Shock Tube Study on the Thermal Decomposition of CH<sub>3</sub>OH

Lu, Ku-We; Matsui, Hiroyuki; Huang, Ching-Liang; Raghunath, P.; Wang, Niann‐Shiah; Lin, Ming Chang

doi:10.1021/jp100535r

Cited by 30 publications

(52 citation statements)

References 52 publications

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“…However, the quantum chemical computations predict the presence of a barrier for this reaction (Ge et al 2010, Lu et al 2010. Therefore, we expect that this reaction should not proceed inside the helium droplets and that the reactions of carbon atoms are terminated after the formation of HCH molecules.…”

Section: Calorimetry Measurementsmentioning

confidence: 99%

Ultra-Low-Temperature Reactions of Carbon Atoms With Hydrogen Molecules

Krasnokutski

Kühn²,

Renzler³

et al. 2016

ApJL

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Abstract:The reactions of carbon atoms with dihydrogen have been investigated in liquid helium droplets at T = 0.37 K. A calorimetric technique was applied to monitor the energy released in the reaction. The barrierless reaction between a single carbon atom and a single dihydrogen molecule was detected. Reactions between dihydrogen clusters and carbon atoms have been studied by high-resolution mass spectrometry. The formation of hydrocarbon cations of the type C m H n + , with m = 1 -4 and n = 1 -15 was observed. With enhanced concentration of dihydrogen, the mass spectra demonstrated the main "magic" peak assigned to the CH 5 + cation. A simple formation pathway and the high stability of this cation suggest its high abundance in the interstellar medium.

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Section: Calorimetry Measurementsmentioning

confidence: 99%

Ultra-Low-Temperature Reactions of Carbon Atoms With Hydrogen Molecules

Krasnokutski

Kühn²,

Renzler³

et al. 2016

ApJL

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“…Although high‐temperature decomposition of diacetyl was considered to be a clean precursor of CH 3 radicals , ketene is generated in substantial quantities as an intermediate in diacetyl flames . To develop reliable kinetic models for combustion of oxidized species , it is important to investigate all significant chemical reactions, including the reactions of such essential intermediate as ketene. Moreover, ketene is recognized as a key intermediate in the flame chemistry of different hydrocarbon fuels .…”

Section: Introductionmentioning

confidence: 99%

“…These hydrocarbons are easily detected by gas analysis, whereas methylidyne CH, triplet 3 CH 2 , and singlet 1 CH 2 can be detected using laser‐induced fluorescence; hence their rate constants with ketene were measured experimentally in , and , respectively. Theoretically, these reactions with CH and CH 2 were addressed in and , respectively. Rate constants of the ketene reactions with other radicals in the current kinetic models were either approximated or derived from experiments a few decades ago and were not reevaluated more recently by advanced up‐to‐date theoretical methods.…”

Section: Introductionmentioning

confidence: 99%

Mechanism and Rate Constants of the CH₃+ CH₂CO Reaction: A Theoretical Study

Semenikhin

Shubina

Savchenkova

et al. 2018

Int J of Chemical Kinetics

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The mechanism of the reaction of ketene with methyl radical has been studied by ab initio CCSD(T)‐F12/cc‐pVQZ‐f12//B2PLYPD3/6‐311G** calculations of the potential energy surface. Temperature‐ and pressure‐dependent reaction rate constants have been computed using the Rice–Ramsperger–Kassel–Marcus (RRKM)–Master Equation and transition state theory methods. Three main channels have been shown to dominate the reaction; the formation of the collisionally stabilized CH3COCH2 radical and the production of the C2H5 + CO and HCCO + CH4 bimolecular products. Relative contributions of the CH3COCH2, C2H5 + CO, and HCCO + CH4 channels strongly depend on the reaction conditions; the formation of thermalized CH3COCH2 is favored at low temperatures and high pressures, HCCO + CH4 is dominant at high temperatures, whereas the yield of C2H5 + CO peaks at intermediate temperatures around 1000 K. The C2H5 + CO channel is favored by a decrease in pressure but remains the second most important reaction pathway after HCCO + CH4 under typical flame conditions. The calculated rate constants at different pressures are proposed for kinetic modeling of ketene reactions in combustion in the form of modified Arrhenius expressions. Only rate constant to form CH3COCH2 depends on pressure, whereas those to produce C2H5 + CO and HCCO + CH4 appeared to be pressure independent.

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“…Email: jmbowma@emory.edu temperatures and pressures for several decades. Recent work can be found in [18][19][20][21][22][23][24]. Methanol is also widely found in the interstellar medium and its mechanism of formation is still a subject of discussion [25].…”

Section: Introductionmentioning

confidence: 99%

Full-dimensional, ab initio potential energy surface for CH₃OH → CH₃+OH

Bowman

2013

Molecular Physics

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An accurate, ab initio potential energy surface (PES) is reported for CH 3 OH including the bound region as well as the barrierless dissociation to CH 3 + OH. The surface is a linear least-squares fit to a total of 45,199 ab initio energies, most of which were computed using CCSD(T)-F12b/aug-cc-pVDZ theory and a small number using CASPT2/aug-cc-pVDZ theory. The latter set was done in the multi-reference region of the PES in order to obtain a realistic description of the OH-CH 3 interaction in the near asymptotic region. The geometries and harmonic frequencies of the stationary points agree very well with direct CCSD(T)-F12b calculations. The three-fold barrier to internal rotation of CH 3 OH is also accurately described by the PES. The zero-point energies of methanol and CH 3 + OH are determined by Diffusion Monte Carlo calculations. The D 0 dissociation energy is 90.1 kcal/mol, in very good agreement with the recent IUPAC evaluation [Ruscic et al., J. Phys. Chem. Ref. Data 34, 573 (2005)] result of 90.25 kcal/mol. Keywords: potential energy surface; ab initio; methanol dissociation energy IntroductionThe rovibrational spectroscopy of methanol has been the subject of numerous experimental [1-8] and theoretical papers [9-17], with a focus on the facile internal torsional motion. Signatures of that motion in the vibrational spectrum of the fundamentals and overtones of the CH and OHstretch modes have been reported in recent experiments.Methanol is a challenging system for an ab initio approach, owing both to the dimensionality of the configuration space (12 vibrational degrees of freedom) and also the need to accurately describe the low-barrier torsional motion. High-level theoretical work on the vibration/torsion energies of CH 3 OH has made use of ab initio-based force fields and a potential that are limited to the region of the minimum of the potential [11][12][13][14][15][16][17]. The most recent of these [15] used electronic energies obtained using coupled-clustersingles-doubles and perturbative treatment of triples excitations (CCSD(T)) theory with large polarised basis sets, i.e. aug-cc-pVTZ. The limited PES we developed [15] was a fit to 19,315 CCSD(T)/aVTZ energies. That PES was used in MULTIMODE-Reaction Path calculations [15,16] of numerous low-lying vibration/torsion energies, which are in good agreement with experiment.That PES does not describe dissociation or near dissociation to any fragments, in particular to CH 3 + OH. These are among the dominant products of the thermal decomposition of CH 3 OH. That decomposition as well as the recombination of CH 3 + OH are important processes in combustion chemistry and have been studied over a range of

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Shock Tube Study on the Thermal Decomposition of CH₃OH

Cited by 30 publications

References 52 publications

Ultra-Low-Temperature Reactions of Carbon Atoms With Hydrogen Molecules

Ultra-Low-Temperature Reactions of Carbon Atoms With Hydrogen Molecules

Mechanism and Rate Constants of the CH₃+ CH₂CO Reaction: A Theoretical Study

Full-dimensional, ab initio potential energy surface for CH₃OH → CH₃+OH

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Shock Tube Study on the Thermal Decomposition of CH3OH

Cited by 30 publications

References 52 publications

Ultra-Low-Temperature Reactions of Carbon Atoms With Hydrogen Molecules

Ultra-Low-Temperature Reactions of Carbon Atoms With Hydrogen Molecules

Mechanism and Rate Constants of the CH3+ CH2CO Reaction: A Theoretical Study

Full-dimensional, ab initio potential energy surface for CH3OH → CH3+OH

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Shock Tube Study on the Thermal Decomposition of CH₃OH

Mechanism and Rate Constants of the CH₃+ CH₂CO Reaction: A Theoretical Study

Full-dimensional, ab initio potential energy surface for CH₃OH → CH₃+OH