UV absorption spectra, kinetics and mechanism for alkyl and alkyl peroxy radicals originating from t-butyl alcohol

Sarka Langer; Evert Ljungström; Jens Sehested; Ole J. Nielsen

doi:10.1016/0009-2614(94)00691-1

UV absorption spectra, kinetics and mechanism for alkyl and alkyl peroxy radicals originating from t-butyl alcohol

Sarka Langer, Evert Ljungström^*, Jens Sehested, Ole J. Nielsen

^*Corresponding author for this work

17 Citations (Scopus)

Abstract

Alkyl and alkyl peroxy radicals from t-butyl alcohol (TBA), HOC(CH₃)₂CH₂^{{radical dot}} and HOC(CH₃)₂CH₂O₂^{{radical dot}} have been studied in the gas phase at 298 K. Two techniques were used: pulse radiolysis UV absorption to measure the spectra and kinetics, and long path-length Fourier transform infrared spectroscopy (FTIR) to identify and quantify the reaction products. Absorption cross sections were quantified over the wavelength range 220-320 nm. At 240 nm, σ_{HOC(CH₃)₂CH₂}=(2.4 ±0.3)×10^-18 and σ_{HOC(CH₃)₂CH₂O₂}=(3.4±0.5)×10^-18 cm² molecule^-1 have been obtained. Observed rate constants for the self-reaction of HOC(CH₃)₂CH₂^{{radical dot}} and HOC(CH₃)₂CH₂O₂^{{radical dot}} radicals were found to be (3.0±0.5)×10^-11 and (7.8±1.5)×10^-12 cm³ molecule^-1 s^-1, respectively. For the reaction of the alkyl radical with O₂ in 1 atm SF₆ a rate constant of (1.8±0.2)×10^-12 cm³ molecule^-1 s^-1 was found. k(HOC(CH₃)₂CH₂O₂^{{radica l dot}}+NO) and k(HOC(CH₃)₂CH₂O₂^{{radica l dot}}+NO₂) were determined to be (4.9±0.9)×10^-12 and (6.7±0.9)×10^-12 cm³ molecule ^-1 s^-1, respectively. In the FTIR experiments products were studied using chlorine-initiated oxidation in TBA/N₂/Cl₂ and TBA/N₂/O₂/Cl₂ mixtures.

Original language	English
Journal	Chemical Physics Letters
Volume	226
Issue number	1-2
Pages (from-to)	165-170
Number of pages	6
ISSN	0009-2614
DOIs	https://doi.org/10.1016/0009-2614(94)00691-1
Publication status	Published - 12 Aug 1994

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10.1016/0009-2614(94)00691-1

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@article{687407d1ba5e4b718e2ff2620b9a1950,

title = "UV absorption spectra, kinetics and mechanism for alkyl and alkyl peroxy radicals originating from t-butyl alcohol",

abstract = "Alkyl and alkyl peroxy radicals from t-butyl alcohol (TBA), HOC(CH3)2CH2{radical dot} and HOC(CH3)2CH2O2{radical dot} have been studied in the gas phase at 298 K. Two techniques were used: pulse radiolysis UV absorption to measure the spectra and kinetics, and long path-length Fourier transform infrared spectroscopy (FTIR) to identify and quantify the reaction products. Absorption cross sections were quantified over the wavelength range 220-320 nm. At 240 nm, σHOC(CH3)2CH2=(2.4 ±0.3)×10-18 and σHOC(CH3)2CH2O2 =(3.4±0.5)×10-18 cm2 molecule-1 have been obtained. Observed rate constants for the self-reaction of HOC(CH3)2CH2{radical dot} and HOC(CH3)2CH2O2{radical dot} radicals were found to be (3.0±0.5)×10-11 and (7.8±1.5)×10-12 cm3 molecule-1 s-1, respectively. For the reaction of the alkyl radical with O2 in 1 atm SF6 a rate constant of (1.8±0.2)×10-12 cm3 molecule-1 s-1 was found. k(HOC(CH3)2CH2O2{radica l dot}+NO) and k(HOC(CH3)2CH2O2{radica l dot}+NO2) were determined to be (4.9±0.9)×10-12 and (6.7±0.9)×10-12 cm3 molecule -1 s-1, respectively. In the FTIR experiments products were studied using chlorine-initiated oxidation in TBA/N2/Cl2 and TBA/N2/O2/Cl2 mixtures.",

author = "Sarka Langer and Evert Ljungstr{\"o}m and Jens Sehested and Nielsen, {Ole J.}",

year = "1994",

month = aug,

day = "12",

doi = "10.1016/0009-2614(94)00691-1",

language = "English",

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journal = "Chemical Physics Letters",

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TY - JOUR

T1 - UV absorption spectra, kinetics and mechanism for alkyl and alkyl peroxy radicals originating from t-butyl alcohol

AU - Langer, Sarka

AU - Ljungström, Evert

AU - Sehested, Jens

AU - Nielsen, Ole J.

PY - 1994/8/12

Y1 - 1994/8/12

N2 - Alkyl and alkyl peroxy radicals from t-butyl alcohol (TBA), HOC(CH3)2CH2{radical dot} and HOC(CH3)2CH2O2{radical dot} have been studied in the gas phase at 298 K. Two techniques were used: pulse radiolysis UV absorption to measure the spectra and kinetics, and long path-length Fourier transform infrared spectroscopy (FTIR) to identify and quantify the reaction products. Absorption cross sections were quantified over the wavelength range 220-320 nm. At 240 nm, σHOC(CH3)2CH2=(2.4 ±0.3)×10-18 and σHOC(CH3)2CH2O2 =(3.4±0.5)×10-18 cm2 molecule-1 have been obtained. Observed rate constants for the self-reaction of HOC(CH3)2CH2{radical dot} and HOC(CH3)2CH2O2{radical dot} radicals were found to be (3.0±0.5)×10-11 and (7.8±1.5)×10-12 cm3 molecule-1 s-1, respectively. For the reaction of the alkyl radical with O2 in 1 atm SF6 a rate constant of (1.8±0.2)×10-12 cm3 molecule-1 s-1 was found. k(HOC(CH3)2CH2O2{radica l dot}+NO) and k(HOC(CH3)2CH2O2{radica l dot}+NO2) were determined to be (4.9±0.9)×10-12 and (6.7±0.9)×10-12 cm3 molecule -1 s-1, respectively. In the FTIR experiments products were studied using chlorine-initiated oxidation in TBA/N2/Cl2 and TBA/N2/O2/Cl2 mixtures.

AB - Alkyl and alkyl peroxy radicals from t-butyl alcohol (TBA), HOC(CH3)2CH2{radical dot} and HOC(CH3)2CH2O2{radical dot} have been studied in the gas phase at 298 K. Two techniques were used: pulse radiolysis UV absorption to measure the spectra and kinetics, and long path-length Fourier transform infrared spectroscopy (FTIR) to identify and quantify the reaction products. Absorption cross sections were quantified over the wavelength range 220-320 nm. At 240 nm, σHOC(CH3)2CH2=(2.4 ±0.3)×10-18 and σHOC(CH3)2CH2O2 =(3.4±0.5)×10-18 cm2 molecule-1 have been obtained. Observed rate constants for the self-reaction of HOC(CH3)2CH2{radical dot} and HOC(CH3)2CH2O2{radical dot} radicals were found to be (3.0±0.5)×10-11 and (7.8±1.5)×10-12 cm3 molecule-1 s-1, respectively. For the reaction of the alkyl radical with O2 in 1 atm SF6 a rate constant of (1.8±0.2)×10-12 cm3 molecule-1 s-1 was found. k(HOC(CH3)2CH2O2{radica l dot}+NO) and k(HOC(CH3)2CH2O2{radica l dot}+NO2) were determined to be (4.9±0.9)×10-12 and (6.7±0.9)×10-12 cm3 molecule -1 s-1, respectively. In the FTIR experiments products were studied using chlorine-initiated oxidation in TBA/N2/Cl2 and TBA/N2/O2/Cl2 mixtures.

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U2 - 10.1016/0009-2614(94)00691-1

DO - 10.1016/0009-2614(94)00691-1

M3 - Journal article

AN - SCOPUS:0013616776

SN - 0009-2614

VL - 226

SP - 165

EP - 170

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 1-2

ER -

UV absorption spectra, kinetics and mechanism for alkyl and alkyl peroxy radicals originating from t-butyl alcohol

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