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Higher-Order Reactions—Ion Clusters and Ion Solvation

  • Paul Kebarle

Abstract

This chapter deals with ion clusters, clustering reactions, and equilibria studied by mass spectrometric detection of ions escaping from ion sources at pressures above 1 Torr. Many of the phenomena encountered in this pressure range have significance beyond the study of ion clusters. Some such features of general importance to ion-molecule reactions at elevated pressures are also included in the discussion.

Keywords

Kcal Mole Entropy Change Methanol Molecule Proton Hydrate Cluster Reaction 
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. 1.
    J. J. Thompson and E. Rutherford, Phil. Mag. 42, 392 (1896).Google Scholar
  2. 2.
    L. B. Loeb, “Basic Processes of Gaseous Electronics,” University of California Press, Berkeley (1955).Google Scholar
  3. 3.
    S. C. Lind, “Radiation Chemistry of Gases”, Reinhold Publishing Corp., New York (1961).Google Scholar
  4. 4.
    P. F. Knewstubb and T. M. Sugden, Mass-spectrometric studies of ionization in flames. I. The spectrometer and its application to ionization in hydrogen flames, Proc. Roy. Soc. (London) A255, 520–537 (1960).Google Scholar
  5. 5.
    A. W. Tickner and P. F. Knewstubb, Mass spectrometry of ions in glow discharges. IV. Water vapour, J. Chem. Phys. 38, 464–469 (1963).CrossRefGoogle Scholar
  6. 6.
    P. Kebarle and E. W. Godbole, Mass spectrometric study of gases at near atmospheric pressures. J. Chem. Phys. 39, 1131–1132 (1963).CrossRefGoogle Scholar
  7. 7.
    P. Kebarle and A. M. Hogg, Heats of hydration and solvation by mass spectrometry, J. Chem. Phys. 42, 798–799 (1965).CrossRefGoogle Scholar
  8. 8.
    J. H. Yang and D. C. Conway, Bonding in ion clusters. I. O4 +, J. Chem. Phys. 40, 1729–1735 (1964).CrossRefGoogle Scholar
  9. 9.
    C. E. Melton and P. S. Rudolf, Mass spectrometric studies of ionic intermediates in the alpha-particle radiolysis of ethylene, J. Chem. Phys. 32, 1128–1131 (1960).CrossRefGoogle Scholar
  10. 10.
    F. J. Field, Reactions of gaseous ions. VIII. Multiple-order Ion-molecule reactions in the ultra-high-pressure mass spectrum of ethylene, J. Am. Chem. Soc. 83, 1523–1534 (1961).CrossRefGoogle Scholar
  11. 11.
    S. Wexler and R. J. Marshall, Consecutive ion molecule reactions in ethylene, J. Am. Chem. Soc. 86, 781–787 (1964).CrossRefGoogle Scholar
  12. 12.
    A. M. Hogg and P. Kebarle, Mass spectrometric study of ions at near atmospheric pressure II. Ammonium ions. J. Chem. Phys. 43, 449–456 (1965).CrossRefGoogle Scholar
  13. 13.
    A. M. Hogg, R. M. Haynes, and P. Kebarle, Ion-solvent molecule interactions studied in the gas phase, J. Am. Chem. Soc. 88, 28–31 (1966).CrossRefGoogle Scholar
  14. 14.
    P. Kebarle, R. M. Haynes, and S. K. Searles, Mass spectrometric study of ions in gases under conventional radiation chemical conditions, ethylene and ethylene and nitric oxide, in “Ion-Molecule Reactions in Gases” (Advances in Chemistry Series, No. 58, P. J. Ausloos, ed.), pp. 210–242, American Chemical Society, Washington, D.C. (1966).Google Scholar
  15. 15.
    P. Kebarle, R. M. Haynes, and S. K. Searles, Mass spectrometric study of ions in Xe, Kr, Ar, Ne at pressures up to 40 Torr, J. Chem. Phys. 47, 1684–1691 (1967).CrossRefGoogle Scholar
  16. 16.
    P. Kebarle and R. M. Haynes, Ion-molecule reactions in the xenon-sensitized ionization of ethylene, J. Chem. Phys. 47, 1676–1683 (1967).CrossRefGoogle Scholar
  17. 17.
    P. Kebarle, R. M. Haynes, and G. J. Collins, Competitive solvation of the hydrogen ion by water and methanol molecules in the gas phase, J. Am. Chem. Soc. 89, 5753–5757 (1967).CrossRefGoogle Scholar
  18. 18.
    P. Kebarle, S. K. Searles, A. Zolla, J. Scarborough, and M. Arshadi, The solvation of the hydrogen ion by water molecules in the gas phase. Heats and entropies of solvation of individual reaction H+(H2O) n -1 + H2O H+(H2O)n, J. Am. Chem. Soc. 89, 6393–6399 (1967).CrossRefGoogle Scholar
  19. 19.
    P. Kebarle, M. Arshadi, and J. Scarborough, Hydration of negative ions in the gas phase, J. Chem. Phys. 49, 817–822 (1968).CrossRefGoogle Scholar
  20. 20.
    P. Kebarle, Mass spectrometric study of ion-solvent molecule interactions in the gas phase, in “Mass Spectrometry in Inorganic Chemistry” (Advances in Chemistry Series, No. 72), pp. 24–47, American Chemical Society, Washington, D.C. (1968).CrossRefGoogle Scholar
  21. 21.
    S. K. Searles and P. Kebarle, Ion-solvent molecule interactions in the gas phase. Enthalpies and entropies for the reactions NH4 +(NH3)n -1 + NH3 = NH4 +(NH3)n, J. Phys. Chem. 72, 742–743 (1968).CrossRefGoogle Scholar
  22. 22.
    J. Wexler, Assa Lifschitz, and A. Quattrochi, High-pressure mass spectrometry with a MeV proton beam. Ethylene, acetylene, methane, in “Ion-Molecule Reactions in the Gas Phase”. (Advances in Chemistry Series, No. 58, P. J. Ausloos, ed.), pp. 193–209, American Chemical Society, Washington, D.C. (1966).Google Scholar
  23. 23.
    D. A. Durden, P. Kebarle, and A. Good, Thermal ion-molecule reaction rate constants at pressures up to 10 Torr with a pulsed mass spectrometer. Reactions in methane, krypton and oxygen. J. Chem. Phys. 50, 805–813 (1969).CrossRefGoogle Scholar
  24. 24.
    A. Good, D. A. Durden, and P. Kebarle, Ion-molecule reactions in pure nitrogen and nitrogen containing traces of water at total pressures 0.5–4 Torr. Kinetics of clustering reactions forming H+(H2O)n, J. Chem. Phys. 52, 212–221 (1970).CrossRefGoogle Scholar
  25. 25.
    A. Good, D. A. Durden, and P. Kebarle, Mechanism and rate constants of ion-molecule reactions leading to formation of H+(H2O)n in moist oxygen and air, J. Chem. Phys. 52, 222–229 (1970).CrossRefGoogle Scholar
  26. 26.
    S. K. Searles and P. Kebarle, Hydration of the potassium ion in the gas phase, enthalpies and entropies of hydration reactions K+(H2O)n -1 + H2O = K+(H2O)n, Can. J. Chem. 47, 2619–2627 (1969).CrossRefGoogle Scholar
  27. 27.
    W. Henkes, Massenspectrometrische Untersuchung von Strahlen aus Kondensiertem Wasserstoff, Z. Naturforsch. 17a, 786–789 (1962).Google Scholar
  28. 28.
    A. M. Hogg and P. Kebarle, NH4 +(NH3)n ions in ammonia at pressures up to 300 Torr, unpublished work.Google Scholar
  29. 29.
    D. C. Conway, Geometrics of O4 +, O4 -, and N4 + by an approximate SCF-MO theory which considers intermolecular differential overlap, J. Chem. Phys. 50, 3864–66 (1969).CrossRefGoogle Scholar
  30. 30.
    D. K. Bohme, D. B. Dunkin, F. C. Fehsenfeld, and E. E. Ferguson, Flowing afterglow studies of ion-molecule association reactions, J. Chem. Phys. 51, 863–872 (1969).CrossRefGoogle Scholar
  31. 31.
    M. Yoshida and P. Kebarle, to be published.Google Scholar
  32. 32.
    F. C. Fehsenfeld and E. E. Ferguson, Origin of water cluster ions in the D region, J. Geophys. Res. 74, 2217–2222 (1969).CrossRefGoogle Scholar
  33. 33.
    N. G. Adams, D. K. Bohme, D. B. Dunkin, F. C. Fehsenfeld, and E. E. Ferguson, Flowing afterglow studies of formation and reaction of cluster ions of O2 +, O2 -, and O-, J. Chem. Phys. to be published.Google Scholar
  34. 34.
    M. Mosesman, F. C. Fehsenfeld, and E. E. Ferguson, J. Chem. Phys., to be published.Google Scholar
  35. 35.
    P. Warneck, Studies of ion-neutral reactions by a photoionization mass spectrometer technique. I. J. Chem. Phys. 46, 502–512 (1967).CrossRefGoogle Scholar
  36. 36.
    P. F. Knewstubb, Ion-molecule reaction in flowing gas stream. Advan. Mass Spectrometry 4, 391–398 (1968).Google Scholar
  37. 37.
    E. E. Ferguson and F. C. Fehsenfeld, Some aspects of the metal in chemistry of the earth’s atmosphere, J. Geophys. Res. 73, 6215–6223 (1968).CrossRefGoogle Scholar
  38. 38.
    D. K. Bohme and F. C. Fehsenfeld, Thermal reactions of O2 + and O- ions in gaseous ammonia, Can. J. Chem. 47, 2715–2717 (1969).CrossRefGoogle Scholar
  39. 39.
    J. Payzant and P. Kebarle, to be published.Google Scholar
  40. 40.
    E. Rabinovitch, The recombination velocity of free atoms. Trans. Faraday Soc. 33, 283–293 (1937).CrossRefGoogle Scholar
  41. 41.
    N. M. Rodriguin and E. H. Rodriguina, “Consecutive Chemical Reactions” (translated by R. F. Schneider), D. Van Nostrand Co., New York (1964).Google Scholar
  42. 42.
    R. H. Fowler and E. A. Guggenheim, “Statistical Thermodynamics,” p. 497, Cambridge University Press, Cambridge, England (1939).Google Scholar
  43. 43.
    I. Džidič and P. Kebarle, Hydration of the alkali ion in the gas phase. Enthalpies and Entropies of reactions: M+(H2O)n -1 + H2O = M+(H2O)n, J. Chem. Phys. 74, 1466–1474 (1970).CrossRefGoogle Scholar
  44. 44.
    M. Arshadi, R. Yamdagni, and P. Kebarle, Hydration of the halide negative ions in the gas phase. Comparison of hydration energies for the alkali positive and halide negative ions, J. Phys. Chem. 74, 1475–1482 (1970).CrossRefGoogle Scholar
  45. 45.
    M. Arshadi and P. Kebarle, Hydration of OH- and O2 - in the gas phase. Comparative solvation of OH- by water and the hydrogen halides, effects of acidity, J. Phys. Chem. 74, 1483–1485 (1970).CrossRefGoogle Scholar
  46. 46.
    R. J. Munson and K. Hoselitz, The mobility of alkali ions in gases—II. The attachment of inert gas atoms to alkali ions, Proc. Roy. Soc. A172, 43–50 (1939).Google Scholar
  47. 47.
    W. A. Chupka, Dissociation energies of some alkali halide complex ions and the hydrated ion K+(H2O), J. Chem. Phys. 30, 458–465 (1959).CrossRefGoogle Scholar
  48. 48.
    A. N. Hayhurst and T. M. Sugden, Mass spectrometry of flames. Proc. Roy. Soc. A293, 36–49 (1966).Google Scholar
  49. 49.
    J. E. Desnoyers and C. Joliceur, in “Modern Aspects of Electrochemistry, No. 5,” (J. O. M. Bockris and B. E. Conway, eds.), pp. 1–89, Plenum Press, New York (1969).Google Scholar
  50. 50.
    Max A. Haney and J. L. Franklin, Mass spectrometric determinations of the proton affinities of various molecules, J. Phys. Chem. 73, 4329 (1969).CrossRefGoogle Scholar
  51. 51.
    R. Yamdagni and P. Kebarle, J. Am. Chem. Soc, 93, 7139 (1971).CrossRefGoogle Scholar
  52. 52.
    T. O. Tiernan and B. Mason Huges, J. Am. Chem. Soc., to be published.Google Scholar
  53. 53.
    J. I. Brauman and L. K. Blair, Gas-phase acidities of alcohols, effects of alkyl groups, J. Am. Chem. Soc. 90, 6561–6562 (1968).CrossRefGoogle Scholar
  54. 54.
    M. De Paz, J. J. Leventhal, and L. Friedman, Tandem mass spectrometer study of D3O+ and solvated derivatives, J. Chem. Phys. 51, 3748–3752 (1969).CrossRefGoogle Scholar
  55. 55.
    P. Kebarle, Can ionic clustering equilibria of the type H+(H2O)n -1 + H2O = H+(H2O)n be measured with mass spectrometric techniques?, J. Chem. Phys., 53, 2129 (1970).CrossRefGoogle Scholar
  56. 56.
    R. S. Narcisi and A. D. Bailey, Mass spectrometric measurements of positive ions at altitudes from 64 to 112 kilometers, J. Geophys. Res. 70, 3687–3700 (1965).CrossRefGoogle Scholar
  57. 57.
    R. S. Narcisi, in “Planetary Electrodynamics” (S. C. Coronit and J. Hughes, eds.), Vol. 2, p. 69, Gordon and Breach, New York-London (1969).Google Scholar
  58. 58.
    E. E. Ferguson and F. C. Fehsenfeld, Water vapor ion cluster concentration in the D region, J. Geophys. Res. 74, 5743–5751 (1969).CrossRefGoogle Scholar
  59. 59.
    R. S. Narcisi and W. Roth, The formation of cluster ions in laboratory sources and the ionosphere, Adv. Electr. Electron Phys. 29, 79 (1970).CrossRefGoogle Scholar
  60. 60.
    D. G. Murcray, J. G. Kyle, F. H. Murcray, and W. J. Williams, Nitric acid and nitric oxide in the lower stratosphere, Nature 218, 78–79 (1968).CrossRefGoogle Scholar
  61. 61.
    W. H. Kasner and M. A. Biondi, Temperature dependence of electron-O2 + ion recombination coefficient, Phys. Rev. 174, 139–144 (1969).CrossRefGoogle Scholar
  62. 62.
    J. L. Magee and K. Funabashi, The clustering of ions in irradiated gases, Rad. Res. 10, 622–625 (1959).CrossRefGoogle Scholar
  63. 63.
    K. M. Bansal and G. R. Freeman, Ionic chain reactions in the radiation-sensitized pyrolysis of ethanol vapor, J. Am. Chem. Soc. 90, 5632–5633 (1968).CrossRefGoogle Scholar
  64. 64.
    M. Yoshida and P. Kebarle, unpublished results.Google Scholar
  65. 65.
    A. R. Anderson, Inorganic gases, in “Fundamental Processes in Radiation Chemistry” (P. J. Ausloos, ed.), p. 298, Interscience Publishers, New York (1968).Google Scholar
  66. 66.
    N. G. Adams, O. K. Bohme, D. B. Dunkin, F. C. Fehsenfeld, and E. E. Ferguson, J. Chem. Phys. (submitted).Google Scholar
  67. 67.
    R. L. Clampitt and L. Gowland, Clustering of cold hydrogen gas on protons, Nature 223, 815–816 (1969).CrossRefGoogle Scholar

Copyright information

© Plenum Press, New York 1972

Authors and Affiliations

  • Paul Kebarle
    • 1
  1. 1.Chemistry DepartmentUniversity of AlbertaEdmontonCanada

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