Oxidation of dimethyl ether: Absolute rate constants for the self reaction of CH3OCH2 radicals, the reaction of CH3OCH2 radicals with O2, and the thermal decomposition of CH3OCH2 radicals

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Standard

Oxidation of dimethyl ether : Absolute rate constants for the self reaction of CH3OCH2 radicals, the reaction of CH3OCH2 radicals with O2, and the thermal decomposition of CH3OCH2 radicals. / Sehested, Jens; Sehested, Knud; Platz, Iesper; Egsgaard, Helge; Nielsen, Ole John.

I: International Journal of Chemical Kinetics, Bind 29, Nr. 8, 01.01.1997, s. 627-636.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt

Harvard

Sehested, J, Sehested, K, Platz, I, Egsgaard, H & Nielsen, OJ 1997, 'Oxidation of dimethyl ether: Absolute rate constants for the self reaction of CH3OCH2 radicals, the reaction of CH3OCH2 radicals with O2, and the thermal decomposition of CH3OCH2 radicals', International Journal of Chemical Kinetics, bind 29, nr. 8, s. 627-636. https://doi.org/10.1002/(SICI)1097-4601(1997)29:8<627::AID-KIN8>3.0.CO;2-W

APA

Sehested, J., Sehested, K., Platz, I., Egsgaard, H., & Nielsen, O. J. (1997). Oxidation of dimethyl ether: Absolute rate constants for the self reaction of CH3OCH2 radicals, the reaction of CH3OCH2 radicals with O2, and the thermal decomposition of CH3OCH2 radicals. International Journal of Chemical Kinetics, 29(8), 627-636. https://doi.org/10.1002/(SICI)1097-4601(1997)29:8<627::AID-KIN8>3.0.CO;2-W

Vancouver

Sehested J, Sehested K, Platz I, Egsgaard H, Nielsen OJ. Oxidation of dimethyl ether: Absolute rate constants for the self reaction of CH3OCH2 radicals, the reaction of CH3OCH2 radicals with O2, and the thermal decomposition of CH3OCH2 radicals. International Journal of Chemical Kinetics. 1997 jan. 1;29(8):627-636. https://doi.org/10.1002/(SICI)1097-4601(1997)29:8<627::AID-KIN8>3.0.CO;2-W

Author

Sehested, Jens ; Sehested, Knud ; Platz, Iesper ; Egsgaard, Helge ; Nielsen, Ole John. / Oxidation of dimethyl ether : Absolute rate constants for the self reaction of CH3OCH2 radicals, the reaction of CH3OCH2 radicals with O2, and the thermal decomposition of CH3OCH2 radicals. I: International Journal of Chemical Kinetics. 1997 ; Bind 29, Nr. 8. s. 627-636.

Bibtex

@article{e69fdb73fcb7459a9e4fe0b3d77897c5,
title = "Oxidation of dimethyl ether: Absolute rate constants for the self reaction of CH3OCH2 radicals, the reaction of CH3OCH2 radicals with O2, and the thermal decomposition of CH3OCH2 radicals",
abstract = "The rate constant for the reaction of CH3OCH2 radicals with O2 (reaction (1)) and the self reaction of CH3OCH2 radicals (reaction (5)) were measured using pulse radiolysis coupled with time resolved UV absorption spectroscopy. k1 was studied at 296 K over the pressure range 0.025-1 bar and in the temperature range 296-473 K at 18 bar total pressure. Reaction (1) is known to proceed through the following mechanism: CH3OCH2 + O2 ↔ CH3OCH2O2# → CH2OCH2O2H# → 2HCHO + OH (kprod) CH3OCH2 + O2 ↔ CH3OCH2O2# + M → CH3OCH2O2 + M (kRO2) k1 = kRO2 + kprod, where kRO2 is the rate constant for peroxy radical production and kprod is the rate constant for formaldehyde production. The k1 values obtained at 296 K together with the available literature values for k1 determined at low pressures were fitted using a modified Lindemann mechanism and the following parameters were obtained: kRO2,0 = (9.4 ± 4.2) × 10-30 cm6 molecule-2 s-1, kRO2,∞ = (1.14 ± 0.04) × 10-11 cm3 molecule-1 s-1, and kprodi,0 = (6.0 ± 0.5) × 10-12 cm3 molecule-1 s-1 where kRO2,0 and kRO2,∞ are the overall termolecular and bimolecular rate constants for formation of CH3OCH2O2 radicals and kprod,0 represents the bimolecular rate constant for the reaction of CH3OCH2 radicals with O2 to yield formaldehyde in the limit of low pressure. kRO2,∞ = (1.07 ± 0.08) × 10-11 exp(-(46 ± 27)/T) cm3 molecule-1 s-1 was determined at 18 bar total pressure over the temperature range 296-473 K. At 1 bar total pressure and 296 K, k3 = (4.1 ± 0.5) × 10-11 cm3 molecule-1 s-1 and at 18 bar total pressure over the temperature range 296-523 K, k5 = (4.7 ± 0.6) × 10-11 cm3 molecule-1 s-1. As a part of this study the decay rate of CH3OCH2 radicals was used to study the thermal decomposition of CH3OCH2 radicals in the temperature range 573-666 K at 18 bar total pressure. The observed decay rates of CH3OCH2 radicals were consistent with the literature value of k2 = 1.6 × 1013exp(-12800/T) s-1. The results are discussed in the context of dimethyl ether as an alternative diesel fuel.",
author = "Jens Sehested and Knud Sehested and Iesper Platz and Helge Egsgaard and Nielsen, {Ole John}",
year = "1997",
month = jan,
day = "1",
doi = "10.1002/(SICI)1097-4601(1997)29:8<627::AID-KIN8>3.0.CO;2-W",
language = "English",
volume = "29",
pages = "627--636",
journal = "International Journal of Chemical Kinetics",
issn = "0538-8066",
publisher = "JohnWiley & Sons, Inc.",
number = "8",

}

RIS

TY - JOUR

T1 - Oxidation of dimethyl ether

T2 - Absolute rate constants for the self reaction of CH3OCH2 radicals, the reaction of CH3OCH2 radicals with O2, and the thermal decomposition of CH3OCH2 radicals

AU - Sehested, Jens

AU - Sehested, Knud

AU - Platz, Iesper

AU - Egsgaard, Helge

AU - Nielsen, Ole John

PY - 1997/1/1

Y1 - 1997/1/1

N2 - The rate constant for the reaction of CH3OCH2 radicals with O2 (reaction (1)) and the self reaction of CH3OCH2 radicals (reaction (5)) were measured using pulse radiolysis coupled with time resolved UV absorption spectroscopy. k1 was studied at 296 K over the pressure range 0.025-1 bar and in the temperature range 296-473 K at 18 bar total pressure. Reaction (1) is known to proceed through the following mechanism: CH3OCH2 + O2 ↔ CH3OCH2O2# → CH2OCH2O2H# → 2HCHO + OH (kprod) CH3OCH2 + O2 ↔ CH3OCH2O2# + M → CH3OCH2O2 + M (kRO2) k1 = kRO2 + kprod, where kRO2 is the rate constant for peroxy radical production and kprod is the rate constant for formaldehyde production. The k1 values obtained at 296 K together with the available literature values for k1 determined at low pressures were fitted using a modified Lindemann mechanism and the following parameters were obtained: kRO2,0 = (9.4 ± 4.2) × 10-30 cm6 molecule-2 s-1, kRO2,∞ = (1.14 ± 0.04) × 10-11 cm3 molecule-1 s-1, and kprodi,0 = (6.0 ± 0.5) × 10-12 cm3 molecule-1 s-1 where kRO2,0 and kRO2,∞ are the overall termolecular and bimolecular rate constants for formation of CH3OCH2O2 radicals and kprod,0 represents the bimolecular rate constant for the reaction of CH3OCH2 radicals with O2 to yield formaldehyde in the limit of low pressure. kRO2,∞ = (1.07 ± 0.08) × 10-11 exp(-(46 ± 27)/T) cm3 molecule-1 s-1 was determined at 18 bar total pressure over the temperature range 296-473 K. At 1 bar total pressure and 296 K, k3 = (4.1 ± 0.5) × 10-11 cm3 molecule-1 s-1 and at 18 bar total pressure over the temperature range 296-523 K, k5 = (4.7 ± 0.6) × 10-11 cm3 molecule-1 s-1. As a part of this study the decay rate of CH3OCH2 radicals was used to study the thermal decomposition of CH3OCH2 radicals in the temperature range 573-666 K at 18 bar total pressure. The observed decay rates of CH3OCH2 radicals were consistent with the literature value of k2 = 1.6 × 1013exp(-12800/T) s-1. The results are discussed in the context of dimethyl ether as an alternative diesel fuel.

AB - The rate constant for the reaction of CH3OCH2 radicals with O2 (reaction (1)) and the self reaction of CH3OCH2 radicals (reaction (5)) were measured using pulse radiolysis coupled with time resolved UV absorption spectroscopy. k1 was studied at 296 K over the pressure range 0.025-1 bar and in the temperature range 296-473 K at 18 bar total pressure. Reaction (1) is known to proceed through the following mechanism: CH3OCH2 + O2 ↔ CH3OCH2O2# → CH2OCH2O2H# → 2HCHO + OH (kprod) CH3OCH2 + O2 ↔ CH3OCH2O2# + M → CH3OCH2O2 + M (kRO2) k1 = kRO2 + kprod, where kRO2 is the rate constant for peroxy radical production and kprod is the rate constant for formaldehyde production. The k1 values obtained at 296 K together with the available literature values for k1 determined at low pressures were fitted using a modified Lindemann mechanism and the following parameters were obtained: kRO2,0 = (9.4 ± 4.2) × 10-30 cm6 molecule-2 s-1, kRO2,∞ = (1.14 ± 0.04) × 10-11 cm3 molecule-1 s-1, and kprodi,0 = (6.0 ± 0.5) × 10-12 cm3 molecule-1 s-1 where kRO2,0 and kRO2,∞ are the overall termolecular and bimolecular rate constants for formation of CH3OCH2O2 radicals and kprod,0 represents the bimolecular rate constant for the reaction of CH3OCH2 radicals with O2 to yield formaldehyde in the limit of low pressure. kRO2,∞ = (1.07 ± 0.08) × 10-11 exp(-(46 ± 27)/T) cm3 molecule-1 s-1 was determined at 18 bar total pressure over the temperature range 296-473 K. At 1 bar total pressure and 296 K, k3 = (4.1 ± 0.5) × 10-11 cm3 molecule-1 s-1 and at 18 bar total pressure over the temperature range 296-523 K, k5 = (4.7 ± 0.6) × 10-11 cm3 molecule-1 s-1. As a part of this study the decay rate of CH3OCH2 radicals was used to study the thermal decomposition of CH3OCH2 radicals in the temperature range 573-666 K at 18 bar total pressure. The observed decay rates of CH3OCH2 radicals were consistent with the literature value of k2 = 1.6 × 1013exp(-12800/T) s-1. The results are discussed in the context of dimethyl ether as an alternative diesel fuel.

UR - http://www.scopus.com/inward/record.url?scp=0031212951&partnerID=8YFLogxK

U2 - 10.1002/(SICI)1097-4601(1997)29:8<627::AID-KIN8>3.0.CO;2-W

DO - 10.1002/(SICI)1097-4601(1997)29:8<627::AID-KIN8>3.0.CO;2-W

M3 - Journal article

AN - SCOPUS:0031212951

VL - 29

SP - 627

EP - 636

JO - International Journal of Chemical Kinetics

JF - International Journal of Chemical Kinetics

SN - 0538-8066

IS - 8

ER -

ID: 227486805