Kinetic Isotope Effects in the Radiation-Induced Decomposition of Crystalline Potassium Nitrate

1969 ◽  
Vol 91 (27) ◽  
pp. 7601-7606 ◽  
Author(s):  
Edwin N. Ladov ◽  
Everett R. Johnson
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Potassium Nitrate ◽  
Kinetic Isotope ◽  
Radiation Induced ◽  
Induced Decomposition

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.

Kinetic Isotope Effects in the Radiation-induced Oxidation of Alcohols by Hydrogen Peroxide in Aqueous Solution

1971 ◽  
Vol 49 (8) ◽  
pp. 1305-1309 ◽  
Author(s):  
C. E. Burchill ◽  
G. F. Thompson
Keyword(s):  
Hydrogen Peroxide ◽  
Kinetic Isotope Effect ◽  
Transfer Reaction ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Chain Oxidation ◽  
Oxidation Of Methanol ◽  
Kinetic Isotope ◽  
Oxidation Of Alcohols ◽  
Radiation Induced

By using selectively deuterated alcohols it is demonstrated that abstractions from both α and β positions of 2-propanol and ethanol contribute to the overall mechanism for the radiation-induced chain oxidation of these alcohols by hydrogen peroxide. Kinetic isotope effects are measured for abstraction of H by OH from 2-propanol and ethanol at both α and β positions and for the H atom transfer reaction from the alcohol to the β radical. The chain oxidation of methanol shows no primary kinetic isotope effect on substitution of CD3OH.

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

Direct dynamics calculations of reaction rate and kinetic isotope effects in enzyme catalysed reactions

2002 ◽  
Vol 122 ◽  
pp. 223-242 ◽  
Author(s):  
Gary Tresadern ◽  
Sara Nunez ◽  
Paul F. Faulder ◽  
Hong Wang ◽  
Ian H. Hillier ◽  
...  
Keyword(s):  
Reaction Rate ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Direct Dynamics ◽  
Kinetic Isotope

Interpretation of Transient-State Kinetic Isotope Effects†

Biochemistry ◽  
1996 ◽  
Vol 35 (1) ◽  
pp. 83-88 ◽  
Author(s):  
Harvey F. Fisher ◽  
Swapan K. Saha
Keyword(s):  
Isotope Effects ◽  
Transient State ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
State Kinetic
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