Mechanism of the Gaseous Hydrolysis reaction of SO2: Small Water Cluster-Catalyzed Versus Participation of NH3
作者单位:Institute of Theoretical ChemistryState Key Laboratory of Theoretical and Computational ChemistryJilin University Department of Chemistry and BiochemistryCalifornia State University
会议名称:《中国化学会第十二届全国量子化学会议》
会议日期:2014年
学科分类:081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学]
摘 要:The effects of ammonia and water molecules on the SO2 hydrolysis were investigated *** structures of the reactant clusters with and without ammonia and subsequent hydrolysis pathways were determined at the CCSD(T)/aug-cc-p VDZ//MP2/aug-cc-PVDZ level of *** results show that for the water-catalyzed hydrolysis of SO2(SO2+n H2O→H2SO3···(H2O)n-1,n=1-5),the decrease trend in energy barrier becomes little as the number of water molecules is increased,still with an energy barrier of 9.5 kcal/mol for the reaction containing five water ***,ammonia is found to have an enhancing catalytic effect for SO2hydrolysis in small water clusters(SO2+n H2O+NH3,n=1-3),substantially lowering the energy barrier from n=1 to 3,and the ammonia-assisted hydrolysis of SO2 involving three water molecules to form hydrated ammonium bisulfate is a barrierless *** rate constants analysis of NH3-catalyzed hydrolysis of SO2 combined with the concentration of NH3 in the atmosphere condition demonstrate that the NH3-catalyzed gas-phase SO2 hydrolysis is feasible and could be of great importance for the sink of *** the importance of SO2 and NH3 in atmospheric aerosols,our results may also give a new insight in understanding the atmospheric nucleation and sulfur-containing aerosol formation.