Reliable prediction of the condensed (solid or liquid) phase enthalpy of formation of organic energetic materials at 298 K through their molecular structures

• A simple method assesses the condensed phase enthalpy of formation of organic energetic compounds.
• It requires only molecular structure of the compound.
• It gives good results as compared to the best quantum mechanical and group additivity models.

A reliable new method is introduced to predict the condensed (solid or liquid) phase enthalpy of formation of organic energetic materials (at 298 K). This model is based on some additive and non-additive functions, which are based on elemental composition and some molecular fragments. The novel correlation is constructed on the basis of experimental data of 222 organic compounds containing different types of energetic bonds such as -O-O-, –N3, –ONO, –NO2, –ONO2 and –NNO2. For 144 compounds of this set, where the best available group additivity method can be used, the root mean square (rms) deviations of the new and group additivity methods from experimental data are 31.0 and 68.2 kJ/mol, respectively. For further 77 energetic compounds, where the computed results of quantum mechanical methods for simple organic energetic compounds were available and the best available group additivity method for some complex molecules can be applied, the rms deviations of the new, quantum mechanical (54 compounds) and group additivity (51 compounds) methods from the measured data are 35.9, 42.1 and 170.6 kJ/mol, respectively.