Abstract: | Density functional theory was used to estimate the lifetime of fluorinated formates, which are primary products from the oxidation of hydrofluoroethers. First, the C? H bond dissociation enthalpies (BDEs) of 10 fluorinated formates, CnF2n + 1OC(O)H (n = 1–4) and CnHF2nOC(O)H (n = 1–3) have been calculated by using the density functional theory with (RO)B3LYP/6‐311G(d,p). Secondly, from these computed BDEs, the rate constants kOH of the hydrogen abstraction reaction between the fluorinated formates and OH radicals have been estimated using the formulation proposed by Heicklen (Int. J. Chem. Kinet. 13 , 651, 1981). We modified the formulation proposed by Heicklen in order to relate BDEs to kOH for formates based on the results of the ab initio studies using standard transition state theory with the G2(MP2) level. Consequently, the kOH of all the formates considered here are estimated to be around 1.5–4.7 × 10?14 cm3 molecule?1 s?1 at 298 K. Their lifetimes concerning with the decomposition by OH radicals (τOH) in atmosphere have been evaluated as 0.4–4.5 years from the estimated kOH. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 524–530, 2002 |