Kinetics of the Reaction of Methyl Radical with Methanol
Bibliographic record
Abstract
This work studied theoretically in details the mechanism, kinetics and thermochemistry of reactions of methyl radical with methanol. The theoretical study was carried out by ab initio molecular orbital theory based on CCSD(T)/B3LYP/6-311++G(3df,2p) methods in conjunction variational transition state theory (VTST). Calculated results showed that, in the temperature range from 300K to 2000K, and the pressure at 760 Torr, temperature dependent rate constants of the reactions were: CH3 + CH3OH ® CH4 + CH2OH k(T) = 2.146´10-27.T4.64.exp(-33.47[kJ/mol/RT), CH3 + CH3OH ® CH4 + CH3O k(T) = 2.583´10-27.T4.52.exp(-29.56[kJ/mol/RT), CH3 + CH3OH ® H + CH3OCH3 k(T) = 1.025´10-23.T3.16.exp(-186.84[kJ/mol/RT) When the reaction temperature is above 730 K, the abstraction process of H in –CH3 group of methanol will occur faster. The abstraction process of H in –OH group dominates when the reaction temperature is below 730 K. Keywords Kinetic, methyl, methanol, ab initio References 1. Slagle, I.R., D. Sarzynski, and D. Gutman, Kinetics of the reaction between methyl radicals and oxygen atoms between 294 and 900 K. The Journal of Physical Chemistry, 1987. 91(16): p. 4375-4379.2. Rutz L., B.H., Bozzelli J. W., Methyl Radical and Shift Reactions with Aliphatic and Aromatic Hydrocarbons: Thermochemical Properties, Reaction Paths and Kinetic Parameters. American Chemical Society, Division Fuel Chemistry, 2004. 49(1): p. 451-452.3. Johnson, D.G., M.A. Blitz, and P.W. Seakins, The reaction of methylidene (CH) with methanol isotopomers. Physical Chemistry Chemical Physics, 2000. 2(11): p. 2549-2553.4. Cribb, P.H., J.E. Dove, and S. Yamazaki, A kinetic study of the pyrolysis of methanol using shock tube and computer simulation techniques. Combustion and Flame, 1992. 88(2): p. 169-185.5. Dombrowsky, C., et al., An Investigation of the Methanol Decomposition Behind Incident Shock Waves. Berichte der Bunsengesellschaft für physikalische Chemie, 1991. 95(12): p. 1685-1687.6. Krasnoperov, L.N. and J.V. Michael, High-Temperature Shock Tube Studies Using Multipass Absorption: Rate Constant Results for OH + CH3, OH + CH2, and the Dissociation of CH3OH. The Journal of Physical Chemistry A, 2004. 108(40): p. 8317-8323.7. Shannon, T.W. and A.G. Harrison, The reaction of methyl radicals with methyl alcohol. Canadian Journal of Chemistry, 1963. 41(10): p. 2455-2461.8. Jodkowski, J.T., et al., Theoretical Study of the Kinetics of the Hydrogen Abstraction from Methanol. 3. Reaction of Methanol with Hydrogen Atom, Methyl, and Hydroxyl Radicals. The Journal of Physical Chemistry A, 1999. 103(19): p. 3750-3765.9. Alecu, I.M. and D.G. Truhlar, Computational Study of the Reactions of Methanol with the Hydroperoxyl and Methyl Radicals. 2. Accurate Thermal Rate Constants. The Journal of Physical Chemistry A, 2011. 115(51): p. 14599-14611.10. Peukert, S.L. and J.V. Michael, High-Temperature Shock Tube and Modeling Studies on the Reactions of Methanol with D-Atoms and CH3-Radicals. The Journal of Physical Chemistry A, 2013. 117(40): p. 10186-10195.11. Anastasi, C. and D.U. Hancock, Reaction of CH3 radicals with methanol in the range 525
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.001 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.003 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".