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A study of the alkene–ozone reactions, 2,3-dimethyl 2-butene + O3 and 2-methyl propene + O3, with photoelectron spectroscopy: measurement of product branching ratios and atmospheric implications

A study of the alkene–ozone reactions, 2,3-dimethyl 2-butene + O3 and 2-methyl propene + O3, with photoelectron spectroscopy: measurement of product branching ratios and atmospheric implications
A study of the alkene–ozone reactions, 2,3-dimethyl 2-butene + O3 and 2-methyl propene + O3, with photoelectron spectroscopy: measurement of product branching ratios and atmospheric implications
The reactions of ozone with the alkenes 2,3-dimethyl 2-butene (DMB) and 2-methyl propene (2MP) have been investigated using a flow-tube interfaced to a u.v. photoelectron spectrometer. These reactions were studied at low pressure at different reagent partial pressures, both with the alkene in excess and ozone in excess. In each case, photoelectron spectra recorded as a function of time have been used to estimate partial pressures of the reagents and products as a function of time using photoionization cross-sections of selected photoelectron bands of the reagents and products, which were measured separately. The yields of all the main products have been determined, some of which have been measured in previous studies. For each reaction, oxygen was observed as a product for the first time and its yield was measured. Kinetics simulations were performed using reaction schemes which were developed for these reactions, which are consistent with that used earlier for the ozone–ethene reaction, in order to determine the main reactions for production of the products. The experimental product yields have been used in a global model to estimate their global annual emissions in the atmosphere. For example, for the reaction of O3 with 2MP the formaldehyde, formic acid and acetone global annual emissions are calculated as 0.4 Tg, 25.0 Gg and 0.16 Tg respectively, which are estimated as 0.02, 0.3 and 0.2% of the total annual emission respectively. For the reaction of O3 with DMB, the acetone yield is higher at 0.9 Tg which is approximately 1% of the total annual estimated emission
1463-9076
17461-17473
Copeland, Grant
1adc6e1f-c40d-4a4d-93e1-91b1900eeb60
Ghosh, Mariana V.
210ab8df-8389-4bf5-9622-9931cc4a9f81
Shallcross, Dudley E.
2beaf7e0-0b00-47d7-86c0-b60470cd6f35
Percival, Carl J.
f819a683-66a0-4ad4-b290-2c99f68dedbc
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Copeland, Grant
1adc6e1f-c40d-4a4d-93e1-91b1900eeb60
Ghosh, Mariana V.
210ab8df-8389-4bf5-9622-9931cc4a9f81
Shallcross, Dudley E.
2beaf7e0-0b00-47d7-86c0-b60470cd6f35
Percival, Carl J.
f819a683-66a0-4ad4-b290-2c99f68dedbc
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f

Copeland, Grant, Ghosh, Mariana V., Shallcross, Dudley E., Percival, Carl J. and Dyke, John M. (2011) A study of the alkene–ozone reactions, 2,3-dimethyl 2-butene + O3 and 2-methyl propene + O3, with photoelectron spectroscopy: measurement of product branching ratios and atmospheric implications. Physical Chemistry Chemical Physics, 13 (39), 17461-17473. (doi:10.1039/C1CP21922G).

Record type: Article

Abstract

The reactions of ozone with the alkenes 2,3-dimethyl 2-butene (DMB) and 2-methyl propene (2MP) have been investigated using a flow-tube interfaced to a u.v. photoelectron spectrometer. These reactions were studied at low pressure at different reagent partial pressures, both with the alkene in excess and ozone in excess. In each case, photoelectron spectra recorded as a function of time have been used to estimate partial pressures of the reagents and products as a function of time using photoionization cross-sections of selected photoelectron bands of the reagents and products, which were measured separately. The yields of all the main products have been determined, some of which have been measured in previous studies. For each reaction, oxygen was observed as a product for the first time and its yield was measured. Kinetics simulations were performed using reaction schemes which were developed for these reactions, which are consistent with that used earlier for the ozone–ethene reaction, in order to determine the main reactions for production of the products. The experimental product yields have been used in a global model to estimate their global annual emissions in the atmosphere. For example, for the reaction of O3 with 2MP the formaldehyde, formic acid and acetone global annual emissions are calculated as 0.4 Tg, 25.0 Gg and 0.16 Tg respectively, which are estimated as 0.02, 0.3 and 0.2% of the total annual emission respectively. For the reaction of O3 with DMB, the acetone yield is higher at 0.9 Tg which is approximately 1% of the total annual estimated emission

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Published date: 2 August 2011
Organisations: Chemistry

Identifiers

Local EPrints ID: 199635
URI: http://eprints.soton.ac.uk/id/eprint/199635
ISSN: 1463-9076
PURE UUID: 6c145135-6c3b-4792-888e-a434fda05d05
ORCID for John M. Dyke: ORCID iD orcid.org/0000-0002-9808-303X

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Date deposited: 19 Oct 2011 10:42
Last modified: 20 Jul 2019 01:27

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