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 β-radical-producing channel (OH + iso-butanol → k β 1-hydroxy-2-methyl-prop-2-yl radical + H2O) 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 β) = 1.84 × 10–10 exp­(−2350/T[K]) cm3 molecule–1 s–1. A recommendation for the overall rate constant, including k β, is made, and comparisons of the results to rate constant recommendations from the literature are discussed.