The various elements of this group differ from one another in their chemical reactivity. Nitrogen differs from the rest of the members of the group due to its smaller size, high electronegativity, high ionization enthalpy and non-availability of d-orbitals. Nitrogen is chemically comparatively less reactive. It is because of high stability of its molecule, N2 in which the two nitrogen atoms are linked by triple bond (N ≡ N) and thus, possess high bond strength (941.4 kJ mol-1).
Among the elements of this group only nitrogen has a unique ability to form p π-p π multiple bonds with itself as well as with carbon oxygen. The multiple bonding in nitrogen occurs due to its small size. Nitrogen, thus, forms a diatomic molecule, N2. On the other hand, phosphorus, arsenic and antimony form tetrahedral molecules in their elemental state with formula E4. Each P atom is linked to three other atoms with P - P - P bond angle equal to 60°. Though phosphorus and heavier members of the family do not form p π-p πmultiple bonds easily, yet the multiple bonding of the type d π-p π can readily occur in these elements. This type of bonding is prominent for the phosphorus as is reflected in the formation of compounds such as POX3, RN = PX2, R3P = O or R3P = CH2 (R = alkylgroup).
Phosphorus and arsenic can form d π-p π bond also with transition metals their compounds like P(C2H3) and As(C6H5)3 an actas ligands. Recently, a few compounds of phosphorus and arsenic having multiple bonding like P = C, P ≡ C, P = N, P = P and As = Asgroups have been synthesized.
The common chemical characteristics of group 15 elements are discussed below:
Reactivity for hydrogen: the elements of group 15 form hydrides having the general formula EH3. All these are covalent in nature. These hydrides are listed below:
Reactivity towards halogen
All the elements of group 15 form two series of halides, i.e. trihalides and pentahalides of the type EX3 and EX5.
Nitrogen does not form pentahalides because of non-availability of the d-orbitals in its valence shell. Penta-halides are more covalent than trihalides. All these trihalides of these elements except those of nitrogen are stable. In case of nitrogen simply NF3 is known to be stable. The trihalides except BiF3 are predominantly covalent in character.