Question

Why pentahalides of phosphorus are more covalent than trihalides?

Answer 1

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The group 15 elements (nitrogen, phosphorus,arsenic,antimony and bismuth) when reacted with halogen atom ,tend to form halides. The halides formed are of two types:

1) Trihalides (MX3)

2) Pentahalides (MX5) where M -15

group element X- halogen atom

The trihalides are formed by all the elements of group 15 while pentahalides are formed by all the elements except nitrogen because there is absence of vacant d- orbital in its outermost shell.

The oxidation state of +5 in pentahalides is more as compared to +3 oxidation state in trihalides. Due to the higher positive oxidation state of central atom in pentahalide state, these atoms will have larger polarizing power than the halogen atom attached to them. The central atom in pentahalide state will tend to polarize more the halide ion to which it is attached.

But In case of trihalides due to +3 oxidation state the central atom will polarize the halogen atom to a lesser extent as compared to pentahalide state. Therefore, more the polarization, larger will be the covalent character of the bond.

Hence due larger polarization of bond in pentahalide state as compared to trihalide state, the pentahalides are more covalent than trihalides.