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DOI: 10.1039/A808091G (Paper) Reference Section for: Phys. Chem. Chem. Phys., 1999, 1, 675-681

Complete falloff curves for the unimolecular decomposition of i-propoxy radicals between 330 and 408 K

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P Devolder, Ch Fittschen, A Frenzel, H Hippler, G Poskrebyshev, F Striebel and Ch Fittschen, A Frenzel, H Hippler, G Poskrebyshev, F Striebel, Viskolcz

Abstract

The temperature and pressure dependence of the rate constant for the unimolecular decomposition of i-propoxy radicals has been determined using the laser photolysis/laser induced fluorescence technique. Important features of the potential energy surface have been calculated by abinitio methods. Experiments have been performed at total pressures between 0.01 and 60 bar of helium and in the temperature range 330–408 K. The low and the high pressure limiting rate constants have been extracted from a complete falloff analysis: k0=[He]×1.0×10-8 exp(-43.8 kJ mol-1/RT) cm3 s-1 and k∞=1.2×1014 exp(-63.7 kJ mol-1/RT) s-1. We estimate an uncertainty for these rate constants of ±30%. Both rate constants have been discussed in terms of statistical unimolecular rate theory. Very good agreement between the calculated and the experimental rate constants has been found.

References

  1. A. C. Baldwin, J. R. Barker, D. M. Golden and D. G. Hendry, J. Phys. Chem., 1977, 81, 2483 CrossRef CAS.
  2. R. Atkinson, Int. J. Chem. Kinet., 1997, 29, 99 CrossRef CAS.
  3. L. Batt, Int. Rev. Phys. Chem., 1987, 6, 53 CAS.
  4. J. Heicklen, J. Adv. Photochem., 1988, 14, 177 Search PubMed.
  5. M. J. Yee Quee and J. C. J. Thynne, J. Phys. Chem., 1968, 72, 2824 CrossRef.
  6. L. Batt, R. D. McCulloch and R. T. Milne, Int. J. Chem. Kinet., 1975, 7, 441.
  7. M. T. H. Liu and K. J. Laidler, Can. J. Chem., 1968, 46, 479 CAS.
  8. J. M. Ferguson and L. Phillips, J. Chem. Soc., 1965, 4416 RSC.
  9. D. L. Cox, R. A. Livermore and L. Phillips, J. Chem. Soc., B, 1966, 245 RSC.
  10. R. J. Balla, H. H. Nelson and J. R. McDonald, Chem. Phys., 1985, 99, 323 CrossRef CAS.
  11. L. Batt, Int. J. Chem. Kinet., 1979, 11, 977 CrossRef CAS.
  12. F. Caralp, M. T. Rayez, W. Forst, N. Gomez, B. Delcroix, C. Fittschen and P. Devolder, J. Chem. Soc., Faraday Trans., 1998, 94, 3321 RSC.
  13. D. Fulle, H. F. Hamann, H. Hippler and J. Troe, J. Chem. Phys., 1996, 105, 983 CrossRef CAS.
  14. G. R. McMillan, J. Kumari and D. L. Snyder, in Chemical Reactions in Urban Atmospheres, ed. C. S. Tuesday, American Elsevier, New York, 1971, p. 34 Search PubMed.
  15. J.-M. Avez, PhD Thesis, University of Lille, France, 1978.
  16. L. Batt and G. N. Robinson, The Chemistry of Amino, Nitroso and Nitro Compounds and Their Derivates, ed. S. Patai, Wiley, Chichester, New York, Brisbane, Totonto, Singapore, 1982 Search PubMed.
  17. J. Bai, H. Okabe and B. Halpern, Chem. Phys. Lett., 1988, 149, 37 CrossRef CAS.
  18. Ch. Mund, Ch. Fockenberg and R. Zellner, Ber. Bunsen-Ges. Phys. Chem., 1998, 102, 709 CAS.
  19. P. Tarte, J. Chem. Phys., 1952, 20, 1570 CAS.
  20. M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomberts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez and J. A. Pople, Gaussian, Inc., Pittsburgh PA, 1995.
  21. B. G. Johnson, P. M. W. Gill and J. A. Pople, J. Chem. Phys., 1993, 98, 5612 CrossRef CAS.
  22. A. D. Becke, J. Chem. Phys., 1993, 101, 5648 CrossRef.
  23. J. A. Pople, A. P. Scott, M. W. Wong and L. Radom, Isr. J. Chem., 1993, 33, 345 CAS.
  24. G. Lendvay and B. Viskolcz, J. Phys. Chem., 1998, 102, 10 777 Search PubMed.
  25. B. Viskolcz, G. Lendvay and L. Seres, J. Phys. Chem. A, 1997, 101, 7119 CrossRef CAS.
  26. J. Berkowitz, G. B. Ellison and D. Gutman, J. Phys. Chem., 1994, 98, 2744 CrossRef CAS.
  27. N. J. Cohen, Phys. Chem. Ref. Data, 1996, 25, 1411 Search PubMed.
  28. CRC Handbook of Chemistry and Physics, ed. D. R. Lide, CRC Press, Boca Raton, 1997, 77th edn Search PubMed.
  29. L. A. Curtiss, K. Raghavachari, P. C. Redfern and J. A. Pople, J. Chem. Phys., 1997, 106, 1063 CrossRef CAS.
  30. J. Troe, Ber. Bunsen-Ges. Phys. Chem., 1983, 87, 161 Search PubMed.
  31. R. G. Gilbert, K. Luther and J. Troe, Ber. Bunsen-Ges. Phys. Chem., 1983, 87, 169 Search PubMed.
  32. J. Troe, J. Chem. Phys., 1977, 66, 4758 CrossRef CAS.
  33. G. Z. Whitten and B. S. Rabinovitch, J. Chem. Phys., 1963, 38, 2466 CrossRef CAS; G. Z. Whitten and B. S. Rabinovitch, J. Chem. Phys., 1964, 41, 1883 CrossRef CAS.
  34. D. Fulle, H. Hippler and F. Striebel, J. Chem. Phys., 1998, 108, 6709 CrossRef CAS.
  35. D. Fulle and H. Hippler, J. Chem. Phys., 1996, 105, 1001 CrossRef CAS.
  36. H. Hippler and J. Troe, in Bimolecular Collisions, ed. J. E. Baggott and M. N. R. Ashfold, The Royal Society of Chemistry, London, 1989, 209 Search PubMed.
  37. U. Hold, T. Lenzer, K. Luther, K. Reihs and A. Symonds, Ber. Bunsen-Ges, Phys. Chem., 1997, 101, 552 CAS.
  38. R. C. Reid, J. M. Prausnitz and B. E. Poling, The Properties of Gases and Liquids, McGraw-Hill, 1987, 4th edn Search PubMed.
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