THE p-BLOCK ELEMENTS

GROUP-15
1. Includes five elements namely nitrogen (N), phosphorus (P), arsenic (As) antimony (Sb) and
bismuth (Bi). This group is regarded as nitrogen family.
2. Electronic configuration:
The general electronic configuration of this group is ns2np3.
3. Properties
(i) 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 screening effect and
increse in number of shells.
(ii) Melting and boiling points
Melting points (except for antimony and bismuth) and boiling points increase on going down the
group from N to Bi.
(iii) Ionization energies
The first ionization energies of the group 15 elements are higher than the corresponding
members of the group 14 elements.
Explanation:
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 (npx1,npy1,npz1) are
stable.
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.
(iv) Electronegativity
The electronegativity values of elements of group 15 are higher than the corresponding elements
of group 14.
Explanation: Due to small size and greater nuclear charge of atoms.
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.
(v) 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.

(vi) Catenation
All the elements show this property but to a much smaller extent than carbon.The lesser tendency
of elements of group 15 to show catenation in comparison to carbon is their low (M-M) bond
dissociation energies.

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(vii) Allotropy
Except nitrogen and bismuth, all other elements of this group show allotropy.For e.g.,
Phosphorous exists as - white, black or red phosphorus
Arsenic exists as - yellow or grey arsenic
Antimony exists as - yellow or silvery grey allotropic forms
(viii) Oxidation states (common O.S -3,+3 and+5)
The tendency to exhibit -3 O.S decreases down the group due to increase in size and metallic
character.In addition to - 3 oxidation state, the elements of group 15 exhibit +3 and +5 oxidation
states. The stability of stability of +5 decreases down the group and+3 increases down the group
due to inert pair effect
Nitrogen exhibits various oxidation states from -3 to +5 in its hydrides, oxides and oxo acids. For
e.g., NH3 Ammonia(-3), N2H4 Hydrazine(-2), N2 Nitrogen(0), N2O Nitrous Oxide(+1), NO
Nitric Oxide(+2), N2O3 Nitrogen trioxide(+3), N2O4 Nitrogen tetraoxide(+4) and N2O5 Nitrogen
pentaoxide.
Note: In case of nitrogen all O.S from+1 to +4 tend to disproportionate in acid solution for e.g.
3HNO2→ HNO3 + H2O +2NO
In case of phosphorous nearly all intermediate O.S disproportionate into +3 and +5 both in alkali
and acid. However +3 O.S of Bi, As and Sb are stable with respect to disproportionation.
Anamolous properties of nitrogen
Like all other first elements of the groups, nitrogen also differs from its family members. The
anomalous behavior of nitrogen is due to its
(i) small size
(ii) high value of ionization energy and electronegativity
(iii) absence of d-orbitals in the valence shell.

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.

Shape of NH3 molecule

• Bond angle: Down the group the bond angle decreases as: NH3> PH3> AsH3> SbH3> BiH3
Explanation:
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:

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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
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:
Decreases as we go down the group.
NH3 > PH3 > AsH3 > SbH3 > BiH3
Explanation:
Due to increase in the size of the central atom,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
Increases from NH3 to BiH3.
NH3< PH3< AsH3 < SbH3 < BiH3
Explanation:
The reducing character depends upon the stability of the hydride. 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.

Oxides:
Combine with oxygen either directly or indirectly to form oxides E2O3 and E2O5. 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.
NOTE: The nitrogen has the ability to form p¶-p¶ multiple bonds on the other hand the
reluctance of P, As, Sb and Bi to form p¶-p¶ multiple bonds-leads to the cage structures for their
oxides.

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
• 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.
(iii) The trihalides are easily hydrolyzed by water. However, the products are
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 different in hydrolysis different chlorides.
• 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 [PCl4]+[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.

Allotropes of phosphorous:
There are three principal allotropic forms of Phosphorus. These are white
phosphorus, red phosphorus and black phosphorus.

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