Deuterium Isotope Effects during RDX Combustion: Mechanistic burn rate-controlling step determination

1991 ◽  
Vol 16 (6) ◽  
pp. 279-286 ◽  
Author(s):  
Scott A. Shackelford ◽  
Stephen L. Rodgers ◽  
Robert E. Askins
Keyword(s):  
Isotope Effects ◽  
Deuterium Isotope Effects ◽  
Burn Rate ◽  
Rate Controlling Step

The inhibited autoxidation of styrene. Part VI. The relative efficiencies and the kinetics for inhibition by N-aryl anilines and N-alkyl anilines

1967 ◽  
Vol 45 (20) ◽  
pp. 2419-2425 ◽  
Author(s):  
I. T. Brownlie ◽  
K. U. Ingold
Keyword(s):  
Aromatic Amine ◽  
Rate Constants ◽  
Isotope Effects ◽  
Peroxy Radical ◽  
Hammett Equation ◽  
Kinetic Expression ◽  
Deuterium Isotope Effects ◽  
Rate Controlling Step

The kinetics and deuterium isotope effects for the N-aryl aniline and N-alkyl aniline inhibited autoxidation of styrene indicate that the rate-controlling step for inhibition involves abstraction of the amino hydrogen by a peroxy radical. The rate constants for this reaction have been correlated by means of the Hammett equation with the σ+ constants of the substituents for diphenylamines (ρ = −0.89) and N-methylanilines (ρ = −1.6). A numerical difference involving a factor of two between the simple kinetic expression applicable to most aromatic amine inhibitors and the expression applicable to most phenols and p-phenylenediamines is suggested. The important role played by the substrate in studies of inhibitor action is emphasized.

Deuterium Isotope Effects during HMX Combustion: Chemical kinetic burn rate control mechanism verified

1989 ◽  
Vol 14 (3) ◽  
pp. 93-102 ◽  
Author(s):  
S. A. Shackelford ◽  
B. B. Goshgarian ◽  
R. D. Chapman ◽  
R. E. Askins ◽  
D. A. Flanigan ◽  
...  
Keyword(s):  
Rate Control ◽  
Control Mechanism ◽  
Isotope Effects ◽  
Chemical Kinetic ◽  
Deuterium Isotope Effects ◽  
Burn Rate

Mechanism of hydration and isomerisation of 4-ethylidene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one. Kinetics, acid-base catalysis and solvent deuterium isotope effects

1979 ◽  
Vol 44 (1) ◽  
pp. 110-122 ◽  
Author(s):  
Jiří Velek ◽  
Bohumír Koutek ◽  
Milan Souček
Keyword(s):  
Aqueous Medium ◽  
Rate Equation ◽  
Kinetic Data ◽  
Isotope Effects ◽  
Base Catalysis ◽  
Quinone Methide ◽  
Reaction Products ◽  
Acid Base ◽  
Deuterium Isotope Effects ◽  
Hydroxybenzyl Alcohol

Competitive hydration and isomerisation of the quinone methide I at 25 °C in an aqueous medium in the region of pH 2.4-13.0 was studied spectrophotometrically. The only reaction products in the studied range of pH are 4-hydroxybenzyl alcohol (II) and 4-hydroxystyrene (III). The form of the overall rate equation corresponds to a general acid-base catalysis. The mechanism of both reactions for three markedly separated pH regions is discussed on the basis of kinetic data and solvent deuterium effect.

Hydrogen/Deuterium-Isotope Effects on NMR Chemical Shifts and Symmetry of Homoconjugated Hydrogen-Bonded Ions in Polar Solution

2000 ◽  
Vol 122 (51) ◽  
pp. 12878-12879 ◽  
Author(s):  
Parwin Schah-Mohammedi ◽  
Ilja G. Shenderovich ◽  
Carsten Detering ◽  
Hans-Heinrich Limbach ◽  
Peter M. Tolstoy ◽  
...  
Keyword(s):  
Chemical Shifts ◽  
Isotope Effects ◽  
Polar Solution ◽  
Nmr Chemical Shifts ◽  
Hydrogen Deuterium ◽  
Deuterium Isotope Effects ◽  
Hydrogen Bonded
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