Reactivity of hydrohaloethers with OH radicals and chlorine atoms: Correlation with molecular properties.

PABLO R. DALMASSO, RAÚL A. TACCONE, JORGE D. NIETO, PABLO M. COMETTO; CARLOS J. COBOS; SILVIA I. LANE

PERGAMON-ELSEVIER SCIENCE LTD

Lugar: Amsterdam; Año: 2014 vol. 91 p. 104 - 104

he reactivity of halogenated ethers, especially hydrochloroethers, with hydroxyl radicals and chlorine atoms was studied by correlating the room-temperature rate coefficients with both the C-H bond dissociation energies and the vertical ionization potentials of the parent molecules. These molecular properties were estimated at the composite G3B3 level of theory. The results suggest that Cl-substituted ethyl-methyl-ethers and ethyl-ethyl-ethers at the beta-position tend to raise the activating effect of the ether linkage -O- and to enhance the possibility of the abstraction of H atoms bonded to alpha-carbon. Derived relationships between the rate coefficients (in cm3 molecule-1 s-1) and ionization potentials (in eV): log kOH = - (1.248 ± 0.065) IP + (1.06 ± 0.73) and log kCl = - (1.46 ± 0.12) IP + (4.5 ± 1.3) allows, in average, to estimate rate coefficients within a factor of 2 to 3. The atmospheric implications of halogenated and hydrogenated ethers are briefly discussed on the basis