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Question: Answered & Verified by Expert
Bond angle in PH3 is closer to 90° while that in NH3 is 104.5°. Which of the following best explains this structural feature?
Chemistryp Block Elements (Group 15, 16, 17 & 18)NEET
Options:
  • A Due to larger size of the lone pair electron cloud, there is larger lone pair – bond pair repulsion in PH3 compared to NH3 .
  • B Higher electronegativity of nitrogen concentrates the bond pair electron cloud near the central atom which increases the bond pair – bond pair repulsion which in turn decreases the bond angle in NH3 .
  • C Energy difference between 3s and 3p orbitals is quite high and hence the lone pair on phosphorous prefers to occupy unhybridized s- orbital rather than hybridized sp3 hybridized orbital which causes its s- orbital energy to increase.
  • D Phosphorous forms pπ-dπ bonds while nitrogen does not.
Solution:
2325 Upvotes Verified Answer
The correct answer is: Energy difference between 3s and 3p orbitals is quite high and hence the lone pair on phosphorous prefers to occupy unhybridized s- orbital rather than hybridized sp3 hybridized orbital which causes its s- orbital energy to increase.
In the hydrides of group 15 and group 16 (except NH3 and H2O ) the energy difference between 3s and 3p orbital’s is quite high. Hybridization increases the energy of 3s orbital so much that lone pair rather prefers to occupy unhybridized s orbital. For example, in PH3 , 600kJmol-1 of energy is required to hybridize the central atom. So, to avoid such energy demanding hybridization P forms bonds with unhybridized p orbitals leaving the lone pair in the spherical s orbital which leads to a bond angle close to 90° .

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