Kinetic study of the gas phase reactions of a series of alcohols with the NO3 radical.

The rate coefficients for the reaction of NO(3) radical with 2-butanol, 3-methyl-2-butanol, and 2,3-dimethyl-2-butanol were determined using relative rate technique in a 50 L glass pyrex photoreactor using in situ FT-IR spectroscopy at room temperature and a pressure of 350-670 Torr. The rate coefficient for the reaction of 2-methyl-2-butanol with NO(3) radical was also determined using, in this case, GC/MS. The rate coefficients calculated (in units of cm(3) molecule(-1) s(-1)) were (2.51 ± 0.42) × 10(-15), (3.06 ± 0.52) × 10(-15), (2.67 ± 0.3) × 10(-15), and (1.57 ± 0.16) × 10(-15), respectively. Results indicate that the reaction occurs by an initial H-abstraction of the alcohols by the NO(3) radical and that NO(3) is more reactive toward a H atom attached to a tertiary carbon than that attached to a secondary or primary carbon. Results are also discussed as related to their homologous structural alkanes and in comparison with the reactivity of other atmospheric oxidants. Atmospheric relevance of the considered reactions is evaluated, concluding that they are potential ozone generators, they have no significant influence on global warming, and the dominant atmospheric loss process for these alcohols is their daytime reaction with OH radicals.