物理化学学报2012，Vol.28Issue(7)：1608-1614,7.DOI:10.3866/PKU.WHXB201204241
柠檬烯和柠檬烯氧化物与硫酸的非均相反应动力学
Heterogeneous Uptake Kinetics of Limonene and Limonene Oxide by Sulfuric Acid Solutions
摘要
Abstract
The heterogeneous uptake of limonene and limonene oxide (also known as 1,8-cineole) by a range of different aqueous sulfuric acid (H2SO4) solutions (30％-80％ (w)) was investigated to develop an understanding of the reactivity of biogenic organic compounds in the atmosphere towards acidic aerosols.Experiments were performed using a rotating wetted-wall reactor coupled to a single photon ionization time-of-flight mass spectrometer.The heterogeneous uptake of the compounds into H2SO4 followed first-order kinetics and the corresponding steady-state uptake coefficients (y) were calculated for the first time.Limonene oxide was found to be more reactive than limonene towards H2SO4.Reactive uptake was observed for limonene oxide in acidic solution containing greater than 30％ (w).The steady-state uptake coefficients of limonene oxide in 30％-50％ (w) H2SO4 solutions at room temperature ranged from (7.100±0.023)×10-5 to (8.150+0.162)×10-3.Furthermore,the reactions of limonene oxide with sulfuric acid in bulk solution were investigated using gas chromatography-mass spectrometry (GC-MS) and electron spray ionization-mass spectroscopy (ESI-MS).Analysis of the products revealed the presence of monoterpenes,terpineols,terpin hydrates,and terpin hydrate diorganosulfate from the bulk solution reaction of limonene oxide with H2SO4.The formation of significantly more hydrophobic organic compounds with lower volatilities suggested that limonene oxide is a significant precursor in the formation of atmospheric secondary organic aerosols.Atransformation mechanism has been proposed based on the products.关键词
柠檬烯/柠檬烯氧化物/硫酸/非均相动力学/稳态摄取系数/有机硫酸酯Key words
Limonene/Limoneneoxide/Sulfuric acid/Heterogeneous kinetics/Steady-state uptake coefficient/Organosulfate分类
化学化工引用本文复制引用
王天鹤,刘泽,王炜罡,葛茂发..柠檬烯和柠檬烯氧化物与硫酸的非均相反应动力学[J].物理化学学报,2012,28(7):1608-1614,7.基金项目
The project was supported by the National Key Basic Research Program of China (973) (2011 CB403401 ) and National Natural Science Foundation of China (40925016, 21077109, 41005070).国家重点基础研究发展规划项目(973) (2011 CB403401)及国家自然科学基金(40925016,21077109,41005070)资助 （973）
