title: Acid-catalyzed heterogeneous reaction of 3-methyl-2-buten-1-ol with hydrogen peroxide.
abstract: Acid-catalyzed heterogeneous oxidation with hydrogen peroxide (H2O2) has been suggested to be a potential pathway for secondary organic aerosol (SOA) formation from isoprene and its oxidation products. However, knowledge of the chemical mechanism and kinetics for this process is still incomplete. 3-Methyl-2-buten-1-ol (MBO321), an aliphatic alcohol structurally similar to isoprene, is emitted by pine forests and widely used in the manufacturing industries. Herein the uptake of MBO321 into H2SO4-H2O2 mixed solution was investigated using a flow-tube reactor coupled to a mass spectrometer. The reactive uptake coefficients (γ) were acquired for the first time and were found to increase rapidly with increasing acid concentration. Corresponding aqueous-phase reactions were performed to further study the mechanism of this acid-catalyzed reaction. MBO321 could convert to 2-methyl-3-buten-2-ol (MBO232) and yield isoprene in acidic media. Organic hydroperoxides (ROOHs) were found to be generated through the acid-catalyzed route, which could undergo a rearrangement reaction and result in the formation of acetone and acetaldehyde. Organosulfates, which have been proposed to be SOA tracer compounds in the atmosphere, were also produced during the oxidation process. These results suggest that the heterogeneous acid-catalyzed reaction of MBO321 with H2O2 may contribute to SOA mass under certain atmospheric conditions.
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. Electronic address: liuqifan@iccas.ac.cn.
authors.forename: Qifan
authors.initials: Q
authors.lastname: Liu
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. Electronic address: wangwg@iccas.ac.cn.
authors.forename: Weigang
authors.initials: W
authors.lastname: Wang
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. Electronic address: gemaofa@iccas.ac.cn.
authors.forename: Maofa
authors.initials: M
authors.lastname: Ge
mesh_terms: D000143:Acids / Q000737:chemistry*; D000393:Air Pollutants / Q000737:chemistry; D002384:Catalysis; D008401:Gas Chromatography-Mass Spectrometry; D045782:Hemiterpenes; D006861:Hydrogen Peroxide / Q000737:chemistry*; D015394:Molecular Structure; D000439:Pentanols / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization
chemical_list: D000143:Acids; D000393:Air Pollutants; D045782:Hemiterpenes; D000439:Pentanols; C009034:prenol; D006861:Hydrogen Peroxide
keywords: Gas–liquid interaction; Organic hydroperoxide; Organosulfate; Secondary organic aerosol; Uptake coefficients