Computational Studies on the Thermodynamic and Kinetic Parameters of Oxidation of 2-Methoxyethanol Biofuel via H-Atom Abstraction by Methyl Radical

Mohamed A. Abdel-Rahman, Tarek M. El-Gogary, Nessreen Al-Hashimi, Mohamed F. Shibl, Kazunari Yoshizawa, Ahmed M. El-Nahas

Research output: Contribution to journalArticle

Abstract

In this work, a theoretical investigation of thermochemistry and kinetics of the oxidation of bifunctional 2-Methoxyethanol (2ME) biofuel using methyl radical was introduced. Potential-energy surface for various channels for the oxidation of 2ME was studied at density function theory (M06-2X) and ab initio CBS-QB3 levels of theory. H-atom abstraction reactions, which are essential processes occurring in the initial stages of the combustion or oxidation of organic compounds, from different sites of 2ME were examined. A similar study was conducted for the isoelectronic n-butanol to highlight the consequences of replacing the ϒ CH2 group by an oxygen atom on the thermodynamic and kinetic parameters of the oxidation processes. Rate coefficients were calculated from the transition state theory. Our calculations show that energy barriers for n-butanol oxidation increase in the order of α ‹ O ‹ ϒ ‹ β ‹ ξ, which are consistent with previous data. However, for 2ME the energy barriers increase in the order α ‹ β ‹ ξ ‹ O. At elevated temperatures, a slightly high total abstraction rate is observed for the bifunctional 2ME (4 abstraction positions) over n-butanol (5 abstraction positions).

Original languageEnglish
Article number15361
JournalScientific reports
Volume9
Issue number1
DOIs
Publication statusPublished - Dec 1 2019

Fingerprint

Biofuels
Thermodynamics
1-Butanol
methyl radical
methyl cellosolve
Oxygen
Temperature

All Science Journal Classification (ASJC) codes

  • General

Cite this

Computational Studies on the Thermodynamic and Kinetic Parameters of Oxidation of 2-Methoxyethanol Biofuel via H-Atom Abstraction by Methyl Radical. / Abdel-Rahman, Mohamed A.; El-Gogary, Tarek M.; Al-Hashimi, Nessreen; Shibl, Mohamed F.; Yoshizawa, Kazunari; El-Nahas, Ahmed M.

In: Scientific reports, Vol. 9, No. 1, 15361, 01.12.2019.

Research output: Contribution to journalArticle

Abdel-Rahman, Mohamed A. ; El-Gogary, Tarek M. ; Al-Hashimi, Nessreen ; Shibl, Mohamed F. ; Yoshizawa, Kazunari ; El-Nahas, Ahmed M. / Computational Studies on the Thermodynamic and Kinetic Parameters of Oxidation of 2-Methoxyethanol Biofuel via H-Atom Abstraction by Methyl Radical. In: Scientific reports. 2019 ; Vol. 9, No. 1.
@article{038afb16dc124285b6d4d3619dbf030e,
title = "Computational Studies on the Thermodynamic and Kinetic Parameters of Oxidation of 2-Methoxyethanol Biofuel via H-Atom Abstraction by Methyl Radical",
abstract = "In this work, a theoretical investigation of thermochemistry and kinetics of the oxidation of bifunctional 2-Methoxyethanol (2ME) biofuel using methyl radical was introduced. Potential-energy surface for various channels for the oxidation of 2ME was studied at density function theory (M06-2X) and ab initio CBS-QB3 levels of theory. H-atom abstraction reactions, which are essential processes occurring in the initial stages of the combustion or oxidation of organic compounds, from different sites of 2ME were examined. A similar study was conducted for the isoelectronic n-butanol to highlight the consequences of replacing the ϒ CH2 group by an oxygen atom on the thermodynamic and kinetic parameters of the oxidation processes. Rate coefficients were calculated from the transition state theory. Our calculations show that energy barriers for n-butanol oxidation increase in the order of α ‹ O ‹ ϒ ‹ β ‹ ξ, which are consistent with previous data. However, for 2ME the energy barriers increase in the order α ‹ β ‹ ξ ‹ O. At elevated temperatures, a slightly high total abstraction rate is observed for the bifunctional 2ME (4 abstraction positions) over n-butanol (5 abstraction positions).",
author = "Abdel-Rahman, {Mohamed A.} and El-Gogary, {Tarek M.} and Nessreen Al-Hashimi and Shibl, {Mohamed F.} and Kazunari Yoshizawa and El-Nahas, {Ahmed M.}",
year = "2019",
month = "12",
day = "1",
doi = "10.1038/s41598-019-51544-8",
language = "English",
volume = "9",
journal = "Scientific Reports",
issn = "2045-2322",
publisher = "Nature Publishing Group",
number = "1",

}

TY - JOUR

T1 - Computational Studies on the Thermodynamic and Kinetic Parameters of Oxidation of 2-Methoxyethanol Biofuel via H-Atom Abstraction by Methyl Radical

AU - Abdel-Rahman, Mohamed A.

AU - El-Gogary, Tarek M.

AU - Al-Hashimi, Nessreen

AU - Shibl, Mohamed F.

AU - Yoshizawa, Kazunari

AU - El-Nahas, Ahmed M.

PY - 2019/12/1

Y1 - 2019/12/1

N2 - In this work, a theoretical investigation of thermochemistry and kinetics of the oxidation of bifunctional 2-Methoxyethanol (2ME) biofuel using methyl radical was introduced. Potential-energy surface for various channels for the oxidation of 2ME was studied at density function theory (M06-2X) and ab initio CBS-QB3 levels of theory. H-atom abstraction reactions, which are essential processes occurring in the initial stages of the combustion or oxidation of organic compounds, from different sites of 2ME were examined. A similar study was conducted for the isoelectronic n-butanol to highlight the consequences of replacing the ϒ CH2 group by an oxygen atom on the thermodynamic and kinetic parameters of the oxidation processes. Rate coefficients were calculated from the transition state theory. Our calculations show that energy barriers for n-butanol oxidation increase in the order of α ‹ O ‹ ϒ ‹ β ‹ ξ, which are consistent with previous data. However, for 2ME the energy barriers increase in the order α ‹ β ‹ ξ ‹ O. At elevated temperatures, a slightly high total abstraction rate is observed for the bifunctional 2ME (4 abstraction positions) over n-butanol (5 abstraction positions).

AB - In this work, a theoretical investigation of thermochemistry and kinetics of the oxidation of bifunctional 2-Methoxyethanol (2ME) biofuel using methyl radical was introduced. Potential-energy surface for various channels for the oxidation of 2ME was studied at density function theory (M06-2X) and ab initio CBS-QB3 levels of theory. H-atom abstraction reactions, which are essential processes occurring in the initial stages of the combustion or oxidation of organic compounds, from different sites of 2ME were examined. A similar study was conducted for the isoelectronic n-butanol to highlight the consequences of replacing the ϒ CH2 group by an oxygen atom on the thermodynamic and kinetic parameters of the oxidation processes. Rate coefficients were calculated from the transition state theory. Our calculations show that energy barriers for n-butanol oxidation increase in the order of α ‹ O ‹ ϒ ‹ β ‹ ξ, which are consistent with previous data. However, for 2ME the energy barriers increase in the order α ‹ β ‹ ξ ‹ O. At elevated temperatures, a slightly high total abstraction rate is observed for the bifunctional 2ME (4 abstraction positions) over n-butanol (5 abstraction positions).

UR - http://www.scopus.com/inward/record.url?scp=85074155482&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85074155482&partnerID=8YFLogxK

U2 - 10.1038/s41598-019-51544-8

DO - 10.1038/s41598-019-51544-8

M3 - Article

C2 - 31653887

AN - SCOPUS:85074155482

VL - 9

JO - Scientific Reports

JF - Scientific Reports

SN - 2045-2322

IS - 1

M1 - 15361

ER -