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Hybridization of PCl₅

PCl₅, phosphorus pentachloride, is sp³d hybridized. It has a trigonal bipyramidal shape with 0 lone pairs on P.

sp³dHybridization
Trigonal bipyramidalShape
90° and 120°Bond angle
0Lone pairs on P
ClClClClClP
Thick wedge: towards you. Dashed: away from you. Lobes with two dots: lone pairs.

How to work it out

  1. Central atom: P, with 5 valence electrons.
  2. Add 1 for each H or halogen around it: 5. O and S add nothing.
  3. Steric number = ½ × (5 + 5) = 5.
  4. 5 atoms are bonded, so 5 − 5 = 0 lone pairs.
  5. 5 electron pairs → sp³d, trigonal bipyramidal arrangement.

Why PCl₅ has this shape

In the trigonal bipyramid, the two axial P–Cl bonds (about 219 pm) are longer than the three equatorial ones (about 204 pm) because axial bonds feel more repulsion. That's why PCl₅ is reactive.

PCl₅ is nonpolar: its shape is symmetrical, so the bond dipoles cancel out.

Hybridization of common molecules

Molecule or ionHybridizationShapeLone pairs
XeF₄sp³d²Square planar2
XeF₂sp³dLinear3
XeF₆sp³d³Distorted octahedral1
XeO₃sp³Trigonal pyramidal1
XeOF₄sp³d²Square pyramidal1
SF₄sp³dSee-saw1
SF₆sp³d²Octahedral0
ClF₃sp³dT-shaped2
BrF₃sp³dT-shaped2
BrF₅sp³d²Square pyramidal1
IF₅sp³d²Square pyramidal1
IF₇sp³d³Pentagonal bipyramidal0
PCl₅sp³dTrigonal bipyramidal0
PCl₃sp³Trigonal pyramidal1
NH₃sp³Trigonal pyramidal1
H₂Osp³Bent (V-shaped)2
CH₄sp³Tetrahedral0
BF₃sp²Trigonal planar0
BeCl₂spLinear0
CO₂spLinear0
SO₂sp²Bent (V-shaped)1
SO₃sp²Trigonal planar0
H₂Ssp³Bent (V-shaped)2
NH₄⁺sp³Tetrahedral0
H₃O⁺sp³Trigonal pyramidal1
NO₃⁻sp²Trigonal planar0
NO₂⁺spLinear0
CO₃²⁻sp²Trigonal planar0
SO₄²⁻sp³Tetrahedral0
ClO₄⁻sp³Tetrahedral0
I₃⁻sp³dLinear3
ICl₄⁻sp³d²Square planar2
PF₆⁻sp³d²Octahedral0
SnCl₂sp²Bent (V-shaped)1

Questions students ask

What is the hybridization of PCl₅?

sp³d. The central P has 5 electron pairs around it: 5 bonds and 0 lone pairs.

What is the shape of PCl₅?

Trigonal bipyramidal. The electron pairs are arranged trigonal bipyramidal.

What is the bond angle in PCl₅?

90° and 120°.

Is PCl₅ polar or nonpolar?

PCl₅ is nonpolar: its shape is symmetrical, so the bond dipoles cancel out.

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