Journal Details

1. Experimental and Computational Investigations on the Tropospheric Photo-oxidation Reactions of 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol Initiated by OH radicals and Cl atoms.

A. Kumar, S. Gonu, S. Vijayakumar, C. B. Ramya & B. Rajakumar. J. Phys. Chem, 2021, 125(2), 523-535.

The gas-phase kinetics for the reactions of OH radicals and Cl atoms with 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol (HF2M2P) were measured at temperatures between 268 and 363 K using the relative rate experimental technique. Methane and acetonitrile were used as reference compounds to measure the rate coefficients of the title reactions. For the reactions of HF2M2P with OH radicals and Cl atoms, the rate coefficients were measured to be (7.07 ± 1.21) × 10–15 and (2.85 ± 0.54) × 10–14 cm3 molecule–1 s–1, respectively, at 298 K. The obtained Arrhenius expressions for the reactions of HF2M2P with OH radicals and Cl atoms are kHF2M2P + OHExp – (268 – 363 K) = (7.84 ± 0.75) × 10–14 exp [−(717 ± 59)/T] and kHF2M2P + ClExp – (268 – 363 K) = (3.21 ± 0.45) × 10–12 exp [−(1395 ± 83)/T] cm3 molecule–1 s–1. In addition to the experimental measurements, computational kinetic calculations were also performed for the title reactions at the M06-2X/MG3S//M06-2X/6-31 + G(d,p) level of theory using advanced methods such as the canonical variational transition-state theory coupled with small curvature tunneling corrections at temperatures between 200 and 400 K. Theoretical calculations reveal that the H-abstraction from the CH3 group is a more favorable reaction channel than that from the OH group. Thermochemistry, branching ratios, cumulative atmospheric lifetime, global warming potential, acidification potential, and photochemical ozone creation potential of HF2M2P were calculated in the present investigation.