Hydrolysis of HNSO₂: A potential route for atmospheric production of H₂SO₄ and NH₃

Abstract

The hydrolysis of sulfonylamine (HNSO 2 ) results in the formation of sulfuric acid along with ammonia, and is of significant interest due to their negative impact on environment and life on Earth. The formation of H 2 SO 4 through the reaction of HNSO 2 with (H 2 O) [2][3][4] has been studied using high level electronic structure calculations. This hydrolysis reaction is a step-wise process, in the first step a H-atom from H 2 O is transferred to the N-atom of HNSO 2 which results in the formation of NH 2 , and in the next step, H 2 SO 4 , NH 3 and water molecule(s) are formed. The results show that the energy barrier associated with the formation of intermediates and product complexes is reduced by 7 to 10 kcal/mol when the number of water molecules is increased from 2 to 4. The rate constant was calculated using canonical variational transition state theory with small curvature tunneling correction over the temperature range of 200 to 1000 K. At 298 K, the calculated rate constant for the formation of intermediate in the first step is 2.24 × 10 −16 , 1.03 × 10 −12 , and 2.10 × 10 −11 cm 3 mol −1 s −1 , respectively, for the reaction with water dimer, trimer and tetramer. The calculated enthalpy and free energy show that the reaction corresponding to the formation of H 2 SO 4 is highly exothermic and exoergic in nature. K E Y W O R D Skinetics, sulfonylamine, sulfuric acid, water dimer, water tetramer, water trimer, aereosol, atmospheric reaction

Mechanism, Kinetics, and Ecotoxicity Assessment of ·OH-Initiated Oxidation Reactions of Sulfoxaflor

“…The M06-2X method is known to be a more reliable method to calculate the energetics, thermochemistry, and kinetics of atmospheric chemical reactions. Previous studies from many research groups − and our group − showed that the results obtained from the M06-2X method are comparable with the available experimental results.…”

Possible atmospheric source of NH2SO3H: the hydrolysis of HNSO2 in the presence of neutral, basic, and acidic catalysts

“…Our results shown in Fig. 3 were found to be very similar to the work reported by Manonmani et al 67 mechanistically and energetically. All the relative energy values matched qualitatively (see Table S1, ESI †).…”

“…The hydrolysis reaction of HNSO 2 without and with neutral catalysts of H 2 O, (H 2 O) 2 , and (H 2 O) 3 has been extensively investigated from a theoretical point of view. 67 Here, these routes were reinvestigated at the CCSD(T)-F12/cc-pVDZ-F12//M06-2X/6-311+G(2df,2pd) level to compare their catalytic effect against the basic and acidic catalysts of NH 3 , CH 3 NH 2 , HCOOH, H 2 SO 4 , H 2 SO 4 Á Á ÁH 2 O, and (H 2 SO 4 ) 2 . Our results shown in Fig.…”

Reaction of Criegee Intermediates with SO2─A Possible Route for Sulfurous Acid Formation in the Atmosphere

“…CBS-QB3 is a high-level composite method in which the geometry optimization and frequency calculation were done at the B3LYP/6-31G­(d,p) level of theory and were followed by a series of single-point energy calculations at the CCSD­(T), MP4SDQ, and MP2 levels of theory with complete basis set (CBS) extrapolation to obtain final energies. Earlier studies reported that CBS-QB3 and G3B3 methods provided better thermochemical results. − The T1 diagnostic value calculated by the CCSD­(T) method for most of the reactive species involved in studied reactions were within the range of 0.01–0.02, showing that the multireference character of the wave function of the reactive species was not significant. For a few cases, the T1 diagnostic value was around 0.03.…”