Colussi, A. J. and Sander, S. P. and Friedl, R. R. (1992) Temperature dependence and mechanism of the reaction between atomic O(^3P) and chlorine dioxide. Journal of Physical Chemistry, 96 (11). pp. 4442-4445. ISSN 0022-3654. doi:10.1021/j100190a058. https://resolver.caltech.edu/CaltechAUTHORS:20150623-154806978
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Abstract
Second-order rate constants for the decay of O(^3P) in excess chlorine dioxide, k_(11), were measured by flash photolysis-atomic resonance fluorescence as a function of total pressure (20-600 Torr argon) and temperature (248-312 K). It was found that (1) k_(11) is pressure dependent with a value, k_b, that is nonzero at zero pressure and (2) both the third-order rate constant (dk_(11)/d[M])_(lMl=O) = k_0, and k_b have negative temperature dependences. These results are consistent with an association reaction leading to an intermediate having two decomposition channels: O + OClO ⇌ ClO_3* (1, 2); ClO3_* + M → + ClO_3 + M (3); ClO_3* → ClO + O_2* (4), with E_(o2) > E_(o4). The measured k_0 values were used in conjunction with Troe's expression for unimolecular decomposition rates in the low-pressure limit to derive a critical energy for ClO_3 of 10 700 cm^(-1), which leads to ΔH_f(ClO_3) = 51.9 ± 5 kcal/mol. This is ~4 kcal/mol smaller than the value derived in our previous room temperature study of this reaction.
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| Alternate Title: | Temperature dependence and mechanism of the reaction between atomic oxygen (3P) and chlorine dioxide | |||||||||
| Additional Information: | © 1992 American Chemical Society. (Received: September 13, 1991; In Final Form: January 9, 1992) The research described in this paper was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under contract with the National Aeronautics and Space Administration. | |||||||||
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| Issue or Number: | 11 | |||||||||
| DOI: | 10.1021/j100190a058 | |||||||||
| Record Number: | CaltechAUTHORS:20150623-154806978 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20150623-154806978 | |||||||||
| Official Citation: | Temperature dependence and mechanism of the reaction between atomic oxygen (3P) and chlorine dioxide A. J. Colussi, S. P. Sander, and R. R. Friedl The Journal of Physical Chemistry 1992 96 (11), 4442-4445 DOI: 10.1021/j100190a058 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 58517 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | George Porter | |||||||||
| Deposited On: | 25 Jun 2015 22:58 | |||||||||
| Last Modified: | 10 Nov 2021 22:06 |
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