Citation:
CUI Feng-Chao, YU Hong-Bo, WANG Qin, YE Wan-Li, LIU Jing-Yao. Mechanism and Kinetics of the CH3OCF2CF2OCH3+Cl Reaction[J]. Acta Physico-Chimica Sinica,
;2011, 27(02): 337-342.
doi:
10.3866/PKU.WHXB20110201
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A direct density functional theory dynamics method was used to determine the mechanism and kinetics of the CH3OCF2CF2OCH3+Cl reaction. Potential energy surface information was obtained at the BB1K/6-31+G(d,p) level. The hydrogen abstraction channels and displacement processes of the two stable conformers (SC1 and SC2) of CH3OCF2CF2OCH3 were taken into consideration. Theoretical rate constants of the individual H-abstraction channels (one from SC1 and two from SC2) were calculated by improved canonical variational transition state theory (ICVT) with a small-curvature tunneling (SCT) correction. The overall rate constant (kT) was obtained by considering the weight factor of each conformer from the Boltzmann distribution function and the contribution of the two conformers to the whole reaction was discussed. The calculated kT(ICVT/SCT) at 296 K agrees well with the experimental value. Since experimental data were lacking for other temperatures, a three-parameter rate constant temperature expression for the total reaction within 200-2000 K was fitted to: kT=0.40×10-14T1.05exp(-206.16/T).
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-
-
[1]
(1) Molina, M. J.; Rowland, F. S. Nature 1974, 249, 810.
-
[2]
(2) Hammitt, J. K.; Camm, F.; Connell, P. S.; Mooz,W. E.;Wolf, K. .;Wuebbles, D. J.; Bamezai, A. Nature 1987, 330, 711.
-
[3]
(3) Zhao, X. S. Acta Phys. -Chim. Sin. 2004, 20, 936.
-
[4]
[赵新生. 物理化学学报, 2004, 20, 936.]
-
[5]
(4) Hanel, R. A.; Conrath, B. J.; Kunde, V. G.; Prabhakara, C.; evah, I.; Salomonson, V. V.;Wolford, G. J. Geophys. Res. 1972, 77, 2629.
-
[6]
(5) Li, L. C.; Zhu, Y. Q.; Cha, D.; Tian, A. M. Acta Phys. -Chim. Sin. 2005, 21, 490
-
[7]
[李来才, 朱元强, 查东, 田安民. 物理化 学报, 2005, 21, 490.]
-
[8]
(6) Marchionni, G.; Visca, M. Eur. Pat. Appl., 1275678A. 2003, (Chem.Abs. 138): 90675.
-
[9]
(7) Sianesi, D.; Marchionni, G.; De Paasquale, R. J. In Organofluorine Chemistry: Principles and Commercial Applications; Banks, R. E. Ed.; Plenum Press: New York, 1994.
-
[10]
(8) Marchionni, G.; Ajroldi, G.; Pezzin, G. In Comprehensive Polymer Science. Second Supplement; Agarwal, S. L., Russom, . Eds.; Pergamon: London, 1996.
-
[11]
(9) Marchionni, G.; Guarda, P. A. U.S. Patent, 5, 744, 651, 1998
-
[12]
(10) Andersen, M. P. S.; Hurley, M. D.;Wallington, T. J.; Blandini, F.; Jensen, N. R.; Librando, V.; Hjorth, J.; Marchionni, G.; vataneo, M.; Visca, M.; Nicolaisen, F. M.; Nielsen, O. J. J. Phys. Chem. A 2004, 108, 1964.
-
[13]
(11) Rudolph, J.; Koppmann, R.; Plass-Dülmer, C. Atoms Environ. 1996, 30, 1887.
-
[14]
(12) Tanaka, P. L.; Oldfield, S.; Neece, J. D.; Mullins, C. B.; Allen, D. T. Environ. Sci. Technol. 2000, 34, 4470.
-
[15]
(13) Tucker, S. C. Truhlar, D. G. New Theoretical Concepts For nderstanding Organic Reaction; Dordrecht, Netherlands: dvanced Study Institute, Kluwer, 1989; pp 291-346.
-
[16]
(14) Lu, D. H.; Truong, T. N.; Melissas, V. S. Comput. Phys. Commum. 1992, 71, 235.
-
[17]
(15) Garrett, B. C.; Truhlar, D. G. J. Phys. Chem. 1991, 95, 10374.
-
[18]
(16) Truhlar, D. G.; Garrett, B. C. Acc. Chem. Res. 1980, 13, 440.
-
[19]
(17) Truhlar, D. G.; Isaacson, A. D.; Garrett, B. C. The Theory of hemical Reaction Dynamics; CRC Press: Boca Raton, 1985.
-
[20]
(18) Truhlar, D. G.; Garrett, B. C. Annu. Rev. Phys. Chem. 1984, 35, 59.
-
[21]
(19) Zhao, Y.; Lynch, B. J.; Truhlar, D. G. J. Phys. Chem. A 2004, 08, 2715.
-
[22]
(20) Becke, A. D. Phys. Rev. A 1988, 38, 3098.
-
[23]
(21) Becke, A. D. J. Chem. Phys. 1996, 104, 1040.
-
[24]
(22) Taghikhani, M.; Parsafar, G. A. J. Phys. Chem. A 2007, 111, 095.
-
[25]
(23) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 09, evision A.01; Gaussian Inc.:Wallingford, CT, 2009.
-
[26]
(24) Corchado, J. C.; Chang, Y. Y.; Fast, P. L.; et al. Polyrate, Version .7; University of Minnesota: Minneapolis, 2009.
-
[27]
(25) Garrett, B. C.; Truhlar, D. G.; Grev, R. S.; Magnuson, A.W. J. Phys. Chem. 1980, 84, 1730.
-
[28]
(26) Lu, D. H.; Truong, T. N.; Melissas, V. S.; Lynch, G. C.; Liu, Y. P.; Garrett, B. C.; Steckler, R.; Isaacson, A. D.; Rai, S. N.; ancock, G. C.; Lauderdale, J. G.; Joseph, T.; Truhlar, D. G. Comput. Phys. Commun. 1992, 71, 235.
-
[29]
(27) Liu, Y. P.; Lynch, G. C.; Truong, T. N.; Lu, D. H.; Truhlar, D. G.; Garrett, B. C. J. Am. Chem. Soc. 1993, 115, 2408.
-
[30]
(28) Truhlar, D. G. J. Comput. Chem. 1991, 12, 266.
-
[31]
(29) Chuang, Y. Y.; Truhlar, D. G. J. Chem. Phys. 2000, 112, 1221.
-
[32]
(30) Huber, K. P.; Herzberg, G. Constants of Diatomic Moleculars (Molecular Spectra and Molecular Structure, Vol. 4). Van ostrand Reinhold: New York, 1979.
-
[33]
(31) Hsu, K. J.; DeMore,W. B. J. Phys. Chem. 1995, 99, 11141.
-
[34]
(32) Louks, L. F.; Larden, K. J. Can. J. Chem. 1967, 45, 2763.
-
[35]
(33) Christensen, L. K.;Wallington, T. J.; Guschin, A.; Hurley, M. D. J. Phys. Chem. A 1999, 103, 4202.
-
[36]
(34) Notario, A.; Mellouki, A.; Le bras, G. Int. J. Chem. Kinet. 2000, 2, 105.
-
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