CiHiOCOCHaCOOH70% HNOi CaHiOCOC(NOi)iH n»n 1.4321 11 98 CiHiOCOCH(CHi)COOH 70% HNOi CaHiOCOC(NOa)aCHi 45(0.1); 7i»D 1.4327 17 98 CaHiOCOCH(CaHí)COOH 70% HNOi CaHiOCOC(NOa)aCaHi 50(0.1); n"D 1.4340 17 98 CiH60COCH(t¡-C.Hi)COOH 70% HNOi CaHsOCOC(NOa)aC,Hi 60(0.1); n»D 1.4393 8 Salts op Polynitro Compounds and Halogen Derivatives Nitronate salt Ci NaO,N=CH(NOi) KO,N=CH(NO,) AgO,N=CH(NO,) (0,N),C=N0, "C«HiN +=N C, Na+[C(NO,),CNJ-K+1C(N0,),CN]" Ag + [C

No abstract

The rates of thermal decomposition of tetranitromethane, bromotrinitromethane, chlorotrinitromethane, and 1,2-dichlorotetranitroethane were determined in a number of solvents. The decomposition of the methane series of compounds in CCh proceeds by a first-order reaction; their specific rate constants are best represented by k = 1016•6 exp((-38,400 ± 1400)/RT). The products of reaction from the thermal decomposition of tetranitromethane are best represented by the equation C(N02)4 = C02 + 0.25N2O + 2.25N02 + 1.25NO.Based on the kinetic data, the rate-determining step for the decomposition of the polynitromethanes is the rupture of the C-N bond. The decomposition of 1,2-dichlorotetranitroethane in solution proceeds at a rate 1.8 X 10s times faster than that of tetranitromethane at 85°. The decomposition proceeds by a first-order reaction with k = 1016•6 exp(-31 , /ß '), the increased rate of decomposition relative to tetranitromethane being due to a much smaller energy of activation.

The rates of decomposition of hexanitroethane were determined in a number of solvents and as the pure solid in the temperature range of 60 to 100°. The products of reaction from the thermal decomposition of the solid are best represented by the equation: (N02)3C-C(N02)s -* 3N02 + NO + N20 + 2C02. Decomposition of hexanitroethane (HNE) for the pure solid and in CC14 proceeds by a first-order reaction; the specific first-order rate constants are, for solid HNE, k = 1018•1 23456 exp( -38,900/RT) sec.-1, and for HNE in CC14, k = 1018•6 exp( -37,800/ñT) sec.-1. The rate of decomposition of hexanitroetha ne in n-heptane is 11.5 times faster, and in cyclohexane it is 23 times faster, than that of the pure solid at 85°. Based on the kinetic data and products of reaction, a mechanism for the decomposition process is proposed.

No abstract