Deconstructing experimental rate constant measurements: Obtaining intrinsic reaction parameters, kinetic isotope effects, and tunneling coefficients from kinetic data for OH+methane, ethane and cyclohexane

2005 ◽  
Vol 176 (1-3) ◽  
pp. 238-249 ◽  
Author(s):  
Amy M. Sage ◽  
Neil M. Donahue
Keyword(s):  
Rate Constant ◽  
Kinetic Data ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Reaction Parameters ◽  
Experimental Rate ◽  
Kinetic Isotope

Radiation-induced Oxidation of 2-Propanol by Nitrous Oxide in Alkaline Aqueous Solution

1972 ◽  
Vol 50 (11) ◽  
pp. 1751-1756 ◽  
Author(s):  
C. E. Burchill ◽  
G. P. Wollner
Keyword(s):  
Aqueous Solution ◽  
Rate Constant ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Chain Mechanism ◽  
Radical Chain ◽  
Kinetic Isotope ◽  
Alkaline Aqueous Solution ◽  
Radiation Induced ◽  
Solution Proceeds

The radiation-induced oxidation of 2-propanol to acetone by N2O in alkaline aqueous solution proceeds via a free radical chain mechanism independent of pH above 12.5. The results are explained by abstraction of H from 2-propanol by O− at both the α and β positions (85% α attack). Chain propagation is by reaction of the α radical anion, (CH3)2ĊO−, with N2O with a rate constant of (3.8 ± 0.4) × 104 M−1 s−1 and by reaction of the β radical, ĊH2(CH3)CHOH, with 2-propanol to give the α radical with a rate constant of 430 ± 30 M−1 s−1.The conclusions are supported by the demonstration of kinetic isotope effects for selectively deuterated alcohols.

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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