Absolute rate constants for F + CH3CHO and CH3CO + O2, relative rate study of CH3CO + NO, and the product distribution of the F + CH3CHO reaction

Jens Sehested; Lene K. Christensen; Ole J. Nielsen; Timothy J. Wallington

doi:10.1002/(SICI)1097-4601(1998)30:12<913::AID-KIN6>3.0.CO;2-5

Absolute rate constants for F + CH₃CHO and CH₃CO + O₂, relative rate study of CH₃CO + NO, and the product distribution of the F + CH₃CHO reaction

Jens Sehested^*, Lene K. Christensen, Ole J. Nielsen, Timothy J. Wallington

^*Corresponding author for this work

27 Citations (Scopus)

Abstract

Using a pulse-radiolysis transient UV-VIS absorption system, rate constants for the reactions of F atoms with CH₃CHO (1) and CH₃CO radicals with O₂ (2) and NO (3) at 295 K and 1000 mbar total pressure of SF₆ was determined to be k₁ = (1.4 ± 0.2) × 10^-10, k₂ = (4.4 ± 0.7) × 10^-12, and k₃ = (2.4 ± 0.7) × 10^-11 cm³ molecule^-1 s^-1. By monitoring the formation of CH₃C(O)O₂ radicals (A > 250nm) and NO₂ (A = 400.5nm) following radiolysis of SF₆/CH₃CHO/O₂ and SF₆/CH₃CHO/O₂/NO mixtures, respectively, it was deduced that reaction of F atoms with CH₃CHO gives (65 ± 9)% CH₃CO and (35 ± 9)% HC(O)CH₂ radicals. Finally, the data obtained here suggest that decomposition of HC(O)CH₂O radicals via C - C bond scission occurs at a rate of <4.7 × 10⁵ S^-1.

Original language	English
Journal	International Journal of Chemical Kinetics
Volume	30
Issue number	12
Pages (from-to)	913-921
Number of pages	9
ISSN	0538-8066
DOIs	https://doi.org/10.1002/(SICI)1097-4601(1998)30:12<913::AID-KIN6>3.0.CO;2-5
Publication status	Published - 1 Jan 1998

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10.1002/(SICI)1097-4601(1998)30:12<913::AID-KIN6>3.0.CO;2-5

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Absolute rate constants for F + CH₃CHO and CH₃CO + O₂, relative rate study of CH₃CO + NO, and the product distribution of the F + CH₃CHO reaction. / Sehested, Jens; Christensen, Lene K.; Nielsen, Ole J. et al.

In: International Journal of Chemical Kinetics, Vol. 30, No. 12, 01.01.1998, p. 913-921.

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

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title = "Absolute rate constants for F + CH3CHO and CH3CO + O2, relative rate study of CH3CO + NO, and the product distribution of the F + CH3CHO reaction",

abstract = "Using a pulse-radiolysis transient UV-VIS absorption system, rate constants for the reactions of F atoms with CH3CHO (1) and CH3CO radicals with O2 (2) and NO (3) at 295 K and 1000 mbar total pressure of SF6 was determined to be k1 = (1.4 ± 0.2) × 10-10, k2 = (4.4 ± 0.7) × 10-12, and k3 = (2.4 ± 0.7) × 10-11 cm3 molecule-1 s-1. By monitoring the formation of CH3C(O)O2 radicals (A > 250nm) and NO2 (A = 400.5nm) following radiolysis of SF6/CH3CHO/O2 and SF6/CH3CHO/O2/NO mixtures, respectively, it was deduced that reaction of F atoms with CH3CHO gives (65 ± 9)% CH3CO and (35 ± 9)% HC(O)CH2 radicals. Finally, the data obtained here suggest that decomposition of HC(O)CH2O radicals via C - C bond scission occurs at a rate of <4.7 × 105 S-1.",

author = "Jens Sehested and Christensen, {Lene K.} and Nielsen, {Ole J.} and Wallington, {Timothy J.}",

year = "1998",

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T1 - Absolute rate constants for F + CH3CHO and CH3CO + O2, relative rate study of CH3CO + NO, and the product distribution of the F + CH3CHO reaction

AU - Sehested, Jens

AU - Christensen, Lene K.

AU - Nielsen, Ole J.

AU - Wallington, Timothy J.

PY - 1998/1/1

Y1 - 1998/1/1

N2 - Using a pulse-radiolysis transient UV-VIS absorption system, rate constants for the reactions of F atoms with CH3CHO (1) and CH3CO radicals with O2 (2) and NO (3) at 295 K and 1000 mbar total pressure of SF6 was determined to be k1 = (1.4 ± 0.2) × 10-10, k2 = (4.4 ± 0.7) × 10-12, and k3 = (2.4 ± 0.7) × 10-11 cm3 molecule-1 s-1. By monitoring the formation of CH3C(O)O2 radicals (A > 250nm) and NO2 (A = 400.5nm) following radiolysis of SF6/CH3CHO/O2 and SF6/CH3CHO/O2/NO mixtures, respectively, it was deduced that reaction of F atoms with CH3CHO gives (65 ± 9)% CH3CO and (35 ± 9)% HC(O)CH2 radicals. Finally, the data obtained here suggest that decomposition of HC(O)CH2O radicals via C - C bond scission occurs at a rate of <4.7 × 105 S-1.

AB - Using a pulse-radiolysis transient UV-VIS absorption system, rate constants for the reactions of F atoms with CH3CHO (1) and CH3CO radicals with O2 (2) and NO (3) at 295 K and 1000 mbar total pressure of SF6 was determined to be k1 = (1.4 ± 0.2) × 10-10, k2 = (4.4 ± 0.7) × 10-12, and k3 = (2.4 ± 0.7) × 10-11 cm3 molecule-1 s-1. By monitoring the formation of CH3C(O)O2 radicals (A > 250nm) and NO2 (A = 400.5nm) following radiolysis of SF6/CH3CHO/O2 and SF6/CH3CHO/O2/NO mixtures, respectively, it was deduced that reaction of F atoms with CH3CHO gives (65 ± 9)% CH3CO and (35 ± 9)% HC(O)CH2 radicals. Finally, the data obtained here suggest that decomposition of HC(O)CH2O radicals via C - C bond scission occurs at a rate of <4.7 × 105 S-1.

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Absolute rate constants for F + CH₃CHO and CH₃CO + O₂, relative rate study of CH₃CO + NO, and the product distribution of the F + CH₃CHO reaction

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