New Group-Contribution Approach to Thermochemical Properties of Organic Compounds: Hydrocarbons and Oxygen-Containing Compounds
Michael D. Frenkel, Sergey P. Verevkin, V N. Emel'yanenko, Robert D. Chirico, Vladimir Diky, Chris D. Muzny
A new group-contribution approach involving systematic corrections for 1,4-non-bonded carbon-carbon and carbon-oxygen interactions has been proposed. Limits of the applicability of the method, associated with the highly branched structures, were established. Experimental data for enthalpies of formation in liquid phase, enthalpies of vaporization, and enthalpies of formation in the gas phase for alkanes, alkenes, alkynes, alkylbenzenes, alkanols, ethers, ketones and aldehydes, carboxylic acids, esters, and carbonates was collected and critically evaluated through dynamic data evaluation as implemented in the NIST ThermoData Engine. An automatic procedure for molecular structure decomposition was developed and algorithms for the assessment of expanded uncertainties for the predicted property values were implemented. The combination of these software tools allows for on-going improvements of the group-contribution parameter set as new experimental data become available. Fifty two group-contribution parameters and their variances were evaluated for the proposed schema. Based on comparison of critically evaluated and predicted data for all classes of compounds studied, the performance of the new group formulation and associated parameters is superior to that originally suggested by Benson and the update by Cohen without an increase in the number of required parameters.
, Verevkin, S.
, Emel'yanenko, V.
, Chirico, R.
, Diky, V.
and Muzny, C.
New Group-Contribution Approach to Thermochemical Properties of Organic Compounds: Hydrocarbons and Oxygen-Containing Compounds, J. Phys. & Chem. Ref. Data (JPCRD), National Institute of Standards and Technology, Gaithersburg, MD, [online], https://doi.org/10.1063/1.4815957
(Accessed September 26, 2023)