Study Of The Kinetics And Product Yields For The Reaction Of Criegee Intermediate Ch2oo With Hno3 Using Mid-infrared Time-resolved Dual-comb Spectroscopy
Luo, Pei-Ling
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https://hdl.handle.net/2142/116535
Description
Title
Study Of The Kinetics And Product Yields For The Reaction Of Criegee Intermediate Ch2oo With Hno3 Using Mid-infrared Time-resolved Dual-comb Spectroscopy
Author(s)
Luo, Pei-Ling
Issue Date
2022-06-21
Keyword(s)
Radicals
Abstract
The reaction of Criegee intermediates with \chem{HNO_3} have been thought to be important in the oxidation of atmospheric \chem{HNO_3} because of the fast reaction rates, over 3 orders of magnitude larger than that of the \chem{OH} + \chem{HNO_3} reaction.\footnote{Khan, M. A. H.; Percival, C. J.; Caravan, R. L.; Taatjes, C. A.; Shallcross, D. E. Environ. Sci.: Processes Impacts 2018, 20, 437–453.} In particular, a new catalytic conversion of the simplest Criegee intermediate \chem{CH_2OO} to \chem{OH} and \chem{HCO} radicals by \chem{HNO_3} was proposed in recent theoretical study.\footnote{Raghunath, P.; Lee, Y.-P.; Lin, M. C. J. Phys. Chem. A 2017, 121, 3871– 3878.} Herein, the mid-infrared dual-comb spectrometers\footnote{Luo, P.-L.; Horng, E.-C. Commun Chem 2020, 3, 95; Luo, P.-L. Opt. Lett. 2020, 45, 6791–6794.} with the capability of widely wavelength tunability and switchable dual-comb and continuous-wave operation modes were employed to investigate the reaction kinetics and determine the branching ratios of the primary product channels in the reaction \chem{CH_2OO} + \chem{HNO_3}. Based on quantitative determinations of \chem{CH_2OO}, \chem{CH_2O}, \chem{OH} and \chem{HO_2} radicals under various experimental conditions, the pressure-dependent yields of the \chem{OH} and \chem{HO_2} product channels of the reaction \chem{CH_2OO} + \chem{HNO_3} were evaluated in this work.
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