title: Theoretical studies on gas-phase reactions of sulfuric acid catalyzed hydrolysis of formaldehyde and formaldehyde with sulfuric acid and H2SO4···H2O complex.
abstract: The gas-phase reactions of sulfuric acid catalyzed hydrolysis of formaldehyde and formaldehyde with sulfuric acid and H2SO4···H2O complex are investigated employing the high-level quantum chemical calculations with M06-2X and CCSD(T) theoretical methods and the conventional transition state theory (CTST) with Eckart tunneling correction. The calculated results show that the energy barrier of hydrolysis of formaldehyde in gas phase is lowered to 6.09 kcal/mol from 38.04 kcal/mol, when the sulfuric acid is acted as a catalyst at the CCSD(T)/aug-cc-pv(T+d)z//M06-2X/6-311++G(3df,3pd) level of theory. Furthermore, the rate constant of the sulfuric acid catalyzed hydrolysis of formaldehyde combined with the concentrations of the species in the atmosphere demonstrates that the gas-phase hydrolysis of formaldehyde of sulfuric acid catalyst is feasible and could be of great importance for the sink of formaldehyde, which is in previously forbidden hydrolysis reaction. However, it is shown that the gas-phase reactions of formaldehyde with sulfuric acid and H2SO4···H2O complex lead to the formation of H2C(OH)OSO3H, which is of minor importance in the atmosphere.
authors.affiliation: Key Laboratory of Atmospheric Composition and Optical Radiation, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences , Hefei 230031, China.
authors.forename: Bo
authors.initials: B
authors.lastname: Long
authors.forename: Xing-Feng
authors.initials: XF
authors.lastname: Tan
authors.forename: Chun-Ran
authors.initials: CR
authors.lastname: Chang
authors.forename: Wei-Xiong
authors.initials: WX
authors.lastname: Zhao
authors.forename: Zheng-Wen
authors.initials: ZW
authors.lastname: Long
authors.forename: Da-Sen
authors.initials: DS
authors.lastname: Ren
authors.forename: Wei-Jun
authors.initials: WJ
authors.lastname: Zhang