Relative rate constant measurements for the gas-phase reactions of hydroxyl radicals with 4-methyl-2-pentanone,trans-4-octene, andtrans-2-heptene

1992 ◽  
Vol 24 (8) ◽  
pp. 703-710 ◽  
Author(s):  
Lawrence N. O'rji ◽  
Daniel A. Stone
Keyword(s):  
Gas Phase ◽  
Hydroxyl Radicals ◽  
Rate Constant ◽  
Relative Rate ◽  
Gas Phase Reactions ◽  
Relative Rate Constant

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.

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

THE SECONDARY HYDROGEN ISOTOPE EFFECTS IN THE PYROLYSIS OF ETHYL-d5 ACETATE AND ETHYL ACETATE-d3

1960 ◽  
Vol 38 (9) ◽  
pp. 1407-1411 ◽  
Author(s):  
Arthur T. Blades ◽  
P. W. Gilderson
Keyword(s):  
Ethyl Acetate ◽  
Rate Constant ◽  
Hydrogen Isotope ◽  
Experimental Error ◽  
Relative Rate ◽  
Isotope Effects ◽  
Relative Rate Constant ◽  
Temperature Ranges ◽  
Relative Rate Constants ◽  
Constant Expression

Rate constant expressions have been obtained for ethyl acetate and ethyl-d5 acetate in the temperature ranges 500–603 °C and 501–614 °C.[Formula: see text]By measuring the relative rate of production of C2H4 and C2D4 from identical mixtures of the two esters at the temperatures 387 and 490 °C, it has been possible to determine the temperature coefficient of the relative rate constant more accurately. This, coupled with the relative rate constants at 500 °C derived from the above equations, gives the relative rate constant expression.[Formula: see text]These data are compared with the intramolecular isotope effect in the decomposition of ethyl-1,1,2,2-d4 acetate, and the differences attributed to secondary isotope effects.The rate of decomposition of ethyl acetate-d3 was found to be identical within experimental error with that of the normal acetate.

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