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Chemical Properties
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
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.
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.
(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
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.
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.