Reactions of primary and secondary butoxy radicals in oxygen at atmospheric pressure

Heiss, Adolphe; Maleissye, J. Tardieu de; Viossat, V.; Sahetchian, Krikor; Pitt, I. G.

doi:10.1002/kin.550230706

Cited by 19 publications

(16 citation statements)

References 35 publications

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“…Substitution of the value 0.008 (®rst set of data) yields k 8 /k 7 2.9Â10 18 molecules/cm 3 and of 0.02 (second set of data) 8.1Â10 18 molecules/cm 3 . These rate constant ratios are comparable to the experimentally obtained ratios of 3.1Â10 18 [4] and 2.6Â10 18 molecules/cm 3 [5], but are signi®cantly larger than the 2.6Â10 16 molecules/cm 3 reported by Heiss et al [18] and 5±10 times larger than the thermochemically estimated ratio of 6Â10 17 . The thermochemical calculations, however, have an inherent uncertainty of a factor of 5 [15].…”

Section: Methodssupporting

confidence: 66%

Formation of Nitrogenous Compounds in the Photooxidation of n-Butane under Atmospheric Conditions

Evmorfopoulou

Glavas

1998

Monatshefte fuer Chemie

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The photooxidation of n-butane under atmospheric conditions in the presence of NO x resulted in the formation of the following nitrogenous products: peroxy acetyl nitrate 23, sec-butyl nitrate 16, n-butyl nitrate 1.3, ethyl nitrate 1.3, peroxy n-butyryl nitrate 1.3, and peroxy propionyl nitrate 0.5% of the initially added odd nitrogen. In addition, an electron capturing compound eluting at the retention time of sec-propyl nitrate was also observed accounting for 5% of initial NO x . Butan-2-one was the major product of conversion of n-butane with a yield of 37%. From product ratios it is evident that the formation of sec-butyl nitrate is favored over that of n-butyl nitrate by a factor of 2.1. The rate of reaction of sec-butoxy radicals with oxygen is equal to their decomposition rate.

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Section: Methodssupporting

confidence: 66%

Formation of Nitrogenous Compounds in the Photooxidation of n-Butane under Atmospheric Conditions

Evmorfopoulou

Glavas

1998

Monatshefte fuer Chemie

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“… Both of these reactions have been studied simultaneously by Batt 98, Atkinson 107, Orlando et al 110, and Rauk et al 124. In addition, Heiss et al 128 used a static reactor to determine the rate constant for formation of acetaldehyde and an ethyl radical in the temperature range 363–503 K, at atmospheric pressure. The rate constant expression was normalized against the reference reaction sec ‐butoxy + O 2 = 2‐butanone + HȮ 2 .…”

Section: Alkoxy Radical Decompositionmentioning

confidence: 99%

Screen for genes differentially expressed during regeneration of the zebrafish caudal fin

Padhi¹,

Joly²,

Tellis

et al. 2004

Developmental Dynamics

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The zebrafish caudal fin constitutes an important model for studying the molecular basis of tissue regeneration. The cascade of genes induced after amputation or injury, leading to restoration of the lost fin structures, include those responsible for wound healing, blastema formation, tissue outgrowth, and patterning. We carried out a systematic study to identify genes that are up-regulated during "initiation" (1 day) and "outgrowth and differentiation" (4 days) of fin regeneration by using two complementary methods, suppression subtraction hybridization (SSH) and differential display reverse transcriptase polymerase chain reaction (DDRT-PCR). We obtained 298 distinct genes/sequences from SSH libraries and 24 distinct genes/sequences by DDRT-PCR. We determined the expression of 54 of these genes using in situ hybridization. In parallel, gene expression analyses were done in zebrafish embryos and early larvae. The information gathered from the present study provides resources for further investigations into the molecular mechanisms of fin development and regeneration.

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“…[4][5][6][7] Extrapolation of k dis /k O2 values determined at higher temperatures to room temperature led the authors to conclude that the reaction with O 2 is the only fate of 2-butoxyl radicals under tropospheric conditions. 8 Alternatively, the rate constant ratio may be discussed in terms of the individual rate constants k dis and k O2 . For k O2 , recent experimental values 6,7 and a semi-empirical estimate 1,9 agree within a factor of 2.…”

Section: Introductionmentioning

confidence: 99%

Relative-rate study of thermal decomposition of the 2-butoxyl radical in the temperature range 280–313 KElectronic supplementary information (ESI) available: See http://www.rsc.org/suppdata/cp/b1/b111474c/

Libuda

Shestakov

Theloke

et al. 2002

Phys. Chem. Chem. Phys.

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The competition between thermal decomposition (k dis ) and reaction with O 2 (k O2 ) has been studied for the 2butoxyl radical in a newly built 210 L photoreactor constructed of quartz. 2-Butoxyl radicals were generated by continuous 254 nm photolysis of 2-butoxyl iodide in the presence of O 2 and NO, using N 2 as a buffer gas. Reaction educts and products were analysed by long-path (29 m) IR absorption using an FTIR spectrometer. The ratio k dis /k O2 was derived from the product ratios of acetaldehyde and butanone, corrected for small amounts of side products. At 280, 298, and 313 K and a total pressure of 1 bar (M ¼ O 2 + N 2 ), k dis /k O2 was determined at O 2 partial pressures between 100 and 1000 mbar. At all temperatures, there was a systematic increase of () with the partial pressure of O 2 which possibly is the result of an additional O 2 independent source of acetaldehyde (%8% of the 2-butoxyl radicals reacting by either of the two competing pathways at 298 K, 1 bar). Pressure-dependence studies between 100 and 1000 mbar support the hypothesis that the additional acetaldehyde originates from the formation of 6-10% chemically activated 2-butoxyl radicals in the temperature range 280-313 K. Correction of (k dis /k O2 ) eff for the O 2 independent yield of acetaldehyde results in k dis /k O2 ¼ (6.8 AE 1.4) Â 10 17 , (2.3 AE 0.5) Â 10 18 , and (5.5 AE 1.1) Â 10 18 molecule cm À3 at 279.8, 298.2, and 313.5 K, respectively, leading to the Arrhenius expression k dis /k O2 ¼ (2.0 AE 0.5) Â 10 26 exp(À45.4 kJ mol À1 /RT) molecule cm À3 at a total pressure of 1 bar. This temperature dependence of k dis /k O2 implies that, depending on temperature, either thermal decomposition or reaction with O 2 is the major loss process of 2-butoxyl radicals under the conditions of the lower troposphere. Using literature values for k O2 , k dis ¼ 3.9 Â 10 12 exp(À47.1 kJ mol À1 /RT) s À1 is derived for a total pressure of 1 bar (M ¼ N 2 + O 2 ), which compares very favourably with a recent theoretical estimate (ab initio + RRKM) by R. Zellner, Phys. Chem. Chem. Phys., 2000, 2, 1907).y Electronic supplementary information (ESI) available: See

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Reactions of primary and secondary butoxy radicals in oxygen at atmospheric pressure

Cited by 19 publications

References 35 publications

Formation of Nitrogenous Compounds in the Photooxidation of n-Butane under Atmospheric Conditions

Formation of Nitrogenous Compounds in the Photooxidation of n-Butane under Atmospheric Conditions

Screen for genes differentially expressed during regeneration of the zebrafish caudal fin

Relative-rate study of thermal decomposition of the 2-butoxyl radical in the temperature range 280–313 KElectronic supplementary information (ESI) available: See http://www.rsc.org/suppdata/cp/b1/b111474c/

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