C2（a3Пu）自由基与含硫小分子反应的温度效应

doi:10.3866/PKU.WHXB201403072

物理化学学报 >> 2014, Vol. 30 >> Issue (5): 797-802.doi: 10.3866/PKU.WHXB201403072

C₂（a³П_u）自由基与含硫小分子反应的温度效应

胡仁志¹, 谢品华¹, 张群², 司福祺¹, 陈旸²

1 中国科学院安徽光学精密机械研究所, 中国科学院环境光学与技术重点实验室, 合肥230031;
2 中国科学技术大学化学物理系, 合肥微尺度物质科学国家实验室, 合肥230026

收稿日期:2013-12-31 修回日期:2014-03-07 发布日期:2014-04-25
通讯作者: 胡仁志，陈旸 E-mail:rzhu@aiofm.ac.cn;yangchen@ustc.edu.cn
基金资助:
国家自然科学基金（61108031，21173205），国家重点基础研究发展规划项目（973）（2010CB923302）及中国科学院知识创新工程（KJCX2-YWN24）资助项目

Temperature Dependence of C₂(a³П_u) Radical Reactions with Sulfur Bearing Molecules

HU Ren-Zhi¹, XIE Pin-Hua¹, ZHANG Qun², SI Fu-Qi¹, CHEN Yang²

1 Key Laboratory of Environmental Optics & Technology, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Science, Hefei 230031, P. R. China;
2 Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, P. R. China

Received:2013-12-31 Revised:2014-03-07 Published:2014-04-25
Contact: HU Ren-Zhi, CHEN Yang E-mail:rzhu@aiofm.ac.cn;yangchen@ustc.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China (61108031, 21173205), National Key Basic Research Program of China (973) (2010CB923302), and Knowledge Innovation Programs of the Chinese Academy of Sciences (KJCX2-YW-N24).

摘要/Abstract

摘要：

运用脉冲激光光解-激光诱导荧光（PLP-LIF）的方法在298-673 K的温度范围内测量了C₂（a³П_u）自由基与含硫小分子（H₂S，SO₂，CS₂）气相反应的双分子反应速率常数. 获得的速率常数可以用Arrhenius 公式表达如下（单位：cm³·molecule^-1·s^-1）：k（H₂S）=（1.61±0.06）×10^-12exp[-（180.91±15.73）/T]，k（SO₂）=（1.26±0.10）×10^-15×exp[（2230.68±27.77）/T]，k（CS₂）=（1.17±0.02）×10^-10 exp[（253.31±7.69）/T]；误差为2σ. 由获得的双分子速率常数及所表现的正温度效应，认为C₂（a³П_u）与H₂S反应遵循抽氢反应机理；C₂（a³П_u与SO₂反应是无能垒的过程,反应速率表现出强的负温度依赖关系；根据较大的双分子速率常数及其呈现的负温度效应我们认为，C₂（a³П_u与CS₂反应遵循加成反应机理.

关键词: C₂（a³П_u）自由基, 激光诱导荧光, 速率常数, 温度效应

Abstract:

The bimolecular rate constants for the gas- phase reactions of C₂(a³П_u) with sulfur-bearing molecules (H₂S, SO₂, CS₂) were measured over the temperature range 298-673 K, by means of pulsed laser photolysis/laser-induced fluorescence technique. The rate constants (cm³·molecule^-1·s^-1) can be fitted by the normal Arrhenius expressions: k(H₂S)=(1.61±0.06)×10^-12exp[-(180.91±15.73)/T], k(SO₂)=(1.26±0.10)×10^-15 exp[(2230.68±27.77)/T], k(CS₂)=(1.17±0.02)×10^-10 exp[(253.31±7.69)/T], where all error estimates are ±2σ and represent the precision of the fit. The observed bimolecular rate constants and positive temperature dependence of k(H₂S) show that the reaction of C₂(a³П_u) with H₂S in the range 298-673 K proceeds via a hydrogen-abstraction mechanism. The bimolecular rate constants for the reaction of C₂(a³П_u) with SO₂ show a strong negative temperature dependence. The high rate constants for the C₂(a³П_u)+CS₂ reaction and negative temperature dependence support an addition mechanism.

Key words: C₂(a³П_u) radical, Laser induced fluorescence, Rate constant, Temperature dependence

胡仁志, 谢品华, 张群, 司福祺, 陈旸. C₂（a³П_u）自由基与含硫小分子反应的温度效应[J]. 物理化学学报, 2014, 30(5): 797-802.

HU Ren-Zhi, XIE Pin-Hua, ZHANG Qun, SI Fu-Qi, CHEN Yang. Temperature Dependence of C₂(a³П_u) Radical Reactions with Sulfur Bearing Molecules[J]. Acta Phys. -Chim. Sin., 2014, 30(5): 797-802.

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201403072

https://www.whxb.pku.edu.cn/CN/Y2014/V30/I5/797

参考文献

(1) Baronavski, A. P.; McDonald, J. R. J. Chem. Phys. 1977, 66, 3300. doi: 10.1063/1.434306
(2) McKellar, A. The Journal of the Royal Astronomical Society of Canada 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. doi: 10.1006/icar.1995.1190
(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. Roy. 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. doi: 10.1086/apj.2003.582.issue-2
(8) Rennick, C. J.; Smith, J. A.; Ashfold, M. N. R.; Orr-Ewing, A. J. Chem. Phys. Lett. 2004, 383, 518. doi: 10.1016/j.cplett.2003.11.089
(9) Gordillo-Vazquez, F. J.; Albella, J. M. J. Appl. Phys. 2003, 94, 6085. doi: 10.1063/1.1617362
(10) Chernicharo, J.; Guelin, M.; Hein, H.; Kahane, C. Astron. Astrophys. 1987, 181, L9.
(11) Saito, S.; Kawaguchi, K.; Yamamoto, S.; Ohishi, M.; Suzuki, H.; Kaifu, N. Astrophys. J. 1987, 317, L115.
(12) Millar, T. J.; Herbst, E. Astron. Astrophys. 1990, 231, 466.
(13) Petrie, S. Mon. Not. Roy. Astron. Soc. 1996, 281, 666. doi: 10.1093/mnras/281.2.666
(14) Velusamy, T.; Kuiper, T. B. H.; Langer, W. D. Astrophys. J. 1995, 451, L75.
(15) Markwick, A. J.; Millar, T. J.; Charnley, S. B. Astrophys. J. 2000, 535, 256. doi: 10.1086/apj.2000.535.issue-1
(16) Hausmann, M.; Homann, B. K. H. Bunsen-Ges. Phys. Chem. 1990, 94, 1308.
(17) Harris, S. J.; Shin, H. S.; Goodwin, D. G. Appl. Phys. Lett. 1995, 66, 891. doi: 10.1063/1.113422
(18) Jones, J. M.; Harding, A.W.; Brown, S. D.; Thomas, K. M. Carbon 1995, 33, 833. doi: 10.1016/0008-6223(94)00183-Z
(19) Schofield, K. Combust. Flame 2001, 124, 137. doi: 10.1016/S0010-2180(00)00189-9
(20) Donnelly, V. M.; Pasternack, L. Chem. Phys. 1979, 39, 427. doi: 10.1016/0301-0104(79)80160-3
(21) Pasternack, L.; McDonald, J. R. Chem. Phys. 1979, 43, 173. doi: 10.1016/0301-0104(79)85185-X
(22) Reisler, H.; Mangir, M.; Wittig, C. J. Chem. Phys. 1979, 71, 2109. doi: 10.1063/1.438583
(23) Reisler, H.; Mangir, M. S.; Wittig, C. J. Chem. Phys. 1980, 73, 2280. doi: 10.1063/1.440377
(24) Pasternack, L.; Baronavski, A. P.; McDonald, J. R. J. Chem. Phys. 1980, 73, 3508. doi: 10.1063/1.440508
(25) Pasternack, L.; Pitts, W. M.; McDonald, J. R. Chem. Phys. 1981, 57, 19. doi: 10.1016/0301-0104(81)80017-1
(26) Pitts, W. M.; Pasternack, L.; McDonald, J. R. Chem. Phys. 1982, 68, 417. doi: 10.1016/0301-0104(82)87050-X
(27) Kruse, T.; Roth, P. Int. J. Chem. Kin. 1999, 31, 11.
(28) Becker, K. H.; Donner, B.; Dinis, C. M. F.; Geiger, H.; Schmidt, F.; Wiesen, P. Z. Phys. Chem. 2000, 214, 503.
(29) Fontijn, A.; Fernandez, A.; Ristanovic, A.; Randall, M. Y.; Jankowiak, J. T. J. Phys. Chem. A 2001, 105, 3182.
(30) Ristanovic, A.; Fernandez, A.; Fontijn, A. J. Phys. Chem. A 2002, 106, 8291. doi: 10.1021/jp014553n
(31) Huang, C. S.; Zhu, Z. Q.; Xin, Y.; Pei, L. S.; Chen, C. X.; Chen, Y. J. Chem. Phys. 2004, 120, 2225. doi: 10.1063/1.1636692
(32) Huang, C. S.; Zhao, D. F.; Pei, L. S.; Chen, C. X.; Chen, Y. Chem. Phys. Lett. 2004, 389, 230. doi: 10.1016/j.cplett.2004.03.080
(33) 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.
(34) Huang, C. S.; Zhu, Z. Q.; Wang, H. L.; Pei, L. S.; Chen, Y. J. Phys. Chem. A 2005, 109, 3921.
(35) Daugey, N.; Caubet, P.; Bergeat, A.; Costes, M.; Hickson, K. M. Phys. Chem. Chem. Phys. 2008, 10, 729.
(36) Páramo, A.; Canosa, A.; Le Picard, S. D.; Sims, I. R. J. Phys. Chem. A 2006, 110, 3121. doi: 10.1021/jp0544787
(37) Páramo, A.; Canosa, A.; Le Picard, S. D.; Sims, I. R. J. Phys. Chem. A 2008, 112, 9591. doi: 10.1021/jp8025336
(38) Hu, R. Z.; Zhang, Q.; Chen, Y. J. Chem. Phys. 2010, 132, 164312. doi: 10.1063/1.3400070
(39) Hu, R. Z.; Zhang, Q.; Chen, Y. J. Chem. Phys. 2010, 133, 114306. doi: 10.1063/1.3480395
(40) Hu, R. Z.; Zhang, Q.; Chen, Y. Acta Phys. -Chim. Sin. 2010, 26, 2619. [胡仁志, 张群, 陈旸. 物理化学学报, 2010, 26, 2619.] doi: 10.3866/PKU.WHXB20100938
(41) Matsugi, A.; Kohsuke, S.; Miyoshi, A. J. Phys. Chem. A 2010, 114, 4580. doi: 10.1021/jp1012494
(42) Li, N.; Huo, R. P.; Zhang, X.; Huang, X. R.; Li, J. L.; Sun, C. C. Chem. Phys. Lett. 2011, 503, 210. doi: 10.1016/j.cplett.2011.01.029
(43) Kolbanovskii, Y. A.; Borisov, Y. A. Mendeleev Commun. 2011, 21, 305. doi: 10.1016/j.mencom.2011.11.003
(44) Huo, R. P.; Zhang, X.; Huang, X. R.; Li, J. L.; Sun, C. C. Mol. Phys. 2012, 110, 2205. doi: 10.1080/00268976.2012.668969
(45) Dangi, B. B.; Maity, S.; Kaiser, R. I.; Mebel, A. M. J. Phys. Chem. A 2013, 117, 11783. doi: 10.1021/jp402700j
(46) Hu, R. Z.; Xie, P. H.; Zhang, Q.; Si, F. Q.; Chen, Y. Acta Phys. -Chim. Sin. 2013, 29, 683. [胡仁志, 谢品华, 张群, 司福祺, 陈旸. 物理化学学报, 2013, 29, 683.] doi: 10.3866/PKU.WHXB201302046
(47) Huo, R. P.; Zhang, X.; Huang, X. R.; Li, J. L.; Sun, C. C. J. Mol. Model. 2013, 19, 1009. doi: 10.1007/s00894-012-1616-8
(48) Yang, X. L.; Xu, G.; Chen, Y.; Chen, C. X. Acta Chim. Sin. 2006, 64, 47. [杨学良, 徐刚, 陈旸, 陈从香. 化学学报, 2006, 64, 47.]
(49) Herzberg, G. Molecular Spectra and Molecular Structure I. Spectra of Diatomic Molecules. Van Nostrand: Princeton, 1950.
(50) Wang, J. H.; Han, K. L.; He, G. Z.; Li, Z. J. Chem. Phys. Lett. 2003, 368, 139. doi: 10.1016/S0009-2614(02)01810-9
(51) Leu, M. T.; Smith, R. H. J. Phys. Chem. 1982, 86, 73. doi: 10.1021/j100390a015
(52) Lin, Y. L.; Wang, N. S.; Lee, Y. P. Int. J. Chem. Kinet. 1985, 17, 1201.
(53) Lafage, C.; Pauwels, J. F.; Carlier, M.; Devolder, P. J. Chem. Soc. Faraday Trans. 2 1987, 83, 731. doi: 10.1039/f29878300731
(54) Wilson, C.; Hirst, D. M. J. Chem. Soc. Faraday Trans. 1994, 90, 3051. doi: 10.1039/ft9949003051
(55) Swinnen, S.; Elsamra, R. M. I.; Nguyen, V. S.; Peeters, J.; Carl, S. A.; Nguyen, M. T. Chem. Phys. Lett. 2011, 513, 201. doi: 10.1016/j.cplett.2011.07.098

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C₂（a³П_u）自由基与含硫小分子反应的温度效应

Temperature Dependence of C₂(a³П_u) Radical Reactions with Sulfur Bearing Molecules

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