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

Czekner, Joseph; Taatjes, Craig A.; Osborn, David L.; Meloni, Giovanni

doi:10.1039/c7cp08221e

Title: Study of low temperature chlorine atom initiated oxidation of methyl and ethyl butyrate using synchrotron photoionization TOF-mass spectrometry

Abstract

The initial oxidation products of methyl butyrate (MB) and ethyl butyrate (EB) are studied using a time- and energy-resolved photoionization mass spectrometer. Reactions are initiated with Cl˙ radicals in an excess of oxygen at a temperature of 550 K and a pressure of 6 Torr. Ethyl crotonate is the sole isomeric product that is observed from concerted HO₂-elimination from initial alkylperoxy radicals formed in the oxidation of EB. Analysis of the potential energy surface of each possible alkylperoxy radical shows that the CH₃CH(OO)CH₂C=O)OCH₂CH₃ (RγO₂) and CH₃CH₂CH(OO)C(=O)OCH₂CH₃ (R_βO₂) radicals are the isomers that could undergo this concerted HO₂-elimination. Two lower-mass products (formaldehyde and acetaldehyde) are observed in both methyl and ethyl butyrate reactions. Secondary reactions of alkylperoxy radicals with HO₂ radicals can decompose into the aforementioned products and smaller radicals. As a result, these pathways are the likely explanation for the formation of formaldehyde and acetaldehyde.

Authors:

^[1];

^[2]; Osborn, David L. ^[2];

^[1]

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

Publication Date:: Thu Feb 01 00:00:00 EST 2018

Research Org.:: Sandia National Lab. (SNL-CA), Livermore, CA (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

OSTI Identifier:: 1595936

Report Number(s):: SAND-2020-0680J
Journal ID: ISSN 1463-9076; PPCPFQ; 683004; TRN: US2100976

Grant/Contract Number:: AC04-94AL85000; 51170; AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Physical Chemistry Chemical Physics. PCCP

Additional Journal Information:: Journal Volume: 20; Journal Issue: 8; Journal ID: ISSN 1463-9076

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

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

Citation Formats


                    Czekner, Joseph, Taatjes, Craig A., Osborn, David L., and Meloni, Giovanni. Study of low temperature chlorine atom initiated oxidation of methyl and ethyl butyrate using synchrotron photoionization TOF-mass spectrometry.  United States: N. p., 2018. 
Web.  doi:10.1039/c7cp08221e.

Copy to clipboard


                    Czekner, Joseph, Taatjes, Craig A., Osborn, David L., & Meloni, Giovanni. Study of low temperature chlorine atom initiated oxidation of methyl and ethyl butyrate using synchrotron photoionization TOF-mass spectrometry.  United States.  https://doi.org/10.1039/c7cp08221e

Copy to clipboard


                    Czekner, Joseph, Taatjes, Craig A., Osborn, David L., and Meloni, Giovanni. Thu .  
"Study of low temperature chlorine atom initiated oxidation of methyl and ethyl butyrate using synchrotron photoionization TOF-mass spectrometry".  United States.  https://doi.org/10.1039/c7cp08221e.  https://www.osti.gov/servlets/purl/1595936.

Copy to clipboard


                    
@article{osti_1595936,

  title        = {Study of low temperature chlorine atom initiated oxidation of methyl and ethyl butyrate using synchrotron photoionization TOF-mass spectrometry},

  author       = {Czekner, Joseph and Taatjes, Craig A. and Osborn, David L. and Meloni, Giovanni},

  abstractNote = {The initial oxidation products of methyl butyrate (MB) and ethyl butyrate (EB) are studied using a time- and energy-resolved photoionization mass spectrometer. Reactions are initiated with Cl˙ radicals in an excess of oxygen at a temperature of 550 K and a pressure of 6 Torr. Ethyl crotonate is the sole isomeric product that is observed from concerted HO2-elimination from initial alkylperoxy radicals formed in the oxidation of EB. Analysis of the potential energy surface of each possible alkylperoxy radical shows that the CH3CH(OO)CH2C=O)OCH2CH3 (RγO2) and CH3CH2CH(OO)C(=O)OCH2CH3 (RβO2) radicals are the isomers that could undergo this concerted HO2-elimination. Two lower-mass products (formaldehyde and acetaldehyde) are observed in both methyl and ethyl butyrate reactions. Secondary reactions of alkylperoxy radicals with HO2 radicals can decompose into the aforementioned products and smaller radicals. As a result, these pathways are the likely explanation for the formation of formaldehyde and acetaldehyde.},

  doi          = {10.1039/c7cp08221e},

  journal      = {Physical Chemistry Chemical Physics. PCCP},

  number       = 8,

  volume       = 20,

  place        = {United States},

  year         = {Thu Feb 01 00:00:00 EST 2018},

  month        = {Thu Feb 01 00:00:00 EST 2018}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1039/c7cp08221e

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 2 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Ethene loss kinetics of methyl butanoate ions studied by threshold photoelectron–photoion coincidence:
journal, April 1999

Mazyar, Oleg A.; Baer, Tomas
International Journal of Mass Spectrometry, Vol. 185-187
DOI: 10.1016/S1387-3806(98)14146-5

Kinetics and branching ratio studies of the reaction of C2H5O2 + HO2 using chemical ionisation mass spectrometry
journal, January 2007

Teresa Raventós-Duran, M.; Percival, Carl J.; McGillen, Max R.
Physical Chemistry Chemical Physics, Vol. 9, Issue 31
DOI: 10.1039/b703038j

Transesterification
journal, June 1993

Otera, Junzo.
Chemical Reviews, Vol. 93, Issue 4
DOI: 10.1021/cr00020a004

Biodiesel and renewable diesel: A comparison
journal, June 2010

Knothe, Gerhard
Progress in Energy and Combustion Science, Vol. 36, Issue 3
DOI: 10.1016/j.pecs.2009.11.004

Substituent effects in the mass spectra of some γ- and β-substituted methyl butyrates
journal, January 1969

Howe, Ian; Williams, Dudley H.; Kingston, David G. I.
J. Chem. Soc. B, Vol. 0, Issue 0
DOI: 10.1039/J29690000439

Oxidation of methyl and ethyl butanoates
journal, April 2010

Hakka, M. H.; Bennadji, H.; Biet, J.
International Journal of Chemical Kinetics, Vol. 42, Issue 4
DOI: 10.1002/kin.20473

Bacterial production of free fatty acids from freshwater macroalgal cellulose
journal, June 2011

Hoover, Spencer W.; Marner, Wesley D.; Brownson, Amy K.
Applied Microbiology and Biotechnology, Vol. 91, Issue 2
DOI: 10.1007/s00253-011-3344-x

Pathways, kinetics and thermochemistry of methyl-ester peroxy radical decomposition in the low-temperature oxidation of methyl butanoate: A computational study of a biodiesel fuel surrogate
journal, September 2014

Tao, Hairong; Lin, Kuang C.
Combustion and Flame, Vol. 161, Issue 9
DOI: 10.1016/j.combustflame.2014.02.012

A Systematic Computational Study on the Reactions of HO ₂ with RO ₂ : The HO ₂ + CH ₃ O ₂ (CD ₃ O ₂ ) and HO ₂ + CH ₂ FO ₂ Reactions
journal, January 2005

Hou, Hua; Wang, Baoshan
The Journal of Physical Chemistry A, Vol. 109, Issue 3
DOI: 10.1021/jp046329e

The Challenge of Efficient Synthesis of Biofuels from Lignocellulose for Future Renewable Transportation Fuels
journal, January 2012

Mäki-Arvela, Päivi; Salminen, Eero; Riittonen, Toni
International Journal of Chemical Engineering, Vol. 2012
DOI: 10.1155/2012/674761

Theoretical studies of the reaction of hydroperoxy radicals (HO2) with ethyl peroxy (CH3CH2O2), acetyl peroxy (CH3C(O)O2), and acetonyl peroxy (CH3C(O)CH2O2) radicals
journal, December 2005

Hasson, Alam S.; Kuwata, Keith T.; Arroyo, Manuel C.
Journal of Photochemistry and Photobiology A: Chemistry, Vol. 176, Issue 1-3
DOI: 10.1016/j.jphotochem.2005.08.012

Product study of the C2H5O2+HO2 reaction in 760 Torr of air at 284–312 K
journal, April 2000

Spittler, M.; Barnes, I.; Becker, K. H.
Chemical Physics Letters, Vol. 321, Issue 1-2
DOI: 10.1016/S0009-2614(00)00315-8

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

Montgomery, J. A.; Frisch, M. J.; Ochterski, J. W.
The Journal of Chemical Physics, Vol. 112, Issue 15
DOI: 10.1063/1.481224

A wide-ranging kinetic modeling study of methyl butanoate combustion
journal, January 2007

Gaïl, S.; Thomson, M. J.; Sarathy, S. M.
Proceedings of the Combustion Institute, Vol. 31, Issue 1
DOI: 10.1016/j.proci.2006.08.051

Experimental Characterization of Ethyl Acetate, Ethyl Propionate, and Ethyl Butanoate in a Homogeneous Charge Compression Ignition Engine
journal, March 2011

Contino, Francesco; Foucher, Fabrice; Mounaïm-Rousselle, Christine
Energy & Fuels, Vol. 25, Issue 3
DOI: 10.1021/ef101602q

Investigation of the radical product channel of the CH3C(O)CH2O2 + HO2 reaction in the gas phase
journal, January 2008

Jenkin, M. E.; Hurley, M. D.; Wallington, T. J.
Physical Chemistry Chemical Physics, Vol. 10, Issue 29
DOI: 10.1039/b802898b

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

Zádor, Judit; Taatjes, Craig A.; Fernandes, Ravi X.
Progress in Energy and Combustion Science, Vol. 37, Issue 4
DOI: 10.1016/j.pecs.2010.06.006

Low Temperature Chlorine-Initiated Oxidation of Small-Chain Methyl Esters: Quantification of Chain-Terminating HO ₂ -Elimination Channels
journal, March 2016

Muller, Giel; Scheer, Adam; Osborn, David L.
The Journal of Physical Chemistry A, Vol. 120, Issue 10
DOI: 10.1021/acs.jpca.6b00148

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

Fisher, E. M.; Pitz, W. J.; Curran, H. J.
Proceedings of the Combustion Institute, Vol. 28, Issue 2
DOI: 10.1016/S0082-0784(00)80555-X

Laminar Burning Velocities of C ₄ –C ₇ Ethyl Esters in a Spherical Combustion Chamber: Experimental and Detailed Kinetic Modeling
journal, October 2012

Dayma, Guillaume; Halter, Fabien; Foucher, Fabrice
Energy & Fuels, Vol. 26, Issue 11
DOI: 10.1021/ef301254q

A Systematic Computational Study of the Reactions of HO ₂ with RO ₂ : The HO ₂ + C ₂ H ₅ O ₂ Reaction
journal, December 2005

Hou, Hua; Li, Jicun; Song, Xinli
The Journal of Physical Chemistry A, Vol. 109, Issue 49
DOI: 10.1021/jp0550098

VUV Photoionization Cross Sections of HO ₂ , H ₂ O ₂ , and H ₂ CO
journal, February 2015

Dodson, Leah G.; Shen, Linhan; Savee, John D.
The Journal of Physical Chemistry A, Vol. 119, Issue 8
DOI: 10.1021/jp508942a

Competitive liquid biofuels from biomass
journal, January 2011

Demirbas, Ayhan
Applied Energy, Vol. 88, Issue 1
DOI: 10.1016/j.apenergy.2010.07.016

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

Lin, Kuang C.; Lai, Jason Y. W.; Violi, Angela
Fuel, Vol. 92, Issue 1
DOI: 10.1016/j.fuel.2011.05.014

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

Montgomery, J. A.; Frisch, M. J.; Ochterski, J. W.
The Journal of Chemical Physics, Vol. 110, Issue 6
DOI: 10.1063/1.477924

Gas-phase heats of formation of keto and enol ions of carbonyl compounds
journal, February 1980

Holmes, John L.; Lossing, F. P.
Journal of the American Chemical Society, Vol. 102, Issue 5
DOI: 10.1021/ja00525a021

Relative kinetic measurements of rate coefficients for the gas-phase reactions of Cl atoms and OH radicals with a series of methyl alkyl esters
journal, December 2010

Schütze, Nicole; Zhong, Xiaoyin; Kirschbaum, Stefan
Atmospheric Environment, Vol. 44, Issue 40
DOI: 10.1016/j.atmosenv.2009.08.011

Biofuels (alcohols and biodiesel) applications as fuels for internal combustion engines
journal, June 2007

Agarwal, Avinash Kumar
Progress in Energy and Combustion Science, Vol. 33, Issue 3
DOI: 10.1016/j.pecs.2006.08.003

Biodiesel production from jatropha oil (Jatropha curcas) with high free fatty acids: An optimized process
journal, August 2007

Kumar Tiwari, Alok; Kumar, Akhilesh; Raheman, Hifjur
Biomass and Bioenergy, Vol. 31, Issue 8
DOI: 10.1016/j.biombioe.2007.03.003

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

Osborn, David L.; Zou, Peng; Johnsen, Howard
Review of Scientific Instruments, Vol. 79, Issue 10
DOI: 10.1063/1.3000004

A comparison of saturated and unsaturated C4 fatty acid methyl esters in an opposed flow diffusion flame and a jet stirred reactor
journal, January 2007

Sarathy, S. M.; Gaïl, S.; Syed, S. A.
Proceedings of the Combustion Institute, Vol. 31, Issue 1
DOI: 10.1016/j.proci.2006.07.019

Theoretical study of the mechanisms and kinetics of the reactions of hydroperoxy (HO ₂ ) radicals with hydroxymethylperoxy (HOCH ₂ O ₂ ) and methoxymethylperoxy (CH ₃ OCH ₂ O ₂ ) radicals
journal, January 2014

Shao, Youxiang; Hou, Hua; Wang, Baoshan
Phys. Chem. Chem. Phys., Vol. 16, Issue 41
DOI: 10.1039/C4CP02747G

Reaction Rate Coefficients of OH Radicals and Cl Atoms with Ethyl Propanoate, n -Propyl Propanoate, Methyl 2-Methylpropanoate, and Ethyl n -Butanoate
journal, October 2009

Cometto, Pablo M.; Daële, Véronique; Idir, Mahmoud
The Journal of Physical Chemistry A, Vol. 113, Issue 40
DOI: 10.1021/jp9061708

A Spectroscopic, Kinetic, and Product Study of the (CH ₃ ) ₂ C(OH)CH ₂ O ₂ Radical Self Reaction and Reaction with HO ₂
journal, January 1996

Boyd, Andrew A.; Lesclaux, Robert; Jenkin, Michael E.
The Journal of Physical Chemistry, Vol. 100, Issue 16
DOI: 10.1021/jp953292c

A Product Yield Study of the Reaction of HO ₂ Radicals with Ethyl Peroxy (C ₂ H ₅ O ₂ ), Acetyl Peroxy (CH ₃ C(O)O ₂ ), and Acetonyl Peroxy (CH ₃ C(O)CH ₂ O ₂ ) Radicals
journal, July 2004

Hasson, Alam S.; Tyndall, Geoffrey S.; Orlando, John J.
The Journal of Physical Chemistry A, Vol. 108, Issue 28
DOI: 10.1021/jp048873t

Reaction Pathways for the Thermal Decomposition of Methyl Butanoate
journal, May 2013

Akbar Ali, Mohamad; Violi, Angela
The Journal of Organic Chemistry, Vol. 78, Issue 12
DOI: 10.1021/jo400569d

Microalgae for biodiesel production and other applications: A review
journal, January 2010

Mata, Teresa M.; Martins, António A.; Caetano, Nidia. S.
Renewable and Sustainable Energy Reviews, Vol. 14, Issue 1, p. 217-232
DOI: 10.1016/j.rser.2009.07.020

Direct detection of OH formation in the reactions of HO ₂ with CH ₃ C(O)O ₂ and other substituted peroxy radicals
journal, January 2008

Dillon, T. J.; Crowley, J. N.
Atmospheric Chemistry and Physics, Vol. 8, Issue 16
DOI: 10.5194/acp-8-4877-2008

Thermal Decomposition of Methyl Butanoate: Ab Initio Study of a Biodiesel Fuel Surrogate
journal, January 2008

Huynh, Lam K.; Violi, Angela
The Journal of Organic Chemistry, Vol. 73, Issue 1
DOI: 10.1021/jo701824n

Mechanistic Study of the CH ₃ O ₂ ^• + HO ₂ ^• → CH ₃ O ₂ H + O ₂ Reaction in the Gas Phase. Computational Evidence for the Formation of a Hydrogen-Bonded Diradical Complex
journal, May 2006

Anglada, Josep M.; Olivella, Santiago; Solé, Albert
The Journal of Physical Chemistry A, Vol. 110, Issue 18
DOI: 10.1021/jp060798u

Calibration and comparison of the Gaussian-2, complete basis set, and density functional methods for computational thermochemistry
journal, December 1998

Petersson, G. A.; Malick, David K.; Wilson, William G.
The Journal of Chemical Physics, Vol. 109, Issue 24
DOI: 10.1063/1.477794

Absolute photoionization cross-sections of selected furanic and lactonic potential biofuels
journal, August 2013

Czekner, Joseph; Taatjes, Craig A.; Osborn, David L.
International Journal of Mass Spectrometry, Vol. 348
DOI: 10.1016/j.ijms.2013.04.020

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

Wang, Juan; Yang, Bin; Cool, Terrill A.
International Journal of Mass Spectrometry, Vol. 292, Issue 1-3
DOI: 10.1016/j.ijms.2010.02.010

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

Curtiss, Larry A.; Raghavachari, Krishnan; Redfern, Paul C.
The Journal of Chemical Physics, Vol. 106, Issue 3
DOI: 10.1063/1.473182

Corrosion of metals for automotive applications in ethanol blended biofuels
journal, December 2008

Eppel, K.; Scholz, M.; Troßmann, T.
Energy Materials, Vol. 3, Issue 4
DOI: 10.1179/174892408X12590734881108

Technical aspects of biodiesel production by transesterification—a review
journal, June 2006

Meher, L.; Vidyasagar, D.; Naik, S.
Renewable and Sustainable Energy Reviews, Vol. 10, Issue 3
DOI: 10.1016/j.rser.2004.09.002

Photoionization mass spectrometer for studies of flame chemistry with a synchrotron light source
journal, September 2005

Cool, Terrill A.; McIlroy, Andrew; Qi, Fei
Review of Scientific Instruments, Vol. 76, Issue 9
DOI: 10.1063/1.2010307

Water-catalyzed gas-phase hydrogen abstraction reactions of CH3O2 and HO2 with HO2: a computational investigation
journal, January 2011

Zhang, Tianlei; Wang, Wenliang; Zhang, Pei
Physical Chemistry Chemical Physics, Vol. 13, Issue 46
DOI: 10.1039/c1cp21563a

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

Dooley, S.; Curran, H. J.; Simmie, J. M.
Combustion and Flame, Vol. 153, Issue 1-2
DOI: 10.1016/j.combustflame.2008.01.005

Enthalpies of Formation, Bond Dissociation Energies and Reaction Paths for the Decomposition of Model Biofuels: Ethyl Propanoate and Methyl Butanoate ^†
journal, May 2007

El-Nahas, Ahmed M.; Navarro, Maria V.; Simmie, John M.
The Journal of Physical Chemistry A, Vol. 111, Issue 19
DOI: 10.1021/jp067413s

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

Ng, Martin Y.; Nelson, Jordan; Taatjes, Craig A.
The Journal of Physical Chemistry A, Vol. 118, Issue 21
DOI: 10.1021/jp500260f

A Kinetic Study of the Reaction between Ethylperoxy Radicals and HO2
journal, February 1994

Maricq, M. Matti; Szente, Joseph J.
The Journal of Physical Chemistry, Vol. 98, Issue 8
DOI: 10.1021/j100059a016

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

Curtiss, Larry A.; Redfern, Paul C.; Raghavachari, Krishnan
The Journal of Chemical Physics, Vol. 109, Issue 1
DOI: 10.1063/1.476538

An experimental and computational study of methyl ester decomposition pathways using shock tubes
journal, January 2009

Farooq, A.; Davidson, D. F.; Hanson, R. K.
Proceedings of the Combustion Institute, Vol. 32, Issue 1
DOI: 10.1016/j.proci.2008.06.084

Kinetics of the CH3O2 + HO2 reaction: A temperature and pressure dependence study using chemical ionization mass spectrometry
journal, January 2007

Raventós-Duran, M. Teresa; McGillen, Max; Percival, Carl J.
International Journal of Chemical Kinetics, Vol. 39, Issue 10
DOI: 10.1002/kin.20269

Absolute Rate Constants for the Reactions of Cl Atoms with a Series of Esters
journal, April 1998

Notario, Alberto; Le Bras, Georges; Mellouki, Abdelwahid
The Journal of Physical Chemistry A, Vol. 102, Issue 18
DOI: 10.1021/jp980416n

Reactions of Cl atoms with alkyl esters: kinetic, mechanism and atmospheric implications
journal, May 2014

Ifang, Stefanie; Benter, Thorsten; Barnes, Ian
Environmental Science and Pollution Research, Vol. 22, Issue 7
DOI: 10.1007/s11356-014-2913-9

Predicting the new carbon nanocages, fullerynes: a DFT study
journal, January 2021

Qasemnazhand, Mohammad; Khoeini, Farhad; Marsusi, Farah
Scientific Reports, Vol. 11, Issue 1
DOI: 10.1038/s41598-021-82142-2

Works referencing / citing this record:

Theoretical studies on the mechanism and kinetic for CH ₃ CH ₂ O + HO ₂ and CH ₃ CHOH + HO ₂ reactions
journal, August 2018

Zhang, Tianlei; Wen, Mingjie; Ju, Yan
Journal of Physical Organic Chemistry, Vol. 32, Issue 2
DOI: 10.1002/poc.3895

Similar Records in DOE PAGES and OSTI.GOV collections:

Isomer-Specific Fuel Destruction Pathways in Rich Flames of Methyl Acetate and Ethyl Formate and Consequences for the Combustion Chemistry of Esters

Journal Article Osswald, Patrick ; Struckmeier, Ulf ; Kasper, Tina ; ... - Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

The influences of fuel-specific destruction pathways on flame chemistry are determined for two isomeric ester fuels, methyl acetate, CH₃(CO)OCH₃, and ethyl formate, H(CO)OC₂H₅, used as model representatives for biodiesel compounds, and their potential for forming air pollutants is addressed. Measurements are presented of major and intermediate species mole fractions in premixed, laminar flat flames using molecular-beam sampling and isomer-selective VUV-photoionization mass spectrometry. The observed intermediate species concentrations depend crucially on decomposition of the different radicals formed initially from the fuels. The methyl acetate structure leads to preferential formation of formaldehyde, while the ethyl formate isomer favors the production of acetaldehyde.more »« less
https://doi.org/10.1021/jp068337w
Hydroxyl radical induced oxidation of diethyl ether in oxygenated aqueous solution. A product and pulse radiolysis study. [Gamma radiation]

Journal Article Schuchmann, M N ; von Sonntag, C - J. Phys. Chem.; (United States)

The reactions of peroxyl radicals derived from diethyl ether were investigated by product analyses and pulse-radiolytic techniques. The products and their G values (in brackets) in the ..gamma.. radiolysis of diethyl ether (10/sup -3/ M) in N/sub 2/O/O/sub 2/-saturated aqueous solutions at 0.43 W kg/sup -1/ are acetaldehyde (0.6), ethanol (0.6), ethyl acetate (2.8), ethyl formate (0.7), formaldehyde (0.4), hydrogen peroxide (2.1), 1-ethoxyethyl hydroperoxide (1.2), and 2-ethoxyacetaldehyde (approx. 0.5). Except for the latter, all products have the 1-ethoxyethylperoxy radical (I) as a precursor. It is formed as the major radical by OH abstraction of the ..cap alpha..-H atom (96%) followedmore »« less
https://doi.org/10.1021/j100208a017
Quantification of Key Peroxy and Hydroperoxide Intermediates in the Low-Temperature Oxidation of Dimethyl Ether

Journal Article Couch, David E. ; Mulvihill, Clayton R. ; Sivaramakrishnan, Raghu ; ... - Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Dimethyl ether (DME) oxidation is a model chemical system with a small number of prototypical reaction intermediates that also has practical importance for low-carbon transportation. Although it has been studied experimentally and theoretically, ambiguity remains in the relative importance of competing DME oxidation pathways in the low-temperature autoignition regime. To focus on the primary reactions in DME autoignition, we measured the time-resolved concentration of five intermediates, CH₃OCH₂OO (ROO), OOCH₂OCH₂OOH (OOQOOH), HOOCH₂OCHO (hydroperoxymethyl formate, HPMF), CH₂O, and CH₃OCHO (methyl formate, MF), from photolytically initiated experiments. We performed these studies at P = 10 bar and T = 450-575 K, using a high-pressure photolysis reactor coupled to a time-of-flight mass spectrometer with tunable vacuum-ultraviolet synchrotron ionization at the Advanced Light Source. Our measurements reveal that the timescale of ROO decay and product formation is much shorter than predicted by current DME combustion models. The models also strongly underpredict the observed yields of CH₂O and MF and do not capture the temperature dependence of OOQOOH and HPMF yields. Adding the ROO + OHmore »« less
https://doi.org/10.1021/acs.jpca.2c06959

Full Text Available
Hydroxyl radical induced oxidation of acetaldehyde dimethyl acetal in oxygenated aqueous solution. Rapid O sub 2 sup sm bullet minus release from the CH sub 3 C(OCH sub 3 ) sub 2 O sub 2 sup sm bullet radical

Journal Article Schuchmann, M N ; Schuchmann, H P ; von Sonntag, C - Journal of the American Chemical Society; (USA)

The oxidative degradation of acetaldehyde dimethyl acetal in dilute aqueous solutions has been studied kinetically by pulse radiolysis and with respect to product formation by both {gamma}-radiolysis and pulse radiolysis. In N{sub 2}O-saturated solutions, H abstraction from the substrate by the OH radical produces the radicals CH{sub 3}CH(OCH{sub 3})OCH{sub 2}{sup {sm bullet}} (1), CH{sub 2}C{sup {sm bullet}}(OCH{sub 3}){sub 2} (2), and {sup {sm bullet}}CH{sub 2}CH(OCH{sub 3}){sub 2} (3). Radicals 1 and 2 have reducing properties and react rapidly with tetranitromethane, yielding nitroform anion. Radical 3 is probably inert toward this compound on the pulse radiolysis time scale. While 1 formsmore »« less
https://doi.org/10.1021/ja00157a060
Atmospheric chemistry of diethyl ether and ethyl tert-butyl ether

Journal Article Wallington, T J ; Japar, S M - Environmental Science and Technology; (USA)

The mechanisms for the Cl-initiated and OH-initiated atmospheric oxidation of diethyl ether and ethyl tert-butyl ether (ETBE) have been determined. For diethyl ether the products are ethyl formate and formaldehyde and its atmospheric oxidation can be represented by C{sub 2}H{sub 5}OC{sub 2}H{sub 5} + OH + 2NO {yields} C{sub 2}H{sub 5}OC(O)H + HCHO + 2NO{sub 2} + HO{sub 2}. The mechanism for the atmospheric oxidation of ETBE is more complex, with 80% of the reaction being accounted for in terms of tert-butyl formate and formaldehyde. The remaining 20% the authors ascribe to 2-ethoxy-2-methylpropanal. The atmospheric oxidation of ETBE can bemore »« less
https://doi.org/10.1021/es00015a005

Similar Records

Title: Study of low temperature chlorine atom initiated oxidation of methyl and ethyl butyrate using synchrotron photoionization TOF-mass spectrometry

Abstract

Citation Formats

Ethene loss kinetics of methyl butanoate ions studied by threshold photoelectron–photoion coincidence: journal, April 1999

Kinetics and branching ratio studies of the reaction of C2H5O2 + HO2 using chemical ionisation mass spectrometry journal, January 2007

Transesterification journal, June 1993

Biodiesel and renewable diesel: A comparison journal, June 2010

Substituent effects in the mass spectra of some γ- and β-substituted methyl butyrates journal, January 1969

Oxidation of methyl and ethyl butanoates journal, April 2010

Bacterial production of free fatty acids from freshwater macroalgal cellulose journal, June 2011

Pathways, kinetics and thermochemistry of methyl-ester peroxy radical decomposition in the low-temperature oxidation of methyl butanoate: A computational study of a biodiesel fuel surrogate journal, September 2014

A Systematic Computational Study on the Reactions of HO 2 with RO 2 : The HO 2 + CH 3 O 2 (CD 3 O 2 ) and HO 2 + CH 2 FO 2 Reactions journal, January 2005

The Challenge of Efficient Synthesis of Biofuels from Lignocellulose for Future Renewable Transportation Fuels journal, January 2012

Theoretical studies of the reaction of hydroperoxy radicals (HO2) with ethyl peroxy (CH3CH2O2), acetyl peroxy (CH3C(O)O2), and acetonyl peroxy (CH3C(O)CH2O2) radicals journal, December 2005

Product study of the C2H5O2+HO2 reaction in 760 Torr of air at 284–312 K journal, April 2000

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

A wide-ranging kinetic modeling study of methyl butanoate combustion journal, January 2007

Experimental Characterization of Ethyl Acetate, Ethyl Propionate, and Ethyl Butanoate in a Homogeneous Charge Compression Ignition Engine journal, March 2011

Investigation of the radical product channel of the CH3C(O)CH2O2 + HO2 reaction in the gas phase journal, January 2008

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

Low Temperature Chlorine-Initiated Oxidation of Small-Chain Methyl Esters: Quantification of Chain-Terminating HO 2 -Elimination Channels journal, March 2016

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

Laminar Burning Velocities of C 4 –C 7 Ethyl Esters in a Spherical Combustion Chamber: Experimental and Detailed Kinetic Modeling journal, October 2012

A Systematic Computational Study of the Reactions of HO 2 with RO 2 : The HO 2 + C 2 H 5 O 2 Reaction journal, December 2005

VUV Photoionization Cross Sections of HO 2 , H 2 O 2 , and H 2 CO journal, February 2015

Competitive liquid biofuels from biomass journal, January 2011

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

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

Gas-phase heats of formation of keto and enol ions of carbonyl compounds journal, February 1980

Relative kinetic measurements of rate coefficients for the gas-phase reactions of Cl atoms and OH radicals with a series of methyl alkyl esters journal, December 2010

Biofuels (alcohols and biodiesel) applications as fuels for internal combustion engines journal, June 2007

Biodiesel production from jatropha oil (Jatropha curcas) with high free fatty acids: An optimized process journal, August 2007

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

A comparison of saturated and unsaturated C4 fatty acid methyl esters in an opposed flow diffusion flame and a jet stirred reactor journal, January 2007

Theoretical study of the mechanisms and kinetics of the reactions of hydroperoxy (HO 2 ) radicals with hydroxymethylperoxy (HOCH 2 O 2 ) and methoxymethylperoxy (CH 3 OCH 2 O 2 ) radicals journal, January 2014

Reaction Rate Coefficients of OH Radicals and Cl Atoms with Ethyl Propanoate, n -Propyl Propanoate, Methyl 2-Methylpropanoate, and Ethyl n -Butanoate journal, October 2009

A Spectroscopic, Kinetic, and Product Study of the (CH 3 ) 2 C(OH)CH 2 O 2 Radical Self Reaction and Reaction with HO 2 journal, January 1996

A Product Yield Study of the Reaction of HO 2 Radicals with Ethyl Peroxy (C 2 H 5 O 2 ), Acetyl Peroxy (CH 3 C(O)O 2 ), and Acetonyl Peroxy (CH 3 C(O)CH 2 O 2 ) Radicals journal, July 2004

Reaction Pathways for the Thermal Decomposition of Methyl Butanoate journal, May 2013

Microalgae for biodiesel production and other applications: A review journal, January 2010

Direct detection of OH formation in the reactions of HO 2 with CH 3 C(O)O 2 and other substituted peroxy radicals journal, January 2008

Thermal Decomposition of Methyl Butanoate: Ab Initio Study of a Biodiesel Fuel Surrogate journal, January 2008

Mechanistic Study of the CH 3 O 2 • + HO 2 • → CH 3 O 2 H + O 2 Reaction in the Gas Phase. Computational Evidence for the Formation of a Hydrogen-Bonded Diradical Complex journal, May 2006

Calibration and comparison of the Gaussian-2, complete basis set, and density functional methods for computational thermochemistry journal, December 1998

Absolute photoionization cross-sections of selected furanic and lactonic potential biofuels journal, August 2013

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

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

Corrosion of metals for automotive applications in ethanol blended biofuels journal, December 2008

Technical aspects of biodiesel production by transesterification—a review journal, June 2006

Photoionization mass spectrometer for studies of flame chemistry with a synchrotron light source journal, September 2005

Water-catalyzed gas-phase hydrogen abstraction reactions of CH3O2 and HO2 with HO2: a computational investigation journal, January 2011

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

Enthalpies of Formation, Bond Dissociation Energies and Reaction Paths for the Decomposition of Model Biofuels: Ethyl Propanoate and Methyl Butanoate † journal, May 2007

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

A Kinetic Study of the Reaction between Ethylperoxy Radicals and HO2 journal, February 1994

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

An experimental and computational study of methyl ester decomposition pathways using shock tubes journal, January 2009

Kinetics of the CH3O2 + HO2 reaction: A temperature and pressure dependence study using chemical ionization mass spectrometry journal, January 2007

Absolute Rate Constants for the Reactions of Cl Atoms with a Series of Esters journal, April 1998

Reactions of Cl atoms with alkyl esters: kinetic, mechanism and atmospheric implications journal, May 2014

Predicting the new carbon nanocages, fullerynes: a DFT study journal, January 2021

Theoretical studies on the mechanism and kinetic for CH 3 CH 2 O + HO 2 and CH 3 CHOH + HO 2 reactions journal, August 2018

Ethene loss kinetics of methyl butanoate ions studied by threshold photoelectron–photoion coincidence:
journal, April 1999

Kinetics and branching ratio studies of the reaction of C2H5O2 + HO2 using chemical ionisation mass spectrometry
journal, January 2007

Transesterification
journal, June 1993

Biodiesel and renewable diesel: A comparison
journal, June 2010

Substituent effects in the mass spectra of some γ- and β-substituted methyl butyrates
journal, January 1969

Oxidation of methyl and ethyl butanoates
journal, April 2010

Bacterial production of free fatty acids from freshwater macroalgal cellulose
journal, June 2011

Pathways, kinetics and thermochemistry of methyl-ester peroxy radical decomposition in the low-temperature oxidation of methyl butanoate: A computational study of a biodiesel fuel surrogate
journal, September 2014

A Systematic Computational Study on the Reactions of HO ₂ with RO ₂ : The HO ₂ + CH ₃ O ₂ (CD ₃ O ₂ ) and HO ₂ + CH ₂ FO ₂ Reactions
journal, January 2005

The Challenge of Efficient Synthesis of Biofuels from Lignocellulose for Future Renewable Transportation Fuels
journal, January 2012

Theoretical studies of the reaction of hydroperoxy radicals (HO2) with ethyl peroxy (CH3CH2O2), acetyl peroxy (CH3C(O)O2), and acetonyl peroxy (CH3C(O)CH2O2) radicals
journal, December 2005

Product study of the C2H5O2+HO2 reaction in 760 Torr of air at 284–312 K
journal, April 2000

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

A wide-ranging kinetic modeling study of methyl butanoate combustion
journal, January 2007

Experimental Characterization of Ethyl Acetate, Ethyl Propionate, and Ethyl Butanoate in a Homogeneous Charge Compression Ignition Engine
journal, March 2011

Investigation of the radical product channel of the CH3C(O)CH2O2 + HO2 reaction in the gas phase
journal, January 2008

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

Low Temperature Chlorine-Initiated Oxidation of Small-Chain Methyl Esters: Quantification of Chain-Terminating HO ₂ -Elimination Channels
journal, March 2016

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

Laminar Burning Velocities of C ₄ –C ₇ Ethyl Esters in a Spherical Combustion Chamber: Experimental and Detailed Kinetic Modeling
journal, October 2012

A Systematic Computational Study of the Reactions of HO ₂ with RO ₂ : The HO ₂ + C ₂ H ₅ O ₂ Reaction
journal, December 2005

VUV Photoionization Cross Sections of HO ₂ , H ₂ O ₂ , and H ₂ CO
journal, February 2015

Competitive liquid biofuels from biomass
journal, January 2011

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

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

Gas-phase heats of formation of keto and enol ions of carbonyl compounds
journal, February 1980

Relative kinetic measurements of rate coefficients for the gas-phase reactions of Cl atoms and OH radicals with a series of methyl alkyl esters
journal, December 2010

Biofuels (alcohols and biodiesel) applications as fuels for internal combustion engines
journal, June 2007

Biodiesel production from jatropha oil (Jatropha curcas) with high free fatty acids: An optimized process
journal, August 2007

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

A comparison of saturated and unsaturated C4 fatty acid methyl esters in an opposed flow diffusion flame and a jet stirred reactor
journal, January 2007

Theoretical study of the mechanisms and kinetics of the reactions of hydroperoxy (HO ₂ ) radicals with hydroxymethylperoxy (HOCH ₂ O ₂ ) and methoxymethylperoxy (CH ₃ OCH ₂ O ₂ ) radicals
journal, January 2014

Reaction Rate Coefficients of OH Radicals and Cl Atoms with Ethyl Propanoate, n -Propyl Propanoate, Methyl 2-Methylpropanoate, and Ethyl n -Butanoate
journal, October 2009

A Spectroscopic, Kinetic, and Product Study of the (CH ₃ ) ₂ C(OH)CH ₂ O ₂ Radical Self Reaction and Reaction with HO ₂
journal, January 1996

A Product Yield Study of the Reaction of HO ₂ Radicals with Ethyl Peroxy (C ₂ H ₅ O ₂ ), Acetyl Peroxy (CH ₃ C(O)O ₂ ), and Acetonyl Peroxy (CH ₃ C(O)CH ₂ O ₂ ) Radicals
journal, July 2004

Reaction Pathways for the Thermal Decomposition of Methyl Butanoate
journal, May 2013

Microalgae for biodiesel production and other applications: A review
journal, January 2010

Direct detection of OH formation in the reactions of HO ₂ with CH ₃ C(O)O ₂ and other substituted peroxy radicals
journal, January 2008

Thermal Decomposition of Methyl Butanoate: Ab Initio Study of a Biodiesel Fuel Surrogate
journal, January 2008

Mechanistic Study of the CH ₃ O ₂ ^• + HO ₂ ^• → CH ₃ O ₂ H + O ₂ Reaction in the Gas Phase. Computational Evidence for the Formation of a Hydrogen-Bonded Diradical Complex
journal, May 2006

Calibration and comparison of the Gaussian-2, complete basis set, and density functional methods for computational thermochemistry
journal, December 1998

Absolute photoionization cross-sections of selected furanic and lactonic potential biofuels
journal, August 2013

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

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

Corrosion of metals for automotive applications in ethanol blended biofuels
journal, December 2008

Technical aspects of biodiesel production by transesterification—a review
journal, June 2006

Photoionization mass spectrometer for studies of flame chemistry with a synchrotron light source
journal, September 2005

Water-catalyzed gas-phase hydrogen abstraction reactions of CH3O2 and HO2 with HO2: a computational investigation
journal, January 2011

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

Enthalpies of Formation, Bond Dissociation Energies and Reaction Paths for the Decomposition of Model Biofuels: Ethyl Propanoate and Methyl Butanoate ^†
journal, May 2007

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

A Kinetic Study of the Reaction between Ethylperoxy Radicals and HO2
journal, February 1994

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

An experimental and computational study of methyl ester decomposition pathways using shock tubes
journal, January 2009

Kinetics of the CH3O2 + HO2 reaction: A temperature and pressure dependence study using chemical ionization mass spectrometry
journal, January 2007

Absolute Rate Constants for the Reactions of Cl Atoms with a Series of Esters
journal, April 1998

Reactions of Cl atoms with alkyl esters: kinetic, mechanism and atmospheric implications
journal, May 2014

Predicting the new carbon nanocages, fullerynes: a DFT study
journal, January 2021

Theoretical studies on the mechanism and kinetic for CH ₃ CH ₂ O + HO ₂ and CH ₃ CHOH + HO ₂ reactions
journal, August 2018