Prediction of Enthalpy of Formation in the Solid State (at 298.15K) using Second-Order Group Contributions. Part 1. Carbon-Hydrogen and Carbon-Hydrogen-Oxygen Compounds

Abstract

A predictive method, based on Benson's group additivity technique, is developed for calculating the enthalpy of formation in the solid phase, at 298.15 K, of carbon-hydrogen compounds and carbon-hydrogen-oxygen compounds. A complete database compiles 398 experimental enthalpies of formation. The whole group contribution values, ring strain corrections, and nonnearest neighbor interactions evaluated are listed. Finally a comparison with Cohen's method indicates that this new estimation method leads to higher precision and reliability.

Benson group additivity values of phosphines and phosphine oxides: Fast and accurate computational thermochemistry of organophosphorus species

“…For organic compounds, Benson group additivity method is an extremely powerful tool as it can be used to estimate thermochemical properties with near chemical accuracy, provided that the underlying data are of sufficient quality. Over the years, several revisions to Benson's work, such as that of Cohen's, have been published and the method has also been completely reformulated, for example, by Salmon and Dalmazzione . Nevertheless, Benson's original work remains the cornerstone for many recent improvements in the field …”

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 dataset comprises 1222 experimental data points including 170 C-H, 341 C-H-O, 158 C-H-N, and 553 C-H-N-O compounds. All values stored in this dataset have been taken mainly from the National Institute of Standards and Technology (NIST) [30] and some recent work [1,7,8,11,31,32]. These values, ranging in molecular masses from 59.06 g·mol −1 up to 942.97 g·mol −1 , are derived from experimental data and range in Table S1).…”

“…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.…”

“…The best known and most widely used of these are the methods developed by Domalski and Hearing [19], Cohen [10], and Salmon and Dalmazzone [7,8]. All these methods are second-order group contribution methods based on the Benson's technique [25] which is primarily developed so as to estimate thermodynamic properties in the gas phase.…”