Slow chain reactions of Br2 and Cl2 with HI: Multiple state analysis and vibrational relaxation of HBr(v = 2) and HCl(v = 1 - 4)

Article abstract of DOI:10.1063/1.444364

Two chain reactions of the general form are studied by realtime detection of infrared chemiluminescence from the vibrationally excited HX(v) products.Both are characterized by k2 << k1.These reactions are initiated by pulsed UV laser photolusis of the diatomic halogens at 355 nm in a flow cell apparatus at 295 K.Observations are made on Δv = -1 fluorescence from individual vibrational levels, and the results are treated with a complete mathematical analysis for the production of multiple vibrational states and their subsequent individual decays.Effects of vibrational cascading on the measurements of k2 are discussed.The chain propagation rate coefficients determined by this technique for k1(X = Br, Cl) and k2(X = Br, Cl) are 8.9(+/- 1.3) * 10^-12, 1.4(+/- 0.3) * 10^-10, 3.4(+/- 0.8) * 10^-13, and 8.5(+/- 1.1) * 10^-17 cm³ molecule^-1 s^-1, respectively.The deactivation rate coefficients for HBr(v = 2) and HCl(v = 1,2,3,4) by HI are 1.7(+/- 0.2) * 10^-12, 1.43 (+/- 0.05) * 10^-13, 6.3(+/- 0.5) * 10^-13, 7.0(+/- 2.4) * 10^-13, and 3.2(+/- 0.7 * 10^-12 cm³ molecule^-1 s^-1, respectively.Vibrational deactivation rate cofficients for HCl(v = 1,2,3,4) by Cl2 are 5.2(+/- 0.3) * 10^-15, 2.2(+/- 0.3) * 10^-14, 4.3(+/- 4.2) * 10^-14, and 2.8(+/- 1.5) * 10^-13 cm³ molecule^-1 s^-1, respectively.The vibrational deactivation efficients of HCl(v = 1 - 4) by HI and Cl2 scale approximately as vⁿ, where n = 2.1(+/- 0.2) and 2.8(+/- 0.2), respectively.

Full text of DOI:10.1063/1.444364

Slow chain reactions of Br 2 and Cl 2 with HI: Multiple state analysis and vibrational
relaxation of HBr (v = 2) and HCl (v = 1–4)
David A. Dolson and Stephen R. Leone
Citation: The Journal of Chemical Physics 77, 4009 (1982); doi: 10.1063/1.444364
View online: http://dx.doi.org/10.1063/1.444364
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/77/8?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:
131.193.242.143 On: Mon, 08 Dec 2014 19:54:33

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:
131.193.242.143 On: Mon, 08 Dec 2014 19:54:33

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:
131.193.242.143 On: Mon, 08 Dec 2014 19:54:33

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:
131.193.242.143 On: Mon, 08 Dec 2014 19:54:33

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:
131.193.242.143 On: Mon, 08 Dec 2014 19:54:33

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:
131.193.242.143 On: Mon, 08 Dec 2014 19:54:33

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:
131.193.242.143 On: Mon, 08 Dec 2014 19:54:33

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:
131.193.242.143 On: Mon, 08 Dec 2014 19:54:33

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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