Thermal Decomposition of ClOOCl

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 time, and they are higher, depending on temperature and pressure, by factors between 1.5 and 4.2 as compared to experimental data on k-1 by Nickolaisen et al. [J. Phys. Chem. 1994, 98, 155] which were derived from the approach of ClO to thermal equilibrium with its dimer ClOOCl. Combination of the present dissociation rate constants with recommended temperature and pressure dependent data on the reverse reaction (k1) demonstrate inconsistencies between the dissociation and recombination rate constants. Summarizing laboratory data on k1 and k-1 above 250 K and field measurements on the ClO + ClO <= => ClOOCl equilibrium in the nighttime polar stratosphere close to 200 K, the expression Kc = k1/k-1 = 3.0 x 10(-27) exp(8433 K/T) cm3 molecule(-1) is derived for the temperature range 200-300 K.