Kinetics and Mechanism of Thermal Decomposition of 1-R-Substituted bis(1,1-Dinitromethyl-3-Nitro- 1,2,4-Triazole-5-yl)

Thermal decomposition kinetics of 1-substituted bis(1,1-dinitromethyl-3-Nitro-1,2,4-triazole- 5-yl) in solution of 1,3-dinitrobenzene is studied with manometric method under isothermal conditions. The limiting stage of thermal decomposition is homolytic break of C-NO2 bond in gem-dinitromethyl group; activation parameters of this stage are calculated. The reactivity of investigated compounds is analyzed. Correlation dependences between logarithm of rate constant, activation energy and steric constant of substituent R are obtained

Kinetics of halogen substituted aniline transformation in anaerobic estuarine sediment

The kinetics of halogen substituted anilines were examined in estuarine sediment collected from Tsurumi river, Japan. Aniline was substituted with F, Cl, Br and I groups at meta or para positions on the aromatic ring. The transformation of all the compounds followed a first-order reaction kinetics with rate constants for the disappearance ranging between 0.002 to 0.006 day−1 or half lives between 108 and 669 days. Results indicated that para substituted anilines transformed two to four times faster compared to meta substituted ones. The rate of transformation followed the order: I > Br > Cl > F. A quantitative structure-activity relationship was evaluated relating the first-order rate constant in sediment with several readily available molecular descriptors: carbon-halogen bond strength, Hammett sigma constants, Taft steric constant, and Lipophilic constant. In addition octanol/water partition coefficients and solubility were included in the correlation. The relationship obtained was only significant between the rate constant and lipophilic constant.