Tropospheric degradation of a series of C6, C7 and C8 biogenic unsaturated alcohols initiated by Cl atoms: Rate coefficients at 298 K and 1 atm

RODRIGO G. GIBILISCO; TERUEL MARIANO ANDRES; PETER WIESEN; IAN BARNES; IUSTINIAN BEJAN

ATMOSPHERIC ENVIRONMENT

PERGAMON-ELSEVIER SCIENCE LTD

Lugar: Amsterdam; Año: 2014 vol. 94 p. 564 - 572

1352-2310

Relative rate coefficients for the gas-phase reactions of Cl atoms with a series of unsaturated biogenic alcohols at (298 ± 3) K and 1 atm have been measured by the relative technique in an environmental chamber with in situ FTIR detection of reactants. The rate coefficients obtained using 1-butene and isobutene as reference compounds were (in units of 10-10 cm3 molecule-1 s-1) as follows: k1(Cl + (E)-CH2(OH)CH=CH(CH2)2CH3) = (3.490.82), k2(Cl + (E)-CH2(OH)CH2CH=CHCH2CH3) = (3.420.79), k3(Cl + (Z)-CH2(OH)CH2CH=CHCH2CH3) = (2.940.72), k4(Cl + (Z)-CH2(OH)CH2CH=CHCH2CH2CH3) = (3.800.86) and k5(Cl + (Z)-CH2(OH)CH2CH=CHCH2CH2CH2CH3) = (4.130.68). This work constitutes the first kinetic study of the reactions cited above. The rate coefficients are compared with those for other unsaturated alcohols and a correlation between the reactivity of unsaturated alcohols toward Cl atoms and the energy of the HOMO of the unsaturated alcohols is presented. The atmospheric lifetimes of the unsaturated alcohols toward the major tropospheric oxidants have been estimated and possible atmospheric implications assessed.