GROUP 15 (VA) ELEMENTS

The Nitrogen Family

nitrogen, phosphorus, arsenic, antimony and bismuth.

Nitrogen and phosphorus are non-metals,
arsenic and antimony metalloids
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and bismuth
is a typical metal.

Element

N
Nitrogen

P
Phosphorus

As
Arsenic

Sb
Antimony

Bi
Bismuth

2,5

2,8,5

2,8,8,5

2,8,18,18,5

2,8,18,32,18,5

Electron config.

[He]
2s22p3

[Ne]
3s23p3

[Ar]3d10
4s24p3

[Kr]4d10
5s25p3

[Xe]4f145d10
6s26p3

Atomic Wt.

14. 0

30. 97

74. 92

121. 75

208. 98

-3 to +5

-3, +3, +5

+3, +5

+3, +5

+3, (+5)

melting pt./oC

-210

44

sublimes

631

272

boiling pt./oC

-1.96

280

616?

1635

1560

density/gcm-3

<0.1

1.8

5.8

6.7

9.7

atomic radius/

0. 74

1. 10

1. 21

1. 41

1. 52

1st IE/ kJmol-1

1402

1060

947

834

703

Electronegativity

3.02

2.10

2.0

1.9

1.9

colourless
gas

white/red
solid
allotropes

grey solid
(yellow/blac
k allotropes)

grey solid
(yellow
allotrope)

silver-white
brittle metal

Simple electron config.

Ooxidation states

Appearance (RTP)

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15

33

51

83

Chemistry of Group 15 elements in relation to Electronic

Structure:
1-The s orbital in these elements is completely filled and p orbitals
are half-filled, s2 p3, making their electronic configuration extra
stable. The tendency of the pair of s electrons to remain inert (the
inert pair effect) increases with increasing atomic number as we go
down the group. Thus, Elements of group 15 are characterized by
their ability to form these covalent molecules using only the p
electrons in bonding, such as the trihalides NF3, PCl3 and hydrides e.
g. NH3, PH3, etc.
2-Depending on the relative electronegativities of the combining
elements, the elements are assigned formal oxidation states of +3 or
3. The negative-oxidation state arise because the electronegativity
of H = 2. 1 and that for N = 3. 02. : (-3) in NH3, (-2) in hydrazine
N2H4, (-1) in hydroxylamine NH2OH, (0) in nitrogen N2, (+1) in
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nitrous oxide
N2O, (+2) in nitric oxide NO, (+3) in nitrous acid 3

3-Valencies of 3 and 5 are shown for the elements of phosphorous,

arsenic and antimony in their compounds with halogens and sulphur,
e.g. PCl3, PCl5, AsF3 and AsF5, SbCl3 and SbCl5. The marked decrease
in the ease of attaining the 5-covalent state (the inert pair effect) which
occurs on going from P to As may be attributed to the relatively weak
screening of nuclear charge by the 18 electrons. The energy required
to promote the valency s electron and so attain the excited
configuration thus increases sharply from P to As.
4-Mettalic and Non-metallic Character:
Within the group, the metallic (electropositive) character increases
down the group. N and P are non metals, As and Sb are metalloids
which show many metallic properties, and Bi is a true metal. This is
shown in the appearance and structure of the elements, their tendency
to form positive ions and the properties of their oxides. Thus the
normal oxides of N and P are strongly acidic. While As and Sb are
amphoteric11/26/16
and Bi is largely basic.
4

Type of bonding:
Generally the bonds formed by the elements of this group are mainly
covalent due to their electronic configuration. Fluorine is the only
element which give a large enough electronegativity difference to
permit ionic bonds with elements of this group as in SbF3 and BiF3
which exist as ionic solids. The M3+ ions, however, are rapidly
hydrolysed in water to SbO+ and BiO+, but this change reversed by
adding 5M HCl.
HO
+
Bi3+
BiO
HO
The tendency to gain three electrons, attaining an inert gas
configuration, and giving the M3- ion occurs only with N. Ionic
nitrides containing the N3- ion are formed by metals which have low
ionization energies (Li3N, Be3N2, Hg3N2, CaN2).
2

In the majority of derivatives of these elements, the bonds are

covalent where the three unpaired electrons form bonds with three
other atoms,
and the resulting molecule is tetrahedral with one 5
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Outer electronic structure of Gp. 15 elements

A coordination number of 4 is obtained by

donating this lone pair to another atom or
ion, for example the NH4+ ion:
Diferences between N2 and the other elements
of Gr 15:

...
N

H
H

Nitrogen cannot extend its coordinations number beyond 4, because the

second shell of electrons is limited to an octet. On the other hand,
phosphorous and the following elements can undergo a much greater
expansion of their valency shells by involving one or two d orbitals and
having sp3d or sp3d2 hybridization. As a result, these elements may have
a coordination numbers of 5 as in PCl5 or even 6 as in [PCl6]-. In
addition, nitrogen cannot form complexes by accepting electrono-pairs
from other ligands but the subsequent elements, due to hybridization, can
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6
form such complexes.

3-Nitrogen also differs from the other elements: in that it can form
strong p - p multiple bonds, and so forms a number of compounds
which have no counterparts in the other elements. These include
nitrates NO3-, Nitrites NO2-, azides N3-, nitrogen N N, and oxides of
nitrogen N2O, NO, NO2, N2O4 and the cyanides C N4-Because nitrogen can form multiple bonds, the oxides N2O3 and
N2O5 are monomeric, while the trioxides and pentoxides of the other
elements are dimeric. Nitrogen is gaseous and diatomic. The triple
bond N N is very stable and consequently nitrogen is relatively
unreative. The other elements are solids and have allotropic forms; the
atoms can form different chain lengths, e.g. White phosphorous
containing P4 molecules and violet phosphorous containing much
bigger molecules and voilet phosphorous containing much bigger
molecules. Other forms are red and black phosphorous. Arsenic and
antimony each have two allotropic forms a reactive tetrahedral for As4
and Sb4 which resembles white phosphorous and much less reactive
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7
metallic forms with layer structures. Bismuth only exists in only one

Chemical Reactivity.
1-Oxides and Oxyacids of nitrogen
Oxides and Oxyacids of nitrogen all exhibit p p multiple
bonding between the nitrogen and oxygen atoms.
Name

Formula

Oxidation
State

Nitrous Oxide

N2 O

+I

Nitric Oxide

NO

+ II

Molecular Structure
.. :N

..

+
N

O:

:N

..

..
O:

:N

Nitrogen dioxide

N2O3

:O

+ III

..

NO2

..

+ IV

:O

..

O:

..

..

..

: O :

..

Dinitrogen tetroxide

.
+
O:

..
O:

..

..
:O

..

.. :N

..

Nitrogen
Sesquixoxide

O:

N2O4

+ IV

:O
N

..
:O

N
O

..

Dinitrogen Pentoxide

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N2O5

+V

..

..

:O :

..

:O
..
:O
..

..

..

..

N
O
..

This does not occur with the heavier elements in the group, and
consequently nitrogen forms a number of compounds which have
no P, As, Sb or Bi analogous.
Nitrogen forms a very wide range of oxides, the lower ones being
neutral, and the higher ones acidic
Nitrous Oxide N2O
Nitrous oxide is a stable, neutral, relatively unreactive gas. It is
prepared by gently heating ammonium nitrate.
NH4NO3 N2O +2H2O
It is used as an anesthetic, as a propellant for whipped, ice-cream
and the preparation of azides.
N2O + NaNH2 NaN3 +H2O
Sodamide
Sodium azide
.
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Nitric Oxide NO:

Nitric oxide is a neutral, colorless gas, it is commercially important in
the manufacture of nitric acid by oxidizing ammonia (Haber process),
and is prepared in the laboratory by the reduction of dilute nitric acid
with copper, or nitrous acid with iodide ions:
3Cu + 8HNO3 2NO + 3 CU (NO3)2 + 4 H2O
2HNO2 + 2I- + 2H+ 2NO + I2 +2H2O
Nitric oxide has eleven valency electrons. It is impossible for them all to
be paired, hence this is an odd electron molecule and the gas is
paramagnetic. However, the liquid and solid states are diamagnetic, since
loose dimers are formed and the
magnetic
effect of unpaired electrons
N
O
Nitric Oxide dimer
cancels out.
O

NO reacts instantly with oxygen forming NO2, and with halogens it gives
nitrosyl halides NOCl. NO can also act as a ligand and form coordination
compounds with transition metal ions, called nitrosyles, as in the
complex nitrosyl
formed between Fe2+ and NO which is responsible10
for
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Nitrogen dioxide NO2

NO2 ia a red-brown poisonous gas and is produced on a large scale by
oxidizing NO in the manufacture of nitric acid. It is prepared in the
laboratory by heating lead nitrate.
2Pb(NO3)2 2PbO + 4NO2 + O2
On cooling, the gas condenses to a colorless solid due to the dimerization
of the dioxide to dinitrogen tetroxide.

N2O4 is a mixed anhydride, because it reacts with water to give a mixture

of nitric and nitrous acids water to give a mixture of nitric and nitrous
acids
The NO2-N2O4 system is a strong oxidizing agent.
Nitrogen Penoxide N2O5
N2O5 is prepared by dehydrating HNO3 with P2O5 and is the anhydride of
HNO3
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11

Nitrous acid HNO2

The structure of the acid contains the nitrite ion NO2- which is plane
triangular, with one position occupied by a lone pair.
.. O:

..
:N

..

..
O:

O:

O:
:N

:N

..

..

..
O:

..

..
O H
..

The nitrite ion is a good coordinating agent and because lone pairs of
electrons are present in the both N and O atoms, either of them can form
a coordinate bond, so that isomerism occurs between M NO2 and
M ONO.
Treatment of a solution of Co2+ ions with NO2- ions results in oxidation of
Co2+ Co3+, then formation of complex [Co(NO2)6]3- ions. Precipitation
of potassium cobaltinitrite K3[Co(NO2)6] is used to detect K+ in
qualitative analysis.
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12

Nitric acid HNO3

Nitric acid is an excellent oxidizing agent when hot and concentrated,
and is now produced in vast quantities by the habor-Bosch process, and
by the obsolete (not used now) Birkeland and Eyde process by sparking
N2 and O2.

When nitric acid is mixed with concentrated sulphuric acid, the

nitronium NO2+ is formed. This is the active species in the nitration of
aromatic organic compounds.
A mixture of HNO3 and HCl in the ratio 1:3 is known, as aqua regia and
has a strong effect on the dissolution of some metals such as gold and
platinum. Its strong oxidizing action is mainly due to the presence of the
nitrite ions as well as the nitrosyl chloride and Cl - ions which have
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13
strongly oxidation

2-Oxides of Phosphorous, Arsenic and Bismuth:

The oxides of Gp 15 elements clearly exemplify two important trends
----The stability of the higher Oxidation State decreases with increasing
atomic number.
-In a given oxidation state, the metallic character of the elements and the
basicity of oxides, increase with increasing atomic number. Thus the
trioxides of P2O3 and As2O3 are acidic, Sb2O3 is amphoteric and Bi2O3 is
strictly basic.
Phosphorous form three main types of oxides
-Phosphorous trioxide P2O3 which is dimeric as P4O6
-Phosphorous dioxide PO2 which exists as (PO2)n
. Phosphorous pentoxide P2O5 which is dimeric P4O10
Less common oxides of composition P4O9, P4O7 and P4O8 are known.
These contain phosphorous in both oxidation states (+3) and (+5), and
consequently hydrolysis with water yield phosphorous acids
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14

Oxyacids of Phosphorous:
Phosphorous forms two series of oxyacids: the phosphoric and
phosphorous series.
In the phosphoric acids the oxidation state of P is (+5) and the
compounds have oxidizing properties, whilst the phosphorous acids
contain P in the (+3) oxidation state, and are reducing agents.

Phosphoric Acids:
The simplest phosphoric acid is H3 PO4, orthophosphoric acid
A large number of phosphoric acids and
their salts the phosphates arise by
sharing oxygen atoms at 1 or 2 corners HO
of the PO4 polyhedron:
For example:
Pyro phosphoric acid
H4P2O7
Tripoly phosphoric Acid
H5P3O10
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Tetra poly phosphoric
5 4 13

O
...
P

OH

H3PO4 orthophosphoric acid

OH

15

Orthophosphoric acid is prepared from phosphate rock,

Ca3(PO4)2 + 3H2 SO4 2H3PO4 + 3CaSO4
These have the structural formula:
O

Orthophosphoric acid is
tribasic,
pyrophosphoric acid is
tetra basic while
metaphosphoric acid is
tribasic.

HO

P
OH

O
HO

HO

Pyrophosphoric acid (tetrabasic)

OH
P

OH

OH

OH
O

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Orthophosphoric acid (tribasic)

OH

Metaphosphoric acid (tribasic)

O

P
O

OH

16

Phosphorous Acids:
These contain phosphorous in (+3) oxidation state and also have P-H
bonds and are therefore reducing agents. Hydrolysis of the trioxide P4O6
yields pyro- and ortho- phosphorous acids which are both dibasic and
O
reducing agents.
HO

Orthophosphorous acid

OH

H
O

O
HO

P
H

OH

Pyrophosphorous acid

Metaphosphorous acid (HPO2)n is prepared from phosphine at low

pressure
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17

Reaction with Hydrogen (Hydrides):

The elements of groups 15 form trihydrides of the general formula MH 3
such as

Structure
All these hydrides are covalent in nature and have pyramidal structure.
These involve sp3 hybridization of the central atom and one of the
tetrahedral position is occupied by a lone pair.
Pyramidal shape of NH3 molecule
Due to the presence of lone pair, the bond
angle in NH3 is less than the normal tetrahedral
angle. It has been found to be 107o. Down the group the bond angle
decreases as:
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18

Reaction with Halogens (Halides)

Nitrogen is unable to form pentahalides owing to the absence of suitable
d orbital, but the subsequent elements can do so and PF5, Pbr5, AsF5,
SbF5 and SbCl5 are known. These molecules have a trigonal bipyramid
3s
3p
3d
shape in the gas phase. Electronic Structure of phosphorus
atom ground state
Excited State

A trigonal bipyramid
Five singly filled orbitals, can form five bonds
sp3d hybridization
is not a regular
structure since some
Cl
bond angles are 90
Cl
And others 120.
P
It is not very stable, and whilst the gaseous halides Cl
Have this Structure, they may accept an additional
Cl
halide Ion which forms a coordinate bond by
Cl
donating a 11/26/16
lone pair into an empty d orbital.
19