Theoretical study of the hydrolysis of sulfur tetrafluoride

Theoretical Study of the Role of a Catalytic Water Molecule in the Hydrolysis of Thionyl Tetrafluoride (SOF4)

“…Therefore, the O–H and S–O bond lengths are shortened, while the S–F and H–F bonds are lengthened in aqueous solution. A similar phenomenon has also been reported for the hydrolysis reaction of SF 4 …”

“…A similar phenomenon has also been reported for the hydrolysis reaction of SF 4 . 29 Overall, the inclusion of implicit solvent (PCM) effects did not significantly change the hydrolysis mechanism of SOF 4 . Therefore, the rate-determining step in the aqueous phase is the same as that determined in the gas phase with reaction heats for product formation for this two-step cleavage HF in an aqueous solution being larger than those in the gas phase.…”

“…Geometries of the reactants, complexes, transition states, intermediates, and products were optimized using Zhao and Truhlar’s hybrid functional M062X using a nonlocal exchange (2X) method with an aug-cc-pV­(T+d)­Z basis set. − An appropriate basis set was chosen for the treatment of sulfur-containing reactions − based on the assumption that d-orbital hybridization is responsible for the origin of sulfur’s hypervalent behavior. ,,, Appropriate descriptors of electronic states were applied for the treatment of transition states and reactivity. Vibrational frequencies were calculated at the same level of theory [M062X/aug-cc-pV­(T+d)­Z] to identify stationary points, while Gibbs free energies were calculated using rigid rotor harmonic oscillator approximations at 298.15 K. Tables S1 and S2 show the harmonic vibrational frequencies for key stationary points and other high energy stationary points of the hydrolysis of SOF 4 in the gas phase at the M06-2X/Aug-cc-pV­(T+d)­Z level of theory, respectively.…”

Computational study of the atmospheric oxidation and global warming potential of thionyl fluoride

“…The formation of by‐products in SF 6 has been the subject of extensive experimental and theoretical investigations in various kinds of discharges, that is, power arc, spark, corona or partial discharge [4–12]. Persistent among the observations is the finding that the major by‐products include SOF 2 , SOF 4 , SO 2 F 2 , S 2 F 10 , and so forth, where SOF 2 is always the most abundant stable decomposition product under electrical discharges, formed from hydrolysis of the primary product sulfur tetrafluoride (SF 4 ) [13–16].…”

Molecular pathways of SOCl2 hydrolysis within mono- and diaqua complexes. A quantum chemical study

“…It was used in explanations of the high hydrolysis and hydration rates of many species including SO 3 [7][8][9][10], SOBr 2 , SOF 2 [11], SF 4 [12], ClONO 2 [13], CO 2 [14,15] [22] and others. However, all such studies are usually based on the mid-level calculations of large clusters demonstrating the potential feasibility of the activation energy decrease with cluster size growth.…”