We have measured the thermal explosion times of nitromethane at 1, 10, and 50 kbar and between 160 and 380 C. At constant pressure, the explosion time decreases as the temperature increases. At constant temperature, the explosion time decreases as the pressure is increased. For a constant explosion time of 10 seconds, at 1 kbar the required temperature is 369 C, at 10 kbar it is 327 C, and at 50 kbar it is 225 C. The increase in decomposition rate with increasing temperature is explainable by Arrhenium-type kinetics. The reasons for the increase in decomposition rate with increasing pressure remain to be determined. We have also measured the thermal explosion times of some isomeric dinitropropanes at a constant pressure of 10 kbar in the temperature range 130 to 310 C. For a constant thermal explosion time of 20 seconds, the dinitropropanes that do not have a hydrogen atom on the same carbon as the dinitro group require a higher temperature than those that have such a hydrogen. Specifically, the temperatures corresponding to a 20 second explosion time at 10 kbar pressure at 2-2-dinitropropane 269 C; 1-1-1-fluorodinitropropane 242 C; 1-1-dinitropropane 172 C; 1-2-dinitropropane 162 C. (Author).

This unique book investigates the synthesis, kinetics, and thermal decomposition properties and processing of energy-producing materials used in propellants, explosives, pyrotechnic, and gas-generating compositions. Thermal Decomposition and Combustion of Explosives and Propellants provides several mechanisms and stages for the thermal decomposition and combustion reactions of most flammable compounds and their mixtures, such asaliphatic and aromatic nitrocompounds, nitramines, nitroesters, organic azides, furazanes, tetrazols, difluoroamines, polynitrous heterocycles, and onium salts. The authors examine the classic problem of the dependence of explosive activity on molecular structure, using applications to predict the stability, compatibility, and the stabilization of explosives and propellant components. They also offer experimental results examining factors such as subsurface decomposition, evaporation, and dispersion of materials, which can be used to control combustion of condensed systems. Providing several approaches to stability, safety, and controlled combustion of flammable substances, Thermal Decomposition and Combustion of Explosives and Propellants is a multi-dimensional resource for graduate students, researchers and professionals interested in chemical kinetics, the combustion and synthesis of high-energy materials, criminal forensics, and the field of explosives, powders, and solid rocket propellants.

Decomposition of nitromethane is reported over the range of 115- 180°C and 0.6-8.5 GPa. About 5 [mu]g of nitromethane is compressed with a diamond-anvil cell, heated to the point that reaction occurs, and held typically 10-20 minutes at the reaction temperature. The cell is cooled and the volatile contents of the cell are frozen as a thin layer in vacuo and an infrared absorption spectrum is recorded. The three volatile products observed are N2O, CO2, and water, with N2O production peaking at 1.5 GPa, 135°C, and 35% of NME; CO2 production peaking at 3.5 GPa, 135°C, and 65% of NME, and water yields at 20-50% of NME at the highest pressure measured, 8.5 GPa and 175°C. Water yields were difficult to quantify due to background contamination. Results indicate three different reactions for solid NME dependent primarily on the pressure of the reaction, and that fluid NME does not decompose at 0.6 GPa and 175°C, although the solid decomposes readily at 1.1 GPa and 120°C. The authors conclude that, while various decomposition mechanisms are possible, the initial step CH3NO2 → /center dot/CH3 + /center dot/NO2 is very unlikely. 14 refs., 5 figs.

Nitro Compounds provides information pertinent to the formation, mechanism, synthesis, and structure of nitro compounds. This book discusses the behavioral uniqueness of the nitro group in electric field. Organized into 50 chapters, this book begins with an overview of the amphoterism of HNO3 and its role in the reactions of HNO3 with organic substances. This text then examines the secondary nitroheptane obtained byvapor-phase nitration of n-heptane with nitrogen dioxide. Other chapters consider the explosion hazard of gaseous mixtures in exothermic reactions of oxidation and nitration. This book discusses as well the method used for the investigation of nitration of phenosulphonic acids. The final chapter deals with the relationship between the structure of nitrofuranoic compounds and the fungicidal, bactericidal, and herbicidal activity. This book is a valuable resource for chemists and organic chemists. Chemical researchers who are interested in the mechanism and synthesis of nitro compounds will also find this book useful.