C2(a3Πu)自由基与若干不饱和碳氢化合物反应的温度效应

doi:10.3866/PKU.WHXB20100938

Abstract

Abstract:

We studied the temperature dependence on the gas phase reactions of theC₂(a³Π_u) radical with several unsaturated hydrocarbons (C₂H₄ (k₁),C₂H₂ (k₂),C₃H₆ (k₃), and 2-C₄H₈ (k₄)) by means of pulsed laser photolysis-laser induced fluorescence (PLP-LIF) technique. The bimolecular rate constants for these reactions were obtained in the temperature range of 298-673 K. The obtained kinetics data were used to derive the following Arrhenius expressions: k₁(T)=(4.53 ±0.05) ×10^-11exp[(196.41 ±5.20)/T], k₂(T)=(3.94 ±0.04) ×10^-11exp[(143.04 ±4.28)/T], k₃(T)=(7.96 ±0.17) ×10^-11exp[(185.10 ±8.86)/T], and k₄(T)=(1.04 ±0.02) ×10^-10exp[(180.34 ±7.67)/T], where all error estimates are ±2σ and represent the precision of the fit. The observed bimolecular rate constants along with the negative temperature dependences of k(T) allow us to reacha conclusion that the reactions of C₂(a³Π_u) with these unsaturated hydrocarbons in the temperature range of 298-673 K proceed via an addition mechanism.

Key words: C₂(a³Π_u) radical, Laser induced fluorescence, Rate constant, Temperature dependence

MSC2000:

O643

HU Ren-Zhi, ZHANG Qun, CHEN Yang. Temperature Dependence of Reactions of C₂(a³Π_u) Radical with Several Unsaturated Hydrocarbons[J].Acta Phys. -Chim. Sin., 2010, 26(10): 2619-2624.

References

1. Baronavski, A. P.; McDonald, J. R. J. Chem. Phys., 1977, 66: 3300
2. McKellar, A. J. R. Astron. Soc. Can., 1960, 54: 97
3. Brault, J. W.; Delbouille, L.; Grevesse, N.; Roland, G.; Sauval, A. J.; Testerman, L. Astron. Astrophys., 1982, 108: 201
4. A'Hearn, M. F.; Millis, R. C.; Schleicher, D. O.; Osip, D. J.; Birch, P. V. Icarus, 1995, 118: 223
5. Bakker, E. J.; van Dishoeck, E. F.; Waters, L. B. F.M.; Schoenmaker, T. Astron. Astrophys., 1997, 323: 469
6. Cecchi-Pestellini, C.; Dalgarno, A. Mon. Not. R. Astron. Soc., 2002, 331: L31
7. Oka, T.; Thorburn, J. A.; McCall, B. J.; Friedman, S. D.; Hobbs, L. M.; Sonnentrucker, P.; Welty, D. E.; York, D. G. Astrophys. J., 2003, 582: 823
8. Rennick, C. J.; Smith, J. A.; Ashfold, M. N. R.; Orr-Ewing, A. J. Chem. Phys. Lett., 2004, 383: 518
9. Gordillo-Vazquez, F. J.; Albella, J. M. J. Appl. Phys., 2003, 94: 6085
10. Ballik, E. A.; Ramsay, D. A. Astrophys. J., 1963, 137: 84
11. Herzberg, G. Molecular spectra and molecular structure I. Spectra of diatomic molecules. Princeton: van Nostrand, 1950
12. Krause, H. F. J. Chem. Phys., 1979, 70: 3871
13. Donnelly, V. M.; Pasternack, L. Chem. Phys., 1979, 39: 427
14. Pasternack, L.; McDonald, J. R. Chem. Phys., 1979, 43: 173
15. Reisler, H.; Mangir, M.; Wittig, C. J. Chem. Phys., 1979, 71: 2109
16. Reisler, H.; Mangir, M.; Wittig, C. Chem. Phys., 1980, 47: 49
17. Mangir, M. S.; Reisler, H.; Wittig, C. J. Chem. Phys., 1980, 73: 829
18. Reisler, H.; Mangir, M. S.; Wittig, C. J. Chem. Phys., 1980, 73: 2280
19. Pasternack, L.; Baronavski, A. P.; McDonald, J. R. J. Chem. Phys., 1980, 73: 3508
20. Pasternack, L.; Pitts,W. M.; McDonald, J. R. Chem. Phys., 1981, 57: 19
21. Pitts, W. M.; Pasternack, L.; McDonald, J. R. Chem. Phys., 1982, 68: 417
22. Kruse, T.; Roth, P. Int. J. Chem. Kin., 1999, 31: 11
23. Becker, K. H.; Donner, B.; Dinis, C. M. F.; Geiger, H.; Schmidt, F.; Wiesen, P. Z. Phys. Chem., 2000, 214: 503
24. Fontijn, A.; Fernandez, A.; Ristanovic, A.; Randall, M. Y.; Jankowiak, J. T. J. Phys. Chem. A, 2001, 105: 3182
25. Ristanovic, A.; Fernandez, A.; Fontijn, A. J. Phys. Chem. A, 2002, 106: 8291
26. Huang, C. S.; Zhu, Z. Q.; Xin, Y.; Pei, L. S.; Chen, C. X.; Chen, Y. J. Chem. Phys., 2004, 120: 2225
27. Huang, C. S.; Zhao, D. F.; Pei, L. S.; Chen, C. X.; Chen, Y. Chem. Phys. Lett., 2004, 389: 230
28. Huang, C. S.; Li, Z. X.; Zhao, D. F.; Xin, Y.; Pei, L. S.; Chen, C. X.; Chen, Y. Chin. Sci. Bull., 2004, 49: 438
29. Huang, C. S.; Zhu, Z. Q.; Wang, H. L.; Pei, L. S.; Chen, Y. J. Phys. Chem. A, 2005, 109: 3921
30. Hu, R. Z.; Zhang, Q.; Chen, Y. J. Chem. Phys., 2010, 132: 164312
31. Daugey, N.; Caubet, P.; Bergeat, A.; Costes, M.; Hickson, K. M. Phys. Chem. Chem. Phys., 2008, 10: 729
32. Páramo, A.; Canosa, A.; Le Picard, S. D.; Sims, I. R. J. Phys. Chem. A, 2006, 110: 3121
33. Páramo, A.; Canosa, A.; Le Picard, S. D.; Sims, I. R. J. Phys. Chem. A, 2008, 112: 9591
34. http://webbook.nist.gov.
35. Ochimizu, T.; Seki, K.; Yagi, M.; Halpern, J. B.; Okabe, H. Chem. Phys. Lett., 1999, 313: 451
36. Berman, M. R.; Fleming, J. W.; Harvey, A. B.; Lin, M. C. Chem. Phys., 1982, 73: 27
37. Lichtin, D.; Lin, M. C. Chem. Phys., 1986, 104: 325
38. Atkinson, R. Chem. Rev., 1985, 85: 69
39. Gu, X. B.; Guo, Y.; Zhang, F. T.; Mebel, A. M.; Kaiser, R. I. Faraday Discuss., 2006, 133: 245
40. Gu, X. B.; Guo, Y.; Zhang, F. T.; Mebel, A. M.; Kaiser, R. I. Chem. Phys., 2007, 335: 95
41. Kaiser, R. I.; Balucani, N.; Charkin, D. O.; Mebel, A. M. Chem. Phys. Lett., 2003, 382: 112
42. Gu, X. B.; Guo, Y.; Mebel, A. M.; Kaiser, R. I. J. Phys. Chem. A, 2006, 110: 11265
43. Leonori, F.; Petrucci, R.; Hickson, K. M.; Segolini, E.; Le Picard, S. D.; Balucani, N.; Foggi, P.; Casavecchia, P. Planet. Space Sci., 2008, 56: 1658
44. Kaiser, R. I.; Le, T. N.; Nguyen, T. L.; Mebel, A. M.; Balucani, N.; Lee, Y. T.; Stahl, F.; Schleyer, P. V.; Schaefer, H. F. Faraday Discuss., 2001, 119: 51
45. Guo, Y.; Kislov, V. V.; Gu, X.; Zhang, F.; Mebel, A. M.; Kaiser, R. I. Astrophys. J., 2006, 653: 1577
46. McKee, K.; Blitz, M. A.; Hughes, K. J.; Pilling, M. J.; Qian, H. B.; Taylor, A.; Seakins, P. W. J. Phys. Chem. A, 2003, 107: 5710
47. Choi, N.; Blitz, M. A.; McKee, K.; Pilling, M. J.; Seakins, P. W. Chem. Phys. Lett., 2004, 384: 68
48. Gannon, K. L.; Glowacki, D. R.; Blitz, M. A.; Hughes, K. J.; Pilling, M. J.; Seakins, P. W. J. Phys. Chem. A, 2007, 111: 6679

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Temperature Dependence of Reactions of C₂(a³Π_u) Radical with Several Unsaturated Hydrocarbons

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Temperature Dependence of Reactions of C2(a3Πu) Radical with Several Unsaturated Hydrocarbons

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Temperature Dependence of Reactions of C₂(a³Π_u) Radical with Several Unsaturated Hydrocarbons