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Dynamics of the gas–liquid interfacial reaction of O(³P) atoms with hydrocarbons

  • We describe an experimental approach to the determination of the nascent internal state distribution of gas-phase products of a gas–liquid interfacial reaction. The system chosen for study is O(³P) atoms with the surface of liquid deuterated squalane, a partially branched long-chain saturated hydrocarbon, C₃₀D₆₂. The nascent OD products are detected by laser-induced fluorescence. Both OD (v′=0) and (v′=1) were observed in significant yield. The rotational distributions in both vibrational levels are essentially the same, and are characteristic of a Boltzmann distribution at a temperature close to that of the liquid surface. This contrasts with the distributions in the corresponding homogeneous gas-phase reactions. We propose a preliminary interpretation in terms of a dominant trapping-desorption mechanism, in which the OD molecules are retained at the surface sufficiently long to cause rotational equilibration but not complete vibrational relaxation. The significant yield of vibrationally excited OD also suggests that the surface is not composed entirely of –CD₃ endgroups, but that secondary and/or tertiary units along the backbone are exposed.

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    This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Journal of Chemical Physics 119, 9985 (2003) and may be found at https://doi.org/10.1063/1.1624833.

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Author:Hailey Kelso, Sven P. K. KöhlerORCiD, David A. Henderson, Kenneth G. McKendrickORCiD
DOI original:https://doi.org/10.1063/1.1624833
Parent Title (English):The Journal of Chemical Physics
Publisher:AIP Publishing
Document Type:Article
Year of Completion:2003
Publishing Institution:Hochschule Hannover
Release Date:2022/06/23
GND Keyword:Gas-Flüssigkeit-System; Sauerstoffatom; Kohlenwasserstoffe; Squalan
Article Number:9985
Page Number:10
Institutes:Fakultät II - Maschinenbau und Bioverfahrenstechnik
DDC classes:660 Technische Chemie
Licence (German):License LogoUrheberrechtlich geschützt