Cool Flames! Radical Reactions in Biofuels and in the Atmosphere

Research output: ThesisDoctoral Thesis

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Cool Flames! Radical Reactions in Biofuels and in the Atmosphere. / Whiting, Fiona; Dillon, Terry James.

2018. 211 p.

Research output: ThesisDoctoral Thesis

Harvard

Whiting, F & Dillon, TJ 2018, 'Cool Flames! Radical Reactions in Biofuels and in the Atmosphere', Doctor of Philosophy, University of York.

APA

Whiting, F., & Dillon, T. J. (2018). Cool Flames! Radical Reactions in Biofuels and in the Atmosphere.

Vancouver

Whiting F, Dillon TJ. Cool Flames! Radical Reactions in Biofuels and in the Atmosphere. 2018. 211 p.

Author

Whiting, Fiona ; Dillon, Terry James. / Cool Flames! Radical Reactions in Biofuels and in the Atmosphere. 2018. 211 p.

Bibtex - Download

@phdthesis{6810b1b85d16426496d24d58391c561c,
title = "Cool Flames! Radical Reactions in Biofuels and in the Atmosphere",
abstract = "A novel apparatus for pulsed laser photolysis generation of radicals coupled withlaser induced uorescence (LIF) detection of OH has been developed at the Universityof York, enabling kinetic studies of atmospheric and combustion-relevant chemicalreactions.Direct LIF detection was used to identify unambiguously OH as a product of O2 +RCO reactions, for the rst time, where R = CH3CH2CH2, (CH3)2CH, (CH3)3C,CH3CH2CH2CH2, (CH3)2CHCH2, and CH3CH2CH(CH3). Pressure- dependent (13 -120 Torr) OH yields were determined by comparison of time-resolved OH LIF proleswith those obtained from the well-characterised CH3CO + O2 ! OH reaction.Results not only illustrate the dependency of OH yield on chain length and degreeof branching within the R group, but also resolve a literature discrepancy forCH3CH2CO + O2 .OH produced from RCO + O2 was used as a spectroscopic marker to study thekinetics of Cl + RCHO. This indirect method produced the rst values for Cl +(CH3)2CHCH2CHO ((3.1 0.6) 10􀀀10 cm3 molecule􀀀1 s􀀀1) and CH3CH2CH(CH3)CHO ((1.2 0.3) 10􀀀10 cm3 molecule􀀀1 s􀀀1) at 298 K, with results for other Cl+ RCHO and OH + RCHO reactions agreeing well with previous literature.Finally, the reactions of RC(O)O2 with HO2 were investigated at temperaturesbetween 293 and 400 K. Preliminary experiments in the absence of HO2 recorded OHproduction from a previously unknown source, potentially RC(O)O2 + RC(O)O2.OH production from RC(O)O2 + HO2, identied for the rst time when R =CH3CH2, (CH3)2CH, (CH3)3C, (CH3)2CHCH2, and CH3CH2CH(CH3), demonstratesthat signicant OH production is a general feature of HO2 + RC(O)O2 reactions.",
author = "Fiona Whiting and Dillon, {Terry James}",
year = "2018",
month = nov,
day = "21",
language = "English",
school = "University of York",

}

RIS (suitable for import to EndNote) - Download

TY - THES

T1 - Cool Flames! Radical Reactions in Biofuels and in the Atmosphere

AU - Whiting, Fiona

AU - Dillon, Terry James

PY - 2018/11/21

Y1 - 2018/11/21

N2 - A novel apparatus for pulsed laser photolysis generation of radicals coupled withlaser induced uorescence (LIF) detection of OH has been developed at the Universityof York, enabling kinetic studies of atmospheric and combustion-relevant chemicalreactions.Direct LIF detection was used to identify unambiguously OH as a product of O2 +RCO reactions, for the rst time, where R = CH3CH2CH2, (CH3)2CH, (CH3)3C,CH3CH2CH2CH2, (CH3)2CHCH2, and CH3CH2CH(CH3). Pressure- dependent (13 -120 Torr) OH yields were determined by comparison of time-resolved OH LIF proleswith those obtained from the well-characterised CH3CO + O2 ! OH reaction.Results not only illustrate the dependency of OH yield on chain length and degreeof branching within the R group, but also resolve a literature discrepancy forCH3CH2CO + O2 .OH produced from RCO + O2 was used as a spectroscopic marker to study thekinetics of Cl + RCHO. This indirect method produced the rst values for Cl +(CH3)2CHCH2CHO ((3.1 0.6) 10􀀀10 cm3 molecule􀀀1 s􀀀1) and CH3CH2CH(CH3)CHO ((1.2 0.3) 10􀀀10 cm3 molecule􀀀1 s􀀀1) at 298 K, with results for other Cl+ RCHO and OH + RCHO reactions agreeing well with previous literature.Finally, the reactions of RC(O)O2 with HO2 were investigated at temperaturesbetween 293 and 400 K. Preliminary experiments in the absence of HO2 recorded OHproduction from a previously unknown source, potentially RC(O)O2 + RC(O)O2.OH production from RC(O)O2 + HO2, identied for the rst time when R =CH3CH2, (CH3)2CH, (CH3)3C, (CH3)2CHCH2, and CH3CH2CH(CH3), demonstratesthat signicant OH production is a general feature of HO2 + RC(O)O2 reactions.

AB - A novel apparatus for pulsed laser photolysis generation of radicals coupled withlaser induced uorescence (LIF) detection of OH has been developed at the Universityof York, enabling kinetic studies of atmospheric and combustion-relevant chemicalreactions.Direct LIF detection was used to identify unambiguously OH as a product of O2 +RCO reactions, for the rst time, where R = CH3CH2CH2, (CH3)2CH, (CH3)3C,CH3CH2CH2CH2, (CH3)2CHCH2, and CH3CH2CH(CH3). Pressure- dependent (13 -120 Torr) OH yields were determined by comparison of time-resolved OH LIF proleswith those obtained from the well-characterised CH3CO + O2 ! OH reaction.Results not only illustrate the dependency of OH yield on chain length and degreeof branching within the R group, but also resolve a literature discrepancy forCH3CH2CO + O2 .OH produced from RCO + O2 was used as a spectroscopic marker to study thekinetics of Cl + RCHO. This indirect method produced the rst values for Cl +(CH3)2CHCH2CHO ((3.1 0.6) 10􀀀10 cm3 molecule􀀀1 s􀀀1) and CH3CH2CH(CH3)CHO ((1.2 0.3) 10􀀀10 cm3 molecule􀀀1 s􀀀1) at 298 K, with results for other Cl+ RCHO and OH + RCHO reactions agreeing well with previous literature.Finally, the reactions of RC(O)O2 with HO2 were investigated at temperaturesbetween 293 and 400 K. Preliminary experiments in the absence of HO2 recorded OHproduction from a previously unknown source, potentially RC(O)O2 + RC(O)O2.OH production from RC(O)O2 + HO2, identied for the rst time when R =CH3CH2, (CH3)2CH, (CH3)3C, (CH3)2CHCH2, and CH3CH2CH(CH3), demonstratesthat signicant OH production is a general feature of HO2 + RC(O)O2 reactions.

M3 - Doctoral Thesis

ER -