Theory of the kinetic isotopic effect in reactions of proton transfer

1972 ◽  
Vol 21 (5) ◽  
pp. 987-993
Author(s):  
�. D. German ◽  
Yu. I. Kharkats
Keyword(s):  
Proton Transfer ◽  
Isotopic Effect ◽  
Kinetic Isotopic Effect

Kinetic Isotopic Effect Studies of Iron–Nitrogen–Carbon Electrocatalysts for Oxygen Reduction Reaction

2019 ◽  
Vol 123 (18) ◽  
pp. 11476-11483 ◽  
Author(s):  
Yechuan Chen ◽  
Tristan Asset ◽  
Rose Lee ◽  
Kateryna Artyushkova ◽  
Plamen Atanassov
Keyword(s):  
Oxygen Reduction Reaction ◽  
Oxygen Reduction ◽  
Reduction Reaction ◽  
Isotopic Effect ◽  
Kinetic Isotopic Effect

Reaction of 1,3-diphenyltriazene with phenyl isocyanate. Solvent effect, activation parameters and kinetic isotopic effect

1981 ◽  
Vol 46 (6) ◽  
pp. 1376-1382
Author(s):  
Erhard Lejdar ◽  
Oldřich Pytela ◽  
Miroslav Večeřa ◽  
Pavel Vetešník
Keyword(s):  
Hydrogen Atom ◽  
Solvent Effect ◽  
Temperature Dependence ◽  
Activation Parameters ◽  
Phenyl Isocyanate ◽  
Isotopic Effect ◽  
Imino Group ◽  
Reaction Velocity ◽  
Kinetic Isotopic Effect ◽  
Previous Communication

Effect of 14 solvents has been studied on the reaction of phenyl isocyanate with 1,3-diphenyltriazene. For ten of these solvents temperature dependence of the reaction velocity has been determined and the respective activation parameters calculated. Hydrogen atom of the triazene imino group has been replaced by deuterium, and the deuterium kinetic isotopic effect has been studied in seven solvents. The results confirm the mechanism suggested in a previous communication.

Cyclization of O-benzoylbenzamidoxime derivatives in water-alcohol media

1985 ◽  
Vol 50 (12) ◽  
pp. 2722-2729 ◽  
Author(s):  
František Grambal ◽  
Jan Lasovský
Keyword(s):  
Reaction Mechanism ◽  
Electron Acceptor ◽  
Activation Parameters ◽  
Isotopic Effect ◽  
Hammett Equation ◽  
Probability Level ◽  
Kinetic Isotopic Effect ◽  
Cyclization Rate ◽  
Two Parameter ◽  
Water Alcohol

O-Benzoylated benzamidoximes give 1,2,4-oxadiazoles (yields above 90%) in water-alcoholic media of pH = 2.45 to 6.20. The cyclization rate has been studied with 28 derivatives containing different substituents. The reaction is accelerated by electron-donor substituents at 4-position of benzamidoxime and by electron-acceptor substituents at 4'-position of benzoyl. The dependence of the rate constants vs σ values of the substituents fulfils the two-parameter Hammett equation at a 99% probability level. The activation parameters have been determined, and effects of polarity of medium, kinetic isotopic effect, and the reaction mechanism are discussed.

Fischer–Tropsch Synthesis: Deuterium Kinetic Isotopic Effect for a 2.5 % Ru/NaY Catalyst

2013 ◽  
Vol 57 (6-9) ◽  
pp. 508-517 ◽  
Author(s):  
Jia Yang ◽  
Wilson D. Shafer ◽  
Venkat Ramana Rao Pendyala ◽  
Gary Jacobs ◽  
Wenping Ma ◽  
...  
Keyword(s):  
Isotopic Effect ◽  
Tropsch Synthesis ◽  
Fischer Tropsch ◽  
Fischer Tropsch Synthesis ◽  
Kinetic Isotopic Effect

Kinetics of acid and nucleophile catalysis of the diazotization of 1-naphthylamine

1986 ◽  
Vol 64 (1) ◽  
pp. 133-137 ◽  
Author(s):  
Julio Casado ◽  
Albino Castro ◽  
Emilia Iglesias ◽  
M. Elena Peña ◽  
José Vázquez Tato
Keyword(s):  
Proton Transfer ◽  
Isotopic Effect ◽  
Formation Equilibria ◽  
High Concentrations ◽  
Kinetics Of ◽  
Rate Controlling Step

The diazotization of 1-naphthylamine has been studied at acidities ranging from 10−2 to 1.5 M. At low acidities nitrosation takes place via the unprotonated form of the amine, and the rate-controlling step is either the interaction with the nitrosating agent or, if high concentrations of a nucleophile are present, the loss of a proton from the protonated nitrosamine (the nucleophiles studied were Cl−, Br−, SCN−, and thiourea). At high acidities the protonated and free amines also react, the former of these reactions involving proton transfer to the solvent. In each case the proposed mechanism was supported by studying the reaction in D2O, which also allowed the isotopic effect of the solvent on the formation equilibria of the various nitrosating agents to be obtained.

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