Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part IV
Group contribution (GC) methods to predict thermochemical properties are eminently important to process design. Following earlier work which presented a GC model in which, for the first time, chemical accuracy (1 kcal/mol or 4 kJ/mol) was accomplished, we here discuss classes of molecules for which...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-05-01
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| Series: | Thermo |
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| Online Access: | https://www.mdpi.com/2673-7264/3/2/18 |
| _version_ | 1827735559921991680 |
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| author | Robert J. Meier Paul R. Rablen |
| author_facet | Robert J. Meier Paul R. Rablen |
| author_sort | Robert J. Meier |
| collection | DOAJ |
| description | Group contribution (GC) methods to predict thermochemical properties are eminently important to process design. Following earlier work which presented a GC model in which, for the first time, chemical accuracy (1 kcal/mol or 4 kJ/mol) was accomplished, we here discuss classes of molecules for which the traditional GC approach does not hold, i.e., many results are beyond chemical accuracy. We report new ring-strain-related parameters which enable us to evaluate the heat of formation of alkyl-substituted cycloalkanes. In addition, the definition of the appropriate group size is important to obtain reliable and accurate data for systems in which the electron density varies continuously but slowly between related species. For this and in the case of ring strain, G4 quantum calculations are shown to be able to provide reliable heats of formation which provide the quantitative data which we can use, in the case of absence of experimental data, to establish group and nearest-neighbour interaction parameters to extend the range of applicability of the GC method whilst retaining chemical accuracy. We also found that the strong van der Waals that overlap in highly congested branched alkanes can be qualitatively investigated by applying DFT quantum calculations, which can provide an indication of the GC approach being inappropriate. |
| first_indexed | 2024-03-11T01:52:40Z |
| format | Article |
| id | doaj.art-ff2a96855e10415896e94f2614d27cd1 |
| institution | Directory Open Access Journal |
| issn | 2673-7264 |
| language | English |
| last_indexed | 2024-03-11T01:52:40Z |
| publishDate | 2023-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Thermo |
| spelling | doaj.art-ff2a96855e10415896e94f2614d27cd12023-11-18T12:53:34ZengMDPI AGThermo2673-72642023-05-013228930810.3390/thermo3020018Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part IVRobert J. Meier0Paul R. Rablen1Pro-Deo Consultant, 52525 Heinsberg, North-Rhine Westphalia, GermanyDepartment of Chemistry and Biochemistry, Swarthmore College, Swarthmore, PA 19081, USAGroup contribution (GC) methods to predict thermochemical properties are eminently important to process design. Following earlier work which presented a GC model in which, for the first time, chemical accuracy (1 kcal/mol or 4 kJ/mol) was accomplished, we here discuss classes of molecules for which the traditional GC approach does not hold, i.e., many results are beyond chemical accuracy. We report new ring-strain-related parameters which enable us to evaluate the heat of formation of alkyl-substituted cycloalkanes. In addition, the definition of the appropriate group size is important to obtain reliable and accurate data for systems in which the electron density varies continuously but slowly between related species. For this and in the case of ring strain, G4 quantum calculations are shown to be able to provide reliable heats of formation which provide the quantitative data which we can use, in the case of absence of experimental data, to establish group and nearest-neighbour interaction parameters to extend the range of applicability of the GC method whilst retaining chemical accuracy. We also found that the strong van der Waals that overlap in highly congested branched alkanes can be qualitatively investigated by applying DFT quantum calculations, which can provide an indication of the GC approach being inappropriate.https://www.mdpi.com/2673-7264/3/2/18enthalpy of formationthermodynamicsprocess designphysico-chemical property predictiongroup contribution methodchemical accuracy |
| spellingShingle | Robert J. Meier Paul R. Rablen Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part IV Thermo enthalpy of formation thermodynamics process design physico-chemical property prediction group contribution method chemical accuracy |
| title | Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part IV |
| title_full | Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part IV |
| title_fullStr | Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part IV |
| title_full_unstemmed | Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part IV |
| title_short | Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part IV |
| title_sort | group contribution revisited the enthalpy of formation of organic compounds with chemical accuracy part iv |
| topic | enthalpy of formation thermodynamics process design physico-chemical property prediction group contribution method chemical accuracy |
| url | https://www.mdpi.com/2673-7264/3/2/18 |
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