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
-
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.
-
-
-
[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) Hoigné, J.; Bader, H.; Haag,W. R.; Staehelin, J. Water Res.1985, 19 (8), 99.
-
[3]
(3) Grosjean, E.; Grosjean, D. Atmos. Environ. 1998, 32 (20),3393. doi: 10.1016/S1352-2310(98)80005-8
-
[4]
(4) Alebi -Jureti , A.; Cvitas, T.; Klasinc, L. Chemosphere 2000, 41 (5), 667. doi: 10.1016/S0045-6535(99)00485-3
-
[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) 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) 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) Atkinson, R.; Arey, J. Chem. Rev. 2003, 103 (12), 4605. doi: 10.1021/cr0206420
-
[9]
(9) Cremer, D.; Crehuet, R.; Anglada, J. J. Am. Chem. Soc. 2001,123 (25), 6127. doi: 10.1021/ja010166f
-
[10]
(10) Yang, J.; Li, Q. S.; Zhang, S.W. J. Comput. Chem. 2008, 29 (2),247.
-
[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) 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) Wayne, R. P. Chemistry of Atmospheres; 3rd ed; OxfordUniversity Press: Oxford, 2000; p 775.
-
[14]
(14) Grosjean, E.; Grosjean, D. J. Atmos. Chem., 1997, 27 (3), 271.doi: 10.1023/A:1005868119515
-
[15]
(15) Bernard, F.; Eyglunent, G.; Daele, V.; Mellouki, A. J. Phys. Chem. A 2010, 114 (32), 8376. doi: 10.1021/jp104451v
-
[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) 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) Martinez, R. I.; Herron, J. T.; Huie, R. E. J. Am. Chem. Soc.1981, 103, 3807. doi: 10.1021/ja00403a031
-
[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) Zhang, S.W.; Truong, N. T. VKLab, Version 1.0; University ofUtah: Salt Lake City, 2001.
-
[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) Resende, S. M.; Ornellas, F. R. Chem. Phys. Lett. 2000, 318 (4-5), 340. doi: 10.1016/S0009-2614(00)00019-1
-
[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) 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) Frisch, M. J.; Trucks, G.W.; Pople, J. A.; et al. Gaussian 03,Revision C.02; Gaussian Inc.: Pittsburgh, PA, 2003.
-
[26]
(26) From the NIST ChemistryWebbook, http:// webbook.nist. v/chemistry.
-
[27]
(27) Huisgen, H. 1,3-Dipolar Cycloaddition Chemistry; Padwa, A.Ed.;Wiley: New York, 1984, Vol.1, Chapter 1.
-
[28]
(28) Kuczkowski, R. L. 1,3- Dipolar Cycloaddition Chemistry,Padwa, A. Ed.;Wiley: New York, 1984, Vol. 2, Chapter 11.
-
[29]
(29) Hammond, G. S. J. Am. Chem. Soc. 1955, 77, 334. doi: 10.1021/ja01607a027
-
[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) Martinez, R. I.; Herron, J. T.; Huie, R. E. J. Am. Chem. Soc.1981, 103 (13), 3807. doi: 10.1021/ja00403a031
-
[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) Gutbrod, R.; Kraka, E.; Cremer, D.; Schindler, R. N. J. Am. Chem. Soc. 1997, 119 (31), 7330. doi: 10.1021/ja970050c
-
[34]
(34) Anglada, J. M.; Bofill, J. M.; Olivella, S.; Sole, A. J. Am. Chem. Soc. 1996, 18 (19), 4636.
-
[1]
-
-
-
[1]
Shuying Zhu , Shuting Wu , Ou Zheng . Improvement and Expansion of the Experiment for Determining the Rate Constant of the Saponification Reaction of Ethyl Acetate. University Chemistry, 2024, 39(4): 107-113. doi: 10.3866/PKU.DXHX202310117
-
[2]
Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO2 by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
-
[3]
Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047
-
[4]
Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N4 site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
-
[5]
Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
-
[6]
Peng YUE , Liyao SHI , Jinglei CUI , Huirong ZHANG , Yanxia GUO . Effects of Ce and Mn promoters on the selective oxidation of ammonia over V2O5/TiO2 catalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 293-307. doi: 10.11862/CJIC.20240210
-
[7]
Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
-
[8]
Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
-
[9]
Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO2 capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
-
[10]
Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095
-
[11]
Hongting Yan , Aili Feng , Rongxiu Zhu , Lei Liu , Dongju Zhang . Reexamination of the Iodine-Catalyzed Chlorination Reaction of Chlorobenzene Using Computational Chemistry Methods. University Chemistry, 2025, 40(3): 16-22. doi: 10.12461/PKU.DXHX202403010
-
[12]
Aili Feng , Xin Lu , Peng Liu , Dongju Zhang . Computational Chemistry Study of Acid-Catalyzed Esterification Reactions between Carboxylic Acids and Alcohols. University Chemistry, 2025, 40(3): 92-99. doi: 10.12461/PKU.DXHX202405072
-
[13]
Ling Fan , Meili Pang , Yeyun Zhang , Yanmei Wang , Zhenfeng Shang . Quantum Chemistry Calculation Research on the Diels-Alder Reaction of Anthracene and Maleic Anhydride: Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 133-139. doi: 10.3866/PKU.DXHX202309024
-
[14]
Jiabo Huang , Quanxin Li , Zhongyan Cao , Li Dang , Shaofei Ni . Elucidating the Mechanism of Beckmann Rearrangement Reaction Using Quantum Chemical Calculations. University Chemistry, 2025, 40(3): 153-159. doi: 10.12461/PKU.DXHX202405172
-
[15]
Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
-
[16]
Qian Huang , Zhaowei Li , Jianing Zhao , Ao Yu . Quantum Chemical Calculations Reveal the Details Below the Experimental Phenomenon. University Chemistry, 2024, 39(3): 395-400. doi: 10.3866/PKU.DXHX202309018
-
[17]
Yong Wang , Yingying Zhao , Boshun Wan . Analysis of Organic Questions in the 37th Chinese Chemistry Olympiad (Preliminary). University Chemistry, 2024, 39(11): 406-416. doi: 10.12461/PKU.DXHX202403009
-
[18]
Mingyang Men , Jinghua Wu , Gaozhan Liu , Jing Zhang , Nini Zhang , Xiayin Yao . 液相法制备硫化物固体电解质及其在全固态锂电池中的应用. Acta Physico-Chimica Sinica, 2025, 41(1): 2309019-. doi: 10.3866/PKU.WHXB202309019
-
[19]
Zihan Lin , Wanzhen Lin , Fa-Jie Chen . Electrochemical Modifications of Native Peptides. University Chemistry, 2025, 40(3): 318-327. doi: 10.12461/PKU.DXHX202406089
-
[20]
Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166
-
[1]
Metrics
- PDF Downloads(609)
- Abstract views(1331)
- HTML views(21)