Citation: CAO Jia, WANG Wen-Liang, GAO Lou-Jun, FU Feng. Mechanism and Thermodynamic Properties of CH₃SO₃ Decomposition[J]. Acta Physico-Chimica Sinica, ;2013, 29(06): 1161-1167. doi: 10.3866/PKU.WHXB201304021 shu

Mechanism and Thermodynamic Properties of CH₃SO₃ Decomposition

CAO Jia ^1,2 ,
WANG Wen-Liang ^2, ,
GAO Lou-Jun ¹ ,
FU Feng ¹

1.
1 College of Chemistry & Chemical engineering, Yan’an University, Yan’an 716000, P. R. China;
2 Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry &Chemical engineering, Shaanxi Normal University, Xi’an 710062, P. R. China

Received Date: 17 December 2012
Available Online: 2 April 2013
Fund Project: 国家自然科学基金(21173139) (21173139)陕西省教育厅科学研究计划(2013JK0667)资助项目 (2013JK0667)

The mechanism and kinetics of unimolecular decomposition of CH₃SO₃ are studied at the G3XMP2//B3LYP/6-311+G(3df,2p) level of theory. Six possible dissociation channels and potential energy surface for the CH₃SO₃ decomposition are investigated. Rate constants over the temperature range of 200-3000 K are calculated using Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The results indicate that the product P1(CH₃+SO₃) is dominant between 200-3000 K. Products P2(CH₃O+SO₂) and P3(HCHO+HOSO) increase significantly at higher temperatures (>3000 K). Products P4(CHSO₂+H₂O), P5(CH₂SO₃+H) and P6(CHSO₃+H₂) show little formation in the temperature range (200-3000 K). The total rate constant can be expressed as k_total=1.40×10¹²T^0.15exp(7831.58/T). Thermodynamic properties including enthalpies of formation (D_fH^Θ_{298 K}, D_fH_{0 K}), entropies (S^Θ_{298 K}), and heat capacities (C_p, 298-2000 K) of all the minima and transition states are predicted from statistical mechanics, and found to be in od agreement with the available experimental values.
- CH₃SO₃,
- Decomposition mechanism,
- Thermodynamic property,
- Rate constant
1. [1]
  
  (1) Zhang, Q. Z.; Sun, T. L.; Zhou, X. H.;Wang,W. X. Chem. Phys.Lett. 2005, 414, 316. doi: 10.1016/j.cplett.2005.08.084
2. [2]
  (2) Tsai, I. C.; Chen, J. P.; Lin, P. Y.;Wang,W. C.; Isaksen, S. A.Chem. Phys. 2010, 10, 3693.
3. [3]
  (3) Cerru, F. G.; Kronenburg, A.; Lindstedt, R. P. Proc. Combust.Inst. 2005, 30, 1227. doi: 10.1016/j.proci.2004.08.083
4. [4]
  (4) Librando, V.; Tringali, G.; Hjorth, J.; Coluccia, S. Environ.Pollut. 2004, 127, 403. doi: 10.1016/j.envpol.2003.08.003
5. [5]
  (5) Barnes, I.; Hjorth, J.; Mihalopoulos, N. Chem. Rev. 2006, 106,940. doi: 10.1021/cr020529+
6. [6]
  (6) Ray, A.; Vassalli, I.; Laverdet, G.; Le Bras, G. J. Phys. Chem.1996, 100, 8895. doi: 10.1021/jp9600120
7. [7]
  (7) Arsene, C.; Barnes, I.; Becker, K. H.; Mocanu, R. Atmos.Environ. 2001, 35, 3769. doi: 10.1016/S1352-2310(01)00168-6
8. [8]
  (8) Patroescu, I. V.; Barnes, I.; Becker, K. H.; Mihalopoulos, N.Atmos. Environ. 1998, 33, 25. doi: 10.1016/S1352-2310(98)00120-4
9. [9]
  (9) Salta, Z.; Kosmas, A. M.; Lesar, A. Comput. Theor. Chem. 2012,1001, 67.
10. [10]
  (10) Wang, X. J.; Long, M. Acta Phys. -Chim. Sin. 2012, 28, 2581.[王秀军, 龙汨. 物理化学学报, 2012, 28, 2581.] doi: 10.3866/PKU.WHXB201207172
11. [11]
  (11) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
12. [12]
  (12) Lee, C.; Yang,W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.doi: 10.1103/PhysRevB.37.785
13. [13]
  (13) Miehlich, B.; Savin, A.; Stoll, H.; Preuss, H. Chem. Phys. Lett.1989, 157, 200. doi: 10.1016/0009-2614(89)87234-3
14. [14]
  (14) Curtiss, L. A.; Redfern, P. C.; Raghavachari, K.; Rassolov, V.;Pople, J. A. J. Chem. Phys. 1999, 110, 4703. doi: 10.1063/1.478385
15. [15]
  (15) Curtiss, L. A.; Redfern, P. C.; Raghavachari, K.; Pople, J. A.J. Chem. Phys. 2001, 114, 108.
16. [16]
  (16) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03,Revision C.02; Gaussian Inc.:Wallingford, CT, 2004.
17. [17]
  (17) Barker, J. R.; lden, D. M. Chem. Rev. 2003, 103, 4577.doi: 10.1021/cr020655d
18. [18]
  (18) Miller, J. A.; Klippenstein, S. J. J. Phys. Chem. A 2006, 110,10528. doi: 10.1021/jp062693x
19. [19]
  (19) Zhang, S.W.; Truong. T. N. VKLab, Version 1.0; University ofUtah: Utah, 2001.
20. [20]
  (20) Duncan,W. T.; Bell, R. L.; Truong, T. N. J. Comput. Chem.1998, 19, 1039.
21. [21]
  (21) Curtiss, L. A.; Raghavachari, K.; Redfern, P. C.; Pople, J. A.J. Chem. Phys. 1997, 106, 1063. doi: 10.1063/1.473182
22. [22]
  (22) Ga Silva, G.; Bozzelli, J.W. J. Phys. Chem. A 2009, 113, 6979.doi: 10.1021/jp902458d
23. [23]
  (23) Barker, J. R.; Ortiz, F.; Lawrence, J. M. P.; et al. Multiwell,Revision 2010; University of Michigan: Ann Arbor, MI, 2010.
24. [24]
  (24) Barker, J. R. Int. J. Chem. Kinet. 2001, 33, 232.
25. [25]
  (25) Barker, J. R. Int. J. Chem. Kinet. 2009, 41, 748. doi: 10.1002/kin.v41:12
26. [26]
  (26) Russell, D.; Johnson, III. NIST Computational ChemistryComparison and Benchmark Database Number 101 Release15b, August 2011. http://cccbdb.nist. v/(accessed Oct 27,2012).
27. [27]
  (27) Hoy, A. R.; Bunker, P. R. J. Mol. Spectrosc. 1979, 74, 1.doi: 10.1016/0022-2852(79)90019-5
28. [28]
  (28) Jackels, C. F. J. Chem. Phys. 1982, 76, 505. doi: 10.1063/1.442752
29. [29]
  (29) Ruscic, B.; Boggs, J. E.; Burcat, A.; Csaszar, A. G.; Demaison,J.; Janoschek, R.; Martin, J. M. L.; Morton, M. L.; Rossi, M. J.J.; Stanton, F.; Szalay, P. G.;Westmoreland, P. R.; Zabel, F.;Berces, T. J. Phys. Chem. Ref. Data 2005, 34, 573.doi: 10.1063/1.1724828
30. [30]
  (30) Ruscic, B.; Pinzon, R. E.; Morton, M. L.; Srinivasan, N. K.; Su,M. C.; Sutherland, J.W.; Michael, J. V. J. Phys. Chem. A 2006,110, 6592. doi: 10.1021/jp056311j
31. [31]
  (31) Wheeler, S. E.; Schaefer, H. F., III. J. Phys. Chem. A 2009, 113,6779. doi: 10.1021/jp9029387
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Mechanism and Thermodynamic Properties of CH₃SO₃ Decomposition