OH-initiated degradation of methyl 2-chloroacetoacetate and ethyl 2-chloroacetoacetate: Kinetics, products and mechanisms at 298 K and atmospheric pressure

VIANNI G. STRACCIA C.; PEDRO L. LUGO; CYNTHIA B. RIVELA; MARIA B. BLANCO; PETER WIESEN; MARIANO A. TERUEL

CHEMOSPHERE

PERGAMON-ELSEVIER SCIENCE LTD

Lugar: Amsterdam; Año: 2021 vol. 274

0045-6535

ate coefficients for the gas-phase reactions of OH radicals with CH3C(O)CHClC(O)OCH3(k1) and CH3C(O)CHClC(O)OCH2CH3(k2) were measured using the relative technique with different reference compounds.The experiments were performed at (298±2) K and 750 Torr of nitrogen or synthetic air byin situFTIRspectroscopy and GC-FID chromatography. The following rate coefficients (in units of cm3molecule1s1)were obtained:k1FTIR¼(2.70±0.51)1011;k1GC-FID¼(2.30±0.71)1011andk2FTIR¼(3.37±0.62)1011;k2GC-FID¼(3.26±0.85)1011. This work reports thefirst kinetic study for thereactions of OH radicals with the mentioned chloroacetoacetates. Additionally, product studies are re-ported in similar conditions of the kinetic experiments. Acetic acid, acetaldehyde, formyl chloride, andmethyl 2-chloro-2-oxoacetate were positively identified and quantified as degradation products. Ac-cording to the identified products, atmospheric chemical mechanisms were proposed. The environ-mental implications of these reactions we