THERMAL-DECOMPOSITION OF ENERGETIC MATERIALS 11 - CONDENSED PHASE STRUCTURAL CHARACTERISTICS AND HIGH-RATE THERMOLYSIS OF DINITROALIPHATIC AND TRINITROALIPHATIC CARBOXYLIC-ACIDS AND CARBONATES

IR spectra of 3,3,3-trinitrobutyric acid, 1, 3,3-dinitrovaleric acid, 2, bis(2,2,2-trinitroethyl)carbonate, 3, and bis(2, 2-dinitropropyl)carbonate, 4, were analyzed from 163K to the decomposition temperature. Below the decomposition temperature most of the structural alterations involve the COOH group. Once decomposition begins, the spectral changes also involve the C-NO//2 groups. The backbone of the gem-dinitroalkyl compounds degrades more readily than the gem-trinitro compounds. Concentration-time profiles of the gas products from high-rate thermolysis ( greater than 75K s** minus **1) show that NO//2 is the predominant initial decomposition product while CO//2 is initially important only from 2. NO is a major initial product of the gem-dinitro series but not the gem-trinitro series. Through the duration of observation, the concentration of the carbon oxidation products increases while left bracket NO//2 right bracket decreases, suggesting that NO//2 is the principal oxidizing agent. The decomposition-to-deflagration transition occurs in the gem-trinitro compounds but not the gem-dinitro compounds under these experimental conditions.