Elucidating the chemical pathways responsible for the sooting tendency of 1 and 2-phenylethanol

Brian D. Etz; Gina M. Fioroni; Richard A. Messerly; Mohammad J. Rahimi; Peter C. St. John; David J. Robichaud; Earl D. Christensen; Brian P. Beekley; Charles S. McEnally; Lisa D. Pfefferle; Yuan Xuan; Shubham Vyas; Robert S. Paton; Robert L. McCormick; Seonah Kim

doi:10.1016/j.proci.2020.06.072

Elucidating the chemical pathways responsible for the sooting tendency of 1 and 2-phenylethanol

Brian D. Etz, Gina M. Fioroni, Richard A. Messerly, Mohammad J. Rahimi, Peter C. St. John, David J. Robichaud, Earl D. Christensen, Brian P. Beekley, Charles S. McEnally, Lisa D. Pfefferle, Yuan Xuan, Shubham Vyas, Robert S. Paton, Robert L. McCormick, Seonah Kim

Research output: Contribution to journal › Conference article › peer-review

11 Scopus citations

Abstract

Yield Sooting Index (YSI) measurements have shown that oxygenated aromatic compounds (OAC) tend to have lower YSI than aromatic hydrocarbon (AHC) compounds. However, this trend is not always true as was observed for the structural isomers 1-phenylethanol (1PE, YSI = 142) and 2-phenylethanol (2PE, YSI = 207), where 2PE contains a YSI more representative of AHC than OAC. Flow reactor experiments and density functional theory (DFT) calculations were performed to examine how oxygen functionality present in 1PE and 2PE alters the reaction pathways leading to the observed difference in soot formation. The proximity of the oxygen functional group to the aromatic ring determines whether the oxygen remains attached to the primary reacting species (for 1PE) or was eliminated early in the combustion sequence (for 2PE). For these alcohols, preservation of the oxygen in the molecule led to further OAC, while loss of the oxygen ledsto AHC and benzyl radical. The direct pathways to AHC and benzyl radical resulted in the higher YSI observed for 2PE.

Original language	English
Pages (from-to)	1327-1334
Number of pages	8
Journal	Proceedings of the Combustion Institute
Volume	38
Issue number	1
DOIs	https://doi.org/10.1016/j.proci.2020.06.072
State	Published - 2021
Externally published	Yes
Event	38th International Symposium on Combustion, 2021 - Adelaide, Australia Duration: Jan 24 2021 → Jan 29 2021

Funding

A portion of this research was conducted as part of the Co-Optimization of Fuels & Engines (Co-Optima) project sponsored by the U.S. Department of Energy \u2013Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies and Vehicle Technologies Offices (DE-EE0007983). Work at the National Renewable Energy Laboratory was performed under Contract No. DE347AC36-99GO10337. CSM, LDP, and BPB are also supported by the National Science Foundation (NSF) under Grant no. CBET 1604983. Computer time was provided by the NSF Extreme Science and Engineering Discovery Environment (XSEDE), Grant no. MCB-090159 and by the National Renewable Energy Laboratory Computational Science Center.

Funders	Funder number
U.S. Department of Energy
Co-Optimization of Fuels & Engines
National Renewable Energy Laboratory Computational Science Center
NSF Extreme Science and Engineering Discovery Environment
Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies and Vehicle Technologies Offices	DE-EE0007983, DE347AC36-99GO10337
National Science Foundation	CBET 1604983
XSEDE	MCB-090159

Keywords

DFT
Flow reactor
Phenylethanol
Soot
Yield sooting index (YSI)

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10.1016/j.proci.2020.06.072

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Etz, B. D., Fioroni, G. M., Messerly, R. A., Rahimi, M. J., St. John, P. C., Robichaud, D. J., Christensen, E. D., Beekley, B. P., McEnally, C. S., Pfefferle, L. D., Xuan, Y., Vyas, S., Paton, R. S., McCormick, R. L., & Kim, S. (2021). Elucidating the chemical pathways responsible for the sooting tendency of 1 and 2-phenylethanol. Proceedings of the Combustion Institute, 38(1), 1327-1334. https://doi.org/10.1016/j.proci.2020.06.072

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title = "Elucidating the chemical pathways responsible for the sooting tendency of 1 and 2-phenylethanol",

abstract = "Yield Sooting Index (YSI) measurements have shown that oxygenated aromatic compounds (OAC) tend to have lower YSI than aromatic hydrocarbon (AHC) compounds. However, this trend is not always true as was observed for the structural isomers 1-phenylethanol (1PE, YSI = 142) and 2-phenylethanol (2PE, YSI = 207), where 2PE contains a YSI more representative of AHC than OAC. Flow reactor experiments and density functional theory (DFT) calculations were performed to examine how oxygen functionality present in 1PE and 2PE alters the reaction pathways leading to the observed difference in soot formation. The proximity of the oxygen functional group to the aromatic ring determines whether the oxygen remains attached to the primary reacting species (for 1PE) or was eliminated early in the combustion sequence (for 2PE). For these alcohols, preservation of the oxygen in the molecule led to further OAC, while loss of the oxygen ledsto AHC and benzyl radical. The direct pathways to AHC and benzyl radical resulted in the higher YSI observed for 2PE.",

keywords = "DFT, Flow reactor, Phenylethanol, Soot, Yield sooting index (YSI)",

author = "Etz, {Brian D.} and Fioroni, {Gina M.} and Messerly, {Richard A.} and Rahimi, {Mohammad J.} and {St. John}, {Peter C.} and Robichaud, {David J.} and Christensen, {Earl D.} and Beekley, {Brian P.} and McEnally, {Charles S.} and Pfefferle, {Lisa D.} and Yuan Xuan and Shubham Vyas and Paton, {Robert S.} and McCormick, {Robert L.} and Seonah Kim",

year = "2021",

doi = "10.1016/j.proci.2020.06.072",

language = "English",

volume = "38",

pages = "1327--1334",

journal = "Proceedings of the Combustion Institute",

issn = "1540-7489",

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note = "38th International Symposium on Combustion, 2021 ; Conference date: 24-01-2021 Through 29-01-2021",

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Etz, BD, Fioroni, GM, Messerly, RA, Rahimi, MJ, St. John, PC, Robichaud, DJ, Christensen, ED, Beekley, BP, McEnally, CS, Pfefferle, LD, Xuan, Y, Vyas, S, Paton, RS, McCormick, RL & Kim, S 2021, 'Elucidating the chemical pathways responsible for the sooting tendency of 1 and 2-phenylethanol', Proceedings of the Combustion Institute, vol. 38, no. 1, pp. 1327-1334. https://doi.org/10.1016/j.proci.2020.06.072

TY - JOUR

T1 - Elucidating the chemical pathways responsible for the sooting tendency of 1 and 2-phenylethanol

AU - Etz, Brian D.

AU - Fioroni, Gina M.

AU - Messerly, Richard A.

AU - Rahimi, Mohammad J.

AU - St. John, Peter C.

AU - Robichaud, David J.

AU - Christensen, Earl D.

AU - Beekley, Brian P.

AU - McEnally, Charles S.

AU - Pfefferle, Lisa D.

AU - Xuan, Yuan

AU - Vyas, Shubham

AU - Paton, Robert S.

AU - McCormick, Robert L.

AU - Kim, Seonah

PY - 2021

Y1 - 2021

N2 - Yield Sooting Index (YSI) measurements have shown that oxygenated aromatic compounds (OAC) tend to have lower YSI than aromatic hydrocarbon (AHC) compounds. However, this trend is not always true as was observed for the structural isomers 1-phenylethanol (1PE, YSI = 142) and 2-phenylethanol (2PE, YSI = 207), where 2PE contains a YSI more representative of AHC than OAC. Flow reactor experiments and density functional theory (DFT) calculations were performed to examine how oxygen functionality present in 1PE and 2PE alters the reaction pathways leading to the observed difference in soot formation. The proximity of the oxygen functional group to the aromatic ring determines whether the oxygen remains attached to the primary reacting species (for 1PE) or was eliminated early in the combustion sequence (for 2PE). For these alcohols, preservation of the oxygen in the molecule led to further OAC, while loss of the oxygen ledsto AHC and benzyl radical. The direct pathways to AHC and benzyl radical resulted in the higher YSI observed for 2PE.

AB - Yield Sooting Index (YSI) measurements have shown that oxygenated aromatic compounds (OAC) tend to have lower YSI than aromatic hydrocarbon (AHC) compounds. However, this trend is not always true as was observed for the structural isomers 1-phenylethanol (1PE, YSI = 142) and 2-phenylethanol (2PE, YSI = 207), where 2PE contains a YSI more representative of AHC than OAC. Flow reactor experiments and density functional theory (DFT) calculations were performed to examine how oxygen functionality present in 1PE and 2PE alters the reaction pathways leading to the observed difference in soot formation. The proximity of the oxygen functional group to the aromatic ring determines whether the oxygen remains attached to the primary reacting species (for 1PE) or was eliminated early in the combustion sequence (for 2PE). For these alcohols, preservation of the oxygen in the molecule led to further OAC, while loss of the oxygen ledsto AHC and benzyl radical. The direct pathways to AHC and benzyl radical resulted in the higher YSI observed for 2PE.

KW - DFT

KW - Flow reactor

KW - Phenylethanol

KW - Soot

KW - Yield sooting index (YSI)

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U2 - 10.1016/j.proci.2020.06.072

DO - 10.1016/j.proci.2020.06.072

M3 - Conference article

AN - SCOPUS:85089524028

SN - 1540-7489

VL - 38

SP - 1327

EP - 1334

JO - Proceedings of the Combustion Institute

JF - Proceedings of the Combustion Institute

IS - 1

T2 - 38th International Symposium on Combustion, 2021

Y2 - 24 January 2021 through 29 January 2021

ER -

Elucidating the chemical pathways responsible for the sooting tendency of 1 and 2-phenylethanol

Abstract

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Keywords

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