A method to estimate the enthalpy of formation of organic compounds with chemical accuracy

作者：Hukkerikar Amol S; Meier Roberti; Sin Gurkan; Gani Rafiqul^*

来源：Fluid Phase Equilibria, 2013, 348: 23-32.

DOI：10.1016/j.fluid.2013.03.018

• Enthalpy of formation
• Group-contribution method
• Quantum mechanical method
• Chemical accuracy
• Benson method

A model that yields chemical accuracy for a broad range of organic molecules is presented. The range of applicability of such an accurate model is very broad: it can be used by chemists to predict equilibria while fostering new chemistries and allow process engineers to make more reliable designs. The model which is group-contribution (GC) based, estimates gas phase standard enthalpy of formations (Delta H-f degrees (gas)) of organic compounds. To achieve the chemical accuracy, a systematic property-data-model analysis, which allows efficient use of knowledge of the experimental data of Delta H-f degrees (gas) gas and the molecular structural information is employed. Based on the findings of property-data-model analysis, new structural parameters are defined and included in the GC-model to provide additional structural information for compounds having large correlation errors and to thereby improve accuracy of Delta H-f degrees (gas) predictions through better correlation of data. For parameter estimation, a data-set containing 861 experimentally measured values of a wide variety of organic compounds (hydrocarbons, oxygenated compounds, nitrogenated compounds, multifunctional compounds, etc.) is used. The developed property model for Delta H-f degrees(gas) is fully predictive and is based exclusively on the molecular structure of the organic compound. Compared to other currently used property prediction methods, the developed GC-model for Delta H-f degrees(gas) provides significant improvement in accuracy with an average absolute error of 1.75 kJ/mol and standard deviation of 2.61 kJ/mol.

• 出版日期2013-6-25