Intermediates in the pyrolysis and mass spectrometry of chlorine monoxide and chlorine heptoxide

Abstract

Chlorine monoxide Cl₂O and chlorine heptoxide Cl₂O₇ have been pyrolyzed and the products analyzed by mass spectrometry. Cl₂O decomposed mainly to Cl₂ and O₂. Cl₂O₇ gave a large yield of Cl₂O and a smaller amount of ClO. No ClO₃ or ClO₄ were observed. The ionization and dissociation of these compounds have also been studied. The ionization potentials of ClO₂ and CIO formed in the pyrolysis of Cl₂O₇ were 10.7 ± 0.1 and 11.1 ± 0.1 eV respectively. The bond dissociation energies D(Cl—OCl) and D(ClO₃—ClO₄) have been determined to be 32.3 ± 2 kcal mole^–1 and 30 ± 4 kcal mole^–1 respectively. Some ionic bond dissociation energies have been calculated for the chlorine oxides and compared with those in other halogen oxides.