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Thermochemical Information from Ion-Molecule Rate Constants

  • Sharon G. Lias
Part of the Lecture Notes in Chemistry book series (LNC, volume 31)

Abstract

In the study of ion-molecule reactions, there has long been practice of inferring exothermicity from the fact that a reaction is observed to occur, or, on occasion, endothermicity from the non-occurrence of a particular reaction. This “bracketing” technique has, for example, been used to establish relative proton affinities by ascertaining whether or not the reaction:
$$M{H^ + } + B \rightleftarrows B{H^ + } + M$$
(1)
occurs preferentially from left to right or from the right to the left. Since the advent of the measurement of equilibrium constants for a bimolecular ion-molecule reactions in 1973 [1], most quantitative thermochemical information about ionmolecule reactions is derived from such measurements. Nevertheless, there are situations in which equilibrium constant determinations can not be made; this happens, for example, when one of the neutral bases is a free radical, or when a fast competing process precludes the establishement of an equilibrium.

Keywords

Proton Affinity Charge Transfer Reaction Diethyl Ketone Negative Temperature Dependence Rate Constant Data 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. 1a).
    M.T. Bowers, D.H. Aue, H.M. Webb, and R.T. Mclver, Jr., J. Am. Chem. Soc. 93 (1971) 4314; For reviews, see:CrossRefGoogle Scholar
  2. 1b).
    S.G. Lias in “Ion Cyclotron Resonance Spectrometry” (H. Hartmann and K.-P. Wanczek, editors), Springer-Verlag Lecture Notes in Chemistry Series, 7 (1978);Google Scholar
  3. 1c).
    D.H. Aue and M.T. Bowers, Chapter 9 in “Gas Phase Ion Chemistry, Vol. 2 (M.T. Bowers, editor), Academic Press (1979).Google Scholar
  4. 2.
    S.G. Lias, D.M. Shold, and P. Ausloos, J. Am. Chem. Soc. 102 (1980) 2540.CrossRefGoogle Scholar
  5. 3.
    J.C. Traeger and R.G. McLoughlin, J. Am. Chem. Soc, 103 (1981) 3647.CrossRefGoogle Scholar
  6. 4.
    T. Baer, J. Am. Chem. Soc. 102 (1980) 2482.CrossRefGoogle Scholar
  7. 5.
    H.M. Rosenstock, R. Buff, M.A.A. Ferreira, S.G. Lias, A.C. Parr, R.L. Stockbauer, and J.L. Holmes, J. Am. Chem. Soc, submitted for publication.Google Scholar
  8. 6.
    All heats of formation of ions cited here are given using the so-called “stationary electron” convention. That is, the integrated heat capacity of the electron is taken to be zero at all temperatures.Google Scholar
  9. 7.
    At this writing, there are several formulations available (listed below) for estimating rate constants for complex-forming collisions of ions with polar molecules. For the results given in Tables 1 and 3, collision rate constants have been calculated using the A.D.O. theory, reference (c) below. In Table 4, we cite the range of values calculated using the different appoaches from references (c), (d), and (e). The rate constants cited or referred to in Tables 5 and 7 are Langevin-Gioumousis-Stevenson values, references (a) and (b). (a) P. Langevin, Ann. Chim. Phys. 5 (1905) 245;Google Scholar
  10. 7(b).
    G. Gioumousis, and D.P. Stevenson, J. Chem. Phys. 29 (1958) 294;CrossRefGoogle Scholar
  11. 7(c).
    M.T. Bowers and T. Su in “Interactions between Ions and Molecules” (P. Ausloos, editor), Plenum (1975);Google Scholar
  12. 7(d).
    W.J. Chesnavich, T. Su, and M.T. Bowers, in “Kinetics of Ion-Molecule Reactions” (P. Ausloos, editor), Plenum (1979);Google Scholar
  13. 7(e).
    D.P. Ridge in “Kinetics of Ion-Molecule Reactions” (P. Ausloos, editor), Plenum (1979).Google Scholar
  14. 8.
    See for example: S.G. Lias, J.R. Eyler, and P. Ausloos, Int. J. Mass Spectrom. Ion Phys. 19 (1976) 219.Google Scholar
  15. 9.
    See for example reference 2 and D.K. Bohme, G.I. Mackay, and H.I. Schiff, J. Chem. Phys. 73 (1980) 4976.Google Scholar
  16. 10.
    See for example S.G. Lias, P. Ausloos, and Z. Horvath, Int. J. Chem. Kinetics, VIII, 725 (1976).Google Scholar
  17. 11.
    M. Mautner, J. Am. Chem. Soc, in press.Google Scholar
  18. 12.
    W. Tsang, Int. J. Chem. Kinetics 10 (1978) 41.Google Scholar
  19. 13.
    S.G. Lias and P. Ausloos, J. Am. Chem. Soc. 100 (1978) 6027.CrossRefGoogle Scholar
  20. 14.
    See for instance, E.A. Moelwyn-Highes, Chapter XXII of “Physical Chemistry”, Pergamon-Press (1961).Google Scholar
  21. 15.
    S.G. Lias, J. Am. Chem. Soc, submitted for publication.Google Scholar
  22. 16.
    P. Ausloos and S.G. Lias, J. Am. Chem. Soc. 100 (1978) 1953.CrossRefGoogle Scholar
  23. 17.
    P. Ausloos and S.G. Lias, J. Am. Chem. Soc. 103 (1981) 3641.CrossRefGoogle Scholar
  24. 18.
    N. Agmon and R.D. Levine, Chem. Phys. Letters, 52 (1977) 197.CrossRefGoogle Scholar
  25. 19.
    S.G. Lias, unpublished results.Google Scholar
  26. 20a).
    J.F. Wolf, R.H. Staley, I. Koppel, M. Taagepera, R.J. McIver, Jr., J.L. Beauchamp, and R.W. Taft, J. Am. Chem. Soc. 99 (1977) 5417; b)Google Scholar
  27. 20b).
    Y.K. Lau, Ph.D. thesis, University of Alberta, 1979Google Scholar
  28. 20c).
    R. Yamdagni and P. Kebarle, J. Am. Chem. Soc. 98 (1976) 1320.Google Scholar
  29. 21a).
    W. Tsang, Int. J. Chem. Kinetics 10 (1978) 821CrossRefGoogle Scholar
  30. 20b).
    A.L. Castelhano, P.R. Marriott, and D. Griller, J. Am. Chem. Soc. 103 (1981) 4262Google Scholar
  31. 20c).
    C.E. Canosa and R.M. Marshall, Int. J. Chem. Kinetics 13 (1981) 303Google Scholar
  32. 20d).
    M. Rossi and D.M. Golden, Int. J. Chem. Kinetics 11 (1979) 969.Google Scholar
  33. 22a).
    F.A. Houle and J.L. Beauchamp, J. Am. Chem. Soc. 101 (1979) 4067Google Scholar
  34. 22a).
    J. Dyke, N. Jonathan, E. Lee, A. Morris, and M. Winter, Phys. Scr. 16 (1977) 197.Google Scholar
  35. 23.
    M. Meot-Ner (Mautner), L.W. Sieck and P. Ausloos, J. Am. Chem. Soc, in press.Google Scholar
  36. 24.
    L.W. Sieck and M. Mautner, to be submitted.Google Scholar
  37. 25.
    V.J. Hammond, W.C. Price, J.P. Teegan, and A.D. Walsh, Disc. Faraday Soc. 9 (1950) 53.CrossRefGoogle Scholar
  38. 26.
    M. Mautner, J. Am. Chem. Soc, submitted for publication.Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1982

Authors and Affiliations

  • Sharon G. Lias
    • 1
  1. 1.National Bureau of StandardsWashington, D. C.USA

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