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Reactions of Three Lactones with Cl, OD, and O3 : Atmospheric Impact and Trends in Furan Reactivity

Ausmeel, S. LU ; Andersen, C.; Nielsen, O. J.; Østerstrøm, Freja F.; Johnson, M. S. and Nilsson, E. J.K. LU (2017) In Journal of Physical Chemistry A 121(21). p.4123-4131
Abstract

Lactones, cyclic esters of hydroxycarboxylic acids, are interesting biofuel candidates as they can be made from cellulosic biomass and have favorable physical and chemical properties for distribution and use. The reactions of γ-valerolactone (GVL), γ-crotonolactone (2(5H)-F), and α-methyl-γ-crotonolactone (3M-2(5H)-F) with Cl, OD, and O3 were investigated in a static chamber at 700 Torr and 298 ± 2 K. The relative rate method was used to determine kGVL+Cl = (4.56 ± 0.51) × 10-11, kGVL+OD = (2.94 ± 0.41) × 10-11, k2(5H)-F+Cl = (2.94 ± 0.41) × 10-11, k2(5H)-F+OD = (4.06 ± 0.073) × 10-12, k3M-2(5H)-F+Cl = (16.1 ± 1.8) ×... (More)

Lactones, cyclic esters of hydroxycarboxylic acids, are interesting biofuel candidates as they can be made from cellulosic biomass and have favorable physical and chemical properties for distribution and use. The reactions of γ-valerolactone (GVL), γ-crotonolactone (2(5H)-F), and α-methyl-γ-crotonolactone (3M-2(5H)-F) with Cl, OD, and O3 were investigated in a static chamber at 700 Torr and 298 ± 2 K. The relative rate method was used to determine kGVL+Cl = (4.56 ± 0.51) × 10-11, kGVL+OD = (2.94 ± 0.41) × 10-11, k2(5H)-F+Cl = (2.94 ± 0.41) × 10-11, k2(5H)-F+OD = (4.06 ± 0.073) × 10-12, k3M-2(5H)-F+Cl = (16.1 ± 1.8) × 10-11, and k3M-2(5H)-F+OD = (12.6 ± 0.52) × 10-12, all rate coefficients in units of cm3 molecule-1 s-1. An absolute rate method was used to determine k2(5H)-F+O3 = (6.73 ± 0.18) × 10-20 and k3M-2(5H)-F+O3 = (5.42 ± 1.23) × 10-19 in units of cm3 molecule-1 s-1. Products were identified for reactions of the lactones with Cl. In the presence of O2 the products are formic acid (HCOOH), formyl chloride (CHClO), and phosgene (CCl2O), and also maleic anhydride (C2H2(CO)2O) for 2(5H)-F. In addition both reactions produced a number of unidentified products that likely belong to molecules with the ring-structure intact. A review of literature data for reactions of other furans show that the reactivity of the lactones are generally lower compared to that of corresponding compounds without the carbonyl group.

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organization
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type
Contribution to journal
publication status
published
subject
in
Journal of Physical Chemistry A
volume
121
issue
21
pages
9 pages
publisher
The American Chemical Society
external identifiers
  • scopus:85020854584
  • wos:000402775000008
ISSN
1089-5639
DOI
10.1021/acs.jpca.7b02325
language
English
LU publication?
yes
id
69dc7196-0ad6-439c-b744-83b3b4a60f79
date added to LUP
2017-07-04 12:15:04
date last changed
2018-01-07 12:10:32
@article{69dc7196-0ad6-439c-b744-83b3b4a60f79,
  abstract     = {<p>Lactones, cyclic esters of hydroxycarboxylic acids, are interesting biofuel candidates as they can be made from cellulosic biomass and have favorable physical and chemical properties for distribution and use. The reactions of γ-valerolactone (GVL), γ-crotonolactone (2(5H)-F), and α-methyl-γ-crotonolactone (3M-2(5H)-F) with Cl, OD, and O<sub>3</sub> were investigated in a static chamber at 700 Torr and 298 ± 2 K. The relative rate method was used to determine k<sub>GVL+Cl</sub> = (4.56 ± 0.51) × 10<sup>-11</sup>, k<sub>GVL+OD</sub> = (2.94 ± 0.41) × 10<sup>-11</sup>, k<sub>2(5H)-F+Cl</sub> = (2.94 ± 0.41) × 10<sup>-11</sup>, k<sub>2(5H)-F+OD</sub> = (4.06 ± 0.073) × 10<sup>-12</sup>, k<sub>3M-2(5H)-F+Cl</sub> = (16.1 ± 1.8) × 10<sup>-11</sup>, and k<sub>3M-2(5H)-F+OD</sub> = (12.6 ± 0.52) × 10<sup>-12</sup>, all rate coefficients in units of cm<sup>3</sup> molecule<sup>-1</sup> s<sup>-1</sup>. An absolute rate method was used to determine k<sub>2(5H)-F+O3</sub> = (6.73 ± 0.18) × 10<sup>-20</sup> and k<sub>3M-2(5H)-F+O3</sub> = (5.42 ± 1.23) × 10<sup>-19</sup> in units of cm<sup>3</sup> molecule<sup>-1</sup> s<sup>-1</sup>. Products were identified for reactions of the lactones with Cl. In the presence of O<sub>2</sub> the products are formic acid (HCOOH), formyl chloride (CHClO), and phosgene (CCl<sub>2</sub>O), and also maleic anhydride (C<sub>2</sub>H<sub>2</sub>(CO)<sub>2</sub>O) for 2(5H)-F. In addition both reactions produced a number of unidentified products that likely belong to molecules with the ring-structure intact. A review of literature data for reactions of other furans show that the reactivity of the lactones are generally lower compared to that of corresponding compounds without the carbonyl group.</p>},
  author       = {Ausmeel, S. and Andersen, C. and Nielsen, O. J. and Østerstrøm, Freja F. and Johnson, M. S. and Nilsson, E. J.K.},
  issn         = {1089-5639},
  language     = {eng},
  month        = {06},
  number       = {21},
  pages        = {4123--4131},
  publisher    = {The American Chemical Society},
  series       = {Journal of Physical Chemistry A},
  title        = {Reactions of Three Lactones with Cl, OD, and O<sub>3</sub> : Atmospheric Impact and Trends in Furan Reactivity},
  url          = {http://dx.doi.org/10.1021/acs.jpca.7b02325},
  volume       = {121},
  year         = {2017},
}