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Exercise · Q17

Q.Determine the hybridisation of the central phosphorus atom in PCl5\text{PCl}_5 and relate it to the trigonal bipyramidal shape of the molecule.

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Phosphorus forms five sigma bonds in PCl5\text{PCl}_5 and carries no lone pairs, giving a steric number of 5. To generate five equivalent hybrid orbitals, phosphorus mixes one 3s3s, three 3p3p and one 3d3d orbital together — sp3dsp^3d hybridisation. This requires promoting phosphorus's ground-state 3s23p33s^2 3p^3 configuration so that all five valence electrons occupy separate orbitals (3s13p33d13s^1 3p^3 3d^1), which then mix into five sp3dsp^3d hybrid orbitals. These five hybrid orbitals are oriented, by the geometry of sp3dsp^3d mixing, toward the corners of a trigonal bipyramid — three equatorial hybrids at 120∘120^{\circ} to one another and two axial hybrids at 90∘90^{\circ} to the equatorial plane — exactly reproducing the trigonal bipyramidal shape (and the axial/equatorial bond-length inequivalence) that VSEPR theo …

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