Atmospheric chemistry of dimethoxymethane (CH3OCH2OCH3): Kinetics and mechanism of its reaction with OH radicals and fate of the alkoxy radicals CH3OCHO(•)OCH3 and CH3OCH2OCH2O(•)

Timothy J. Wallington; Michael D. Hurley; James C. Ball; Ann M. Straccia; Jesper Platz; Lene Krogh Christensen; Jens Sehested; Ole John Nielsen

Atmospheric chemistry of dimethoxymethane (CH₃OCH₂OCH₃): Kinetics and mechanism of its reaction with OH radicals and fate of the alkoxy radicals CH₃OCHO(•)OCH₃ and CH₃OCH₂OCH₂O(•)

Timothy J. Wallington^*, Michael D. Hurley, James C. Ball, Ann M. Straccia, Jesper Platz, Lene Krogh Christensen, Jens Sehested, Ole John Nielsen

^*Corresponding author for this work

44 Citations (Scopus)

Abstract

The rate constant for the reaction of dimethoxymethane (DMM) with OH radicals was determined to be (4.6 ± 1.6) × 10^-12 at 346 ± 3 K using a pulse radiolysis/transient UV absorption absolute rate technique and (5.3 ± 1.0) × 10^-12 cm³ molecule^-1 s^-1 at 295 ± 2 K using an FTIR-smog chamber relative rate technique. The reaction of OH radicals with DMM occurs via an H-atom abstraction mechanism with 76% of the attack occurring on the -CH₃ end groups and 24% on the central - CH₂ - unit. The atmospheric fate of the alkoxy radicals CH₃OCH₂OCH₂O(•) and CH₃OCHO(•)OCH₃ at 296 K in 700 Torr of air was investigated using an FTIR-smog chamber technique. The sole atmospheric fate of CH₃OCHO(•)OCH₃ radicals is reaction with O₂ to give dimethyl carbonate (CH₃OC(O)OCH₃) and HO₂ radicals. At least three loss processes were identified for CH₃OCH₂OCH₂O(•) radicals. In 1 atm of air at 295 K, 84 ± 4% of the CH₃OCH₂OCH₂O(•) radicals react with O₂ while 7 ± 3% undergo H-atom elimination; the fate of the remaining 9% is unclear. OH radical-initiated oxidation of DMM in 1 atm of air at 296 K results in a yield of 24% dimethyl carbonate and 69% methoxymethyl formate; the oxidation mechanism of the remaining 7% of DMM is unclear. Relative rate techniques were used to measure rate constants for the reaction of Cl atoms with CH₃OCH₂OCH₃ and CH₃OCH₂OCHO of (1.4 ± 0.2) × 10^-10 and (3.6 ± 0.6) × 10^-11 cm³ molecule^-1 s^-1, respectively. Results are discussed in the context of the atmospheric chemistry of DMM.

Original language	English
Journal	Journal of Physical Chemistry A
Volume	101
Issue number	29
Pages (from-to)	5302-5308
Number of pages	7
ISSN	1089-5639
Publication status	Published - 17 Jul 1997

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Wallington, T. J., Hurley, M. D., Ball, J. C., Straccia, A. M., Platz, J., Christensen, L. K., Sehested, J., & Nielsen, O. J. (1997). Atmospheric chemistry of dimethoxymethane (CH₃OCH₂OCH₃): Kinetics and mechanism of its reaction with OH radicals and fate of the alkoxy radicals CH₃OCHO(•)OCH₃ and CH₃OCH₂OCH₂O(•). Journal of Physical Chemistry A, 101(29), 5302-5308.

Atmospheric chemistry of dimethoxymethane (CH₃OCH₂OCH₃) : Kinetics and mechanism of its reaction with OH radicals and fate of the alkoxy radicals CH₃OCHO(•)OCH₃ and CH₃OCH₂OCH₂O(•). / Wallington, Timothy J.; Hurley, Michael D.; Ball, James C. et al.

In: Journal of Physical Chemistry A, Vol. 101, No. 29, 17.07.1997, p. 5302-5308.

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

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title = "Atmospheric chemistry of dimethoxymethane (CH3OCH2OCH3): Kinetics and mechanism of its reaction with OH radicals and fate of the alkoxy radicals CH3OCHO(•)OCH3 and CH3OCH2OCH2O(•)",

abstract = "The rate constant for the reaction of dimethoxymethane (DMM) with OH radicals was determined to be (4.6 ± 1.6) × 10-12 at 346 ± 3 K using a pulse radiolysis/transient UV absorption absolute rate technique and (5.3 ± 1.0) × 10-12 cm3 molecule-1 s-1 at 295 ± 2 K using an FTIR-smog chamber relative rate technique. The reaction of OH radicals with DMM occurs via an H-atom abstraction mechanism with 76% of the attack occurring on the -CH3 end groups and 24% on the central - CH2 - unit. The atmospheric fate of the alkoxy radicals CH3OCH2OCH2O(•) and CH3OCHO(•)OCH3 at 296 K in 700 Torr of air was investigated using an FTIR-smog chamber technique. The sole atmospheric fate of CH3OCHO(•)OCH3 radicals is reaction with O2 to give dimethyl carbonate (CH3OC(O)OCH3) and HO2 radicals. At least three loss processes were identified for CH3OCH2OCH2O(•) radicals. In 1 atm of air at 295 K, 84 ± 4% of the CH3OCH2OCH2O(•) radicals react with O2 while 7 ± 3% undergo H-atom elimination; the fate of the remaining 9% is unclear. OH radical-initiated oxidation of DMM in 1 atm of air at 296 K results in a yield of 24% dimethyl carbonate and 69% methoxymethyl formate; the oxidation mechanism of the remaining 7% of DMM is unclear. Relative rate techniques were used to measure rate constants for the reaction of Cl atoms with CH3OCH2OCH3 and CH3OCH2OCHO of (1.4 ± 0.2) × 10-10 and (3.6 ± 0.6) × 10-11 cm3 molecule-1 s-1, respectively. Results are discussed in the context of the atmospheric chemistry of DMM.",

author = "Wallington, {Timothy J.} and Hurley, {Michael D.} and Ball, {James C.} and Straccia, {Ann M.} and Jesper Platz and Christensen, {Lene Krogh} and Jens Sehested and Nielsen, {Ole John}",

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TY - JOUR

T1 - Atmospheric chemistry of dimethoxymethane (CH3OCH2OCH3)

T2 - Kinetics and mechanism of its reaction with OH radicals and fate of the alkoxy radicals CH3OCHO(•)OCH3 and CH3OCH2OCH2O(•)

AU - Wallington, Timothy J.

AU - Hurley, Michael D.

AU - Ball, James C.

AU - Straccia, Ann M.

AU - Platz, Jesper

AU - Christensen, Lene Krogh

AU - Sehested, Jens

AU - Nielsen, Ole John

PY - 1997/7/17

Y1 - 1997/7/17

N2 - The rate constant for the reaction of dimethoxymethane (DMM) with OH radicals was determined to be (4.6 ± 1.6) × 10-12 at 346 ± 3 K using a pulse radiolysis/transient UV absorption absolute rate technique and (5.3 ± 1.0) × 10-12 cm3 molecule-1 s-1 at 295 ± 2 K using an FTIR-smog chamber relative rate technique. The reaction of OH radicals with DMM occurs via an H-atom abstraction mechanism with 76% of the attack occurring on the -CH3 end groups and 24% on the central - CH2 - unit. The atmospheric fate of the alkoxy radicals CH3OCH2OCH2O(•) and CH3OCHO(•)OCH3 at 296 K in 700 Torr of air was investigated using an FTIR-smog chamber technique. The sole atmospheric fate of CH3OCHO(•)OCH3 radicals is reaction with O2 to give dimethyl carbonate (CH3OC(O)OCH3) and HO2 radicals. At least three loss processes were identified for CH3OCH2OCH2O(•) radicals. In 1 atm of air at 295 K, 84 ± 4% of the CH3OCH2OCH2O(•) radicals react with O2 while 7 ± 3% undergo H-atom elimination; the fate of the remaining 9% is unclear. OH radical-initiated oxidation of DMM in 1 atm of air at 296 K results in a yield of 24% dimethyl carbonate and 69% methoxymethyl formate; the oxidation mechanism of the remaining 7% of DMM is unclear. Relative rate techniques were used to measure rate constants for the reaction of Cl atoms with CH3OCH2OCH3 and CH3OCH2OCHO of (1.4 ± 0.2) × 10-10 and (3.6 ± 0.6) × 10-11 cm3 molecule-1 s-1, respectively. Results are discussed in the context of the atmospheric chemistry of DMM.

AB - The rate constant for the reaction of dimethoxymethane (DMM) with OH radicals was determined to be (4.6 ± 1.6) × 10-12 at 346 ± 3 K using a pulse radiolysis/transient UV absorption absolute rate technique and (5.3 ± 1.0) × 10-12 cm3 molecule-1 s-1 at 295 ± 2 K using an FTIR-smog chamber relative rate technique. The reaction of OH radicals with DMM occurs via an H-atom abstraction mechanism with 76% of the attack occurring on the -CH3 end groups and 24% on the central - CH2 - unit. The atmospheric fate of the alkoxy radicals CH3OCH2OCH2O(•) and CH3OCHO(•)OCH3 at 296 K in 700 Torr of air was investigated using an FTIR-smog chamber technique. The sole atmospheric fate of CH3OCHO(•)OCH3 radicals is reaction with O2 to give dimethyl carbonate (CH3OC(O)OCH3) and HO2 radicals. At least three loss processes were identified for CH3OCH2OCH2O(•) radicals. In 1 atm of air at 295 K, 84 ± 4% of the CH3OCH2OCH2O(•) radicals react with O2 while 7 ± 3% undergo H-atom elimination; the fate of the remaining 9% is unclear. OH radical-initiated oxidation of DMM in 1 atm of air at 296 K results in a yield of 24% dimethyl carbonate and 69% methoxymethyl formate; the oxidation mechanism of the remaining 7% of DMM is unclear. Relative rate techniques were used to measure rate constants for the reaction of Cl atoms with CH3OCH2OCH3 and CH3OCH2OCHO of (1.4 ± 0.2) × 10-10 and (3.6 ± 0.6) × 10-11 cm3 molecule-1 s-1, respectively. Results are discussed in the context of the atmospheric chemistry of DMM.

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M3 - Journal article

AN - SCOPUS:0031187009

SN - 1089-5639

VL - 101

SP - 5302

EP - 5308

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

IS - 29

ER -

Atmospheric chemistry of dimethoxymethane (CH₃OCH₂OCH₃): Kinetics and mechanism of its reaction with OH radicals and fate of the alkoxy radicals CH₃OCHO(•)OCH₃ and CH₃OCH₂OCH₂O(•)

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