OH-initiated degradation of a series of hexenols in the troposphere. Rate coefficients at 298K and 1 atm

RODRIGO G. GIBILISCO, ANA N. SANTIAGO AND MARIANO A. TERUEL

PERGAMON-ELSEVIER SCIENCE LTD

Lugar: Amsterdam; Año: 2013 vol. 77 p. 358 - 358

he kinetics of the reactions of OH radicals with three C6 unsaturated alcohols at 298 K and atmospheric pressure were investigated using solid phase microextraction (SPME) with GC-FID detection of the organics. Rate coefficients (in cm3 molecule-1 s-1) of k1(OH + (E)-CH2OHCH=CH(CH2)2CH3) = (1.0  0.3) x 10-10, k2(OH + (E)-CH2OHCH2CH=CHCH2CH3) = (1.2  0.2) x 10-10 and k3(OH + (Z)-CH2OHCH2CH=CHCH2CH3) = (1.4  0.3) x 10-10 were obtained by the relative rate method using methyl methacrylate and (E)-2-buten-1-ol as references. Rate coefficients were compared with previous determinations and reactivity trends were developed and rationalized in terms of the effect and position of substituents in the unsaturated alcohol. A correlation between the reactivity of unsaturated alcohols towards OH radicals and the energy of the HOMO of the unsaturated alcohol is presented. Additionally, product identification under atmospheric conditions was performed for the first time fo