Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part V
Group Contribution (GC) methods to predict thermochemical properties are eminently important in chemical process design. Following our earlier work in which a Group Contribution (GC) model was presented to account for the gas-phase heat of formation of organic molecules which, for the first time, re...
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| Format: | Article |
| Language: | English |
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MDPI AG
2024-02-01
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| Series: | Applied Sciences |
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| Online Access: | https://www.mdpi.com/2076-3417/14/5/1929 |
| _version_ | 1797264866986164224 |
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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 in chemical process design. Following our earlier work in which a Group Contribution (GC) model was presented to account for the gas-phase heat of formation of organic molecules which, for the first time, revealed chemical accuracy (1 kcal/mol or 4 kJ/mol), we here present Group Contribution parameters for a range of additional series of molecules allowing the application to a wider range of molecules whilst, mostly, retaining chemical accuracy. The new classes of molecules include amines, alkylesters, and various substituted benzenes, including t-butyl-benzenes, phenols, methoxybenzenes, anilines, benzaldehydes, and acetophenones, and finally furans and indoles/indolines. As in our previous works on this theme, again the critical selection of experimental data was crucial. Not meeting the criterion for chemical accuracy occurred when steric interactions such as nearest neighbour substituents on a benzene ring were present, something which does not fit with the characteristics of the Group Contribution method. We also report some cases for which the experimental value does not seem correct, but where both the G4 and GC model values agree well. In general, in line with accounts in the literature, the G4 method performs really well. Contrary to other related works, we have applied conformational averaging to obtain a slightly more realistic G4 result. Although the difference is generally only a few kJ/mol, this may still be relevant when attempting the development of a model with chemical accuracy, e.g., 4.2 kJ/mol. |
| first_indexed | 2024-04-25T00:35:43Z |
| format | Article |
| id | doaj.art-acf507bb89914263b96f689659f91c11 |
| institution | Directory Open Access Journal |
| issn | 2076-3417 |
| language | English |
| last_indexed | 2024-04-25T00:35:43Z |
| publishDate | 2024-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Applied Sciences |
| spelling | doaj.art-acf507bb89914263b96f689659f91c112024-03-12T16:39:30ZengMDPI AGApplied Sciences2076-34172024-02-01145192910.3390/app14051929Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part VRobert 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 in chemical process design. Following our earlier work in which a Group Contribution (GC) model was presented to account for the gas-phase heat of formation of organic molecules which, for the first time, revealed chemical accuracy (1 kcal/mol or 4 kJ/mol), we here present Group Contribution parameters for a range of additional series of molecules allowing the application to a wider range of molecules whilst, mostly, retaining chemical accuracy. The new classes of molecules include amines, alkylesters, and various substituted benzenes, including t-butyl-benzenes, phenols, methoxybenzenes, anilines, benzaldehydes, and acetophenones, and finally furans and indoles/indolines. As in our previous works on this theme, again the critical selection of experimental data was crucial. Not meeting the criterion for chemical accuracy occurred when steric interactions such as nearest neighbour substituents on a benzene ring were present, something which does not fit with the characteristics of the Group Contribution method. We also report some cases for which the experimental value does not seem correct, but where both the G4 and GC model values agree well. In general, in line with accounts in the literature, the G4 method performs really well. Contrary to other related works, we have applied conformational averaging to obtain a slightly more realistic G4 result. Although the difference is generally only a few kJ/mol, this may still be relevant when attempting the development of a model with chemical accuracy, e.g., 4.2 kJ/mol.https://www.mdpi.com/2076-3417/14/5/1929enthalpy of formationreaction enthalpythermodynamicsprocess designphysico-chemical property predictiongroup contribution method |
| spellingShingle | Robert J. Meier Paul R. Rablen Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part V Applied Sciences enthalpy of formation reaction enthalpy thermodynamics process design physico-chemical property prediction group contribution method |
| title | Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part V |
| title_full | Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part V |
| title_fullStr | Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part V |
| title_full_unstemmed | Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part V |
| title_short | Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part V |
| title_sort | group contribution revisited the enthalpy of formation of organic compounds with chemical accuracy part v |
| topic | enthalpy of formation reaction enthalpy thermodynamics process design physico-chemical property prediction group contribution method |
| url | https://www.mdpi.com/2076-3417/14/5/1929 |
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