Rate Coefficients for the Gas-Phase Reactions of Hydroxyl Radicals with a Series of Methoxylated Aromatic Compounds

2015 ◽  
Vol 119 (24) ◽  
pp. 6179-6187 ◽  
Author(s):  
Amélie Lauraguais ◽  
Iustinian Bejan ◽  
Ian Barnes ◽  
Peter Wiesen ◽  
Cécile Coeur
Keyword(s):  
Gas Phase ◽  
Hydroxyl Radicals ◽  
Aromatic Compounds ◽  
Rate Coefficients ◽  
Gas Phase Reactions ◽  
Methoxylated Aromatic

Rate Coefficients for the Gas-Phase Reaction of Chlorine Atoms with a Series of Methoxylated Aromatic Compounds

2014 ◽  
Vol 118 (10) ◽  
pp. 1777-1784 ◽  
Author(s):  
Amélie Lauraguais ◽  
Iustinian Bejan ◽  
Ian Barnes ◽  
Peter Wiesen ◽  
Cécile Coeur-Tourneur ◽  
...  
Keyword(s):  
Gas Phase ◽  
Aromatic Compounds ◽  
Rate Coefficients ◽  
Phase Reaction ◽  
Chlorine Atoms ◽  
Gas Phase Reaction ◽  
Methoxylated Aromatic

scholarly journals Atmospheric fate of two relevant unsaturated ketoethers: kinetics, products and mechanisms for the reaction of hydroxyl radicals with (<i>E</i>)-4-methoxy-3-buten-2-one and 1-(<i>E</i>)-1-methoxy-2-methyl-1-penten-3-one

2020 ◽  
Author(s):  
Rodrigo Gastón Gibilisco ◽  
Ian Barnes ◽  
Iustinian Gabriel Bejan ◽  
Peter Wiesen
Keyword(s):  
Gas Phase ◽  
Hydroxyl Radicals ◽  
Relative Rate ◽  
Reaction Chamber ◽  
Oxidation Products ◽  
Rate Coefficients ◽  
Gas Phase Reactions ◽  
Ozone Formation Potential ◽  
Nitrogen Containing Compounds ◽  
First Time

Abstract. The kinetics of the gas-phase reactions of hydroxyl radicals with two unsaturated methoxy-ketones at (298 ± 3) K and 1 atm of synthetic air have been studied for the first time using the relative rate technique in an environmental reaction chamber by in situ FTIR spectrometry. The rate coefficients obtained using propene and isobutene as reference compounds were (in units of 10–10 cm3 molecule−1 s−1) as follows: k1(OH + (E)-4-methoxy-3-buten-2-one) = (1.42 ± 0.12), and k2(OH + 1-(E)-1-methoxy-2-methyl-1-penten-3-one) = (3.34 ± 0.43). In addition, quantification of the main oxidation products has been performed and degradation mechanisms for these reactions were developed. The formation products and kinetic data confirm that the reactions proceed mainly via an addition of the OH radical to the double bond. Gas phase products, identified and quantified from these reactions, are carbonyls like methyl formate, methyl glyoxal and 2,3-pentanedione and long-lived nitrogen containing compounds such as PAN and PPN. Atmospheric lifetimes and the ozone formation potential have been estimated and possible atmospheric implications assessed.

Direct Kinetic Study of Reactions of Hydroxyl Radicals with Alkyl Formates

2004 ◽  
Vol 218 (4) ◽  
pp. 479-492 ◽  
Author(s):  
István Szilágyi ◽  
Sándor Dóbé ◽  
Tibor Bérces ◽  
Ferenc Márta ◽  
Béla Viskolcz
Keyword(s):  
Gas Phase ◽  
Hydroxyl Radicals ◽  
Room Temperature ◽  
Methyl Formate ◽  
Ethyl Formate ◽  
Rate Coefficients ◽  
Resonance Fluorescence ◽  
Gas Phase Reactions ◽  
Temperature Rate ◽  
Fast Flow

AbstractRate coefficients were determined for the gas phase reactions of hydroxyl radicals with a series of alkyl formats. Experiments were carried out using the isothermal fast flow method coupled with resonance fluorescence detection. The obtained room temperature rate coefficients are (in 10−13cm3 molecule−1s−1 units): 1.83 ± 0.33 (methyl formate), 9.65 ± 0.43 (ethyl formate), 18.73 ± 0.83 (isopropyl formate), 6.77 ± 0.38 (tert-butyl formate) and 1.62 ± 0.13 (methyl chloroformate). These results are compared with the literature data. In addition estimations are made for the partial reactivities of the formate group and for the hydrocarbon groups adjacent to HC(O)O. Moreover, it has been found that the partial reactivity of the HC(O)O group (in reactions of OH with formates) is two orders of magnitude smaller than that of the HC(O) group (in reactions of OH with aldehydes). This has been explained using the results of ab initio calculations at the G3MP2//MP2(full)/6-31G(d) level of theory.

scholarly journals Experimental and computational kinetics investigations for the reactions of Cl atoms with series of unsaturated ketones in gas phase

2017 ◽  
Author(s):  
Siripina Vijayakumar ◽  
Avinash Kumar ◽  
Balla Rajakuma
Keyword(s):  
Gas Phase ◽  
State Theory ◽  
Rate Coefficients ◽  
Gas Phase Reactions ◽  
Temperature Dependent ◽  
Unsaturated Ketones ◽  
Temperature Range ◽  
Computational Calculations ◽  
Temperature Rate ◽  
Cl Atoms

Abstract. Temperature dependent rate coefficients for the gas phase reactions of Cl atoms with 4-hexen-3-one and 5-hexen-2-one were measured over the temperature range of 298–363 K relative to 1-pentene, 1,3-butadiene and isoprene. Gas Chromatography (GC) was used to measure the concentrations of the organics. The derived temperature dependent Arrhenius expressions are k4-hexen-3-one+Cl (298–363 K) = (2.82 ± 1.76)×10−12exp [(1556 ± 438)/T] cm3 molecule−1 s−1 and k5-hexen-2-one+Cl (298–363 K) = (4.6 ± 2.4)×10−11exp[(646 ± 171)/T] cm3 molecule−1 s−1. The corresponding room temperature rate coefficients are (5.54 ± 0.41)×10−10 cm3 molecule−1 s−1 and (4.00 ± 0.37)×10−10 cm3 molecule−1 s−1 for the reactions of Cl atoms with 4-hexen-3-one and 5-hexen-2-one respectively. To understand the mechanism of Cl atom reactions with unsaturated ketones, computational calculations were performed for the reactions of Cl atoms with 4-hexen-3-one, 5-hexen-2-one and 3-penten-2-one over the temperature range of 275–400 K using Canonical Variational Transition state theory (CVT) with Small Curvature Tunneling (SCT) in combination with CCSD(T)/6-31+G(d, p)//MP2/6-311++G(d, p) level of theory. Atmospheric implications, reaction mechanism and feasibility of the title reactions are discussed in this manuscript.

The gas phase reactions of hydroxyl radicals with a series of aliphatic ethers over the temperature range 240-440 K

1988 ◽  
Vol 20 (1) ◽  
pp. 41-49 ◽  
Author(s):  
Timothy J. Wallington ◽  
Renzhang Liu ◽  
Philippe Dagaut ◽  
Michael J. Kurylo
Keyword(s):  
Gas Phase ◽  
Hydroxyl Radicals ◽  
Gas Phase Reactions ◽  
Temperature Range ◽  
Aliphatic Ethers
Sign in / Sign up

Export Citation Format

Share Document