Kinetics of 1,6-hydrogen migration in alkyl radical reaction class

Ratkiewicz, Artur

doi:10.1007/s11144-012-0518-1

Cited by 5 publications

(6 citation statements)

References 53 publications

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“…3−23 It usually occurs on a femtosecond time scale 4,[14][15][16]20 and is faster than the molecular bond breaking in dissociation. It may therefore be relevant for controlling chemical bond scission or new bond formation in biological radiation damage processes 8,21,22 or in industry relevant reactions such as combustion 20,24 and catalysis. 25 The six-membered ring of the pyridine molecule, C 5 H 5 N (Figure 1), which contains one nitrogen atom that replaces the methine group (CH−) in benzene, has many astrochemical, biological, and industrial applications and for that reason is of great relevance to studies of fragmentation processes.…”

Section: Introductionmentioning

confidence: 99%

“…The hydrogen migration may thus open new reaction pathways that could not be achieved when reactions start from the initial molecular geometries. − It usually occurs on a femtosecond time scale ,− , and is faster than the molecular bond breaking in dissociation. It may therefore be relevant for controlling chemical bond scission or new bond formation in biological radiation damage processes ,, or in industry relevant reactions such as combustion , and catalysis …”

Section: Introductionmentioning

confidence: 99%

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Observation of the Hydrogen Migration in the Cation-Induced Fragmentation of the Pyridine Molecules

Wąsowicz

Pranszke

2016

J. Phys. Chem. A

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The ability to selectively control chemical reactions related to biology, combustion, and catalysis has recently attracted much attention. In particular, the hydrogen atom relocation may be used to manipulate bond-breaking and new bond-forming processes and may hold promise for far-reaching applications. Thus, the hydrogen atom migration preceding fragmentation of the gas-phase pyridine molecules by the H(+), H2(+), He(+), He(2+), and O(+) impact has been studied experimentally in the energy range of 5-2000 eV using collision-induced luminescence spectroscopy. Formation of the excited NH(A(3)Π) radicals was observed among the atomic and diatomic fragments. The structure of the pyridine molecule is lacking of the NH group, therefore observation of its A(3)Π → X(3)Σ(-) emission bands is an evidence of the hydrogen atom relocation prior to the cation-induced fragmentation. The NH(A(3)Π) emission yields indicate that formation of the NH radicals depends on the type of selected projectile and can be controlled by tuning its velocity. The plausible collisional mechanisms as well as fragmentation channels for NH formation in pyridine are discussed.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Observation of the Hydrogen Migration in the Cation-Induced Fragmentation of the Pyridine Molecules

Wąsowicz

Pranszke

2016

J. Phys. Chem. A

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“…Although these studies on short‐chain alkenyl radicals provide useful clues to estimate kinetics of long‐chain alkenyl radicals, further investigation on long‐chain alkenyl radicals are still desired. For instance, the alkenyl radicals with short carbon chains cannot undergo 1,6 or 1,7 H‐migrations, which were suggested to be significant in unimolecular reactions of long‐chain alkyl radicals . In addition, the location of double bond in long‐chain alkenyl radicals has more complicated effect than that in short‐chain alkenyl radicals.…”

Section: Introductionmentioning

confidence: 99%

Unimolecular Reaction Properties for the Long‐Chain Alkenyl Radicals

Bian

Wang

Zhang

et al. 2015

Int J of Chemical Kinetics

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Although alkenyl radicals are important intermediates involved in both alkanes and alkenes combustion, previous kinetic studies on them are very limited, especially for the long‐chain alkenyl radicals. To deeply investigate unimolecular reaction activities of long‐chain alkenyl radicals, a series of octenyl (C8H15) radicals were chosen to study the reaction kinetics of three typical types of reactions (i.e., intramolecular radical addition, internal H‐migration, and bond dissociation) in this work. The CBS‐QB3 method was used to build potential energy surfaces for these reactions, and the transition state theory was applied to obtain the high‐pressure limit rate constants. Some general rules are observed from our systematic calculations in respect of structure–activity relationships.

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“…Hence, the proposed model, which can describe a wide variety of gas-phase hydrogen abstractions between hydrocarbons in the range 300 to 1300 K, can be considered to provide reliable rate coefficient predictions RC-TST theory proposed by Truong et al 19,20,88,98,99 Reaction differences between the rate constants of 2 reactions are mainly due to differences in interactions between the reactive moiety and their different substituents. 100 Any arbitrary (Continues) Global symmetry numbers,σ gl and σ ≠ gl , being the "transfer coefficient" α and intrinsic activation barrier E 0 , respectively, were easily determined by experimental fitting. 8,36,104…”

Section: Evans-polanyi Equation For Kinetic Constant Predictionsmentioning

confidence: 99%

“…Using the RC-TST, Ratkiewicz et al have studied 1,5hydrogen migration in alkyl radical reactions, [49][50][51] C-C bond β-scission reactions, and intermolecular hydrogen migration in alkyl radicals and 1,6-hydrogen migration. 100 Wang et al have applied this method and high-level calculation methods to calculate thermal kinetic parameters. 98 Kungwan and Truong have used RC-TST equation to investigate the hydrogen reaction class of ·CH 3 with alkane reactions.…”

Section: Rc-tst Theory At the Quantum Chemical Levelmentioning

confidence: 99%

Advances in modeling hydrocarbon cracking kinetic predictions by quantum chemical theory: A review

Shi

2018

Int J Energy Res

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Summary In the modeling of hydrocarbon thermal cracking processes, complicated reaction networks of multicomponent reactants make kinetic parameter predictions very challenging. To solve this problem, the additivity method and Evans‐Polanyi equation were proposed for the prediction of kinetic factors. As the calculation of kinetic parameters using quantum chemical theory was used for higher accuracy, new additivity methods at the quantum theory level were developed for the prediction of thermodynamic kinetic parameters. At the same time, a reaction class transition state theory RC‐TST, analogous to the Evans‐Polanyi equation, was proposed by considering quantum factors for kinetic constant evaluation. Quantum calculation methods promoted mechanistic studies of electronic effects to accurately reveal the kinetic constant rules with different structural factors. Under these circumstances, kinetic parameter predictions by different quantum chemical computation methods were firstly introduced and reviewed. Meanwhile, development of the new additivity method and RC‐TST theory at the quantum chemistry level were summarized, and the new outlook on electronic effects with an appropriate quantum chemical computational method into the new additivity method was conducted to develop more perspicuous and accuracy in a simplified method for the calculation of complicated thermal cracking reaction.

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Kinetics of 1,6-hydrogen migration in alkyl radical reaction class

Cited by 5 publications

References 53 publications

Observation of the Hydrogen Migration in the Cation-Induced Fragmentation of the Pyridine Molecules

Observation of the Hydrogen Migration in the Cation-Induced Fragmentation of the Pyridine Molecules

Unimolecular Reaction Properties for the Long‐Chain Alkenyl Radicals

Advances in modeling hydrocarbon cracking kinetic predictions by quantum chemical theory: A review

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