1 research outputs found
Theoretical Studies on Gas-Phase Reactions of Sulfuric Acid Catalyzed Hydrolysis of Formaldehyde and Formaldehyde with Sulfuric Acid and H<sub>2</sub>SO<sub>4</sub>···H<sub>2</sub>O Complex
No full textThe gas-phase reactions of sulfuric
acid catalyzed hydrolysis of
formaldehyde and formaldehyde with sulfuric acid and H<sub>2</sub>SO<sub>4</sub>···H<sub>2</sub>O 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 H<sub>2</sub>SO<sub>4</sub>···H<sub>2</sub>O complex lead to the formation
of H<sub>2</sub>C(OH)OSO<sub>3</sub>H, which is of minor importance
in the atmosphere
