Kinetics of Thermal Decomposition of o-Nitrophenyl Azide

A Computational Study on the Mechanism and Kinetics of the Pyrolysis of 2-Nitrophenyl Azide

“…b Dyall, measured in decalin solution (0.01 M). c Dyall et al, measured in decalin solution (0.2 M) at T =360.2 and 372.6 K. d Birkhimer et al., measured in di- n -butyl-phthalate solution (0.1 M) at T = 349.4, 354.9, and 364.0 K. e Fagley et al, measured in heptane solution (4.9 × 10 -5 M) at T = 344.9 K and in di- n -butylphthalate solution (0.12 M) at T = 357.6 K, respectively.…”

“…Many phenyl azides with unsaturated ortho -substituents can be pyrolyzed in order to yield cyclic products following the general scheme depicted in Figure . Experimental studies on the reaction rates of the pyrolysis of a large number of substituted phenyl azides show that the formation of a delocalized heterocyclic ring system can be regarded as the driving force for this reaction. − For the compounds under consideration, a clean first-order kinetic behavior has been reported. − ,− The reaction rates of pure liquid azides differ only slightly from the rates in solution. The latter are invariant with respect to the nature of the solvent used in the experimental measurements, suggesting little or no specific solvation effects between the solvent and the phenyl azides .…”

“…Experimental studies on the reaction rates of the pyrolysis of a large number of substituted phenyl azides show that the formation of a delocalized heterocyclic ring system can be regarded as the driving force for this reaction. − For the compounds under consideration, a clean first-order kinetic behavior has been reported. − ,− The reaction rates of pure liquid azides differ only slightly from the rates in solution. The latter are invariant with respect to the nature of the solvent used in the experimental measurements, suggesting little or no specific solvation effects between the solvent and the phenyl azides . In addition, the experimental results indicate that the reaction proceeds without any side reactions: the sum of the concentrations of the reactant and the products is reported to remain constant throughout the kinetic measurements. ,, The absence of side reactions as well as the fact that a negative value for the entropy of activation is found for almost all compounds measured experimentally 9,10 both indicate the presence of a cyclic transition state.…”

“…[6][7][8][9][10] For the compounds under consideration, a clean first-order kinetic behavior has been reported. [6][7][8][9][11][12][13] The reaction rates of pure liquid azides differ only slightly from the rates in solution. The latter are invariant with respect to the nature of the solvent used in the experimental measurements, suggesting little or no specific solvation effects between the solvent and the phenyl azides.…”

Kinetics of Reactions in Solution

“…Kinetic studies have also been made on the first order decomposition of o-nitrophenyl azide in several solvents and in the pure liquid (229), phenylazotriphenylmethane in several solvents (230), thiourea in aqueous solution (231) and nitramide in dioxane-water mixtures (232).…”