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Consider a reaction 

PCl5 (g) → PC3 (g) + Cl2 (g) 

1. What is the change in hybridisation state of phosphorus? 

2. Explain why does PCl5 decomposes easily?

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1. When PCl5 decomposes to PCl3 , the hybridisation of P changes from sp3d to sp3.

2. In PCl5 , the five sp3d orbitals of P overlap with the singly occupied p orbitals of Cl atoms to form five P-CI sigma bonds. Three P-Cl bonds which lie in one plane and make an angle of 120° with each other are called equatorial bonds. The remaining two P – Cl bonds, called axial bonds, one lie above and the other lie below the equatorial plane, make an angle of 90° with the plane. As the axial bond pairs suffer more repulsive interaction from the equatorial bond pairs, axial bonds are slightly longer and hence slightly weaker than the equatorial bonds. This makes PCl5 molecule more reactive and hence it decomposes easily.

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