Atmospheric chemistry of HFC-272ca: Spectrokinetic investigation of the CH3CF2CH2O2 radical, its reactions with NO and NO2, and the fate of the CH3CF2CH2O radical

Trine E. Møgelberg; Ole J. Nielsen; Jens Sehested; Timothy J. Wallington; Michael D. Hurley

doi:10.1021/j100007a033

Atmospheric chemistry of HFC-272ca: Spectrokinetic investigation of the CH₃CF₂CH₂O₂ radical, its reactions with NO and NO₂, and the fate of the CH₃CF₂CH₂O radical

Trine E. Møgelberg, Ole J. Nielsen^*, Jens Sehested, Timothy J. Wallington, Michael D. Hurley

^*Corresponding author af dette arbejde

7 Citationer (Scopus)

Abstract

A pulse radiolysis technique has been used to investigate the UV absorption spectrum of the CH₃CF₂CH₂O₂ radical from HFC-272ca, CH₃CF₂CH₃. The absorption cross sections were quantified in the wavelength range 220-320 nm; at 250 nm the absorption cross section for CH₃CF₃CH₂O₂ was σ = (451 ± 59) × 10^-20 cm² molecule^-1. By following the increase in NO₂ at 400 nm, the rate constant for the reaction of CH₃CF₂CH₂O₂ with NO was determined to be (8.5 ± 1.9) × 10^-12 cm³ molecule^-1 s^-1. The reaction of CH₃CF₂CH₂O₂ with NO₂ was found to have a reaction rate constant of (6.8 ± 0.5) × 10^-12 cm³ molecule^-1 s^-1. The kinetics of the reaction of CH₃CF₂CH₃ with F atoms and CH₃CF₂CH₂ with O₂ were studied. The rate constants were (2.8 ± 0.9) × 10^-11 and (1.10 ± 0.03) × 10^-12 cm³ molecule^-1 s^-1, respectively. The observed rate constant for the self-reaction of CH₃CF₂CH₂O₂ radicals was (8.6 ± 0.4) × 10^-12 cm³ molecule^-1 s^-1. The reaction of CH₃CF₂CH₂O₂ radicals with NO gives CH₃CF₂CH₂O radicals; the dominant atmospheric fate of CH₃CF₂CH₂O radicals is reaction with O₂ to give CH₃CF₂CHO. As part of the present work, relative rate techniques were used to measure rate constants at 296 ± 2 K for the reactions of Cl and F atoms with CH₃CF₂CH₃, with the values being (1.7 ± 0.2) × 10^-14 and (3.3 ± 0.8) × 10^-11 cm³ molecule^-1 s^-1, respectively.

Originalsprog	Engelsk
Tidsskrift	Journal of Physical Chemistry
Vol/bind	99
Udgave nummer	7
Sider (fra-til)	1995-2001
Antal sider	7
ISSN	0022-3654
DOI	https://doi.org/10.1021/j100007a033
Status	Udgivet - 1 jan. 1995

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10.1021/j100007a033

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Citationsformater

Atmospheric chemistry of HFC-272ca : Spectrokinetic investigation of the CH₃CF₂CH₂O₂ radical, its reactions with NO and NO₂, and the fate of the CH₃CF₂CH₂O radical. / Møgelberg, Trine E.; Nielsen, Ole J.; Sehested, Jens et al.

I: Journal of Physical Chemistry, Bind 99, Nr. 7, 01.01.1995, s. 1995-2001.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer review

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title = "Atmospheric chemistry of HFC-272ca: Spectrokinetic investigation of the CH3CF2CH2O2 radical, its reactions with NO and NO2, and the fate of the CH3CF2CH2O radical",

abstract = "A pulse radiolysis technique has been used to investigate the UV absorption spectrum of the CH3CF2CH2O2 radical from HFC-272ca, CH3CF2CH3. The absorption cross sections were quantified in the wavelength range 220-320 nm; at 250 nm the absorption cross section for CH3CF3CH2O2 was σ = (451 ± 59) × 10-20 cm2 molecule-1. By following the increase in NO2 at 400 nm, the rate constant for the reaction of CH3CF2CH2O2 with NO was determined to be (8.5 ± 1.9) × 10-12 cm3 molecule-1 s-1. The reaction of CH3CF2CH2O2 with NO2 was found to have a reaction rate constant of (6.8 ± 0.5) × 10-12 cm3 molecule-1 s-1. The kinetics of the reaction of CH3CF2CH3 with F atoms and CH3CF2CH2 with O2 were studied. The rate constants were (2.8 ± 0.9) × 10-11 and (1.10 ± 0.03) × 10-12 cm3 molecule-1 s-1, respectively. The observed rate constant for the self-reaction of CH3CF2CH2O2 radicals was (8.6 ± 0.4) × 10-12 cm3 molecule-1 s-1. The reaction of CH3CF2CH2O2 radicals with NO gives CH3CF2CH2O radicals; the dominant atmospheric fate of CH3CF2CH2O radicals is reaction with O2 to give CH3CF2CHO. As part of the present work, relative rate techniques were used to measure rate constants at 296 ± 2 K for the reactions of Cl and F atoms with CH3CF2CH3, with the values being (1.7 ± 0.2) × 10-14 and (3.3 ± 0.8) × 10-11 cm3 molecule-1 s-1, respectively.",

author = "M{\o}gelberg, {Trine E.} and Nielsen, {Ole J.} and Jens Sehested and Wallington, {Timothy J.} and Hurley, {Michael D.}",

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T1 - Atmospheric chemistry of HFC-272ca

T2 - Spectrokinetic investigation of the CH3CF2CH2O2 radical, its reactions with NO and NO2, and the fate of the CH3CF2CH2O radical

AU - Møgelberg, Trine E.

AU - Nielsen, Ole J.

AU - Sehested, Jens

AU - Wallington, Timothy J.

AU - Hurley, Michael D.

PY - 1995/1/1

Y1 - 1995/1/1

N2 - A pulse radiolysis technique has been used to investigate the UV absorption spectrum of the CH3CF2CH2O2 radical from HFC-272ca, CH3CF2CH3. The absorption cross sections were quantified in the wavelength range 220-320 nm; at 250 nm the absorption cross section for CH3CF3CH2O2 was σ = (451 ± 59) × 10-20 cm2 molecule-1. By following the increase in NO2 at 400 nm, the rate constant for the reaction of CH3CF2CH2O2 with NO was determined to be (8.5 ± 1.9) × 10-12 cm3 molecule-1 s-1. The reaction of CH3CF2CH2O2 with NO2 was found to have a reaction rate constant of (6.8 ± 0.5) × 10-12 cm3 molecule-1 s-1. The kinetics of the reaction of CH3CF2CH3 with F atoms and CH3CF2CH2 with O2 were studied. The rate constants were (2.8 ± 0.9) × 10-11 and (1.10 ± 0.03) × 10-12 cm3 molecule-1 s-1, respectively. The observed rate constant for the self-reaction of CH3CF2CH2O2 radicals was (8.6 ± 0.4) × 10-12 cm3 molecule-1 s-1. The reaction of CH3CF2CH2O2 radicals with NO gives CH3CF2CH2O radicals; the dominant atmospheric fate of CH3CF2CH2O radicals is reaction with O2 to give CH3CF2CHO. As part of the present work, relative rate techniques were used to measure rate constants at 296 ± 2 K for the reactions of Cl and F atoms with CH3CF2CH3, with the values being (1.7 ± 0.2) × 10-14 and (3.3 ± 0.8) × 10-11 cm3 molecule-1 s-1, respectively.

AB - A pulse radiolysis technique has been used to investigate the UV absorption spectrum of the CH3CF2CH2O2 radical from HFC-272ca, CH3CF2CH3. The absorption cross sections were quantified in the wavelength range 220-320 nm; at 250 nm the absorption cross section for CH3CF3CH2O2 was σ = (451 ± 59) × 10-20 cm2 molecule-1. By following the increase in NO2 at 400 nm, the rate constant for the reaction of CH3CF2CH2O2 with NO was determined to be (8.5 ± 1.9) × 10-12 cm3 molecule-1 s-1. The reaction of CH3CF2CH2O2 with NO2 was found to have a reaction rate constant of (6.8 ± 0.5) × 10-12 cm3 molecule-1 s-1. The kinetics of the reaction of CH3CF2CH3 with F atoms and CH3CF2CH2 with O2 were studied. The rate constants were (2.8 ± 0.9) × 10-11 and (1.10 ± 0.03) × 10-12 cm3 molecule-1 s-1, respectively. The observed rate constant for the self-reaction of CH3CF2CH2O2 radicals was (8.6 ± 0.4) × 10-12 cm3 molecule-1 s-1. The reaction of CH3CF2CH2O2 radicals with NO gives CH3CF2CH2O radicals; the dominant atmospheric fate of CH3CF2CH2O radicals is reaction with O2 to give CH3CF2CHO. As part of the present work, relative rate techniques were used to measure rate constants at 296 ± 2 K for the reactions of Cl and F atoms with CH3CF2CH3, with the values being (1.7 ± 0.2) × 10-14 and (3.3 ± 0.8) × 10-11 cm3 molecule-1 s-1, respectively.

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