Citation: ZHANG Tian-Lei, WANG Wei-Na, LIU Chang, LU Na, CHEN Miao, GUO Sha, WANG Wen-Liang. Computational Study of the Reaction Mechanism and Kinetics of CH₃CHC(CH₃)COOCH₃ Ozonolysis[J]. Acta Physico-Chimica Sinica, ;2013, 29(11): 2313-2320. doi: 10.3866/PKU.WHXB201310083 shu

Computational Study of the Reaction Mechanism and Kinetics of CH₃CHC(CH₃)COOCH₃ Ozonolysis

ZHANG Tian-Lei ^1,2 ,
WANG Wei-Na ¹ ,
LIU Chang ¹ ,
LU Na ¹ ,
CHEN Miao ¹ ,
GUO Sha ¹ ,
WANG Wen-Liang ^1,

1.
1 Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, P. R. China;
2 School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong 723001, Shaanxi Province, P. R. China

Received Date: 9 July 2013
Available Online: 8 October 2013
Fund Project: 国家自然科学基金(21173139) (21173139)陕西师范大学国家级大学生创新性实验计划(1110718008)资助项目 (1110718008)

The reaction mechanism for the ozonolysis of trans-CH₃CHC(CH₃)COOCH₃ as well as the isomerization reaction of CH₃CHOO and CH₃OC(O)C(CH₃)OO) without and with a water molecule were investigated at the G3B3 level. The profile of the potential energy surface (PES) was constructed. Ozone adds to trans-CH₃CHC(CH₃)COOCH₃ via a cyclic transition state to produce a highly unstable primary ozonide that can decompose readily to form P1(CH₃CHOO + CH₃OC(O)C(CH₃)O) and P₂(CH₃CHO + CH₃OC(O)C(CH₃)OO) because the bond breaks in different positions. The total rate constants over the temperature range of 200-1200 K are obtained using the conventional transition state theory with Wigner tunneling correction. The calculated rate constant is 7.55×10^-18 cm³·molecule^-1·s^-1 at 294 K, in od agreement with previous experimental data for similar reactions. The isomerization reaction of CH₃CHOO and CH₃OC (O)C(CH₃)OO) with a water molecule can occur via α-addition process and β-hydrogen transfer mechanism. The former is more favorable than the latter. Compared with the naked isomerization reactions of CH₃CHOO and CH₃OC(O)C(CH₃)OO), the presence of water molecules makes isomerization reactions much easier.
- CH₃CHC(CH₃)COOCH₃,
- O₃,
- Density functional theory,
- Reaction mechanism,
- Rate constant
1. [1]
  
  (1) Xie, F. An Analysis of Stratosphere Troposphere Exchange andStratosphericWater Vapor and Ozone. Ph.D. Dissertation,Lanzhou University, Lanzhou, 2011. [谢飞. 平流层对流层物质交换以及平流层水汽与臭氧的研究[D]. 兰州: 兰州大学,2011.]
2. [2]
  (2) Hoigné, J.; Bader, H.; Haag,W. R.; Staehelin, J. Water Res.1985, 19 (8), 99.
3. [3]
  (3) Grosjean, E.; Grosjean, D. Atmos. Environ. 1998, 32 (20),3393. doi: 10.1016/S1352-2310(98)80005-8
4. [4]
  (4) Alebi -Jureti , A.; Cvitas, T.; Klasinc, L. Chemosphere 2000, 41 (5), 667. doi: 10.1016/S0045-6535(99)00485-3
5. [5]
  (5) Li, L. C.; Zou, Q.; Tian, A. M. Acta Chim. Sin. 2003, 61 (10),1524. [李来才, 邹勤, 田安民, 化学学报, 2003, 61 (10),1524.]
6. [6]
  (6) Li, L. C.; Tian, A. M.; Xu, M. H. Acta Chim. Sin. 2003, 61 (8),1256. [李来才, 田安民, 徐明厚, 化学学报, 2003, 61 (8),1256.]
7. [7]
  (7) Wang, Y. C.; Dai, G. L.; Geng, Z. Y.; Lü, L. L.;Wang, D. M.Acta Phys. -Chim. Sin. 2004, 20 (9), 1071. [王永成, 戴国梁,耿志远, 吕玲玲, 王冬梅. 物理化学学报, 2004, 20 (9), 1071.]doi: 10.3866/PKU.WHXB20040903
8. [8]
  (8) Atkinson, R.; Arey, J. Chem. Rev. 2003, 103 (12), 4605. doi: 10.1021/cr0206420
9. [9]
  (9) Cremer, D.; Crehuet, R.; Anglada, J. J. Am. Chem. Soc. 2001,123 (25), 6127. doi: 10.1021/ja010166f
10. [10]
  (10) Yang, J.; Li, Q. S.; Zhang, S.W. J. Comput. Chem. 2008, 29 (2),247.
11. [11]
  (11) Gillies, J. Z.; Gillies, C.W.; Lovas, F. J.; Matsumura, K.;Suenram, R. D.; Kraka, E.; Cremer, D. J. Am. Chem. Soc. 1991,113 (17), 6408. doi: 10.1021/ja00017a008
12. [12]
  (12) Sun, T. L.;Wang, Y. D.; Zhang, C. X.; Sun, X. M.; Hu, J. T. Acta Chim. Sin. 2011, 69 (17), 1965. [孙廷利, 王玉东, 张晨曦, 孙孝敏, 胡敬田. 化学学报, 2011, 69 (17), 1965.]
13. [13]
  (13) Wayne, R. P. Chemistry of Atmospheres; 3rd ed; OxfordUniversity Press: Oxford, 2000; p 775.
14. [14]
  (14) Grosjean, E.; Grosjean, D. J. Atmos. Chem., 1997, 27 (3), 271.doi: 10.1023/A:1005868119515
15. [15]
  (15) Bernard, F.; Eyglunent, G.; Daele, V.; Mellouki, A. J. Phys. Chem. A 2010, 114 (32), 8376. doi: 10.1021/jp104451v
16. [16]
  (16) Sun, Y. H.; Cao, H. J.; Han, D. D.; Li, J.; He, M. X. Chem. Phys.2012, 402, 6. doi: 10.1016/j.chemphys.2012.03.015
17. [17]
  (17) Sun, Y. H.; Cao, H. J.; Han, D. D.; Li, J.; He, M. X. Struct. Chem. 2013, 24 (5), 1451. doi: 10.1007/s11224-012-0170-4.
18. [18]
  (18) Martinez, R. I.; Herron, J. T.; Huie, R. E. J. Am. Chem. Soc.1981, 103, 3807. doi: 10.1021/ja00403a031
19. [19]
  (19) Neeb, P.; Sauer, F.; Horie, O.; Moortgat, G. K. Atmos. Environ.1997, 31 (10), 1417. doi: 10.1016/S1352-2310(96)00322-6
20. [20]
  (20) Zhang, S.W.; Truong, N. T. VKLab, Version 1.0; University ofUtah: Salt Lake City, 2001.
21. [21]
  (21) Baboul, A. G.; Curtiss, L. A.; Redfern, P. C.; Raghavachari, K.J. Chem. Phys. 1999, 110 (16), 7650. doi: 10.1063/1.478676
22. [22]
  (22) Resende, S. M.; Ornellas, F. R. Chem. Phys. Lett. 2000, 318 (4-5), 340. doi: 10.1016/S0009-2614(00)00019-1
23. [23]
  (23) Du, B. N.; Zhang,W. C.; Feng, C. J.; Zhou, Z. Y. J. Mol. Struct. -Theochem 2004, 712 (1-3), 101. doi: 10.1016/j.theochem.2004.10.009
24. [24]
  (24) Si,W. J.; Gao, S. P.; Ju, G. Z. Acta Phys. -Chim. Sin. 2003, 19,974. [司维江, 禚淑萍, 居冠之, 物理化学学报, 2003, 19,974.] doi: 10.3866/PKU.WHXB20031019
25. [25]
  (25) Frisch, M. J.; Trucks, G.W.; Pople, J. A.; et al. Gaussian 03,Revision C.02; Gaussian Inc.: Pittsburgh, PA, 2003.
26. [26]
  (26) From the NIST ChemistryWebbook, http:// webbook.nist. v/chemistry.
27. [27]
  (27) Huisgen, H. 1,3-Dipolar Cycloaddition Chemistry; Padwa, A.Ed.;Wiley: New York, 1984, Vol.1, Chapter 1.
28. [28]
  (28) Kuczkowski, R. L. 1,3- Dipolar Cycloaddition Chemistry,Padwa, A. Ed.;Wiley: New York, 1984, Vol. 2, Chapter 11.
29. [29]
  (29) Hammond, G. S. J. Am. Chem. Soc. 1955, 77, 334. doi: 10.1021/ja01607a027
30. [30]
  (30) Bond, R. A. B.; Martincigh, B. S.; Mika, J. R.; Simoyi, R. H.J. Chem. Educ. 1998, 75 (9), 1158. doi: 10.1021/ed075p1158
31. [31]
  (31) Martinez, R. I.; Herron, J. T.; Huie, R. E. J. Am. Chem. Soc.1981, 103 (13), 3807. doi: 10.1021/ja00403a031
32. [32]
  (32) Gutbrod, R.; Schindler, R. N.; Kraka, E.; Cremer, D. Chem. Phys. Lett. 1996, 252 (3-4), 221. doi: 10.1016/0009-2614(96)00126-1
33. [33]
  (33) Gutbrod, R.; Kraka, E.; Cremer, D.; Schindler, R. N. J. Am. Chem. Soc. 1997, 119 (31), 7330. doi: 10.1021/ja970050c
34. [34]
  (34) Anglada, J. M.; Bofill, J. M.; Olivella, S.; Sole, A. J. Am. Chem. Soc. 1996, 18 (19), 4636.
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Computational Study of the Reaction Mechanism and Kinetics of CH3CHC(CH3)COOCH3 Ozonolysis

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Computational Study of the Reaction Mechanism and Kinetics of CH₃CHC(CH₃)COOCH₃ Ozonolysis