Prediction of Enthalpy of Formation in the Solid State (at 298.15K) Using Second-Order Group Contributions—Part 2: Carbon-Hydrogen, Carbon-Hydrogen-Oxygen, and Carbon-Hydrogen-Nitrogen-Oxygen Compounds

Abstract

A program has been undertaken to develop a new group contribution method, based on Benson’s group additivity technique, estimate as precisely as possible solid state enthalpies of formation, at 298.15K, of C–H compounds, C–H–O compounds, and C–H–N–O compounds. A set of 1017 experimental values of the enthalpy of formation has been studied and compared to the predicted values of this new method as well as the method of Domalski and Hearing. This new estimation technique leads to a higher precision and reliability. With the inclusion of additional group values, a wider range of compounds can be studied (compared to the Domalski and Hearing technique). Comparison with a quantum mechanical method [Rice et al., Combust. Flame 118, 445 (1999)] shows that the list of group contribution values, ring strain corrections, and non-nearest neighbor interactions provided here yields better estimates overall.

Prediction of the Strength of Energetic Materials Using the Condensed and Gas Phase Heats of Formation

“…Domalski [18], Cohen [19], and Salmon [20] have extended this method to find the thermochemical data for condensed phase as well as gas phase. Holmes and Aubry [21] have revised and extend the group additivity values (GAV) for a wide variety of compounds containing C, H, N, O, S, and halogens.…”

“…In general, these effects are relatively small but they are taken into account somewhat by the use of ring strain corrections and non-nearest neighbor interactions. [22] Taking into account the whole environment of each central atom enhances accuracy, reliability, and the range of applicability of the method [20]. This kind of approach has generally been accepted by scientists and engineers owing to its simplicity and precision.…”

Prediction of the condensed phase heat of formation of energetic compounds

“…The reliability of the new method will be tested for important classes of energetic compounds including polynitro arene, polynitro heteroarene, acyclic and cyclic nitramine, nitrate ester and nitroaliphatic compounds. The estimated results of this method will be compared with the calculated values of group additivity method of Salmon and Dalmazzone [13] as well as outputs of complex quantum mechanical method [6,7].…”

“…They used surface electrostatic potentials of individual molecules for computation of heats of sublimation and vaporization as recommended by Politzer and co-workers [11,12]. Salmon and Dalmazzone [13] developed a suitable group contribution method that can be applied for large classes of CHNO energetic compounds in the solid state (at 298.15 K). Applications of their method have some restrictions for complex molecular structures such as the definition of many group additivity values, ring strain corrections and the non-nearest neighbor interactions.…”

Thermochemistry and quantum chemical calculations of two dibenzocycloalkane nitriles

“…The experimental solid phase enthalpies of formation are not being compared with values calculated by means of the group additivity method. Two well known parameter sets, those recommended by Domalski and Hearing [25] and by Salmon and Dalmazzone [26], give significantly different values for multiply substituted benzenes in their solid state, and so are plausibly disparate for the current compounds.…”