Kinetics of the dissociation and cis-trans isomerization of o,o'-azodioxytoluene (dimeric o-nitrosotoluene) |
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Authors: | Michel Azoulay Gunnar Wettermark |
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Institution: | Division of Physical Chemistry, The Royal Institute of Technology, S-100 44 Stockholm 70, Sweden |
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Abstract: | The dimer-monomer reactions were investigated for the system cis and transo,o'-azodioxytoluene-o-nitrosotoluene in acetonitrile solvent. For the reaction cis dimer-monomer the following thermodynamic and activation parameters have been derived: ΔH°=58.5±2.5 kJ mole?1, ΔS°=206.2±3.8 J mole?1 K?1, ΔH≠=63.6±3.3 kJ mole?1, ΔS≠=6.3±0.3 J mole?1 K?1. The corresponding values for the reaction trans dimer-monomer are: ΔH°=45.6±2.1 kJ mole?1, ΔS°=162.7±7.1 J mole?1 K?1, ΔH≠=80.8±2.9 kj mole?1, ΔS≠=-13.4±0.8 mole?1 K?1. There is no evidence of a direct cis-trans isomerization (i.e. a reaction not proceeding via the monomer). NMR and various perturbation techniques monitoring the visible absorption of the monomer were employed. |
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