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NEET CHEMISTRYMedium

The correct order of increasing bond angles in the following species is:

A

Cl₂O < ClO₂ < ClO₂⁻

B

ClO₂ < Cl₂O < ClO₂⁻

C

Cl₂O < ClO₂⁻ < ClO₂

D

ClO₂⁻ < Cl₂O < ClO₂

Step-by-Step Solution

  1. Analyze ClO2ClO_2 (Chlorine Dioxide): The central Cl atom has 7 valence electrons. It forms double bonds with two O atoms and has one unpaired electron (odd electron species). The repulsion from a single odd electron is less than that of a full lone pair. The hybridization is effectively sp2sp^2 with the odd electron in an orbital. The bond angle is approximately 117.6° (close to 120°).

  2. Analyze Cl2OCl_2O (Dichlorine Monoxide): The central atom is Oxygen (sp3sp^3 hybridized). It has 2 bond pairs (with Cl) and 2 lone pairs. Normally, 2 lone pairs would compress the angle (as in H2OH_2O, 104.5°). However, the Chlorine atoms are large and bulky, leading to significant steric repulsion (van der Waals repulsion) which opens up the bond angle to approximately 110.9° (greater than the tetrahedral angle of 109.5°).

  3. Analyze ClO2ClO_2^- (Chlorite Ion): The central atom is Chlorine (sp3sp^3 hybridized). It has 2 bond pairs (with O) and 2 lone pairs. The strong lone pair-lone pair repulsion on the central Chlorine atom compresses the bond angle. The angle is experimentally found to be approximately 110–111°.

  4. Conclusion: Comparing the specific values often used in this context (ClO2110111ClO_2^- \approx 110-111^\circ and Cl2O111Cl_2O \approx 111^\circ), the order is often debated. However, based on the standard answer key for this AIPMT 2010 question, the order follows ClO2<Cl2O<ClO2ClO_2^- < Cl_2O < ClO_2, implying the lone pair repulsion in the chlorite ion compresses the angle slightly more than the net result of steric hindrance in Cl2OCl_2O.

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