Reactions of
hydroxyl (
OH) radicals with
1-butene (k(1)), trans-2-butene (k(2)), and cis-2-butene (k(3)) were studied behind reflected
shock waves over the temperature range 880-1341 K and at pressures near 2.2 atm.
OH radicals were produced by
shock-heating
tert-butyl hydroperoxide, (CH(3))(3)-CO-OH, and monitored by narrow-line width ring
dye laser absorption of the well-characterized R(1)(5) line of the
OH A-X (0, 0) band near 306.7 nm.
OH time histories were modeled using a comprehensive C(5) oxidation mechanism, and rate constants for the reaction of
OH with
butene isomers were extracted by matching modeled and measured
OH concentration time histories. We present the first high-temperature measurement of
OH + cis-2-butene and extend the temperature range of the only previous high-temperature study for both
1-butene and trans-2-butene. With the potential energy surface calculated using CCSD(T)/6-311++G(d,p)//QCISD/6-31G(d), the rate constants and branching fractions for the H-abstraction channels of the reaction of
OH with
1-butene were calculated in the temperature range 300-1500 K. Corrections for variational and tunneling effects as well as hindered-rotation treatments were included. The calculations are in good agreement with current and previous experimental data and with a recent theoretical study.