Modeling of thermodynamics of substituted toluene derivatives and benzylic radicals <i>via</i> group additivity

İnce, Alper Can; Carstensen, Hans-Heinrich; Sabbe, Maarten; Reyniers, Marie-Françoise; Marin, Guy

doi:10.1002/aic.16350

Cited by 6 publications

(6 citation statements)

References 25 publications

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“…Therefore, CBS-QB3 was chosen as the method for the ab initio calculations for all carbenium ions for the GAV determination. CBS-QB3-calculated GAVs exist for (un)saturated hydrocarbons, , radical hydrocarbons, , aromatic hydrocarbons, organosulfur compounds, and oxygenated hydrocarbons, which ensures consistency with the GAVs developed in this work.…”

Section: Resultsmentioning

confidence: 65%

Ab Initio Group Additive Values for Thermodynamic Carbenium Ion Property Prediction

Ureel

Vermeire

Sabbe

2022

Ind. Eng. Chem. Res.

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Carbenium ions are important intermediates in both zeolite and plasma chemistry. The construction of kinetic models for zeolite and plasma chemistry requires the incorporation of thermodynamic properties of these carbenium ions. In this way, thermodynamic equilibrium is incorporated resulting in more accurate and general kinetic models, which facilitate rational zeolite design and plasma process development. In this work, a consistent set of 46 group additive values (GAVs) and non-nearest neighbor interactions (NNIs) is determined for the standard enthalpy of formation, standard molar entropy, and heat capacity. The GAVs are regressed based on 165 quantum chemistry calculations with the CBS-QB3 composite method for carbenium ions as CBS-QB3 was proven a valid method for carbenium property prediction. The presented group additive approach gives the first GAVs and NNIs for entropy and heat capacity and 33 novel values for enthalpy prediction. The determined non-nearest neighbor interactions account for the effect of longer range hyperconjugation, resonance stabilization, and inductive stabilization, which are shown to be crucial for the carbenium stability. The presented group additivity scheme ensures an accurate prediction of all properties with a mean absolute error of 4.82 kJ/mol, 4.92 J/(mol·K), and 1.95 J/(mol·K) for the standard enthalpy of formation, standard molar entropy, and heat capacity, respectively. The reported GAVs and NNIs ensure the thermodynamic property prediction of paraffinic, olefinic, alkynic, aromatic, and five- and six-ring naphthenic cations.

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Section: Resultsmentioning

confidence: 65%

Ab Initio Group Additive Values for Thermodynamic Carbenium Ion Property Prediction

Ureel

Vermeire

Sabbe

2022

Ind. Eng. Chem. Res.

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“…A dataset, named “Lignin QM”, containing the standard enthalpy of formation, the standard entropy, and heat capacities at 46 temperatures of 3926 cyclic and polycyclic hydrocarbons and oxygenates is constructed. Part of the data has been published by Ince, − Khandavilli, , and Vermeire. , The remainder is unpublished work by Carstensen. All properties are calculated using the CBS-QB3 method, , to which spin–orbit corrections (SOC) and empirical bond additive corrections (BAC) are added for calculating the enthalpy of formation.…”

Section: Methodsmentioning

confidence: 99%

Learning Molecular Representations for Thermochemistry Prediction of Cyclic Hydrocarbons and Oxygenates

et al. 2021

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Accurate thermochemistry estimation of polycyclic molecules is crucial for kinetic modeling of chemical processes that use renewable and alternative feedstocks. In kinetic model generators, molecular properties are estimated rapidly with group additivity, but this method is known to have limitations for polycyclic structures. This issue has been resolved in our work by combining a geometry-based molecular representation with a deep neural network trained on ab initio data. Each molecule is transformed into a probabilistic vector from its interatomic distances, bond angles, and dihedral angles. The model is tested on a small experimental dataset (200 molecules) from the literature, a new medium-sized set (4000 molecules) with both open-shell and closed-shell species, calculated at the CBS-QB3 level with empirical corrections, and a large G4MP2-level QM9-based dataset (40 000 molecules). Heat capacities between 298.15 and 2500 K are calculated in the medium set with an average deviation of about 1.5 J mol–1 K–1 and the standard entropy at 298.15 K is predicted with an average error below 4 J mol–1 K–1. The standard enthalpy of formation at 298.15 K has an average out-of-sample error below 4 kJ mol–1 on a QM9 training set size of around 15 000 molecules. By fitting NASA polynomials, the enthalpy of formation at higher temperatures can be calculated with the same accuracy as the standard enthalpy of formation. Uncertainty quantification by means of the ensemble standard deviation is included to indicate when molecules that are on the edge or outside of the application range of the model are evaluated.

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“…The group additivity concept introduced by Benson was extended to calculate the activation energies and other thermochemical properties by Marin and coworkers, ,, and it is useful to predict the activation energies of various reactions.…”

Section: Computational Methodsmentioning

confidence: 99%

Kinetic Investigation of the Pyrolysis of Isobutyric Anhydride and Isobutyric Acid

Liu

Jiang

Shi

et al. 2020

Ind. Eng. Chem. Res.

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Low-carbon ketenes are produced by the pyrolysis of corresponding anhydrides or acids. In this work, the pyrolysis experiments of isobutyric anhydride (IBAN) and isobutyric acid (IBA) were carried out to investigate the pyrolysis kinetics. Results showed that the pyrolysis temperature of IBA is far higher than that of IBAN, and dimethylketene (DMK, the main product) selectivity during IBA pyrolysis is much lower than that during IBAN pyrolysis. Furthermore, compared with the four-centered transition state of acid pyrolysis, a more stable six-centered transition state of anhydride pyrolysis was obtained by computational chemistry, which is the reason for the lower pyrolysis temperature of anhydrides. The reaction network of IBAN pyrolysis and the corresponding kinetics were discussed as well. Finally, the effect of different functional groups (methyl, vinyl, and ethynyl groups) on the activation energies of anhydride pyrolysis was investigated, providing references for low-carbon anhydride pyrolysis.

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Modeling of thermodynamics of substituted toluene derivatives and benzylic radicals via group additivity

Cited by 6 publications

References 25 publications

Ab Initio Group Additive Values for Thermodynamic Carbenium Ion Property Prediction

Ab Initio Group Additive Values for Thermodynamic Carbenium Ion Property Prediction

Learning Molecular Representations for Thermochemistry Prediction of Cyclic Hydrocarbons and Oxygenates

Kinetic Investigation of the Pyrolysis of Isobutyric Anhydride and Isobutyric Acid

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