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Issue 24, 2003
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A discharge-flow study of Cl2O3

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Abstract

The discharge-flow technique coupled with UV-absorption spectroscopy has been used to study the production of dichlorine trioxide, Cl2O3, from the reaction between ClO and OClO radicals. The absorption cross section of Cl2O3 was determined to be (1.44 ± 0.10) × 10−17 cm2 molecule−1 at λmax = 267 nm (all errors reported are two standard deviations of the statistical error). The equilibrium constant for the process ClO + OClO + M ⇌ Cl2O3 + M was measured in the temperature range 243–298 K. A Second-Law analysis yielded values of ΔrH[circle, cut, short horiz bar] = −57.9 ± 2.1 kJ mol−1 and ΔrS[circle, cut, short horiz bar] = −132.6 ± 7.9 J K−1 mol−1. The rate coefficient for the formation of Cl2O3 was measured with helium as the third body at a concentration of ∼7.3 ± 1016 molecule cm−3 over the temperature range 243–283 K. Analysis of these data employing the conventional form of the rate equation for the low-pressure limit, k0(T) = k0(300)·(T/300)n, resulted in values of k0(300) = (2.83 ± 0.04) × 10−32 cm6 molecule−2 s−1 and n = −4.32 ± 0.1. These spectroscopic, thermochemical and kinetic data are compared with previously reported values.

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Publication details

The article was received on 09 Sep 2003, accepted on 15 Oct 2003 and first published on 06 Nov 2003


Article type: Paper
DOI: 10.1039/B311005B
Citation: Phys. Chem. Chem. Phys., 2003,5, 5409-5418

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    A discharge-flow study of Cl2O3

    T. J. Green, M. Islam, P. Guest, K. Hickson, C. E. Canosa-Mas and R. P. Wayne, Phys. Chem. Chem. Phys., 2003, 5, 5409
    DOI: 10.1039/B311005B

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