scholarly journals Laboratory Studies of Carbon Kinetic Isotope Effects on the Production Mechanism of Particulate Phenolic Compounds Formed by Toluene Photooxidation: A Tool To Constrain Reaction Pathways

2014 ◽  
Vol 119 (1) ◽  
pp. 5-13 ◽  
Author(s):  
Satoshi Irei ◽  
Jochen Rudolph ◽  
Lin Huang ◽  
Janeen Auld ◽  
Fabrice Collin ◽  
...  
Keyword(s):  
Phenolic Compounds ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Reaction Pathways ◽  
Production Mechanism ◽  
Laboratory Studies ◽  
Kinetic Isotope ◽  
Toluene Photooxidation

scholarly journals Dependence between the photochemical age of light aromatic hydrocarbons and the carbon isotope ratios of atmospheric nitrophenols

2019 ◽  
Vol 19 (8) ◽  
pp. 5495-5509
Author(s):  
Marina Saccon ◽  
Anna Kornilova ◽  
Lin Huang ◽  
Jochen Rudolph
Keyword(s):  
Carbon Isotope ◽  
Organic Compounds ◽  
Mechanistic Model ◽  
Isotope Effects ◽  
Isotope Ratios ◽  
Kinetic Isotope Effects ◽  
Laboratory Studies ◽  
Carbon Isotope Ratios ◽  
Kinetic Isotope ◽  
Volatile Organic

Abstract. Concepts were developed to establish relationships between the stable carbon isotope ratios of nitrophenols in the atmosphere and the photochemical processing of their precursors, light aromatic volatile organic compounds. These concepts were based on the assumption that nitrophenols are formed dominantly from the photo-oxidation of aromatic volatile organic compounds (VOCs). A mass balance model as well as various scenarios based on the proposed mechanism of nitrophenol formation were formulated and applied to derive the time-integrated exposure of the precursors to processing by OH radicals (∫[OH]dt) from ambient observations made between 2009 and 2012 in Toronto, Canada. The mechanistic model included the possibility of isotopic fractionation during intermediate steps, rather than only during the initial reaction step. This model takes kinetic isotope effects for the reaction of the precursor VOC with the hydroxyl radical and their respective rate constants into account, as well as carbon isotope ratio source signatures. While many of these values are known, there are some, such as the kinetic isotope effects of reactions of first- and second-generation products, which are unknown. These values were predicted in this study based on basic principles and published laboratory measurements of kinetic carbon isotope effects and were applied to the mechanistic model. Due to the uncertainty of the estimates based on general principles, three scenarios were used with different values for isotope effects that were not known from laboratory studies. Comparison of the dependence between nitrophenol carbon isotope ratios and ∫[OH]dt with published results of laboratory studies and ambient observations was used to narrow the range of plausible scenarios for the mechanistic model. The results also suggests that mass-balance-based models do not adequately describe the dependence between nitrophenol carbon isotope ratios and ∫[OH]dt.

scholarly journals Dependence between the Photochemical Age of Light Aromatic Hydrocarbons and the Carbon Isotope Ratios of Atmospheric Nitrophenols

2018 ◽  
Author(s):  
Marina Saccon ◽  
Anna Kornilova ◽  
Lin Huang ◽  
Jochen Rudolph
Keyword(s):  
Mass Balance ◽  
Carbon Isotope ◽  
Mechanistic Model ◽  
Isotope Effects ◽  
Isotope Ratios ◽  
Kinetic Isotope Effects ◽  
Oh Radicals ◽  
Laboratory Studies ◽  
Carbon Isotope Ratios ◽  
Kinetic Isotope

Abstract. Concepts were developed to establish relationships between the stable carbon isotope ratios of nitrophenols in the atmosphere and photochemical processing of their precursors, light aromatic volatile organic compounds. The concepts are based on the assumption that nitrophenols are formed dominantly from the photo-oxidation of aromatic VOC. A mass balance model as well as various scenarios based on the proposed mechanism of nitrophenol formation were formulated and applied to derive the time integrated exposure of the precursors to processing by OH-radicals (∫[OH]dt) from ambient observations taken between 2009 and 2012 in Toronto, Canada. The mechanistic model included the possibility of isotopic fractionation during intermediate steps, rather than during the initial reaction step alone. This model included knowledge of kinetic isotope effects of the precursor VOC with the hydroxyl radical and their respective rate constants, as well as isotope ratio source signatures. While many of these values are known, there were some, such as the kinetic isotope effects of reactions of the intermediate compounds, which were unknown. These values were predicted based on basic principles and published laboratory measurements of normal kinetic carbon isotope effects and were applied to the mechanistic models. Due to uncertainty of the estimates based on general principles three scenarios were used with different values for isotope effect that were not known from laboratory studies. Comparison of the dependence between nitrophenol carbon isotope ratios and ∫[OH]dt with published results of laboratory studies and ambient observations was used to narrow the range of plausible scenarios of the mechanistic model and to eliminate the mass balance based model as useful formulation of a the dependence between nitrophenol carbon isotope ratios and ∫[OH]dt.

Theoretical Simulations of Heavy-Atom Kinetic Isotope Effects in Aliphatic Claisen Rearrangement

2020 ◽  
Vol 124 (51) ◽  
pp. 10678-10686
Author(s):  
Yuqing Xu ◽  
Kin-Yiu Wong ◽  
Meishan Wang ◽  
Desheng Liu ◽  
Wenkai Zhao ◽  
...  
Keyword(s):  
Claisen Rearrangement ◽  
Isotope Effects ◽  
Heavy Atom ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Theoretical Simulations
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