Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis: reactions with SO2, H2O and decomposition under boundary layer conditions

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Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis : reactions with SO2, H2O and decomposition under boundary layer conditions. / Newland, Mike J.; Rickard, Andrew R.; Alam, Mohammed S.; Vereecken, Luc; Muñoz, Amalia; Ródenas, Milagros; Bloss, William J.

In: Physical Chemistry Chemical Physics, Vol. 17, No. 6, 14.02.2015, p. 4076-4088.

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@article{cbbb9206780d42b98a3b7f3cdd4d6fa3,
title = "Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis: reactions with SO2, H2O and decomposition under boundary layer conditions",
abstract = "The removal of SO2 in the presence of alkene-ozone systems has been studied for ethene, cis-but-2-ene, trans-but-2-ene and 2,3-dimethyl-but-2-ene, as a function of humidity, under atmospheric boundary layer conditions. The SO2 removal displays a clear dependence on relative humidity for all four alkene-ozone systems confirming a significant reaction for stabilised Criegee intermediates (SCI) with H2O. The observed SO2 removal kinetics are consistent with relative rate constants, k(SCI + H2O)/k(SCI + SO2), of 3.3 (±1.1) × 10-5 for CH2OO, 26 (±10) × 10-5 for CH3CHOO derived from cis-but-2-ene, 33 (±10) × 10-5 for CH3CHOO derived from trans-but-2-ene, and 8.7 (±2.5) × 10-5 for (CH3)2COO derived from 2,3-dimethyl-but-2-ene. The relative rate constants for k(SCI decomposition)/k(SCI + SO2) are -2.3 (±3.5) × 1011 cm-3 for CH2OO, 13 (±43) × 1011 cm-3 for CH3CHOO derived from cis-but-2-ene, -14 (±31) × 1011 cm-3 for CH3CHOO derived from trans-but-2-ene and 63 (±14) × 1011 cm-3 for (CH3)2COO. Uncertainties are ±2σ and represent combined systematic and precision components. These values are derived following the approximation that a single SCI is present for each system; a more comprehensive interpretation, explicitly considering the differing reactivity for syn- and anti-SCI conformers, is also presented. This yields values of 3.5 (±3.1) × 10-4 for k(SCI + H2O)/k(SCI + SO2) of anti-CH3CHOO and 1.2 (±1.1) × 1013 for k(SCI decomposition)/k(SCI + SO2) of syn-CH3CHOO. The reaction of the water dimer with CH2OO is also considered, with a derived value for k(CH2OO + (H2O)2)/k(CH2OO + SO2) of 1.4 (±1.8) × 10-2. The observed SO2 removal rate constants, which technically represent upper limits, are consistent with decomposition being a significant, structure dependent, sink in the atmosphere for syn-SCI.",
author = "Newland, {Mike J.} and Rickard, {Andrew R.} and Alam, {Mohammed S.} and Luc Vereecken and Amalia Mu{\~n}oz and Milagros R{\'o}denas and Bloss, {William J.}",
year = "2015",
month = feb,
day = "14",
doi = "10.1039/C4CP04186K",
language = "English",
volume = "17",
pages = "4076--4088",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "6",

}

RIS

TY - JOUR

T1 - Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis

T2 - reactions with SO2, H2O and decomposition under boundary layer conditions

AU - Newland, Mike J.

AU - Rickard, Andrew R.

AU - Alam, Mohammed S.

AU - Vereecken, Luc

AU - Muñoz, Amalia

AU - Ródenas, Milagros

AU - Bloss, William J.

PY - 2015/2/14

Y1 - 2015/2/14

N2 - The removal of SO2 in the presence of alkene-ozone systems has been studied for ethene, cis-but-2-ene, trans-but-2-ene and 2,3-dimethyl-but-2-ene, as a function of humidity, under atmospheric boundary layer conditions. The SO2 removal displays a clear dependence on relative humidity for all four alkene-ozone systems confirming a significant reaction for stabilised Criegee intermediates (SCI) with H2O. The observed SO2 removal kinetics are consistent with relative rate constants, k(SCI + H2O)/k(SCI + SO2), of 3.3 (±1.1) × 10-5 for CH2OO, 26 (±10) × 10-5 for CH3CHOO derived from cis-but-2-ene, 33 (±10) × 10-5 for CH3CHOO derived from trans-but-2-ene, and 8.7 (±2.5) × 10-5 for (CH3)2COO derived from 2,3-dimethyl-but-2-ene. The relative rate constants for k(SCI decomposition)/k(SCI + SO2) are -2.3 (±3.5) × 1011 cm-3 for CH2OO, 13 (±43) × 1011 cm-3 for CH3CHOO derived from cis-but-2-ene, -14 (±31) × 1011 cm-3 for CH3CHOO derived from trans-but-2-ene and 63 (±14) × 1011 cm-3 for (CH3)2COO. Uncertainties are ±2σ and represent combined systematic and precision components. These values are derived following the approximation that a single SCI is present for each system; a more comprehensive interpretation, explicitly considering the differing reactivity for syn- and anti-SCI conformers, is also presented. This yields values of 3.5 (±3.1) × 10-4 for k(SCI + H2O)/k(SCI + SO2) of anti-CH3CHOO and 1.2 (±1.1) × 1013 for k(SCI decomposition)/k(SCI + SO2) of syn-CH3CHOO. The reaction of the water dimer with CH2OO is also considered, with a derived value for k(CH2OO + (H2O)2)/k(CH2OO + SO2) of 1.4 (±1.8) × 10-2. The observed SO2 removal rate constants, which technically represent upper limits, are consistent with decomposition being a significant, structure dependent, sink in the atmosphere for syn-SCI.

AB - The removal of SO2 in the presence of alkene-ozone systems has been studied for ethene, cis-but-2-ene, trans-but-2-ene and 2,3-dimethyl-but-2-ene, as a function of humidity, under atmospheric boundary layer conditions. The SO2 removal displays a clear dependence on relative humidity for all four alkene-ozone systems confirming a significant reaction for stabilised Criegee intermediates (SCI) with H2O. The observed SO2 removal kinetics are consistent with relative rate constants, k(SCI + H2O)/k(SCI + SO2), of 3.3 (±1.1) × 10-5 for CH2OO, 26 (±10) × 10-5 for CH3CHOO derived from cis-but-2-ene, 33 (±10) × 10-5 for CH3CHOO derived from trans-but-2-ene, and 8.7 (±2.5) × 10-5 for (CH3)2COO derived from 2,3-dimethyl-but-2-ene. The relative rate constants for k(SCI decomposition)/k(SCI + SO2) are -2.3 (±3.5) × 1011 cm-3 for CH2OO, 13 (±43) × 1011 cm-3 for CH3CHOO derived from cis-but-2-ene, -14 (±31) × 1011 cm-3 for CH3CHOO derived from trans-but-2-ene and 63 (±14) × 1011 cm-3 for (CH3)2COO. Uncertainties are ±2σ and represent combined systematic and precision components. These values are derived following the approximation that a single SCI is present for each system; a more comprehensive interpretation, explicitly considering the differing reactivity for syn- and anti-SCI conformers, is also presented. This yields values of 3.5 (±3.1) × 10-4 for k(SCI + H2O)/k(SCI + SO2) of anti-CH3CHOO and 1.2 (±1.1) × 1013 for k(SCI decomposition)/k(SCI + SO2) of syn-CH3CHOO. The reaction of the water dimer with CH2OO is also considered, with a derived value for k(CH2OO + (H2O)2)/k(CH2OO + SO2) of 1.4 (±1.8) × 10-2. The observed SO2 removal rate constants, which technically represent upper limits, are consistent with decomposition being a significant, structure dependent, sink in the atmosphere for syn-SCI.

U2 - 10.1039/C4CP04186K

DO - 10.1039/C4CP04186K

M3 - Article

C2 - 25562069

VL - 17

SP - 4076

EP - 4088

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 6

ER -