Modeling the influence of resonance stabilization on the kinetics of hydrogen abstractions

Sabbe, Maarten; Vandeputte, Aäron G.; Reyniers, Marie-Françoise; Waroquier, Michel; Marin, Guy

doi:10.1039/b919479g

Cited by 56 publications

(122 citation statements)

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“…Reaction rate coefficients of reactions belonging to the reaction families (i) hydrogen abstraction by carbon-centered radicals, (ii) hydrogen abstraction by hydrogen atoms, (iii) carbon-centered β-scission/carbon-centered radical addition and (iv) hydrogen-centered β-scission/hydrogen atom addition were calculated using the group additive databases developed by Marin and coworkers [56][57][58][59]. These authors applied Benson's group additivity concept to transition state theory and derived group additive values from CBS-QB3 calculations at the high-pressure limit.…”

Section: Hydrogen Abstraction and Radical Decomposition Reactionsmentioning

confidence: 99%

Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol

Bruycker

Herbinet

Carstensen

et al. 2016

Combustion and Flame

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. Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol. Combustion and Flame, Elsevier, 2016, 171, pp.237-251. 1 Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol AbstractThe reactivity of unsaturated alcohols with a C=C double bond in the β-and γ-positions to the hydroxyl group is not well established. The pyrolysis and oxidation of two such unsaturated alcohols have been studied, i.e. 3-methyl-2-butenol (prenol) and 3-methyl-3-butenol (isoprenol). Experiments at three equivalence ratios, i.e. φ = 0.5, φ = 1.0 and φ = ∞ (pyrolysis), were performed using an isothermal jet-stirred quartz reactor at temperatures ranging from 500 to 1100 K, a pressure of 0.107 MPa and a residence time of 2 s. The reactant and product concentrations were quantified using gas chromatography. A kinetic model has been developed using the automatic network generation tool "Genesys". Several important rate coefficients are obtained from new quantum chemical calculations. Overall, there is a good agreement between model calculated mole fraction profiles and experimental data. Reaction path analysis reveals that isoprenol consumption is dominated by a unimolecular reaction to formaldehyde and isobutene. At the applied operating conditions, the equivalence ratio has no effect on the isoprenol conversion profile. Pyrolysis and oxidation of prenol is dominated by radical chemistry, with hydrogen abstractions from prenol forming resonantly stabilized radicals as dominating conversion path. Oxidation and decomposition of the resulting radicals are predicted to form 3-methyl-2-butenal and 2-methyl-1,3-butadiene, which have been detected as important products in the reactor effluent.

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Section: Hydrogen Abstraction and Radical Decomposition Reactionsmentioning

confidence: 99%

Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol

Bruycker

Herbinet

Carstensen

et al. 2016

Combustion and Flame

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“…The group additivity values (GAVs) can be obtained from high-level quantum chemical calculations. The method has proven to be successful in predicting rate coefficients of addition reactions and hydrogen abstractions for hydrocarbons 26,34 and H 2 additions, 1,2-hydrogen shifts and cyclization reactions for silicon-containing compounds. [35][36][37] The aim of this work is to extend the previously developed additivity schemes for Arrhenius parameters of hydrogen abstraction reactions between hydrocarbons to sulfur containing compounds.…”

Section: Introductionmentioning

confidence: 99%

“…[22][23][24][25][26][27][28][29][30][31][32][33] Sumathi et al 27,28 proposed a method to obtain accurate kinetic data for hydrogen abstraction reactions using supergroups that encompass the reactive moiety of the transition state structure. The major advantage of these supergroups is that they can account for non-atom-centered contributions, i.e.…”

Section: Introductionmentioning

confidence: 99%

“…32,33 In this approach the rate coefficient of a target reaction can be calculated by multiplying the rate coefficient of a reference reaction with a set of four correction factors accounting for effects of symmetry, tunneling, partition function and potential energy. In this work, the group additivity (GA) method as proposed by Saeys et al 25 and further extended by Sabbe et al 26 is used to model the kinetics of hydrogen abstractions involving organosulfur compounds. This method makes use of the additivity of enthalpy and entropy for reactants and transition state.…”

Section: Introductionmentioning

confidence: 99%

“…[35][36][37] The aim of this work is to extend the previously developed additivity schemes for Arrhenius parameters of hydrogen abstraction reactions between hydrocarbons to sulfur containing compounds. 25,26 To this end, Arrhenius parameters are obtained from high-level quantum chemical calculations. Although hydrogen abstraction reactions have been extensively studied in literature, 27,28,[38][39][40] kinetic data for abstractions involving sulfur compounds are still scarce and only very limited attention has been given to the influence of neighboring S and CQS groups on the kinetics of a C-H-C type of hydrogen abstraction reactions.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Kinetics of α hydrogen abstractions from thiols, sulfides and thiocarbonyl compounds

Vandeputte

Sabbe

Reyniers

et al. 2012

Phys. Chem. Chem. Phys.

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Hydrogen abstraction reactions involving organosulfur compounds play an important role in many industrial, biological and atmospheric processes. Despite their chemical relevance, little is known about their kinetics. In this work a group additivity model is developed that allows predicting the Arrhenius parameters for abstraction reactions of a hydrogen atoms from thiols, alkyl sulfides, alkyl disulfides and thiocarbonyl compounds by carbon-centered radicals at temperatures ranging from 300 to 1500 K. Rate coefficients for 102 hydrogen abstractions were obtained using conventional transition state theory within the high-pressure limit. Electronic barriers were calculated using the CBS-QB3 method and the rate coefficients were corrected for tunneling and hindered rotation about the transitional bond. Group additivity values for 46 groups are determined. To account for resonance and hyperconjugative stabilization in the transition state, 8 resonance corrections were fitted to a set of 32 reactions. The developed group additivity scheme was validated using a test set containing an additional 30 reactions. The group additivity scheme succeeds in reproducing the rate coefficients on average within a factor of 2.4 at 300 K and 1.4 at 1000 K. Mean absolute deviations of the Arrhenius parameters amount to, respectively, 2.5 kJ mol À1 for E a and 0.13 for log A, both at 300 and 1000 K. This work hence illustrates that the recently developed group additivity methods for Arrhenius parameters extrapolate successfully to hetero-element containing compounds.

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First principle‐based simulation of ethane steam cracking

et al. 2011

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A consistent set of ab initio-based kinetic and thermodynamic data is applied for the simulation of an ethane steam cracking furnace. The thermodynamic data are calculated using accurate quantum chemical CBS-QB3 calculations including corrections for hindered internal rotation. The kinetics are obtained from CBS-QB3-based group additive models. With these thermodynamic and kinetic data, simulations for pilot and industrial ethane steam cracking reactors over a wide range of process conditions are performed. It is shown that, without adjusting any parameter, the main product yields can be predicted within 15% rel. of the experimentally observed cracking yields. This indicates the tremendous potential of integrating ab initio methods with engineering models for accurate reactor simulations.

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Modeling the influence of resonance stabilization on the kinetics of hydrogen abstractions

Cited by 56 publications

References 58 publications

Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol

Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol

Kinetics of α hydrogen abstractions from thiols, sulfides and thiocarbonyl compounds

First principle‐based simulation of ethane steam cracking

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