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