Temperature dependent rate coefficient for the Cl + ClONO2 reaction

R. J. Yokelson, James B. Burkholder, Leah Goldfarb, R. W. Fox, Mary K. Gilles, A. R. Ravishankara

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16 Scopus citations


The rate coefficient for reaction 1, Cl + ClONO2 → products was measured between 195 and 354 K. Cl atoms were generated by pulsed laser photolysis of Cl2 in an excess of ClONO2. The temporal profiles of Cl atom loss and NO3 product formation were monitored using resonance fluorescence and tunable diode laser absorption at 662 nm, respectively. The long path absorption system was used to measure k1 between 200 and 298 K while the resonance fluorescence system was employed between 195 and 354 K. Thermal decomposition of ClONO2 prevented measurements at temperatures greater than 354 K. The two techniques yielded rate coefficients which are in excellent agreement. An Arrhenius rate coefficient expression of k1 = (6.0 ± 0.4) × 10-12 exp[(140 ± 30)/T] cm3 molecule-1 s-1 and room temperature rate constant of k1(298 K) = (9.6 ± 1.0) × 10-12 cm3 molecule-1 s-1 were derived from data at T ≤ 298 K. The quoted error limits are 2σ and include estimated systematic errors. Our results are compared with previous measurements, and values of k1 for atmospheric modeling are recommended.

Original languageEnglish
Pages (from-to)13976-13983
Number of pages8
JournalJournal of Physical Chemistry
Issue number38
StatePublished - 1995


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