Thermal decomposition of ClOOCl

The Journal of Physical Chemistry. a
R Bröske, F Zabel

Abstract

ClOOCl was prepared in situ in a temperature controlled photoreactor (v = 420 L) by photolyzing OClO/N2 mixtures in the wavelength range 300-500 nm at temperatures between 242 and 261 K and total pressures between 2 and 480 mbar. After switching off the lights, excess NO2 was added, and IR and UV spectra were monitored simultaneously as a function of time. By spectral stripping of all other known UV absorbers (in particular, other chlorine oxides and chlorine nitrate), we determined rate constants k-1 of the reaction ClOOCl (+M) --> ClO + ClO (+M) from the first-order decay of the residual UV absorption of ClOOCl at 246 and 255 nm. k-1,0 = [N2] x 7.6 x 10(-9) exp[(-53.6 +/- 6.0) kJ mol(-1)/RT] cm3 molecule(-1) s(-1) (2sigma) was derived for the low-pressure limiting rate constant. Application of Troe's expression for the limiting low-pressure rate constants of unimolecular decomposition reactions leads to E0 = Delta(r)H0(0)(ClOOCl-->ClO+ClO) = 66.4 +/- 3.0 kJ mol(-1). k-1,0 started to fall off from the pressure proportional low pressure behavior at p approximately 30 mbar; however, reliable extrapolation to the high pressure limit was not possible. The decomposition rate constants of ClOOCl were directly measured for the first ...Continue Reading

References

Jul 13, 2006·The Journal of Physical Chemistry. a·J PlengeE Rühl

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Citations

Aug 3, 2010·Physical Chemistry Chemical Physics : PCCP·Valerio Ferracci, David M Rowley
Apr 15, 2010·Proceedings of the National Academy of Sciences of the United States of America·Michelle L SanteeLucien Froidevaux
Oct 22, 2019·Atmospheric Chemistry and Physics·J Eric Klobas, David M Wilmouth
Aug 19, 2007·The Journal of Physical Chemistry. a·Jingyao Liu, John R Barker

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