Theoretical prediction of condensed phase heat of formation of nitramines, nitrate esters, nitroaliphatics and related energetic compounds

Enthalpy of formation of CL-20

“…The experimentally determined enthalpy of formation ( 298 f H Δ ) of ε-CL-20 [4][5][6] is of the order of ~400 kJ/mol ( Table 1). The close estimate of the enthalpy of formation of solid CL-20 was obtained by the empirical approaches [8,9] and atom equivalent method [13][14][15] developed for the prediction of enthalpies of formation of energetic compounds. However, a substantially larger 298 f H Δ value of ~550 kJ/mol was suggested recently from quantum chemical calculations combined with isodesmic reactions.…”

Artificial Neural Network-Group Contribution Method for Predicting Standard Enthalpy of Formation in the Solid State: C–H, C–H–O, C–H–N, and C–H–N–O Compounds

“…This property gives information about the thermodynamic stability of any chemical compound and allows the calculation of enthalpies of reaction [2]. Also, it is used to estimate combustion properties and explosive and propellant properties [3,4] and to calculate other thermodynamic functions.…”

“…Therefore, having a reliable and accurate method for estimating f H • of compounds from their molecular structures is absolutely necessary and especially if the compound concerned is toxic, or has other hazardous properties. In the literature, several methods for estimating f H • with good accuracy have been proposed to fill the gaps between existing compounds and their experimental values of f H • [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17]. For the gas and liquid phases, it is now possible to calculate f H • values for some compounds with reasonable accuracy [5,18].…”

“…In the case of the solid state, the scenery is a little bit different, only a few estimation methods have been reported to predict the standard enthalpy of formation in the solid phase f H • solid of organic compounds from their molecular structures [4,7,8,10,12,19]. This is because of the effects of molecular packing and polymorphism in some solid compounds, and that the prediction of this property in the solid state needs a good knowledge of the most stable or most likely molecular structure.…”

“…More recently, Keshavarz [4,12,26] has proposed several simple correlations to estimate f H • solid for some classes of energetic compounds using the contribution of some simple polar groups and specific molecular fragments. The author has employed limited lists of energetic compounds in his works, viz., 192 C-H-N-O energetic compounds [12], 29 nitro-aromatic compounds [26], and 78 C-H-N-O nitro-compounds [4]. The average absolute deviations of these three correlations compared with experimental data are 27.8 kJ·mol −1 , 10.6 kJ·mol −1 , and 42.3 kJ·mol −1 , respectively.…”