Thermodynamic Information from Ion-Molecule Equilibrium Constant Determinations

  • Sharon G. Lias
Part of the Lecture Notes in Chemistry book series (LNC, volume 7)

Abstract

According to the principles of thermodynamics, the equilibrium constant of any chemical equilibrium gives information about the thermochemistry of the chemical reactions in the forward and reverse directions:
$$ - RT\ln {K_{eq}} = \Delta {G^o} = \Delta {H^o} - T\Delta {S^o}$$
(I)
Equation I has been applied extensively to the derivation of thermochemical information, particularly in the liquid phase.

Keywords

Entropy Enthalpy Benzene Toluene MeOH 

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References

  1. 1.
    For reviews see: (a) P. Kebarle, Chapter 7 in “Ion-Molecule Reactions (J. L. Franklin, ed.), Plenum Press, New York, (1972);Google Scholar
  2. 1a.
    (b) E. E. Ferguson, Chapter 8 in “Ion-Molecule Reactions (J. L. Franklin, ed.), Plenum Press, New York (1972);Google Scholar
  3. 1b.
    (c) P. Kebarle in “Interactions Between Ions and Molecules (P. Ausloos, ed.), Plenum Press, New York (1975)Google Scholar
  4. 2.
    M. T. Bowers, D. H. Aue, H. M. Webb, and R. T. Mclver Jr., J. Am. Chem. Soc. 93, 4314 (1971)CrossRefGoogle Scholar
  5. 3.
    R. T. Mclver, and J. R. Eyler, J. Am. Chem. Soc. 93, 6334 (1971)CrossRefGoogle Scholar
  6. 4.
    A. E. Roche, M. M. Sutton, D. K. Böhme, and H. I. Schiff, J. Chem. Phys. 55, 5480 (1971)CrossRefGoogle Scholar
  7. 5.
    S.-L. Chong, R. A. Myers Jr., and J. L. Franklin, J. Chem. Phys. 56, 2427 (1971)CrossRefGoogle Scholar
  8. 6.
    J. B. Briggs, R. Yamdagni, and P. Kebarle, J. Am. Chem. Soc. 94, 5128 (1972)CrossRefGoogle Scholar
  9. 7.
    J. M. Hopkins and L. I. Bone, J. Chem. Phys. 58, 1473 (1973)CrossRefGoogle Scholar
  10. 8.
    R. S. Hemsworth, H. W. Rundle, D. K. Bohme, H. I. Schiff, D. B. Dunkin, and F. C. Fehsenfeld, J. Chem. Phys. 59, 61 (1973)CrossRefGoogle Scholar
  11. 9.
    R. Yamdagni and P. Kebarle, J. Am. Chem. Soc. 95, 4050 (1973)CrossRefGoogle Scholar
  12. 10.
    K. Hiroaka, R. Yamdagni, and P. Kebarle, J. Am. Chem. Soc. 95, 6833 (1973)CrossRefGoogle Scholar
  13. 11.
    R. Yamdagni and P. Kebarle, J. Am. Chem. Soc. 98, 1320 (1976)CrossRefGoogle Scholar
  14. 12.
    F. C. Fehsenfeld, W. Lindinger, H. I. Schiff, R. S. Hemsworth, and D. K. Bohme, J. Chem. Phys. 64, 4887 (1976)CrossRefGoogle Scholar
  15. 13.
    G. G. Meisels, R. K. Mitchum, and J. P. Freeman, J. Phys. Chem. 80, 2845 (1976)CrossRefGoogle Scholar
  16. 14.
    Y. K. Lau and P. Kebarle, J. Am. Chem. Soc. 98, 7452 (1976)CrossRefGoogle Scholar
  17. 15.
    M. Meot-Ner and F. H. Field, J. Chem. Phys. 66, 4527 (1977)CrossRefGoogle Scholar
  18. 16.
    K. G. Hartman and S. G. Lias, Int. J. Mass Spectrom. Ion Phys., submitted for publicationGoogle Scholar
  19. 17.
    S. F. Kasper and J. L. Franklin, J. Chem. Phys. 56, 1156 (1972)CrossRefGoogle Scholar
  20. 18.
    W. G. Henderson, M. Taagepera, D. Holtz, R. T. Mclver Jr., J. L. Beauchamp and R. W. Taft, J. Am. Chem. Soc. 94, 4728 (1972)CrossRefGoogle Scholar
  21. 19.
    D. H. Aue, H. M. Webb, and M. T. Bowers, J. Am. Chem. Soc. 94, 4726 (1972)CrossRefGoogle Scholar
  22. 20.
    S.-L. Chong and J. L. Franklin, J. Am. Chem. Soc. 94, 6347 (1972)CrossRefGoogle Scholar
  23. 21.
    E. M. Arnett, F. M. Jones III, M. Taagepera, W. G. Henderson, J. L. Beauchamp, D. Holtz, and R. W. Taft, J. Am. Chem. Soc. 94, 4724 (1972)CrossRefGoogle Scholar
  24. 22.
    D. H. Aue, H. M. Webb, and M. T. Bowers, J. Am. Chem. Soc. 95, 2699 (1973).CrossRefGoogle Scholar
  25. 23.
    D. K. Bohme, R. S. Hemsworth, H. W. Rundle, and H. I. Schiff, J. Chem. Phys. 58, 3504 (1973)CrossRefGoogle Scholar
  26. 24.
    R. T. McIver Jr., J. A. Scott, and J. M. Riveros, J. Am. Chem. Soc. 95, 2706 (1973)CrossRefGoogle Scholar
  27. 25.
    D. K. Bohme, R. S. Hemsworth, and H. W. Rundle, J. Chem. Phys. 59, 77 (1973)CrossRefGoogle Scholar
  28. 26.
    D. K. Bohme, R. S. Hemsworth, and H. W. Rundle, J. Chem. Phys. 59, 77 (1973)CrossRefGoogle Scholar
  29. 27.
    A. G. Harrison and A. S. Blair, Int. J. Mass Spectrom. Ion Phys. 12, 175 (1973)CrossRefGoogle Scholar
  30. 28.
    R. T. Nlclver Jr., and J. H. Silvers, J. Am. Chem. Soc. 95, 8462 (1973)CrossRefGoogle Scholar
  31. 29.
    P. F. Fennelly, R. S. Hemsworth, H. I. Schiff, and D. K. Bohme, J. Chem. Phys. 59, 6405 (1973)CrossRefGoogle Scholar
  32. 30.
    R. H. Staley and J. L. Beauchamp, J. Am. Chem. Soc. 96, 1604 (1974)CrossRefGoogle Scholar
  33. 31.
    R. Yamdagni and P. Kebarle, Can. J. Chem. 52, 861 (1974)CrossRefGoogle Scholar
  34. 32.
    R. T. Mclver Jr., and J. Scott Miller, J. Am. Chem. Soc. 96, 4323 (1974)CrossRefGoogle Scholar
  35. 33.
    T. B. McMahon and P. Kebarle, J. Am. Chem. Soc. 96, 5940 (1974)CrossRefGoogle Scholar
  36. 34.
    E. M. Arnett, L. E. Small, R. T. Mclver Jr., and J. Scott Miller, J. Am. Chem. Soc. 96, 5638 (1974)CrossRefGoogle Scholar
  37. 35.
    D. K. Bohme, G. I. Mackay, H. I. Schiff, and R. S. Hemsworth, J. Chem. Phys. 61, 2175 (1974)CrossRefGoogle Scholar
  38. 36.
    W. J. Hehre, R. T. Mclver Jr., J. A. Pople, and P. v. R. Schleyer, J. Am. Chem. Soc. 96, 7162 (1974)CrossRefGoogle Scholar
  39. 37.
    H. I. Schiff and D. K. Bohme, Int. J. Mass Spectrom. Ion Phys. 16, 167 (1975)CrossRefGoogle Scholar
  40. 38.
    R. H. Staley and J. L. Beauchamp, J. Chem. Phys. 62, 1998 (1975)CrossRefGoogle Scholar
  41. 39.
    J. D. Payzant, H. I. Schiff, and D. K. Bohme, J. Chem. Phys. 63, 149 (1975)CrossRefGoogle Scholar
  42. 40.
    J. F. Wolf, P. G. Harch, R. W. Taft, and W. J. Hehre, J. Am. Chem. Soc. 97, 2902 (1975)CrossRefGoogle Scholar
  43. 41.
    J. F. Wolf, P. G. Harch, and R. W. Taft, J. Am. Chem. Soc. 97, 2904 (1975)CrossRefGoogle Scholar
  44. 42.
    D. H. Aue, H. M. Webb, and M. T. Bowers, J. Am. Chem. Soc. 98, 311 (1976)CrossRefGoogle Scholar
  45. 43.
    G. I. Mackay, R. S. Hemsworth, and D. K. Bohme, Can. J. Chem. 54, 1624 (1976)CrossRefGoogle Scholar
  46. 44.
    J. L. Devlin III, J. F. Wolf, R. W. Taft, and W. J. Hehre, J. Am. Chem. Soc. 98, 1990 (1976)CrossRefGoogle Scholar
  47. 45.
    L. F. Wolf, J. L. Devlin III, D. J. DeFrees, R. W. Taft, and W. J. Hehre, J. Am. Chem. Soc. 98, 5097 (1977)CrossRefGoogle Scholar
  48. 46.
    S. K. Pollack, J. F. Wolf, B. A. Levi, R. W. Taft, and W. J. Hehre, J. Am. Chem. Soc. 99, 1350 (1977)CrossRefGoogle Scholar
  49. 47.
    J. F. Wolf, R. H. Staley, I. Koppel, M. Taagepera, R. T. Mclver Jr., J. L. Beauchamp, and R. W. Taft, J. Am. Chem. Soc. 99, 5417 (1977)CrossRefGoogle Scholar
  50. 48.
    P. Ausloos and S. G. Lias, J. Am. Chem. Soc. 99, 4198 (1977)CrossRefGoogle Scholar
  51. 49.
    P. Ausloos and S. G. Lias, Chem. Phys. Lett., in pressGoogle Scholar
  52. 50.
    T. B. McMahon, R. J. Blint, D. P. Ridge, and J. L. Beauchamp, J. Am. Chem. Soc. 94, 8934 (1972)CrossRefGoogle Scholar
  53. 51.
    R. J. Blint, T. B. McMahon, and J. L. Beauchamp, J. Am. Chem. Soc. 96, 1269 (1974)CrossRefGoogle Scholar
  54. 52.
    J. A. Jackson, S. G. Lias and P. Ausloos, J. Am. Chem. Soc, in pressGoogle Scholar
  55. 53.
    J.-L. M. Abboud, W. J. Hehre, and R. W. Taft, J. Am. Chem. Soc. 98, 6072 (1976)CrossRefGoogle Scholar
  56. 54.
    M. Meot-Ner and F. H. Field, Chem. Phys. Lett. 44, 484 (1976)CrossRefGoogle Scholar
  57. 55.
    S. G. Lias, Chem. Phys. Lett., in pressGoogle Scholar
  58. 56.
    V. G. Aninich, M. T. Bowers, R. M. O’Malley, and K. R. Jennings, Int. J. Mass Spectrom. Ion Phys. 11, 99 (1973)CrossRefGoogle Scholar
  59. 57.
    V. G. Anicich and M. T. Bowers, Int. J. Mass Spectrom. Ion Phys. 13, 351 (1974)CrossRefGoogle Scholar
  60. 58.
    L. W. Sieck and R. Gorden Jr., Int. J. Mass Spectrom. Ion Phys. 19, 269 (1976)CrossRefGoogle Scholar
  61. 59.
    S. G. Lias, P. Ausloos, and Z. Horvath, Int. J. Chem. Kinetics, VIII 725 (1976)CrossRefGoogle Scholar
  62. 60.
    J. F. Wolf, J. L. Devlin III, R. W. Taft, M. Wolfsberg, and W. J. Hehre, J. Am. Chem. Soc. 98, 287 (1976)CrossRefGoogle Scholar
  63. 61.
    T. B. McMahon, P. G. Miasek, and J. L. Beauchamp, Int. J. Mass Spectrom. Ion Phys. 21, 63 (1976)CrossRefGoogle Scholar
  64. 62.
    S. G. Lias and P. Ausloos, J. Am. Chem. Soc. 99, 4831 (1977)CrossRefGoogle Scholar
  65. 63.
    J. J. Solomon and F. H. Field, J. Am. Chem. Soc. 95, 4483 (1973)CrossRefGoogle Scholar
  66. 64.
    J. J. Solomon, M. Meot-Ner, and F. H. Field, J. Am. Chem. Soc. 96, 3727 (1974)CrossRefGoogle Scholar
  67. 65.
    J. J. Solomon and F. H. Field, J. Am. Chem. Soc. 97, 2625 (1975)CrossRefGoogle Scholar
  68. 66.
    M. Meot-Ner, J. J. Solomon, and F. H. Field, J. Am. Chem. Soc. 98, 1025 (1976)CrossRefGoogle Scholar
  69. 67.
    J. J. Solomon and F. H. Field, J. Am. Chem. Soc. 98, 1567 (1976)CrossRefGoogle Scholar
  70. 68.
    A. Goren and B. Munson, J. Phys. Chem. 80, 2848 (1976)CrossRefGoogle Scholar
  71. 69.
    J. L. Beauchamp, M. C. Caserio, and T. B. McMahon, J. Am. Chem. Soc. 96, 6243 (1974)CrossRefGoogle Scholar
  72. 70.
    (a) P. Langevin, Ann. Chim. Phys. 5, 245 (1905);Google Scholar
  73. 70a.
    (b) G. Gioumousis and D. P. Stevenson, J. Chem. Phys. 29, 294 (1958)CrossRefGoogle Scholar
  74. 71.
    (a) T. Su and M. T. Bowers, J. Am. Chem. Soc. 95, 1370 (1973);CrossRefGoogle Scholar
  75. 71a.
    (b) T. Su and M. T. Bowers, Int. J. Mass Spectrom. Ion Phys. 12, 347 (1973);CrossRefGoogle Scholar
  76. 71b.
    (c) T. Su and M. T. Bowers, Int. J. Mass Spectrom. Ion Phys. 17, 211 (1975)CrossRefGoogle Scholar
  77. 72.
    H. Eyring, J. O. Hirschfelder, and H. S. Taylor, J. Chem. Phys. 4, 479 (1936)CrossRefGoogle Scholar
  78. 73.
    K. Yang and T. Ree, J. Chem. Phys. 35, 588 (1961)CrossRefGoogle Scholar
  79. 74.
    (a) H. M. Rosenstock, K. Draxl, B. W. Steiner, and J. T. Herron, J. Phys. and Chem. Ref. Data 6, Suppl. 1(1977);CrossRefGoogle Scholar
  80. 74a.
    (b) G. G. Hall, Faraday Disc, Chem. Soc. 54, 7 (1972)CrossRefGoogle Scholar
  81. 75.
    (a) L. Asbrink, E. Lindholm and O. Edquist, Chem. Phys. Lett. 5, 609 (1970);CrossRefGoogle Scholar
  82. 75a.
    (b) L. Salem, “The Molecular Orbital Theory of Conjugated Systems,” W. A. Benjamin, Inc., New York (1966);Google Scholar
  83. 75b.
    (c) G. Herzberg, “Electronic Spectra of Polyatomic Molecules”, Van Nostrand, Princeton (1966)Google Scholar
  84. 76.
    (a) G. Herzberg, “Spectra of Diatomic Molecules,” Van Nostrand, New York (1950);Google Scholar
  85. 76a.
    (b) D. W. Turner, C. Baker, A. D. Baker, and C. R. Brundle, “Molecular Photoelectron Spectroscopy,” Wiley-Interscience, New York (1970)Google Scholar
  86. 77.
    K. Tanaka, G. I. Mackay, and D. K. Bohme, Can J. Chem., in press.Google Scholar
  87. 78.
    V. Dyczmons, V. Staemmler, and W. Kutzelnigg, Chem. Phys. Lett. 5, 361 (1970).CrossRefGoogle Scholar
  88. 79.
    W. R. Davidson, M. T. Bowers, T. Su, and D. H. Aue, Int. J. Mass Spectrom. Ion Phys. 24, 83 (1977)CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1978

Authors and Affiliations

  • Sharon G. Lias
    • 1
  1. 1.Institute for Materials ResearchNational Bureau of StandardsUSA

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