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Chlorine dioxide isomerization

  1. Sep 22, 2015 #1
    O=Cl=O → O--Cl-O- → (cyclic)O-Cl-O

    This is an intramolecular reaction which isn't all that common.

    The double bonds break, causing the O's to each have a negative charge. This forms an ion. The ion bends and eventually the 2 O's bond with each other forming a ring.

    But would this really happen? I mean yes, sunlight is enough to split Cl2 into 2 Cl radicals but would it be enough to break the O-Cl double bond so that the ion can form?
  2. jcsd
  3. Sep 23, 2015 #2


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    To begin with: Why should two negative ions form a bond? They repel each other and also have no unpaired electrons for bonding.
    The second point: ClO2 is already bent. Probably there are also bonding resonance valence structures contributing to the energetic stabilization of the molecule. Note that this is not an isomerisation.
  4. Sep 24, 2015 #3
    The oxygens can use their lone pairs to form bonds just like they do when bonding with other molecules. And yes I know that there is a form that has a triple bond and a single bond that is a resonance structure. But the cyclic peroxide is not a resonance structure, it is an isomer.
  5. Sep 24, 2015 #4


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    But where should the lone pairs go to, if both oxygens already have a filled octet?
    Also, I was not referring to a resonance structure with a triple and a single bond but in the peroxidic resonance structure.
    While this resonance structure makes but a small contribution to the bonding in the electronic ground state, one may wonder whether there exists an excited electronic state which is mainly peroxidic.
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