High-temperature rate constant determination for the reaction of OH with iso-butanol.

This work presents the first direct experimental study of the rate constant for the reaction of OH with iso-butanol (2-methyl-1-propanol) at temperatures from 907 to 1147 K at near-atmospheric pressures. OH time-histories were measured behind reflected shock waves using a narrow-linewidth laser absorption method during reactions of dilute mixtures of tert-butylhydroperoxide (as a fast source of OH) with iso-butanol in excess. The title reaction's overall rate constant (OH + iso-butanol →(k(overall)) all products) minus the rate constant for the ß-radical-producing channel (OH + iso-butanol →(k(ß)) 1-hydroxy-2-methyl-prop-2-yl radical + H(2)O) was determined from the pseudo-first-order rate of OH decay. A two-parameter Arrhenius fit of the experimentally determined rate constant in the current temperature range yields the expression (k(overall) - k(ß)) = 1.84 × 10(-10) exp(-2350/T[K]) cm(3) molecule(-1) s(-1). A recommendation for the overall rate constant, including k(ß), is made, and comparisons of the results to rate constant recommendations from the literature are discussed.