Mutual combination of ClO radicals
| Autor: | N. Basco, J. E. Hunt |
|---|---|
| Rok vydání: | 1979 |
| Předmět: |
Absorption spectroscopy
Chemistry Stereochemistry Radical Organic Chemistry Analytical chemistry Molar absorptivity medicine.disease_cause Biochemistry Inorganic Chemistry Combination reaction Wavelength Reaction rate constant medicine Physical and Theoretical Chemistry Equilibrium constant Ultraviolet |
| Zdroj: | International Journal of Chemical Kinetics. 11:649-664 |
| ISSN: | 1097-4601 0538-8066 |
| DOI: | 10.1002/kin.550110611 |
| Popis: | The mutual combination reaction is proposed as the rate-limiting step in the removal of ClO radicals at moderate pressures. The third--order rate constants measured at room temperature were k1(Ar) = 3.51 ± 0.14 × 109 l2/mol2·ec; k1(He) ≈ 2.8 × 109 l2/mol2·sec, and k1(O2) ≈ 7.9 × 109 l2/mol2·sec. There is also an independent second-order reaction for which k3 ≈ 8 × 106 l/mol·sec. A new absorption spectrum has been observed in the ultraviolet and attributed to Cl2O2. The extinction coefficient for Cl2O2 has been measured at six wavelengths, and, between 292 and 232 nm, it increases from 0.4 × 103 to 2.9 × 103 l/mol·cm. In the presence of the chlorine atom scavengers OClO or Cl2O, Cl2O2 exists in equilibrium with ClO. The equilibrium constant Ke1 = 3.1 ± 0.1 × 106 l/mol at 298 K, and, with ΔS10 estimated to be −133 ± 11 J/K·mol, ΔH10 = −69 ± 3 kJ/mol and ΔHf0(Cl2O2) = 136 ± 3 kJ/mol. |
| Databáze: | OpenAIRE |
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