Rate and mechanism of the reactions of OH and Cl with 2‐methyl‐3‐buten‐2‐ol

An environmental chamber/Fourier transform infrared system was used to determine the rate coefficient k 1 for the gas‐phase reaction of OH with 2‐methyl‐3‐buten‐2‐ol (MBO, (CH 3 ) 2 C(OH)CH=CH 2 ), relative to the rate of its reaction with ethylene (k 2 ) and propylene (k 3 ). Experiments performed at 295±1 K, in 700 torr total pressure of air, gave k 1 = (6.9±1.0) × 10 −11 cm 3 molecule −1 s −1 . At 295±1 K, the reaction of OH with MBO yielded, on a per mole basis, (52±5)% acetone, (50±5)% glycolaldehyde, and (35±4)% formaldehyde. The production of acetone from the oxidation of MBO may be of significance globally. The kinetics and mechanism of the reaction of chlorine atoms with MBO (k 15 ) have also been studied at 700 torr total pressure of air and 295±1 K. The rate coefficient was determined using a relative rate technique, with ethane (k 16 ), ethylene (k 17 ), and cyclohexane (k 18 ) as reference compounds. The value of k 15 was found to be (3.3±0.4) × 10 −10 cm 3 molecule −1 s −1 at 295 K. The major carbon‐containing products obtained in the Cl‐atom oxidation of MBO were acetone (47±5)%, chloroacetaldehyde (53±5)%, HCOCl (<11%), and formaldehyde (6 ± 2)%.