellow or  – antimony
antimony Explosive antimony
 Out of the three, the stable forms are yellow and metallic antimony
Bi  radioactive and emits  rays half life 1.9  1019 years
15TH GROUP ELEMENTS

PHOSPHINE
15TH GROUP ELEMENTS

Preparation of Phosphine

Ca3P2 + 6H2O 3Ca(OH)2 + 2PH3

Calcium Calcium phosphine
phosphide hydroxide

Ca3P2 + 6HCl 3CaCl2 + 2PH3

Calcium Calcium phosphine
phosphide chloride
15TH GROUP ELEMENTS

From phosphorus

P4 + 3NaOH + 3H2O PH3 + 3NaH2PO2

White Phosphine Sodium
Phosphorus hypophosphite

From phosphonium iodide

PH4I + KOH KI+ H2O + PH3

Phosphonium Phosphine
iodide
15TH GROUP ELEMENTS

THE PROPERTIES OF PHOSPHINE

 It is a colourless gas with fish smell and is highly poisonous.

 It explodes in contact with traces of oxidising agents like HNO 3,

Cl2 and Br2 vapours.

 It is slightly soluble in water.

 The solution of PH3 in water decomposes in presence of light

giving red phosphorus and H2.
15TH GROUP ELEMENTS

THE PROPERTIES OF PHOSPHINE

PH3 + 4Cl2 PCl5 + 3HCl

Phosphorus
pentachloride

3CuSO4 + 2PH3 Cu3P2 + 3H2SO4

Copper
phosphide
15TH GROUP ELEMENTS

THE PROPERTIES OF PHOSPHINE

3HgCl2 + 2PH3 Hg3P2 + 6HCl

Mercuric Mercuric
chloride phosphide

4PH3 P4 + 3H2

PH3 + HBr PH4Br

phosphonium bromide
15TH GROUP ELEMENTS

THE PROPERTIES OF PHOSPHINE

 The spontaneous combustion of phosphine is technically used in

Holme’s signals.
 Containers containing calcium carbide and calcium phosphide are
pierced and thrown in the sea when the gases evolved burn and
serve as a signal.
 It is also used in smoke screens.
15TH GROUP ELEMENTS

THE USES OF PHOSPHINE

CaC2 + 2H2O Ca(OH)2 + C 2 H2
Calcium Acetylene
carbide
Ca3P2 + 6H2O 3Ca(OH)2 + 2PH3
Calcium Phosphine
phosphide
A mixture of Ca3P2 and CaC2 is used in
Holme’s signal for navigation
15TH GROUP ELEMENTS

PHOSPHORUS TRICHLORIDE
15TH GROUP ELEMENTS

Preparation of Phosphorus trichloride


P4 + 6Cl2 4PCl3
Phosphorus
trichloride

P4 + 8SOCl2 4PCl3 + 2S2Cl2 + 4SO2
Thionyl Phosphorus
chloride trichloride
15TH GROUP ELEMENTS

Properties of PCl3

PCl3 + 3H2O H3PO3 + 3HCl

Phosphorous
acid
PCl3 + Cl2 PCl5
Phosphorous
penta chloride
15TH GROUP ELEMENTS

Properties of PCl3

3CH3COOH + PCl3 3CH3COCl + H3PO3

Acetic acid Acetyl chloride

3C2H5OH + PCl3 3C2H5Cl + H3PO3

Ethanol Chloroethane

3AgCN + PCl3 P(CN)3 + 3AgCl

Silver cyanide Silver chloride
15TH GROUP ELEMENTS

Structure of PCl3
 Pyramidal shape
 Phosphorus is sp3 hybridised
P
 Phosphorus has lone pair of electron
Cl Cl
Cl
15TH GROUP ELEMENTS

PHOSPHORUS PENTACHLORIDE
15TH GROUP ELEMENTS

Preparation of Phosphorus pentachloride

P4 + 10Cl2 4PCl5
(excess) Phosphorus pentachloride

P4 + 10SO2Cl2 4PCl5 + 10SO2

Sulfuryl
chloride
15TH GROUP ELEMENTS

Properties of PCl5

PCl5 + H2O POCl3 + 2HCl

Phosphorus
oxychloride
POCl3 + 3H2O H3PO4 + 3HCl
Phosphoric
acid
PCl5  PCl3 + Cl2
Phosphorus
trichloride
15TH GROUP ELEMENTS

Properties of PCl5
C2H5OH + PCl5 C2H5Cl + POCl3 + HCl
Ethanol Chloroethane

CH3COOH + PCl5 CH3COCl + POCl3 + HCl

Acetic acid Acetyl chloride
15TH GROUP ELEMENTS

PCl5 as a powerful chlorinating agent

2Ag + PCl5 2AgCl + PCl3
Silver
chloride

Sn + 2PCl5 SnCl4 + 2PCl3

Tin
chloride
15TH GROUP ELEMENTS

Structure of PCl5 Cl
Cl

240 pm
In gaseous and liquid phases, it has a
trigonal bipyramidal structure.
In the solid state it exists as an P 2 0 2 pm
ionic solid, in which the cation,
is tetrahedral and the anion , isCl Cl
octahedral.
Cl
PCl5 has a trigonal bi pyramidal structure
15TH GROUP ELEMENTS

OXOACIDS OF
PHOSPHOROUS
15TH GROUP ELEMENTS

Oxoacids of phosphorous
 In oxy acids, phosphorus is tetrahedrally surrounded by other atoms .

P
15TH GROUP ELEMENTS

Oxyacids of phosphorous

General structure

 All these acids contain at least one P = O bond and one P–OH bond.

P
OH
15TH GROUP ELEMENTS
Hypophosphorous or phosphinic acid H3PO2
i) Hypophosphorus acid or
Phosphinic acid (H3PO2)
Oxyacid
two P – H bonds, one P – OH
bond and one P = O bond.
O
Structure P
H OH
H
Oxidation
+1
state of P
15TH GROUP ELEMENTS

Hypophosphorous or phosphinic acid H3PO2

2P4 + 3Ba(OH)2 + 6H2O 3Ba(H2PO2)2 + 2PH3

White phosphorus ppt

Ba(H2PO2)2 + H2SO4 2H3PO2 + BaSO4

ppt
15TH GROUP ELEMENTS
Orthophosphorus acid or Phosphonic acid H3PO3

ii) Orthophosphorus acid(H3PO3)

Oxyacid
one P – H bond, two P – OH
bonds and one P = O bond.

O
Structure P
HO OH
H
Oxidation
+3
state of P
15TH GROUP ELEMENTS
Orthophosphorus acid H3PO3

P2O3 + 3H2O 2H3PO3

PCl3 + 3H2O H3PO3 + 3HCl

Properties of H3PO3

4H3PO3 3H3PO4 + PH3
Ortho phosphine
Phosphoric acid
15TH GROUP ELEMENTS
Pyrophosphorus acid (H4P2O5)
iii) Pyrophosphorus acid (H4P2O5)
two P – H bonds,
Oxyacid two P – OH bonds
two P = O bonds
one P – O – P bond
O O
Structure H–P – O–P – H

OH OH
Oxidation
+3
state of P
15TH GROUP ELEMENTS

Pyrophosphorus acid (H4P2O5)

PCl3 + H3PO3 + 2H2O H4P2O5 + 3HCl

15TH GROUP ELEMENTS
Hypophosphoric acid (H4P2O6)
iv) Hypophosphoric acid (H4P2O6)

two P = O bonds,
four P – OH bonds,
Oxyacid
One P-P bond.

O O
Structure H–O – P –P – O –H

OH OH
Oxidation
+4
state of P
15TH GROUP ELEMENTS

Hypophosphoric acid (H4P2O6)

Properties of H4P2O6


H4 P2 O6 H3PO3 + HPO3
15TH GROUP ELEMENTS
Orthophosphoric acid H3PO4
v) Orthophosphoric acid (H3PO4)

Oxyacid three P – OH bonds,

one P = O bond.

=
Structure P
HO HO HO

Oxidation
+5
state of P
15TH GROUP ELEMENTS
Orthophosphoric acid H3PO4

P4O10 + 6H2O 4H3PO4

Ca3(PO4)2 + 3H2SO4 3CaSO4 + 2H3PO4

H3PO4 3H+ + PO 3–
4
15TH GROUP ELEMENTS
Pyrophosphoric acid H4P2O7
vi) Pyrophosphoric acid (H4P2O7)

Oxyacid four P – OH bonds,

two P = O bonds,
one P – O – P bond
O O
Structure P P
HO O OH
OH OH
Oxidation
+5
state of P
15TH GROUP ELEMENTS

Pyrophosphoric acid H4P2O7


2H3PO4 H4 P2 O7 + H2 O
15TH GROUP ELEMENTS
Poly metaphosphoric acid (HPO3)n

vi) Poly metaphosphoric

Oxyacid
acid (HPO3)n

O OH O
Structure P P P
O O O O
OH O OH
Oxidation
+5
state of P
15TH GROUP ELEMENTS

Polymetaphosphoric acid (HPO3)n

 Polymetaphosphoric acid is prepared by heating mixture of

phosphorus acid and Br2 in a sealed tube.

 It is also called glacial phosphoric acid.

15TH GROUP ELEMENTS
Polymetaphosphoric acid (HPO3)n
Characteristics
Acids which contain P–H bonds have strong reducing tendency.
Eg. 4 Ag NO3 + 2H2O + H3PO2  ® 4 Ag + 4 HNO3 + H3PO4

P – H bonds in oxoacids do not ionise to give H + ions.

Only H atoms attached to Oxygen in P–OH form ionise and cause basicity.
15TH GROUP ELEMENTS

VA GROUP ELEMENTS
PREVIOUS QUESTIONS
JEE - MAINS
15TH GROUP ELEMENTS

1. Which of the following compounds has a P – P bond?

[J.M.O.L - 2015]

1) H4P2O5 2) H4P2O6 3) H4P2O7 4) (HPO3)3

Solution
: O O

HO – P – P – OH
HO OH ( H 4 P2 O6 )
15TH GROUP ELEMENTS
2. Which one of the following properties is not shown by NO ?
1) It is diamagnetic in gaseous state [JEEMAINS-2014]
2) It is neutral oxide
3) It combines with oxygen to form nitrogen dioxide
4) It's bond order is 2.5

Solution
:
NO is paramagnetic in nature due to the presence of unpaired electron.
15TH GROUP ELEMENTS
3. Sodium carbonate cannot be used in place of for the identification of
Ca2+,Ba2+ and Sr2+ ions (in group V) during mixture analysis because:
(JEE MAINS ONLINE-2013)
1) Na+ ions will interfere with the
detection of Ca2+,Ba2+, Sr2+ ions
2) Mg2+ ions will also be precipitated
3) Concentration of ions is very low
4) Sodium ions will react with acid radicals
Solution
:
can precipitate all , , ions.
15TH GROUP ELEMENTS
4. The molecule having smallest bond angle is: (AIEEE-2012)
1) AsCl3 2) SbCl3 3) PCl3 4) NCl3

Solution
:
Bond angle from NCl3 to BiCl3 due to the in E.N of central atom.
15TH GROUP ELEMENTS
5. Although CN- ion and N2 molecule are isoelectronic, yet N2 molecule is
chemically inert because of : (JEE MAIN
2010]
1) Uneven electron distribution
2) Presence of more number of electrons in bonding orbitals
3) Absence of bond polarity
4) Lone bond energy Pyro phosphoric acid
Solution
:
N2 is chemically inert due to absence of bond polarity.
15TH GROUP ELEMENTS
6. The nitrogen oxides that contains N - N bonds are [IIT 2009]
1) N2O 2) N2O3 3) N2O4 4) N2O5

Solution
:
Both N2O and N2O3 contain N-N bond.
15TH GROUP ELEMENTS
7. The reaction of P4 with X leds selectively to P4O6. The X is
2) A mixture of O2 and N2 [IIT 2009]
1) Dry O2
3) Moist O2 4) O2 in the presence of aqueous NaOH

Solution
:
P4 + 3O2 P4O6
15TH GROUP ELEMENTS
8. The percentage of p-character in the orbitals forming P - P bonds in
P4 is [IIT 2007]
1) 25 2) 33 3) 50 4) 75
Solution
:
sp3 hybridization.
15TH GROUP ELEMENTS
9. Regular use of which of the following fertilizers increases the
acidity of soil? [AIEEE 2007]
1) KNO3 2) NH2CONH2
3) (NH4)2CO3 4) (NH4)2SO4
Solution
:
Ammonium sulphate under goes cationic hydrolysis to release H +
ions and hence soil acidity increases
15TH GROUP ELEMENTS
10. Which one of the following substances has the highest proton
affinity. [AIEEE 2007]
1) H2S 2) NH3 3) PH3 4) H2O

Solution
:
NH3 being a base has high proton
afinity.
15TH GROUP ELEMENTS
11. Which is the most thermodynamically stable allotropic forms of
phosphorus? (IIT JEE-2005)
1) Red 2) White 3) Black 4) Yellow

Solution
:
Black ‘P’ is most thermodynamically stable allotropic form of ‘P’.
15TH GROUP ELEMENTS
12. Blue liquid which is obtained on reacting equimolar amounts of two
gases at - 300C is (IITJ EE-
2005) 2) N2O3 3) N2O4 4) N2O5
1) N O
2

Solution
: C
NO + NO2 N2O3
Blue liquid
15TH GROUP ELEMENTS
13. When rain is accompanied by a thunderstorm, the collected rain
water will have a pH value. [AEEE
1) Slightly higher than that when the thunderstorm is not there
2003]
2) Uninfluenced by occurrence of thunderstorm
3) Which depends on the amount of dust in air
4) Slightly lower than that of rain water without thunderstorm.

Solution
:
Rain water accompained by thunderstorm is more acidic and
hence it’s PH is low.
15TH GROUP ELEMENTS
14. What may be expected to happen when phosphine gas is mixed with
chlorine gas? (AIEEE-2003)
1) PCl3 and HCl are formed and the mixture warms up
2) PCl5 and HCl are formed and the mixture cools down
3) PH3 and Cl2 are formed with warming up
4) The mixture only cools down
Solution
:
3 P3HCl
15TH GROUP ELEMENTS
15. Polyphosphates are used as water softening agents because they
1) Form soluble complexes with anionic species (IIT JEE-2002)
2) Precipitate anionic species
3) Form soluble complexes with cationic species
4) Precipitate cationic species
Solution
:
Polyphosphates from soluble complexes with cationic species like and
hence hardness is removed.

Ex: - Calgon
15TH GROUP ELEMENTS
16. In case of nitrogen, NCl3 is possible but not NCl5 while in case of
phosphorus, PCl3 as well as PCl5 are possible. It is due to
1) Availability of vacant d oribitals in P but not in N (AIEEE-2002)
2) Lower electronegativity of P than N
3) Lower tendency of H-bond formatino in P than N
4) Occurence of P in solid while N in
gaseous state at room temperature.
Solution
:
‘N’ has no vacant ‘d’ orbitals but ‘P’ has vacant ‘d’ orbitals.
15TH GROUP ELEMENTS
17. The number of bonds in P4O10 is (AIEEE-2002)
1) 6 2) 16 3) 20 4) 7

Solution
:
Each ‘P’ forms 4 ‘’ bonds and hence total number of ‘’ bonds is 16.
15TH GROUP ELEMENTS
18. Ammonia can be dried by (IITJ EE-
2000)
1) Conc. H2SO4 2) P4O10 3) CaO 4) anhydrous CaCl2

Solution
:
CaO donot react with NH3.
15TH GROUP ELEMENTS
19. The number of P - O - P bonds in cyclic meta phosphoric acid is
(IIT JEE-2000)
1) Zero 2) Two 3) Three 4) Four

Solution
:
O O O
P P
HO OH
O O
P
Cyclictrimetaphosphoric acid
15TH GROUP ELEMENTS

1. Ammonia on reaction with chlorine forms an explosive NCl3, What

is the mole ratio of NH3 and Cl2 required for this reaction?
1) 8 : 3 2) 1 : 1 3) 1 : 3 4) 10 : 1 [TS E – 2015]

Solution
:
NH3 + 3Cl2 NCl3 + 3HCl
15TH GROUP ELEMENTS

2. Match the following [TS M - 2015]

LIST – I LIST – II
Oxoacids of Phosphorous Oxidation state of Phosphorous
A) Meta phosphoric I) + 4
B) Phosphorus acid II) + 1
C) Hypo phosphoric III) + 2
D) Hypo phosphorus acid IV) + 3
V) + 5
A B C D
1) V IV II I
2) IV III I II
3) III IV II I
4) V IV I II
15TH GROUP ELEMENTS

3. Nitrogen has unique ability to form Pπ – Pπ multiple bonds with

itself and with order elements due to
[AP M - 2015]
1) Small size and low electronegativity
2) Large size and high electronegativity
3) Large size and low electronegativity
4) Small size and high electronegativity
15TH GROUP ELEMENTS

4. What is the ratio between the rate of decomposition of N 2O5 to

rate of formation of NO2?
[AP M - 2015]
2N2O5 (g) 4NO2(g) + O2(g)

1) 1 : 4

2) 4 : 1

3) 2 : 1

4) 1 : 2
15TH GROUP ELEMENTS
5. The correct arrangement of following acids of phosphorus in the
increasing order of oxidation state of phosphorus is [E-2014]
1) Pyrophosphoric acid < orthophosphorous acid < hypophosphorous acid
2) Hypophosphorous acid< orthophosphorous acid < Pyrophosphoric acid
3) Hypophosphorous acid<Pyrophosphoric
acid < orthophosphorous acid
4) Pyrophosphoric acid < hypophosphorous acid < orthophosphorous
acid
Solution
: +1 +3 +5
H 𝟑 PO 𝟐 <H𝟑 PO 𝟑 <H 𝟒 P𝟐 O𝟕
15TH GROUP ELEMENTS
6. Which of the following is not correct? [E-2013]
1) Pyrophosphoric acid is a tetrabasic acid
2) Pyrophosphoric acid contains P-O-P linkage
3) Pyrophosphoric acid contains two P-H bonds
4) Orthophosphoric acid can be prepared by dissolving P 4O10 in water

Solution
:
O O
HO P O P OH
OH OH
There are no P-H bonds
15TH GROUP ELEMENTS
7. The catalyst and promoter respectively used in the Haber’s process
of industrial synthesis of ammonia are (EAMCET 2012)
1) Mo, V2O5 2) V2O5,Fe
3) Fe, Mo 4) Mo, Fe
Solution
:
Fe - Catalyst
Mo - Promoter
15TH GROUP ELEMENTS
8. The total no.of 𝛔 and 𝛑 bonds in pyrophosphoric acid are
respectively
(MED-2011)
1) 8,2 2) 10, 2 3) 12, 2 4) 8, 4

Solution
:
O O
HO P O P OH
OH OH
12, 2 bonds
15TH GROUP ELEMENTS
9. The gases evolved in the decomposition of lead nitrate are (E-2011)
1) N2O3, NO 2) NO2,O2 3) N2,O3,O2 4) N2O,O2

Solution
:
2Pb2PbO + 4
15TH GROUP ELEMENTS
10. A metal M on heating in nitrogen gas gives Y.Y on treatment with
H2O gives a colourless gas which when passed through CuSO4
solution gives a blue colour, Y is : [E - 2010]
1) M(NO3)2 2) M3 N2 3) NH3 4) MO

Solution
:
3Mg + N2  Mg3N2
Mg3N2 + 6H2O  3Mg(OH)2+2NH3
15TH GROUP ELEMENTS
11. Which pair of oxyacids of phosphorus contains ‘P-H’ bonds ?
1) H PO , H PO 2) H PO , H P O (E2009)
3 4 3 3 3 5 4 2 7

3) H3PO3, H3PO2 4) H3PO2, HPO3

Solution
: O
O

P P

H OH H OH
OH H
15TH GROUP ELEMENTS
12. The correct order of reducing abilities of hydrides of VA group
elements is (E-2008)
1) NH3 < PH3 < AsH3 < SbH3 < BiH3
2) NH3 > PH3 > AsH3 > SbH3 > BiH3
3) NH3 < PH3 > AsH3 > SbH3 > BiH3
4) SbH3 > BiH3 > AsH3 > NH3 > PH3
Solution
:
Reducing ability of VA group hydrides increases
from NH3 to BiH3 due to the decrease in stability.
15TH GROUP ELEMENTS
13. The following are some statements related to VA group hydrides,
I) Reducing property increases from NH3 to BiH3
II) Tendency to donate lone pair decreases from NH3 to BiH3
III) Thermal stability of hydrides decreases from NH3 to BiH3.
(E-2007)
IV) Bond angle of hydrides decreases from NH3 to BiH3.
1) I, II, III and IV 2) I, III and IV
3) I, II and IV 4) I and IV
15TH GROUP ELEMENTS
14. Which of the following is not a peroxy acid? (E
2007)
1) perphosphoric acid 2) Pernitric acid
3) Perdisulphuric acid 4) Perchloric acid

Solution
:
HClO4 is not peroxy acid.
15TH GROUP ELEMENTS
15. Hydrolysis of NCl3 gives NH3 and X. Which of the following is X ?
(E-2006)
1) HClO4 2) HClO3 3) HOCl 4) HClO2

Solution
:
NCl3+3H2O NH3+3HOCl
15TH GROUP ELEMENTS
16. Which of the following is not correct ? (E-
2005)
1) Ammonia is used as refrigerant
2) A mixture of Ca(CN)2 and C is known as nitrolim
3) A mixture of Ca(H2PO4)2 and CaSO4.2H2O is known as
super phosphate of lime
4) Hydrolysis of NCl3 gives NH3 and HOCl
Solution
:
A mixture of CaCN2+C is called nitrolim.
15TH GROUP ELEMENTS
17. The number of oxygen atoms bonded to one phosphorus atom in
P4O6 is (E-2004)
1) 4 2) 3 3) 6 4) 5
Solution
: ..
P
O O
O P
..

P
..

O O
P
15TH GROUP ELEMENTS
18. Two oxides of nitrogen, NO and NO2 react together at 253K and
form a compound of nitrogen X.X reacts with water to yield another
compound of nitrogen, Y. The shape of the anion of Y molecule is
1) Tetrahedral 2) Triangular planar (E-2003)
3) Square planar 4) Pyramidal
Solution
: 253K
NO + NO2 N 2 O3
N2O3 + H2O2HNO2

e.p =
Shape – Triangular planar
15TH GROUP ELEMENTS
19. What are the products formed when ammonia reacts with excess
chlorine ? (E-
2002)
1) N2 and NCl3 2) NCl3 and HCl
3) N2 and NH4Cl 4) N2 and HCl
Solution
:
NH3 + 3Cl2  NCl3 + 3HCl
Excess Cl2
15TH GROUP ELEMENTS
20. When bauxite powder is mixed with coke and reacted with nitrogen
at 2075 K, carbon monoxide and X are formed. What is the gas
formed when X is reacted with water ? (E-2002)
1) NH3 2) N2 3) N2O 4) O2

Solution
:
AlN + 3H2O  Al
15TH GROUP ELEMENTS
21. The products formed when heavy water is reacted with magnesium
nitride, are (E-
2002)
1) NH3, Mg(OH)2 2) NH3, Mg(OD)2
3) ND3, Mg(OH)2 4) ND3, Mg(OD)2
Solution
:
+ 62 + 3Mg
15TH GROUP ELEMENTS
22. What are the oxidation numbers of nitrogen in NH 4NO3 ? (E-2001)
1) +3, –5 2) –3, +5 3) +3, –6 4) +2, +2

Solution
:
⊕
NH 𝟒  − 3
−
NO 𝟑 + 5
15TH GROUP ELEMENTS
23. An oxide of nitrogen (X) is formed when Z is reacted with P 2O5. X
is soluble in water and gives Z. Which one of the following is Z?
1) HNO3 2) H2N2O2 3) HNO2 4) HN3

Solution
:
H
Z X

+ 2HN
Z
15TH GROUP ELEMENTS
24. Which of the following doesn't given nitrogen on heating?
1) NaN3 2) NaNO2
3) NH4NO3 4) Vapours of HNO3 and Cu metal

Solution
:
NH4NO3 on decompostion gives N2O
15TH GROUP ELEMENTS
25. In P4O10 the number of oxygen atoms bonded to each phosphorus
atom is
O
1) 3 2) 4
P
3) 5 4) 6 O O
O O
Solution O P P O
:

O P O

O
15TH GROUP ELEMENTS

Thank
you…