The Reaction of Methyl Radicals With Methyl Alcohol

Shannon, T. W.; Harrison, Alex G.

doi:10.1139/v63-361

Cited by 24 publications

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References 9 publications

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“…The results in Table I1 also allow calculation of the ratio (kH/kD)(k15/kl~) when CD3 radicals replace the free CH3 radicals in reactions [15] and [ I G ] . For the scavengeable and the unscavengeable methane in both the liquid and the gas phases, the results indicate that The conclusions of earlier photolytic studies in methanol (17,18) cast seine doubt upon the suggestion that the scavengeable methane is formed by methyl radical reactions during the radiolysis of ethanol. Shannon and Harrison (17) studied reactions [18] and [19] in the gas phase.…”

Section: Ethane Formationmentioning

confidence: 83%

“…[l3] [17] in the calculations because the contributions of the corresponding reactions [17'] and [17"] would tend to cancel each other. The unscavengeable yield of methane is only 12% of the total methane yield in the gas phase and 20% in the liquid phase radiolysis of ethanol (Table IV), so little error is introduced into the calculation of the kinetic parameters by using the total methane yields in calculating the values for the scavengeable reactions.…”

Section: Ethane Formationmentioning

confidence: 99%

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The Radiolysis of Ethanol: Iv. Deuterated Ethanols in the Liquid and Gas Phases

Myron¹,

Freeman²

1965

Can. J. Chem.

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The value of G (-ethanol) in the vapor phase is nearly double that in the liquid phase. Part of the difference appears to be due to the recombination of radicals in liquid cages. Ethanol molecules, on the average, break into s~llaller fragments in the gas than in the liquid phase radiolysis. The isotopic con~positions of the hydroge? produced from various deuterated ethanols are consistent with the suggestion that the reactlon CH,CH?OH+ + CH3CH,OH + CH3CHzOH?+ + CH3CH?O occurs t o a significant extent in the liquid but not in the gas phase. This reaction probably involves the shift of a hydrogen atom along a hydrogen bond. The reaction C?HjOH?+ + e,,~; + C?H50 + H 2 does not occur to an appreciable extent in the liquid phase. I n the liquid phase the relative contributions of the three different groups in the ethanol molecule to hydrogen production are in the order CN2 > OH >> CH3. H similar trend occurs in the gas, although the contributions of the three groups are more nearly equal in this phase. Isotope effects, in the range kn/ku = 2.2-3.9 per bond, occur in the methane formation mechanism. The isotope effects are some\vhat srllaller in the liquid than in the vapor phase and somewhat smaller in the inhibited than in the uninhibited systems. H comparison of product distributions in the liquid and gas radiolyses of several compounds by y-rays and by a-particles indicates that L.E.T. effects can also occur in the gas phase. ISTRODUCTIONI t has been suggested that the reaction [I] CH,CH?OH+ + CHJCM~OH + CH3CH20Me+ + CH3CH20 occurs in the liquid phase radiolysis of ethanol (I). Since this reaction merely involves the shift of a hydrogen atom along a hydrogen bond, it should occur to a smaller extent in the vapor than in the liquid phase. This hypothesis can be tested by irradiating C 2 H 5 0 D and CzD5013 in the liquid and vapor states to determine the contributions of the hydroxyl hydrogen to the product hydrogen in the two phases. I t is expected that the contribution of the hydroxyl hydrogen will be greater in the liquid phase. The present paper reports the results of this test. TO increase the confidence that inay be placed in the results and their interpretation, the isotopic colnposition of the product hydrogen froin CHsCDnOH, CD3CH20H, and CzDBOD is also reported.Ryan et al. (2) have recently observed that reaction [I] does not occur to an appreciable extent in a mass spectrometer, but that the reaction occurs very readily. However, all of the reactions [3]-[5] occurred readily under the salne conditions as those used for the ethanol study, so the situation is not clear.

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Section: Ethane Formationmentioning

confidence: 83%

Section: Ethane Formationmentioning

confidence: 99%

The Radiolysis of Ethanol: Iv. Deuterated Ethanols in the Liquid and Gas Phases

Myron¹,

Freeman²

1965

Can. J. Chem.

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“…Một số kết quả nghiên cứu cho thấy việc sử dụng ancol làm nhiên liệu cũng có thể ảnh hưởng đến sức khỏe con người bởi các sản phẩm phụ là andehit [7,8]. Phản ứng của gốc tự do metyl với metanol, etanol đã được nghiên cứu nhiều, đầy đủ cả về lý thuyết và thực nghiệm [9][10][11][12][13][14], nhưng với propanol-2 còn rất hạn chế. Cho đến thời điểm này, qua khảo sát, chúng tôi chỉ tìm thấy một nghiên cứu thực nghiệm từ năm 1968 của P. Gray và A. A.…”

Section: đặT Vấn đề unclassified

Theoretical Study of the Formation Methane in the Reaction of Methyl Radical with Propanol-2

Tho¹,

Liem²,

Mai³

et al. 2018

NST

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The reaction paths of the reaction of methyl radical with propanol-2 (i-C3H7OH) were investigated in detail using density functional theory at B3LYP/6-311++G(3df,2p) level. There were seven reaction pathways which form seven products including CH4 + (CH3)2COH, CH4 + (CH3)2CHO, CH4 + CH3CHOHCH2, CH3OH + CH3CHCH3, C2H6 + CH3CHOH, (CH3)2CH-O-CH3 + H and (CH3)3CH + OH. The results of analysis of the reaction paths and thermokinetic parameters showed that methane could be generated from three different channels. The removed H-atom from secondary carbon atom in the propanol-2 molecule is the most favorable of this reaction system. Keywords Methyl, propanol-2, B3LYP, transition state References [1] I. R. Slagle, D. Sarzyński, and D. Gutman, “Kinetics of the reaction between methyl radicals and oxygen atoms between 294 and 900 K,” Journal of Physical Chemistry, 1987.[2] L. Rutz, H. Bockhorn, and J. W. Bozzelli, “Methyl radical and shift reactions with aliphatic and aromatic hydrocarbons: Thermochemical properties, reaction paths and kinetic parameters,” in ACS Division of Fuel Chemistry, Preprints, 2004.[3] N. H. Tho and N. X. Sang, “Theoretical study of the addition and hydrogen abstraction reactions of methyl radical with formaldehyde and hydroxymethylene,” J. Serb. Chem. Soc.; OnLine First - OLF, 2018.[4] D. Ferro-Costas et al., “The Influence of Multiple Conformations and Paths on Rate Constants and Product Branching Ratios. Thermal Decomposition of 1-Propanol Radicals,” Journal of Physical Chemistry A, p. 4790−4800, 2018.[5] M. T. Holtzapple et al., “Biomass Conversion to Mixed Alcohol Fuels Using the MixAlco Process,” Applied Biochemistry and Biotechnology, 1999.[6] C. R. Shen and J. C. Liao, “Metabolic engineering of Escherichia coli for 1-butanol and 1-propanol production via the keto-acid pathways,” Metabolic Engineering, 2008.[7] A. Frassoldati et al., “An experimental and kinetic modeling study of n-propanol and iso-propanol combustion,” Combustion and Flame, vol. 157, pp. 2–16, 2010.[8] M. Z. Jacobson, “Effects of ethanol (E85) versus gasoline vehicles on cancer and mortality in the United States,” Environmental Science and Technology, 2007.[9] P. Gray and A. A. Herod, “Methyl radical reactions with ethanol and deuterated ethanols,” Transactions of the Faraday Society, 1968.[10] Z. F. Xu, J. Park, and M. C. Lin, “Thermal decomposition of ethanol. III. A computational study of the kinetics and mechanism for the CH3+C2H5OH reaction,” Journal of Chemical Physics, 2004.[11] N. H. Tho and D. T. Quang, “Nghiên cứu lý thuyết đường phản ứng của gốc metyl với etanol,” Vietnam Journal of Chemistry, vol. 56, no. 3, pp. 373–378, Jun. 2018.[12] N. H. Tho and N. X. Sang, “Kinetics of the Reaction of Methyl Radical with Methanol,” VNU Journal of Science: Natural Sciences and Technology; Vol 34 No 1DO - 10.25073/2588-1140/vnunst.4725 , Mar. 2018.[13] T. W. Shannon and A. G. Harrison, “The reaction of methyl radicals with methyl alcohol,” Canadian Journal of Chemistry, vol. 41, pp. 2455–2461, 1963.[14] S. L. Peukert and J. V. Michael, “High-temperature shock tube and modeling studies on the reactions of methanol with d-atoms and CH3-radicals,” Journal of Physical Chemistry A, 2013.[15] P. Gray and A. A. Herod, “Methyl radical reactions with isopropanol and methanol, their ethers and their deuterated derivatives,” Transactions of the Faraday Society, 1968.[16] A. D. Becke, “Density functional thermochemistry. I. The effect of the exchange only gradient correction,” Journal of Chemical Physics, vol. 96, p. 2155, 1992.[17] A. D. Becke, “Density-functional thermochemistry. II. The effect of the Perdew-Wang generalized-gradient correlation correction,” The Journal of Chemical Physics, vol. 97, p. 9173, 1992.[18] A. D. Becke, “Density-functional thermochemistry. III. The role of exact exchange,” The Journal of Chemical Physics, vol. 98, p. 5648, 1993.[19] W. Yang, R. G. Parr, and C. Lee, “Various functionals for the kinetic energy density of an atom or molecule,” Physical Review A, vol. 34 (6), pp. 4586–4590, 1986.[20] W. J. Hehre, L. Radom, P. V. R. Schleyer, and J. A. Pople, Ab Initio Molecular Orbital Theory. 1986.[21] M. P. Andersson and P. Uvdal, “New scale factors for harmonic vibrational frequencies using the B3LYP density functional method with the triple-zeta basis set 6-311+G(d,p).,” The journal of physical chemistry. A, vol. 109, pp. 2937–2941, 2005.[22] Frisch, M. J.; Trucks, G. W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.; Cheeseman, J. R., M. Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, J. L. Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, T. Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, and Y. . et al. Honda, “Gaussian 09 Revision C.01, Gaussian Inc. Wallingford CT.,” Gaussian 09 Revision C.01. 2010.[23] G. Herzberg, Electronic Spectra and Electronic Structure of Polyatomic Molecules. 1966.[24] L. M. Sverdlov, M. A. Kovner, and E. P. Krainov, Vibrational spectra of polyatomic molecules. New York; Chichester; Jerusalem; London: Wiley ; Israel Program for Scientific Translations, 1974.[25] E. Hirota, “Anharmonic potential function and equilibrium structure of methane,” Journal of Molecular Spectroscopy, vol. 77, pp. 213–221, 1979.[26] P. Venkateswarlu and W. Gordy, “Methyl alcohol. II. Molecular structure,” The Journal of Chemical Physics, 1955.[27] E. . B. Goos A.; Ruscic, B., “Extended Third Millennium Ideal Gas and Condensed Phase Thermochemical Database for Combustion with Updates from Active Thermochemical Tables,” http://garfield.chem.elte.hu/Burcat/burcat.html August-2018.

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“…Email: nguyenhuutho04@gmail.com https://doi.org/10.25073/2588-1140/vnunst.4725 metyl với metanol đã được nghiên cứu rất nhiều kể cả về thực nghiệm lẫn lý thuyết [7][8][9][10][11][12]. Phản ứng này tuân theo cơ chế tách bậc 2 qua hai hướng:…”

Section: đặT Vấn đề unclassified

“…CH3 + CH3OH  CH4 + CH2OH (R1) CH3 + CH3OH  CH4 +CH3O (R2) Kết quả thực nghiệm động học của phản ứng R1 lần đầu tiên được công bố bởi Shannon và cộng sự năm 1963. Theo đó, bằng kỹ thuật phân tích phổ khối, ở nhiệt độ 406-472K, Shannon tìm thấy biểu thức tốc độ k=3,9910 -13 [cm 3 /molecule s].e -43,48 [kJ/mole]/RT [7]. Năm 1987, hằng số tốc độ của phản ứng này được Tsang tổng kết lại qua biểu thức k=1,1210 -15 [cm 3 /molecule s] (T/298 K) 3,10 .e -29,02 [kJ/mole]/RT trong phạm vi 300-2500K [13].…”

Section: đặT Vấn đề unclassified

Kinetics of the Reaction of Methyl Radical with Methanol

Tho

Sang²

2018

NST

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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 <T/K < 603. Journal of the Chemical Society, Faraday Transactions, 1990. 86(14): p. 2553-2555.12. Dombrowsky, C. and H.G. Wagner, An investigation of the reaction between CH3 radicals and methanol at high temperatures. Berichte der Bunsengesellschaft für physikalische Chemie, 1989. 93(5): p. 633-637.13. Tsang, W., Chemical Kinetic Data Base for Combustion Chemistry. Part 2. Methanol. Journal of Physical and Chemical Reference Data, 1987. 16(3): p. 471-508.14. Becke, A.D., Density‐functional thermochemistry. II. The effect of the Perdew–Wang generalized‐gradient correlation correction. The Journal of Chemical Physics, 1992. 97(12): p. 9173-9177.15. Becke, A.D., Density‐functional thermochemistry. I. The effect of the exchange‐only gradient correction. The Journal of Chemical Physics, 1992. 96(3): p. 2155-2160.16. Becke, A.D., Density‐functional thermochemistry. III. The role of exact exchange. The Journal of Chemical Physics, 1993. 98(7): p. 5648-5652.17. Yang, W., R.G. Parr, and C. Lee, Various functionals for the kinetic energy density of an atom or molecule. Physical Review A, 1986. 34(6): p. 4586-4590.18. Hehre W. , R.L., Schleyer P. V. R. , and Pople J. A. and 30, Ab Initio Molecular Orbital Theory. 1986, New York: Wiley.19. Andersson, M.P. and P. Uvdal, New Scale Factors for Harmonic Vibrational Frequencies Using the B3LYP Density Functional Method with the Triple-ζ Basis Set 6-311+G(d,p). The Journal of Physical Chemistry A, 2005. 109(12): p. 2937-2941.20. Raghavachari, K., et al., A fifth-order perturbation comparison of electron correlation theories. Chemical Physics Letters, 1989. 157(6): p. 479-483.21. M.J. Frisch, G.W.T., H.B. Schlegel, et al., GAUSSIAN 09, Revision C.01, Gaussian Inc., Wallingford CT, 2010.22. Robson Wright, M., Theories of Chemical Reactions, in An Introduction to Chemical Kinetics. 2005, John Wiley & Sons, Ltd. p. 99-164.23. Goos, E.B., A.; Ruscic, B., Extended Third Millennium Ideal Gas and Condensed Phase Thermochemical Database for Combustion with Updates from Active Thermochemical Tables. http://garfield.chem.elte.hu/Burcat/burcat.html, October, 2017.

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The Reaction of Methyl Radicals With Methyl Alcohol

Cited by 24 publications

References 9 publications

The Radiolysis of Ethanol: Iv. Deuterated Ethanols in the Liquid and Gas Phases

The Radiolysis of Ethanol: Iv. Deuterated Ethanols in the Liquid and Gas Phases

Theoretical Study of the Formation Methane in the Reaction of Methyl Radical with Propanol-2

Kinetics of the Reaction of Methyl Radical with Methanol

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