Atmospheric degradation of 3-methylfuran: kinetic and products study

Abstract

A study of the kinetics and products obtained from the reactions of 3-methylfuran with the main atmospheric oxidants has been performed. The rate coefficients for the gas-phase reaction of 3-methylfuran with OH and NO<sub>3</sub> radicals have been determined at room temperature and atmospheric pressure (air and N<sub>2</sub> as bath gases), using a relative method with different experimental techniques. The rate coefficients obtained for these reactions were (in units cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup>) <i>k</i><sub>OH</sub> = (1.13 ± 0.22) × 10<sup>−10</sup> and <i>k</i><sub>NO<sub>3</sub></sub> = (1.26 ± 0.18) × 10<sup>−11</sup>. Products from the reaction of 3-methylfuran with OH, NO<sub>3</sub> and Cl atoms in the absence and in the presence of NO have also been determined. The main reaction products obtained were chlorinated methylfuranones and hydroxy-methylfuranones in the reaction of 3-methylfuran with Cl atoms, 2-methylbutenedial, 3-methyl-2,5-furanodione and hydroxy-methylfuranones in the reaction of 3-methylfuran with OH and NO<sub>3</sub> radicals and also nitrated compounds in the reaction with NO<sub>3</sub> radicals. The results indicate that, in all cases, the main reaction path is the addition to the double bond of the aromatic ring followed by ring opening in the case of OH and NO<sub>3</sub> radicals. The formation of 3-furaldehyde and hydroxy-methylfuranones (in the reactions of 3-methylfuran with Cl atoms and NO<sub>3</sub> radicals) confirmed the H-atom abstraction from the methyl group and from the aromatic ring, respectively. This study represents the first product determination for Cl atoms and NO<sub>3</sub> radicals in reactions with 3-methylfuran. The reaction mechanisms and atmospheric implications of the reactions under consideration are also discussed

Measurements of the Kinetics of the Reaction of OH Radicals with 3‐Methylfuran at Low Pressure

“…Their study was conducted using three methods. The first two methods employed a Teflon‐coated chamber coupled with either GC‐MS or GC‐FID, whereas the third method utilized a Pyrex glass reaction chamber coupled with FTIR . The rate constant measured here at 298 K is in excellent agreement within the reported uncertainty of each of these previous measurements.…”

“…Tapia et al. measured a rate constant of (11 ± 2) × 10 −11 cm 3 molecule −1 s −1 at 298 K and 760 Torr using relative rate techniques with trans‐2‐butene, 5‐ methylfurfural, and propene as the reference compounds and OH radicals generated by photolysis of methyl nitrite. Their study was conducted using three methods.…”

“…The reaction is thought to proceed by OH‐addition to the C‐2 or C‐5 position (Fig. ) resulting in the production of 2‐methyl‐butenedial, 3‐methyl‐2,5‐furanodione, and hydroxyl‐methylfuranones . The rate constant for the OH + 3‐methylfuran reaction at room temperature and atmospheric pressure has been reported to be (9.26 ± 0.24) × 10 −11 cm 3 molecule −1 s −1 by Atkinson et al.…”

“…In the atmosphere, 3‐methylfuran can react with NO 3 , Cl , and O 3 but a reaction with the OH radical is expected to dominate during the daytime . The reaction is thought to proceed by OH‐addition to the C‐2 or C‐5 position (Fig.…”

Absolute photoionization cross sections of furanic fuels: 2‐ethylfuran, 2‐acetylfuran and furfural

“…With novel production methods able to derive these compounds from biomass, these potential biofuels have a large enough source to be used on an industrial scale. While combustion and decomposition studies of furanic biofuels have been performed, many furanic derivatives have not been studied extensively.…”