Low Temperature Chlorine-Initiated Oxidation of Small-Chain Methyl Esters: Quantification of Chain-Terminating HO2-Elimination Channels

Muller, Giel; Scheer, Adam; Osborn, David L.; Taatjes, Craig A.; Meloni, Giovanni

doi:10.1021/acs.jpca.6b00148

Title: Low Temperature Chlorine-Initiated Oxidation of Small-Chain Methyl Esters: Quantification of Chain-Terminating HO₂-Elimination Channels

Abstract

In this paper, Cl-initiated oxidation reactions of three small-chain methyl esters, methyl propanoate (CH₃CH₂COOCH₃; MP), methyl butanoate (CH₃CH₂CH₂COOCH₃; MB), and methyl valerate (CH₃CH₂CH₂CH₂COOCH₃; MV), are studied at 1 or 8 Torr and 550 and 650 K. Products are monitored as a function of mass, time, and photoionization energy using multiplexed photoionization mass spectrometry coupled to tunable synchrotron photoionization radiation. Pulsed photolysis of molecular chlorine is the source of Cl radicals, which remove an H atom from the ester, forming a free radical. In each case, after addition of O₂ to the initial radicals, chain-terminating HO₂-elimination reactions are observed to be important. Branching ratios among competing HO₂-elimination channels are determined via absolute photoionization spectra of the unsaturated methyl ester coproducts. At 550 K, HO₂-elimination is observed to be selective, resulting in nearly exclusive production of the conjugated methyl ester coproducts, methyl propenoate, methyl-2-butenoate, and methyl-2-pentenoate, respectively. However, in MV, upon raising the temperature to 650 K, other HO₂-elimination pathways are observed that yield methyl-3-pentenoate and methyl-4-pentenoate. In each methyl ester oxidation reaction, a peak is observed at a mass consistent with cyclic ether formation, indicating chain-propagating OH loss/ring formation pathways via QOOH intermediates. Evidence is observed for the participation of resonance-stabilizedmore »« less

Authors:

Muller, Giel ^[1]; Scheer, Adam ^[2]; Osborn, David L. ^[3]; Taatjes, Craig A. ^[3]; Meloni, Giovanni ^[1]

Univ. of San Francisco, CA (United States)
Pacific Gas and Electric Company, San Francisco, CA (United States)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)

Publication Date:: Wed Feb 24 00:00:00 EST 2016

Research Org.:: Sandia National Lab. (SNL-CA), Livermore, CA (United States); Univ. of San Francisco, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA); SNL Laboratory Directed Research and Development (LDRD) Program; Univ. of San Francisco (United States)

OSTI Identifier:: 1472257

Report Number(s):: SAND2018-9564J
Journal ID: ISSN 1089-5639; 667489

Grant/Contract Number:: AC04-94AL85000; AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Additional Journal Information:: Journal Volume: 120; Journal Issue: 10; Journal ID: ISSN 1089-5639

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Muller, Giel, Scheer, Adam, Osborn, David L., Taatjes, Craig A., and Meloni, Giovanni. Low Temperature Chlorine-Initiated Oxidation of Small-Chain Methyl Esters: Quantification of Chain-Terminating HO2-Elimination Channels.  United States: N. p., 2016. 
Web.  doi:10.1021/acs.jpca.6b00148.

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                    Muller, Giel, Scheer, Adam, Osborn, David L., Taatjes, Craig A., & Meloni, Giovanni. Low Temperature Chlorine-Initiated Oxidation of Small-Chain Methyl Esters: Quantification of Chain-Terminating HO2-Elimination Channels.  United States.  https://doi.org/10.1021/acs.jpca.6b00148

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                    Muller, Giel, Scheer, Adam, Osborn, David L., Taatjes, Craig A., and Meloni, Giovanni. Wed .  
"Low Temperature Chlorine-Initiated Oxidation of Small-Chain Methyl Esters: Quantification of Chain-Terminating HO2-Elimination Channels".  United States.  https://doi.org/10.1021/acs.jpca.6b00148.  https://www.osti.gov/servlets/purl/1472257.

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@article{osti_1472257,

  title        = {Low Temperature Chlorine-Initiated Oxidation of Small-Chain Methyl Esters: Quantification of Chain-Terminating HO2-Elimination Channels},

  author       = {Muller, Giel and Scheer, Adam and Osborn, David L. and Taatjes, Craig A. and Meloni, Giovanni},

  abstractNote = {In this paper, Cl-initiated oxidation reactions of three small-chain methyl esters, methyl propanoate (CH3CH2COOCH3; MP), methyl butanoate (CH3CH2CH2COOCH3; MB), and methyl valerate (CH3CH2CH2CH2COOCH3; MV), are studied at 1 or 8 Torr and 550 and 650 K. Products are monitored as a function of mass, time, and photoionization energy using multiplexed photoionization mass spectrometry coupled to tunable synchrotron photoionization radiation. Pulsed photolysis of molecular chlorine is the source of Cl radicals, which remove an H atom from the ester, forming a free radical. In each case, after addition of O2 to the initial radicals, chain-terminating HO2-elimination reactions are observed to be important. Branching ratios among competing HO2-elimination channels are determined via absolute photoionization spectra of the unsaturated methyl ester coproducts. At 550 K, HO2-elimination is observed to be selective, resulting in nearly exclusive production of the conjugated methyl ester coproducts, methyl propenoate, methyl-2-butenoate, and methyl-2-pentenoate, respectively. However, in MV, upon raising the temperature to 650 K, other HO2-elimination pathways are observed that yield methyl-3-pentenoate and methyl-4-pentenoate. In each methyl ester oxidation reaction, a peak is observed at a mass consistent with cyclic ether formation, indicating chain-propagating OH loss/ring formation pathways via QOOH intermediates. Evidence is observed for the participation of resonance-stabilized QOOH in the most prominent cyclic ether pathways. Finally, stationary point energies for HO2-elimination pathways and select cyclic ether formation channels are calculated at the CBS-QB3 level of theory and assist in the assignment of reaction pathways and final products.},

  doi          = {10.1021/acs.jpca.6b00148},

  journal      = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},

  number       = 10,

  volume       = 120,

  place        = {United States},

  year         = {Wed Feb 24 00:00:00 EST 2016},

  month        = {Wed Feb 24 00:00:00 EST 2016}

}

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Study of low temperature chlorine atom initiated oxidation of methyl and ethyl butyrate using synchrotron photoionization TOF-mass spectrometry
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Title: Low Temperature Chlorine-Initiated Oxidation of Small-Chain Methyl Esters: Quantification of Chain-Terminating HO2-Elimination Channels

Abstract

Citation Formats

Definition of biodiesel journal, May 2007

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Properties and use of jatropha curcas oil and diesel fuel blends in compression ignition engine journal, February 2003

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Comparisons of NO emissions and soot concentrations from biodiesel-fuelled diesel engine journal, June 2012

Effects of low concentration biodiesel blend application on modern passenger cars. Part 1: Feedstock impact on regulated pollutants, fuel consumption and particle emissions journal, May 2010

An experimental comparison of methods to use methanol and Jatropha oil in a compression ignition engine journal, September 2003

Performance and emission study of Mahua oil (madhuca indica oil) ethyl ester in a 4-stroke natural aspirated direct injection diesel engine journal, July 2005

Combustion Properties of Spray Flames of Canola Methyl Ester and Diesel Blends at Lean Inlet Equivalence Ratios journal, January 2014

PM, carbon, and PAH emissions from a diesel generator fuelled with soy-biodiesel blends journal, July 2010

Influence of Fatty Acid Methyl Esters on Fuel properties of Biodiesel Produced from the Seeds Oil of Curcubita pepo journal, September 2011

Detailed Kinetic Mechanism for the Oxidation of Vegetable Oil Methyl Esters: New Evidence from Methyl Heptanoate journal, September 2009

Experimental and kinetic modeling of methyl octanoate oxidation in an opposed-flow diffusion flame and a jet-stirred reactor journal, January 2011

Comparative Study of the Autoignition of Methyl Decenoates, Unsaturated Biodiesel Fuel Surrogates journal, August 2013

Experimental and Kinetic Modeling Study of the Oxidation of Methyl Hexanoate journal, April 2008

Detailed chemical kinetic mechanism for the oxidation of biodiesel fuels blend surrogate journal, May 2010

352. The oxidation of hydrocarbons and their derivatives. Part II. Structural effects in the ester series journal, January 1956

Surrogate fuels for the simulation of diesel engine combustion of novel biofuels journal, May 2014

Chemical Kinetic Mechanism Reduction Scheme for Diesel Fuel Surrogate journal, March 2014

A reduced chemical kinetic mechanism of a diesel fuel surrogate (n-heptane/toluene) for HCCI combustion modelling journal, October 2014

Combustion chemical kinetics of biodiesel and related compounds (methyl and ethyl esters): Experiments and modeling – Advances and future refinements journal, August 2013

Detailed chemical kinetic mechanisms for combustion of oxygenated fuels journal, January 2000

Autoignition measurements and a validated kinetic model for the biodiesel surrogate, methyl butanoate journal, April 2008

Experimental and chemical kinetic modeling study of small methyl esters oxidation: Methyl (E)-2-butenoate and methyl butanoate journal, December 2008

Oxidation of methyl and ethyl butanoates journal, April 2010

The role of the methyl ester moiety in biodiesel combustion: A kinetic modeling comparison of methyl butanoate and n-butane journal, February 2012

Low temperature (550–700 K) oxidation pathways of cyclic ketones: dominance of HO 2 -elimination channels yielding conjugated cyclic coproducts journal, January 2015

Kinetics of elementary reactions in low-temperature autoignition chemistry journal, August 2011

Low-temperature combustion chemistry of novel biofuels: resonance-stabilized QOOH in the oxidation of diethyl ketone journal, January 2014

Formally direct pathways and low-temperature chain branching in hydrocarbon autoignition: the cyclohexyl + O2 reaction at high pressure journal, January 2009

Directly measuring reaction kinetics of ˙QOOH – a crucial but elusive intermediate in hydrocarbon autoignition journal, January 2013

A coordinated investigation of the combustion chemistry of diisopropyl ketone, a prototype for biofuels produced by endophytic fungi journal, March 2014

“Imaging” combustion chemistry via multiplexed synchrotron-photoionization mass spectrometry journal, January 2008

Synchrotron Photoionization Study of Mesitylene Oxidation Initiated by Reaction with Cl( 2 P) or O( 3 P) Radicals journal, April 2014

Study of tert -Amyl Methyl Ether Low Temperature Oxidation Using Synchrotron Photoionization Mass Spectrometry journal, August 2015

The multiplexed chemical kinetic photoionization mass spectrometer: A new approach to isomer-resolved chemical kinetics journal, October 2008

Facile Rearrangement of 3-Oxoalkyl Radicals is Evident in Low-Temperature Gas-Phase Oxidation of Ketones journal, September 2013

Low-temperature combustion chemistry of biofuels: pathways in the initial low-temperature (550 K–750 K) oxidation chemistry of isopentanol journal, January 2012

A complete basis set model chemistry. V. Extensions to six or more heavy atoms journal, February 1996

A complete basis set model chemistry. VI. Use of density functional geometries and frequencies journal, February 1999

A complete basis set model chemistry. VII. Use of the minimum population localization method journal, April 2000

Combining Synchronous Transit and Quasi-Newton Methods to Find Transition States journal, January 1993

Assessment of Gaussian-2 and density functional theories for the computation of enthalpies of formation journal, January 1997

Assessment of Gaussian-2 and density functional theories for the computation of ionization potentials and electron affinities journal, July 1998

He(I) and He(II) photoelectron spectra of some substituted ethylenes journal, January 1978

Absolute cross-sections for dissociative photoionization of some small esters journal, May 2010

Direct observation and kinetics of a hydroperoxyalkyl radical (QOOH) journal, February 2015

Deuterium-isotope Effects in the Autoxidation of Aralkyl Hydrocarbons. Mechanism of the Interaction of PEroxy Radicals 1 journal, July 1957

Combustion chemical kinetics of biodiesel and related compounds (methyl and ethyl esters): Experiments and modeling – Advances and future refinements journal, August 2013

Experimental and Kinetic Modeling Study of the Oxidation of Methyl Hexanoate journal, April 2008

Low-temperature combustion chemistry of biofuels: pathways in the initial low-temperature (550 K–750 K) oxidation chemistry of isopentanol journal, January 2012

Study of low temperature chlorine atom initiated oxidation of methyl and ethyl butyrate using synchrotron photoionization TOF-mass spectrometry journal, January 2018

Quantum chemical study of the ( Z )-2-penten-1-ol (HOCH 2 –CH = CHCH 2 CH 3 ) + OH + O 2 reactions journal, September 2016

Title: Low Temperature Chlorine-Initiated Oxidation of Small-Chain Methyl Esters: Quantification of Chain-Terminating HO₂-Elimination Channels

Definition of biodiesel
journal, May 2007

Co-solvents transesterification of cotton seed oil into biodiesel: Effects of reaction conditions on quality of fatty acids methyl esters
journal, August 2014

Properties and use of jatropha curcas oil and diesel fuel blends in compression ignition engine
journal, February 2003

Rheological Behavior of Castor Oil Biodiesel
journal, September 2005

Performance, combustion and emission tests of a metro-bus running on biodiesel-ULSD blended (B20) fuel
journal, July 2014

Comparisons of NO emissions and soot concentrations from biodiesel-fuelled diesel engine
journal, June 2012

Effects of low concentration biodiesel blend application on modern passenger cars. Part 1: Feedstock impact on regulated pollutants, fuel consumption and particle emissions
journal, May 2010

An experimental comparison of methods to use methanol and Jatropha oil in a compression ignition engine
journal, September 2003

Performance and emission study of Mahua oil (madhuca indica oil) ethyl ester in a 4-stroke natural aspirated direct injection diesel engine
journal, July 2005

Combustion Properties of Spray Flames of Canola Methyl Ester and Diesel Blends at Lean Inlet Equivalence Ratios
journal, January 2014

PM, carbon, and PAH emissions from a diesel generator fuelled with soy-biodiesel blends
journal, July 2010

Influence of Fatty Acid Methyl Esters on Fuel properties of Biodiesel Produced from the Seeds Oil of Curcubita pepo
journal, September 2011

Detailed Kinetic Mechanism for the Oxidation of Vegetable Oil Methyl Esters: New Evidence from Methyl Heptanoate
journal, September 2009

Experimental and kinetic modeling of methyl octanoate oxidation in an opposed-flow diffusion flame and a jet-stirred reactor
journal, January 2011

Comparative Study of the Autoignition of Methyl Decenoates, Unsaturated Biodiesel Fuel Surrogates
journal, August 2013

Experimental and Kinetic Modeling Study of the Oxidation of Methyl Hexanoate
journal, April 2008

Detailed chemical kinetic mechanism for the oxidation of biodiesel fuels blend surrogate
journal, May 2010

352. The oxidation of hydrocarbons and their derivatives. Part II. Structural effects in the ester series
journal, January 1956

Surrogate fuels for the simulation of diesel engine combustion of novel biofuels
journal, May 2014

Chemical Kinetic Mechanism Reduction Scheme for Diesel Fuel Surrogate
journal, March 2014

A reduced chemical kinetic mechanism of a diesel fuel surrogate (n-heptane/toluene) for HCCI combustion modelling
journal, October 2014

Combustion chemical kinetics of biodiesel and related compounds (methyl and ethyl esters): Experiments and modeling – Advances and future refinements
journal, August 2013

Detailed chemical kinetic mechanisms for combustion of oxygenated fuels
journal, January 2000

Autoignition measurements and a validated kinetic model for the biodiesel surrogate, methyl butanoate
journal, April 2008

Experimental and chemical kinetic modeling study of small methyl esters oxidation: Methyl (E)-2-butenoate and methyl butanoate
journal, December 2008

Oxidation of methyl and ethyl butanoates
journal, April 2010

The role of the methyl ester moiety in biodiesel combustion: A kinetic modeling comparison of methyl butanoate and n-butane
journal, February 2012

Low temperature (550–700 K) oxidation pathways of cyclic ketones: dominance of HO ₂ -elimination channels yielding conjugated cyclic coproducts
journal, January 2015

Kinetics of elementary reactions in low-temperature autoignition chemistry
journal, August 2011

Low-temperature combustion chemistry of novel biofuels: resonance-stabilized QOOH in the oxidation of diethyl ketone
journal, January 2014

Formally direct pathways and low-temperature chain branching in hydrocarbon autoignition: the cyclohexyl + O2 reaction at high pressure
journal, January 2009

Directly measuring reaction kinetics of ˙QOOH – a crucial but elusive intermediate in hydrocarbon autoignition
journal, January 2013

A coordinated investigation of the combustion chemistry of diisopropyl ketone, a prototype for biofuels produced by endophytic fungi
journal, March 2014

“Imaging” combustion chemistry via multiplexed synchrotron-photoionization mass spectrometry
journal, January 2008

Synchrotron Photoionization Study of Mesitylene Oxidation Initiated by Reaction with Cl( ² P) or O( ³ P) Radicals
journal, April 2014

Study of tert -Amyl Methyl Ether Low Temperature Oxidation Using Synchrotron Photoionization Mass Spectrometry
journal, August 2015

The multiplexed chemical kinetic photoionization mass spectrometer: A new approach to isomer-resolved chemical kinetics
journal, October 2008

Facile Rearrangement of 3-Oxoalkyl Radicals is Evident in Low-Temperature Gas-Phase Oxidation of Ketones
journal, September 2013

Low-temperature combustion chemistry of biofuels: pathways in the initial low-temperature (550 K–750 K) oxidation chemistry of isopentanol
journal, January 2012

A complete basis set model chemistry. V. Extensions to six or more heavy atoms
journal, February 1996

A complete basis set model chemistry. VI. Use of density functional geometries and frequencies
journal, February 1999

A complete basis set model chemistry. VII. Use of the minimum population localization method
journal, April 2000

Combining Synchronous Transit and Quasi-Newton Methods to Find Transition States
journal, January 1993

Assessment of Gaussian-2 and density functional theories for the computation of enthalpies of formation
journal, January 1997

Assessment of Gaussian-2 and density functional theories for the computation of ionization potentials and electron affinities
journal, July 1998

He(I) and He(II) photoelectron spectra of some substituted ethylenes
journal, January 1978

Absolute cross-sections for dissociative photoionization of some small esters
journal, May 2010

Direct observation and kinetics of a hydroperoxyalkyl radical (QOOH)
journal, February 2015

Deuterium-isotope Effects in the Autoxidation of Aralkyl Hydrocarbons. Mechanism of the Interaction of PEroxy Radicals ¹
journal, July 1957

Combustion chemical kinetics of biodiesel and related compounds (methyl and ethyl esters): Experiments and modeling – Advances and future refinements
journal, August 2013

Experimental and Kinetic Modeling Study of the Oxidation of Methyl Hexanoate
journal, April 2008

Low-temperature combustion chemistry of biofuels: pathways in the initial low-temperature (550 K–750 K) oxidation chemistry of isopentanol
journal, January 2012

Study of low temperature chlorine atom initiated oxidation of methyl and ethyl butyrate using synchrotron photoionization TOF-mass spectrometry
journal, January 2018

Quantum chemical study of the ( Z )-2-penten-1-ol (HOCH ₂ –CH = CHCH ₂ CH ₃ ) + OH + O ₂ reactions
journal, September 2016