Thermodynamic and kinetic properties of the reaction Cl + O2 + MClOO + M in the range 160-300 K and 1-1000 bar

Article abstract of DOI:10.1063/1.461543

The reaction Cl + O2 + M<*>ClOO + M was studied by laser flash photolysis in the bath gases M = He, Ar, N2, and O2 over the temperature range 160-300 K and the pressure range 1-1000 bar.UV absorptions of ClOO were monitored, a maximum absorption cross section of ?(248 nm) = 3.4*10^-17 cm² was determined.An expression for the equilibrium constant K_p = 5.3*10^-6 exp( + 23.4 kJ mol^-1/RT) bar^-1 was derived between 180 and 300 K, which, by a third law analysis, yields Η₀ deg = -20.2 +/- 0.2 kJ mol^-1.Limiting low pressure rate coefficients for Cl + O2 recombination of k₀ = 8.8*10^-34 (T/300 K)^-3.0, k₀ = 1.6*10^-33 (T/300 K)^-2.9, k₀ = 1.4*10^-33 (T/300 K)^-3.9 cm⁶ s^-1 were obtained over the range 160-260 K, as well as k₀ (160 K) = 2.2*10^-32 cm⁶ s^-1.Rate constants for the reactions Cl + ClOO -> Cl2 + O2 or 2ClO, ClOO + ClOO -> products, and ClOO + Cl2 -> Cl2O + ClO were also derived.The recombination Cl + O2( + M) -> ClOO( + M) at pressures above 10 bar shows a transition to a high pressure plateau and, at pressures above 200 bar, to diffusion control.It is suggested that, like O + O2( + M) -> O3( + M), the reaction is governed by a radical complex mechanism.

Full text of DOI:10.1063/1.461543

Thermodynamic and kinetic properties of the reaction Cl+O2+M=ClOO+M in the
range 160–300 K and 1–1000 bar
S. Baer, H. Hippler, R. Rahn, M. Siefke, N. Seitzinger, and J. Troe
Citation: The Journal of Chemical Physics 95, 6463 (1991); doi: 10.1063/1.461543
View online: http://dx.doi.org/10.1063/1.461543
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/95/9?ver=pdfcov
Published by the AIP Publishing
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
136.165.238.131 On: Sun, 21 Dec 2014 12:27:10

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
136.165.238.131 On: Sun, 21 Dec 2014 12:27:10

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
136.165.238.131 On: Sun, 21 Dec 2014 12:27:10

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
136.165.238.131 On: Sun, 21 Dec 2014 12:27:10

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
136.165.238.131 On: Sun, 21 Dec 2014 12:27:10

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
136.165.238.131 On: Sun, 21 Dec 2014 12:27:10

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
136.165.238.131 On: Sun, 21 Dec 2014 12:27:10