Mechanistic insights into the reaction of CF3CCl3 with SO3: Theory and experiment
-
Zhi-Zheng Liu
,
Zhi-Rong Chen
Abstract
Reaction mechanism of 1,1,1-trifluorotrichloroethane (CF3CCl3) and sulphur trioxide (SO3) in the presence of mercury salts (Hg2SO4 and HgSO4) was studied applying the density functional theory (DFT) at the UB3LYP/6-31+G(d,p) level. It was found that this reaction occurs in the free radical chain path as follows: mercury(I) sulphate free radical is generated by heat, causing CF3CCl3 to produce the CF3CCl2 free radical which reacts with SO3 leading to the formation of CF3CCl2OSO2 decomposing into CF3COCl and SO2Cl. The SO2Cl free radical triggers CF3CCl3 to regenerate CF3CCl2 which recycles the free radical growth reaction. This elementary reaction has the highest energy barrier and it is therefore the rate control step of the whole reaction path. Experiment data can confirm the existence of the mercury(I) salt free radical and the free radical initiation stage. So, mercury salts play the role of initiators not that of catalysts. The results agree well with our hypothesis.
[1] Anello, L. G., Eibeck, R. E., & Robinson, M. A. (1982). U.S. Patent No. 4340548. Washington, D.C., USA: U.S. Patent and Trademark Office. Suche in Google Scholar
[2] Benning, A. F, & Park, J. D. (1946). U.S. Patent No. 2396076. Washington, D.C., USA: U.S. Patent and Trademark Office. Suche in Google Scholar
[3] Christian, G. D. (2003). Analytical chemistry (6th ed.). New York, NY, USA: Wiley. Suche in Google Scholar
[4] Farnell, L., Pople, J. A., & Radom, L. (1983). Structural predictions for open-shell systems: a comparative assessment of ab initio procedures. The Journal of Physical Chemistry, 87, 79–82. DOI: 10.1021/j100224a019. http://dx.doi.org/10.1021/j100224a01910.1021/j100224a019Suche in Google Scholar
[5] Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G. A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H. P., Izmaylov, A. F., Bloino, J., Zheng, G., Sonnenberg, J. L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J. A., Jr., Peralta, J. E., Ogliaro, F., Bearpark, M., Heyd, J. J., Brothers, E., Kudin, K. N., Staroverov, V. N., Keith, T., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J. C., Iyengar, S. S., Tomasi, J., Cossi, M., Rega, N., Millam, N. J., Klene, M., Knox, J. E., Cross, J. B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R. E., Yazyev, O., Austin, A. J., Cammi, R., Pomelli, C., Ochterski, J. W., Martin, R. L., Morokuma, K., Zakrzewski, V. G., Voth, G. A., Salvador, P., Dannenberg, J. J., Dapprich, S., Daniels, A. D., Farkas, Ö., Foresman, J. B., Ortiz, J. V., Cioslowski, J., & Fox, D. J. (2010). Gaussian09, Revision B.01 [computer software]. Wallingford, CT, USA: Gaussian, Inc. Suche in Google Scholar
[6] House, J. E., & House, K. A. (2010). Descriptive inorganic chemistry (2nd ed.). Burlington, MA, USA: Academic Press. Suche in Google Scholar
[7] Lei, Y., Sun, Q., Chen, Z., & Shen, J. (2009). Theoretical calculations on the thermodynamics for the synthesis reactions of polyoxymethylene dimethyl ethers. Acta Chimica Sinica, 67, 767–772. Suche in Google Scholar
[8] Liu, J., Zheng, C. G.,& Qiu, J. R. (2007). Studies on quantum chemistry calculation method of mercury reactions in combustion flue gas. Kung Cheng Je Wu Li Hsueh Pao/Journal of Engineering and Thermophysics, 28, 519–521. Suche in Google Scholar
[9] Marangoni, L., Guglielmo, G., & Conte, L. (1980). Preparation of CF3COCl: investigation of operating parameters. Journal of Fluorine Chemistry, 16, 572. DOI: 10.1016/s0022-1139(00)84084-1. http://dx.doi.org/10.1016/S0022-1139(00)84084-110.1016/S0022-1139(00)84084-1Suche in Google Scholar
[10] March, J. (1992). Advanced organic chemistry: Reactions, mechanisms, and structure (4th ed.). New York, NY, USA: Wiley-Interscience. Suche in Google Scholar
[11] Paucksch, H., Massonne, J., Bohm, H., & Fernschild, G. (1973). U.S. Patent No. 3725475. Washington, D.C., USA: U.S. Patent and Trademark Office. Suche in Google Scholar
[12] Qiu, Y. X, Fang, H., Zhang, Y., & Wang, S. G. (2004). Theoretical studies on the structure of Hg(I)-hydroxidic compounds. Acta Chimica Sinica, 62, 556–560. Suche in Google Scholar
[13] Rogers, D. W. (2011). Concise physical chemistry. New York, NY, USA: Wiley. Suche in Google Scholar
[14] Ruudorufu, U., Fuerushirudo, G., & Hirushu, U. (1981). JP Patent No. 56501649. Tokyo, Japan: Japan Patent Office. Suche in Google Scholar
[15] Schlegel, H. B., & Sosa, C. (1988). Ab initio molecular orbital calculations on F+H2 → HF+H and OH+H2 → H2O+H using unrestricted Moller-Plesset perturbation theory with spin projection. Chemical Physics Letters, 145, 329–333. DOI: 10.1016/0009-2614(88)80016-2. http://dx.doi.org/10.1016/0009-2614(88)80016-210.1016/0009-2614(88)80016-2Suche in Google Scholar
[16] Wang, H., Yang, H., Di, G., Wen, Z., Ran, X., Shi, Q., Luo, R., & Yang, Y. (2001). DFT kinetic study of the pyrolysis mechanism of toluene used for carbon matrix. Acta Chimica Sinica, 59, 17–21. Suche in Google Scholar
[17] Wei, T. J., & Zhang, J. W. (1990). Assay of chloroacetyl chloride. Chinese Journal of Pharmaceuticals, 21, 25–26. Suche in Google Scholar
[18] Yoshida, T., Kanetani, T., & Misaki, S. (1985). JP Patent No. 60237040. Tokyo, Japan: Japan Patent Office. Suche in Google Scholar
© 2012 Institute of Chemistry, Slovak Academy of Sciences
Artikel in diesem Heft
- Immobilization in biotechnology and biorecognition: from macro- to nanoscale systems
- Bond-graph description and simulation of membrane processes: Permeation in a compartmental membrane system
- Design simulations for a biogas purification process using aqueous amine solutions
- Experimental and numerical investigation of pressure drop coefficient and static pressure difference in a tangential inlet cyclone separator
- Trace elements in Variegated Bolete (Suillus variegatus) fungi
- N,N′-methylenedipyridinium Pt(II) and Pt(IV) hybrid salts: synthesis, crystal and molecular structures of [(C5H5N)2CH2] · [PtCl4] and [(C5H5N)2CH2] · [PtCl6]
- Formation of membranes based on polyacrylonitrile and butadiene-acrylonitrile elastomer in the presence of copper ions
- One-step synthesis of solid sulfonic acid catalyst and its application in the acetalization of glycerol: crystal structure of cis-5-hydroxy-2-phenyl-1,3-dioxane trimer
- Mechanistic insights into the reaction of CF3CCl3 with SO3: Theory and experiment
- Near-infrared imaging for quantitative analysis of active component in counterfeit dimethomorph using partial least squares regression
- Corrosion of titanium diboride in molten FLiNaK(eut)
- Domino synthesis of novel series of 4-substituted 5-thioxo-1,2,4-triazolidin-3-one derivatives
- Erratum to: “Nguyen Hoang Loc, Nguyen Thanh Giang: Effects of elicitors on the enhancement of asiaticoside biosynthesis in cell cultures of centella (Centella asiatica L. Urban)”, Chemical Papers 66 (7) 642–648 (2012)
Artikel in diesem Heft
- Immobilization in biotechnology and biorecognition: from macro- to nanoscale systems
- Bond-graph description and simulation of membrane processes: Permeation in a compartmental membrane system
- Design simulations for a biogas purification process using aqueous amine solutions
- Experimental and numerical investigation of pressure drop coefficient and static pressure difference in a tangential inlet cyclone separator
- Trace elements in Variegated Bolete (Suillus variegatus) fungi
- N,N′-methylenedipyridinium Pt(II) and Pt(IV) hybrid salts: synthesis, crystal and molecular structures of [(C5H5N)2CH2] · [PtCl4] and [(C5H5N)2CH2] · [PtCl6]
- Formation of membranes based on polyacrylonitrile and butadiene-acrylonitrile elastomer in the presence of copper ions
- One-step synthesis of solid sulfonic acid catalyst and its application in the acetalization of glycerol: crystal structure of cis-5-hydroxy-2-phenyl-1,3-dioxane trimer
- Mechanistic insights into the reaction of CF3CCl3 with SO3: Theory and experiment
- Near-infrared imaging for quantitative analysis of active component in counterfeit dimethomorph using partial least squares regression
- Corrosion of titanium diboride in molten FLiNaK(eut)
- Domino synthesis of novel series of 4-substituted 5-thioxo-1,2,4-triazolidin-3-one derivatives
- Erratum to: “Nguyen Hoang Loc, Nguyen Thanh Giang: Effects of elicitors on the enhancement of asiaticoside biosynthesis in cell cultures of centella (Centella asiatica L. Urban)”, Chemical Papers 66 (7) 642–648 (2012)
