INTRODUCTION

The p-block contains several elements of great social and economic

importance as well as chemical interest. Examples include the use of
aluminium as a structural material, the importance of silicon and germanium
as semiconductors, and the use of sulphur, phosphorus and nitrogen in
fertilizers.
The elements belonging to groups 13 to 18 of the periodic table are the p-
block elements. They are also called as representative elements or normal
elements. The chemistry of p-block elements plays an important role in our
daily life. The three p-block elements oxygen, silicon and aluminium are
most abundant in earth's crust. Carbon and sulphur are the two p-block
elements that occur in free state.
The p-block elements have relatively little in common except that their outer
elections are in p orbitals. This contrasts with the considerable similarities in
properties of the elements of the s-block and also between those of the d-
block. The p-block is more notable for trends.
Each group in the p-block has its own characteristic properties and hence
they are called as representative elements. Depending upon the number of
valence electrons, the elements of the p-block exhibit variable oxidation
states.
. The general electronic configuration of these elements is ns2np1-6. They
involve the filling up of 'p' orbitals of their outermost shells, when their 's'
orbitals are already filled. Some of the 'p' block elements such as boron,
carbon, nitrogen, and oxygen, form very important compounds. The
occurrence, preparation and properties of these elements and the chemistry
of their compounds are focused here

Group 15 elements (Nitrogen family)

Occurrence and Uses of Phosphorus
Phosphorus is widely distributed in nature. It does not occur in free state
since it can be very easily oxidised. It is usually present in rocks in the
combined state as phosphates. The main phosphate rocks are:
Phosphorite: Ca3(PO4)2
Fluorapatite: 3Ca3(PO4)2 . CaF2
Chlorapatite: 3Ca3(PO4)2 . CaCl2
Phosphorus compounds play an important role in life processes. P is an
essential constituent of animal and plant matter. It is present in bones, blood
and brain of animal body and also in living cells. Several of its compounds
have also industrial applications. The most important of these chemicals are
orthophosphoric acid and phosphatic fertilizers

Atomic Properties- Electronic Configuration

The atoms of group 15 have five electrons in the outermost shell, two in s
and three in p sub-shell. The general electronic configuration of this group
may be expressed as ns2np3.
Electronic configuration of group 15 elements

Physical Characteristics of group 15 Elements

The important physical constants of group 15 elements are given below:

Some important physical constants of group 15 elements
N P As Pb Bi
Atomic radius (pm) 70 110 120 140 150
212 (P3
Ionic radius (pm) 171 (N3 - ) 222 (As3 - ) 76 (Sb3 + )
-)
Ionisation energy IE1(k.J
1402 1012 947 834 703
mo1-1)
IE2 2856 1903 1798 1594 1610
IE3 4577 2910 2736 2443 2446
Electronegativity 30 2.1 2.0 1.9 1.9
544.
Melting point (K) 63 317.1 1089 904
4
Boiling point (K) 77 553.5 888 1860 1837
 N P As Pb Bi
9.80
Density (g cm- 3) 0.879 0.879 5.778 6.697
8

The important physical characteristics are discussed below:

Atomic and ionic radii
The atomic and ionic radii of group 15 elements are smaller than the atomic
radii of the corresponding group 14 elements. This is because of increased
nuclear charge. On going down the group, the atomic radii increase due to
the increase in number of shells.
Melting and boiling points
Melting points (except for antimony and bismuth) and boiling points
increase on going down the group from N to Bi.
Ionization energies
The first ionization energies of the group 15 elements are higher than the
corresponding members of the group 14 elements.
Explanation:
The larger ionization energy is due to greater nuclear charge, small size and
stable configuration of the atoms of group 15 elements. The electronic
configuration of atoms of group 15 is half filled,
energ
ies. On going down the group, the ionization energies decrease. This is due
to increase in atomic size and screening effect, which overweigh the effect
of increased nuclear charge.
Electronegativity
The electronegativity values of elements (of group 15 are higher than the
corresponding elements of group 14.
Explanation:
The elements of group 15 have smaller size and greater nuclear charge of
atoms and therefore they have higher electronegativity values. On going
down the group the electronegativity value decreases. This is due to increase
in size of the atoms and shielding effect of inner electron shells on going
down the group.
Metallic character
The elements of group 15 are less metallic. However on going down the
group, the metallic character increases from N to Bi. For e.g.,, N and P are
non-metallic, As and Sb are partly non-metallic while Bi is a metal.
Catenation
The elements of group 15 also show a tendency to form bonds with itself
known as catenation. All these elements show this property but to a much
smaller extent than carbon. For e.g., hydrazine (H2N-NH2) has two N atoms
bonded together, hydrazoic acid, (N3H), has three N-atoms, azide ion, ,
has also three N atoms bonded together, while diphosphine (P2H4) has two
phosphorus atoms bonded together. The lesser tendency of elements of
group 15 to show catenation in comparison to carbon is their low (M-M)
bond dissociation energies.
Bond C-C N-N P-P As - As
Bond energy 353.3 163.8 201.6 147.4
Allotropy
Except nitrogen and bismuth, all other elements of this group show
allotropy.
For e.g.,
Phosphorus exists as - white, black or red phosphorus
Arsenic exists as - yellow or grey arsenic
Antimony exists as - yellow or silvery grey
allotropic forms.
Oxidation states
These elements have five electrons in the valence shell. The loss of five
electrons is quite difficult because of energy considerations. Hence they do
not form ionic compounds by loss of 5 electrons. On the other hand, these
elements can also gain three electrons to complete their octets. But gain of 3
electrons is also not energetically favorable. However, they do form N3-and
P3- ions by gaining three electrons from highly electropositive elements, e.g.
Mg3N2, Ca3P2.
In addition to - 3 oxidation state, the elements of group 15 exhibit +3 and +5
oxidation states. For e.g., phosphorus forms pentahalides such as PF5, PCl5
(+5 oxidation state) and trihalides PCl3, PF3 (+3 oxidation state).
Nitrogen exhibits various oxidation states from -3 to +5 in its hydrides,
oxides and oxo acids.
For e.g.,
Compound Oxidation state
NH3 Ammonia -3
N2H4 Hydrozine -2
N2 Nitrogen 0
N2O Nitrous Oxide +1
NO Nitric Oxide +2
N2O3 Nitrogen trioxide +3
N2O4 Nitrogen tetraoxide +4
N2O5 +5

Chemical Properties

Elemental state and chemical reactivity

Nitrogen is a colorless gas and exists as diatomic. The two nitrogen atoms
are held together by triple bond and have very high bond dissociation energy
(945 kJ mol-1).

Due to the presence of triple bond, which has very high bond dissociation
energy, the nitrogen molecule bas very low reactivity. However, the
tendency to form multiple bonds (pp-pp) is limited only to nitrogen. On the
other hand, phosphorus, arsenic and antimony exist in various forms
containing single bonded atoms. For e.g., phosphorus exists as tetrahedral P4
molecules.
Structure of P4 molecule

In this case, four P atoms lie at the comers of a regular tetrahedron. Each P is
bonded to three P atoms by single P - P bonds. Therefore, it exists as solid.
Therefore, nitrogen exists as gas while phosphorus exists as solid.

Hydrides
The elements of groups 15 form trihydrides of the general formula MH3
such as

These hydrides can be obtained by different chemical reactions:

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.

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:

Explanation:
In all these hydrides, four electron pairs, three bond pairs and one lone pair
surround the central atom. Now, as we move down the group from N to Bi,
the size of the atom goes on increasing and its electronegativity decreases.
Consequently, the position of bond pair shifts more and more away from the
central atom in moving from NH3 to BiH3. For e.g., the bond pair in NH3 is
close to N in N-H bond than the bond pair in P-H bond in PH3. As a result,
the force of repulsion between the bonded pair of electrons in NH3 is more
than in PH3. In general, the force of repulsion between bonded pairs of
electrons decreases as we move from NH3 to BiH3 and therefore, the bond
angle also decreases in the same order.
Basic strength
All these hydrides have one lone pair of electrons on their central atom.
Therefore, they act as Lewis bases. They can donate an electron pair to
electron deficient species (Lewis acids). Down the group, the basic character
of the hydrides decreases. For e.g., NH3 is distinctly basic; PH3 is weakly
basic; AsH3, SbH3 and BiH3 are very weakly basic.
Explanation:
Nitrogen atom has the smallest size among the hydrides. Therefore, the lone
pair is concentrated on a small region and electron density on it is the
maximum. Consequently, its electron releasing tendency is maximum. As
the size of the central atom increases down the family, the electron density
also decreases. As a result, the electron donor capacity or the basic strength
decreases down the group.
Thermal stability
Thermal stability of the hydrides of group 15 elements decreases as we go
down the group. Therefore, NH3 is most stable and BiH3 is least stable. The
stability of the hydrides of group 15 elements decreases in the order:
NH3 > PH3 > AsH3 > SbH3 > BiH3
Explanation:
This is due to the fact that on going down the group, the size of the central
atom increases and therefore, its tendency to form stable covalent bond with
small hydrogen atom decreases. As a result the M~H bond strength
decreases and therefore thermal stability decreases.
Reducing character
The reducing character of the hydrides of group 15 elements increases from
NH3 to BiH3. Thus, increasing order of reducing character is as follows:
NH3< PH3< AsH3 < SbH3 < BiH3
Explanation:
The reducing character depends upon the stability of the hydride. The
greater the instability of an hydride, the greater is its reducing character.
Since the stability of group 15 hydrides decreases from NH3 to BiH3, hence
the reducing character increases.
Boiling points
Ammonia (240 K) has a higher boiling point than phosphine (190 K) and
then the boiling point increases down the group because of increase in size.

Explanation:
The abnormally high boiling point of ammonia is due to its tendency to form
hydrogen bonds.

In PH3 and other hydrides, the intermolecular forces are Van der Waals'
forces. These van der Waals' forces increase with increase in molecular size
and therefore, boiling points increase on moving from PH3 to BiH3. The
main trends are summarized below.

Oxides
The elements of group 15 combine with oxygen either directly or indirectly
to form oxides. The important oxides of group 15 elements along with their
oxidation states are listed in table.
Thus, it is nitrogen, which forms all oxides having oxidation states +1 to +5.
All the oxides of nitrogen except N2O and NO and phosphorus are strongly
acidic: oxides of arsenic are weakly acidic; oxides of antimony are
amphoteric while those of bismuth are weakly basic.
There is an important difference between the oxides of nitrogen and other
group congeners in their structures. The nitrogen has the ability to form pp-
pp multiple bonds and this is present in its structures. On the other hand the
reluctance of P, As, Sb and Bi to form pp-pp multiple bonds-leads to the
cage structures for their oxides. The structures of some oxides are given in
Fig 9 (a) and 9 (b).
Oxides of group 15 elements in different oxidation states
Structures of oxides of N and P

Halides
Group 15 elements form two series of halides of
the type MX3, (trihalides) and MX5,
(pentahalides). The trihalides are formed by all the
elements while pentahalides are formed by all the
elements except nitrogen. Nitrogen cannot form
pentahalides due to the absence of vacant d-
orbitals in its outermost shell. Similarly the last
element, Bi has little tendency to form
pentahalides because +5 oxidation state of Bi is less stable than +3 oxidation
state due to inert pair effect
(a) Trihalides
(i) The trihalides have pyramidal structure and have one lone pair. In these
cases, the central atom involves sp3 hybridization.
(ii) The trihalides are mainly covalent with the exception of BiF3, which is
ionic.
Structure of PCl5
(iii) The trihalides are easily hydrolyzed by water. However, the products are
different in hydrolysis of different chlorides.

Antimony and bismuth trichlorides are only partially hydrolyzed to form

oxychlorides.

The trihalides of P, As and Sb (especially fluorides and chlorides) act as

Lewis acids and combine with Lewis bases:

(b) Pentahalides
(i) In pentahalides the P undergoes sp3d hybridization and have trigonal
bipyramidal geometry.
(ii) The pentahalides are thermally less stable than the trihalides. For e.g.,
PCl5, exists as molecules in the gas phase but exist as [PCl5]+[PCl6]- in the
crystalline state. PBr5, and PI5, also exist in the ionic form as [PBr4]+
[PBr6]- and [PI4]+I- respectively in the solid state.
Structure of PF5

Allotropes of Phosphorus

Elemental phosphorus is obtained by heating phosphate rock with coke and

silica in an electric furnace at about 1770 K. The phosphorus so formed is
white phosphorus.
The reaction may be represented as:

There are three principal allotropic forms of Phosphorus. These are white
phosphorus, red phosphorus and black phosphorus.
(a) White phosphorus or Yellow phosphorus
(i) It is a soft waxy solid with garlic smell.
(ii) It is poisonous in nature.
(iii) It turns yellowish on exposure to light. For this reason, it is also called
yellow phosphorus.
(iv) It is not soluble in water but soluble in carbon disulphide.
(v) It undergoes spontaneous combustion in air and produces greenish glow.
(vi) It exists as P4 molecules both in solid and vapor state. The four atoms in
P4 molecule occupy the corners of regular tetrahedron as shown in Fig. 7
(b) Red Phosphorus
It is prepared by heating white phosphorus to about 540 K in an inert
atmosphere of nitrogen for several hours.
(i) It is a hard crystalline solid without any smell.
(ii) It is non-poisonous in nature.
(iii) It is insoluble in water as well as in carbon disulphide.
(iv) It is more stable and relatively less reactive.
(v) It consists of tetrahedral units of P4 linked to one another to constitute
linear chains.
(c) Black Phosphorus
It is prepared by heating white phosphorus to about 470 K under high
pressure of 1200 atmospheres in inert atmosphere.

(i) It has metallic lustre.

(ii) It is most inactive form of phosphorus.
(iii) It has a layer type structure in which each layer consists of phosphorus
atoms.
Some physical properties of three forms of Phosphorus are given below.
Red
Property White phosphorus Black Phosphorous
phosphorus
White, but turns yellow
Colour Dark red Black
on exposure
White, but turns yellow
Colour Dark red Black
on exposure
Waxy solid, can be cut Brittle Crystalline with
State
with knife powder greasy touch
Smell Garlic smell Odorless
Density 1.84 2.1 2.69
Ignition
307 K 533 K 673 K
temperature
Melting point 317 K Does not melt 860 K

The elements of group 15 form a large number of oxoacids.

(i) Oxoacids of nitrogen
The important oxoacids of nitrogen are given in the table below.
Oxo acids of nitrogen
Oxidation state
Name Formula Nature
of N
H4N2O Highly explosive, difficult to
Nitroxylic acid +2
4 get in pure state
Nitrous acid HNO2 +3 Weak acid and unstable
Nitric acid HNO3 +5 Strong acid and stable
Peroxynitric
HNO3 +5 Unstable and explosive
acid

Out of the oxoacids of nitrogen, nitric acid is the most important. It is very
strong oxidising agent and is quite useful.
(ii) Oxoacids or phosphorus
Phosphorus forms a number of oxoacids as given in below table.
Oxoacids or phosphorus
Name Formula Oxidation state of P
Hypophosphorus acid H3PO2 +1
Phosphorus acid H3PO3 +3
Hypophosphoric acid H4P2O6 +4
Orthophosphoric acid H3PO4 -
Diphosphoric acid (Pyrophosphoric acid) H4P2O7 +5
Metaphosphoric acid HPO3 +5
Peroxophosphoric acid H3PO5 +7
Among the oxoacids of phosphorus, orthophosphoric acid is the most
important and is used in the manufacture of phosphate fertilizers.
The structures of oxoacids of phosphorus are systematically given ahead:
The formulae of oxoacids of P can be remembered as:
The prefix
a) meta acid is used for the acid obtained by the loss of one water molecule.
b) pyro acid is used for the acid obtained by heating two molecules with loss
of one water molecule.
c) hypo is generally used for the acid having lower oxygen content than the
parent acid.
However. it may be noted that metaphosphoric acid does not exist as simple
monomer; it exists are cyclometaphosphoric acid or polymetaphosphoric
acid.
Phosphatic fertilizers
The fertility of soil can be enhanced by using chemical fertilizers, which
provide the essential plant nutrients, potassium, nitrogen and phosphorus.
The most important phosphatic fertilizer is the superphosphate of lime,
Ca(H2PO4)2.
This is produced directly from phosphate rock by treatment with
concentrated sulphuric acid. In this way the insoluble phosphate rock is
rendered soluble in water to improve the release of Phosphorus to the soil for
the uptake by the plants.

Phosphatic rock generally contains fluoride, which reacts with H2SO4 to

give hydrogen fluoride, which in turn generates other side products. The
gaseous side-products are removed by washing with water in a scrubber.
Almost 90% of the phosphate rock mined goes into the production of
phosphatic fertilizers; the remaining 10% is used for the production of
elemental phosphorus.
Treatment of phosphate rock with phosphoric acid yields triple super
phosphate, Ca(H2PO4)2.H2O which is free from calcium sulphate and
hence contains a greater percentage of Phosphorus: