Skip to main content
SpringerLink
Log in

Dielectric Polarization of Fluids Comprising Rigid Dipoles and Molecules with Internal Rotational Degrees of Freedom

  • Chapter
Reactive and Flexible Molecules in Liquids

Part of the book series: NATO ASI Series ((ASIC,volume 291))

Abstract

From the molecular theory of dielectric polarization an expression for the average moment is obtained, which formally agrees with the results of the Onsager-Böttcher-Scholte-model. The reaction field and the cavity field are replaced by the results of a molecular statistical theory. A simple approximation is proposed, which is exact at low densities, and in fair agreement with the results of the simulations of the Stockmayer fluid at high densities. The approximation is applied in order to explain the density and temperature dependence of the dielectric permittivity of pure fluids (CH3F, CF3H, CF3C1, H2O, CH3CN), and mixtures with non-polar solvents.

In order to describe the dielectric permittivity of molecules with internal rotational degrees of freedom, such as CO(OR)2, PO(OR)3 (R = CH3, CH2CH3), an equilibrium between the conformeres is assumed. The dipole moment and the energies of the conformeres are calculated by semi-empirical and ab initio methods (MINDO/3, MNDO, STO-3G, 3-21G, 4-31G, 4-31G*). The reaction field stabilizes the conformere with the higher dipole moment, which is the less stable conformere. Reasonable agreement between theoretical and experimental results is found for the variation of the average dipole moment with temperature and concentration.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 39.99
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 54.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

Literature

  1. Debye, P., Polare Molekeln, Hirzel, Leipzig (1929).

    Google Scholar 

  2. Onsager, L., J. Am Chem. Soc. 58., 1468 (1936)

    Google Scholar 

  3. Cholte, T.G., Physica 15, 437 (1949).

    Article  Google Scholar 

  4. Fröhlich, H., Theory of Dielectrics, 2nd ed., Oxford U.P. (1968).

    Google Scholar 

  5. Böttcher, C.J., Theory of Electric Polarization, 2nd ed., Vol. 1 (1973); Vol. 2 (1978), Elsevier Amsterdam.

    Google Scholar 

  6. Kirkwood, J.G., J. Chem. Phys. 7, 911 (1939).

    Article  CAS  Google Scholar 

  7. Schröer, W., Ber. Bunsenges. Phys. Chem. 86, 916 (1986).

    Google Scholar 

  8. Nienhuis, G. and Deutch, J.M., J. Chem. Phys. 55, 4213 (1971).

    Article  CAS  Google Scholar 

  9. Ramshaw, J.D., a) J. Chem. Phys, 57, 2684 (1972); b) ibid 66, 3134 (1977); c) ibid 68, 4149 (1978).

    Google Scholar 

  10. Hoye, J.S. and Stell, G., J. Chem. Phys. 61, 562 (1974); 64, 1952 (1976).

    Google Scholar 

  11. de Leeuw, S., Perram, J.S. and Smith, E.R. Proc. Roy. Soc., London, A373, 27, 57 (1980).

    Google Scholar 

  12. Pollock, E.L. and Alder, B.G., Physica A102, 1 (1980).

    Google Scholar 

  13. Alder, B.G., Alley, E. and Pollock, E.L., Ber. Bunsenges. Phys. Chem. 85, 944 (1981).

    CAS  Google Scholar 

  14. Neumann, M., Mol. Phys. 50, 841 (1983).

    Article  CAS  Google Scholar 

  15. Neumann, M. and Steinhauser O., Mol. Phys. 39, 437 (1981).

    Article  Google Scholar 

  16. Levesque, D., Patey G.N. and Weis, J.J., Mol. Phys, 34, 1077 (1977).

    Article  CAS  Google Scholar 

  17. Patey, G.N., Levesque, D. and Weis, J.J., Mol. Phys. 45, 737 (1982).

    Article  Google Scholar 

  18. Neumann, M. and Steinhauser, O., Chem. Phys. Lett. 95, 417 (1983).

    Article  CAS  Google Scholar 

  19. Adams, D.J., Mol. Phys. 40, 1261 (1980).

    Article  CAS  Google Scholar 

  20. Wertheim, M.S., J. Chem. Phys. 55, 4291 (1971).

    Article  CAS  Google Scholar 

  21. Patey, G.N., Mol. Phys. 34, 427 (1977).

    Article  CAS  Google Scholar 

  22. Patey, G.N., Mol. Phys. 35, 1413 (1978).

    Article  CAS  Google Scholar 

  23. Buckingham, A.D. and Joslin, C.G., Mol. Phys. 40, 1513 (1980).

    Article  CAS  Google Scholar 

  24. Buckingham, A.D. and Pople J.A., Trans. Farad. Soc. 61, 1179 (1955).

    Article  Google Scholar 

  25. Buckingham, A.D., Adv. in Chem. Phys. 12, 107 (1967).

    CAS  Google Scholar 

  26. Joslin, C.G., Mol. Phys. 47, 693 (1982).

    Article  CAS  Google Scholar 

  27. Buckingham, A.D. and Pople, J.D., Proc. Phys. Soc. 68A, 905 (1955).

    CAS  Google Scholar 

  28. Fries, P.H. and Patey, G.N., J. Chem. Phys. 82, 429 (1985).

    Article  CAS  Google Scholar 

  29. Lee, L.Y., Fries, P.H. and Patey, G.N., Mol. Phys. 55, 751 (1985).

    Article  CAS  Google Scholar 

  30. Adelman, S.A. and Deutch, J.M., Adv. Chem. Phys. 31, 103 (1975).

    Article  CAS  Google Scholar 

  31. Stell, G., Patey, G.N. and Hoye, J.S., Adv. Chem. Phys. 48, 183 (1981).

    Article  CAS  Google Scholar 

  32. Madden, P. and Kivilson, D., Adv. Chem. Phys. 61, 411 (1984)

    Google Scholar 

  33. W. Schröer, Adv. Chem. Phys. 63, 720 (1985).

    Google Scholar 

  34. Wertheim, M.S. a) Mol. Phys. 26, 1426 (1973); b) ibid 33, 95 (1977); c) ibid 36, 1217 (1978).

    Google Scholar 

  35. Wertheim, M.S., Am. Rev. Phys. Chem. 30, 471 (1979).

    Article  CAS  Google Scholar 

  36. Schröer, W., Thesis, Cambridge (1981).

    Google Scholar 

  37. Schröer, W., Mol. Phys. 41, 239 (1980).

    Article  Google Scholar 

  38. Uhlenbeck, G.E. and Ford, G.W., Studies in Statistical Mechanics 1, 123, North Holland, Amsterdam (1962).

    Google Scholar 

  39. Rushbrooke, G.S. in Physics of Simple Liquids Temperley, N.N.V, Rushbrooke, G.S. and Rowlinson J.S. eds. Elsevier. Amsterdam, p. 25 (1968).

    Google Scholar 

  40. Stell, G. in The Equilibrium Theory of Classical Fluids Frisch, H.L. and Lebowitz J.L. eds. Benjamin, New York, p. II - 171 (1964).

    Google Scholar 

  41. Lebowitz, J.L., Stell G. and Baer, S., J. Math. Phys. 6, 1282 (1965).

    Article  Google Scholar 

  42. Lebowitz, J.L. and Percus, J.K., J. Math. Phys. 4, 248 (1961).

    Article  Google Scholar 

  43. Rushbrooke, G.S., Mol. Phys. 37, 761 (1979).

    Article  CAS  Google Scholar 

  44. Jepsen, D.W. and Friedman, H., J. Chem. Phys. 38, 846 (1963).

    Article  CAS  Google Scholar 

  45. Jepsen, D.W., J. Chem. Phys. 44, 774 (1966).

    Article  CAS  Google Scholar 

  46. Joslin, C.G., Mol. Phys. 42, 1507 (1981).

    Article  CAS  Google Scholar 

  47. Baron, V., Mol. Phys, 28, 809 (1974).

    Article  Google Scholar 

  48. Barnes, A.N.H., Sutton, L. E. Trans Farad Soc. 67, 2926 (1971)

    Article  CAS  Google Scholar 

  49. Sutter, H., Cole, R.H., a) J. Chem. Phys. 52, 132 (1970) b) ibid 96, 2014 (1967)

    Google Scholar 

  50. Perram, J.W. and Wertheim, M.S., J. Comp. Phys. 58, 409 (1985).

    Article  CAS  Google Scholar 

  51. Frenkel, D., Mulder, B.M., Mol. Phys. 55, 1171, 1193 (1985).

    Google Scholar 

  52. Perera, A., Kusalik, P.G. and Patey, G.N., J. Chem. Phys. 87, 1295 (1987).

    CAS  Google Scholar 

  53. Joslin, C.G., Mol. Phys. 47, 771 (1982).

    Article  CAS  Google Scholar 

  54. Schröer, W. and Rybarsch, C., Chem. Phys. Lett. 126, 342 (1986).

    Google Scholar 

  55. Mandel, M. and Mazur, P., Physica 24, 116 (1958).

    Article  CAS  Google Scholar 

  56. Harary, F., Graph Theory Addison-Wesley, London (1969).

    Google Scholar 

  57. Schröer, W. and Rybarsch, C., Chem. Phys. Lett. 131, 500 (1986).

    Article  Google Scholar 

  58. Orville. Thomas, W.J. ed., Internal Rotation in Molecules, John Wiley, London (1974).

    Google Scholar 

  59. Mizushima, S.I., Structure of Molecules and Internal Rotations, Academic Press, New York (1954).

    Google Scholar 

  60. Smyth, C.P. in Ref. 58, p. 29.

    Google Scholar 

  61. Lippert, E., Chatzidimitriou-Dreismann, C.A. and Naumann, K.H., Adv. Chem. Phys. 57 311 (1984)

    Article  CAS  Google Scholar 

  62. Abraham, R.J. and Bretschneider, E. in Ref. 58, p. 481.

    Google Scholar 

  63. Ref. [5], p. 145

    Google Scholar 

  64. QCPE Nr. 464

    Google Scholar 

  65. QCPE Nr. 437

    Google Scholar 

  66. Mizushima, S. and Kubo, M., Bull. Chem. Soc. Jap. 13, 174 (1938).

    Article  CAS  Google Scholar 

  67. Yasumi, M., J. Chem. Soc. Jap. 60, 1208 (1939).

    Article  CAS  Google Scholar 

  68. Thomson, G., J. Chem. Soc. 1228 (1939).

    Google Scholar 

  69. Oberhammer, H., Z. Naturforsch. A28, 1140 (1973).

    Google Scholar 

  70. Khetrapal, C.L., Govil, G. and Yeh, H.S.C., J. Mol. Struct. 116, 303 (1984).

    Article  CAS  Google Scholar 

  71. Stockhausen, M. and Wessels, V. priv. Comm. (1987) Wessels, V., Diplom-Thesis, Münster (1987)

    Google Scholar 

  72. Katolichenko, V.I., Egorov, Yu.P., Borovikov, Yu.,Ya. and Semenic, V.Ya., Theoret.; Eksperm. Khim 10, 88 (1974).

    Google Scholar 

  73. Mortimer, F.S., Spectrochimica Acta 9, 270 (1957).

    Article  CAS  Google Scholar 

  74. F. Marsault-Hérail, J. Chim. Phys. 68, 274 (1971).

    Google Scholar 

  75. Katolichenko, V.I., Egerov, Yu.P., Borovikov, Yu.Ya. and Golik, G.A., Zh. Obshch. Khim. 43, 2490 (1973).

    CAS  Google Scholar 

  76. Labrenz, D. (1984) Diplom-Thesis, Bremen

    Google Scholar 

  77. Schröer, W., Naumann, K.D., Domke, W.D. and Lippert E. in Molecular Liquids, Buckingham, A.D., Lippert, Bratos, E.S., eds. Wiley, New York, p. 309 (1978).

    Google Scholar 

  78. Katon, J.E., Cohen M.D., a) Can. J. Chem. 53, 1378 (1974); b) ibid 54, 1994 (1975).

    Google Scholar 

  79. Bingham, R.C., Dewar M.J.S., Lo D.H., J. Am. Chem. Soc. 97, 1285, 1294 (1975).

    Article  Google Scholar 

  80. Dewar, M.J.S., Thiel, W., J. Am. Chem. Soc. 99, 4899, 4907 (1977).

    Article  Google Scholar 

  81. Binkley, J.S., Pople J.A., Mehre, W.J., J. Am. Chem. Soc. 102, 939 (1980).

    Article  CAS  Google Scholar 

  82. T.G. Copland, R.H. Cole, J. Chem. Phys. 64, 1741 (1976).

    Article  Google Scholar 

  83. Franck, E.U. in: Organic Liquids, Buckingham, A.D., Lippert, E., Bratos, S. eds. Wiley, New York, p. 181 (1978).

    Google Scholar 

  84. Labrenz, D., Thesis Bremen 1988

    Google Scholar 

  85. David, H.G., Hamann, S.D., Pearse, J.F., J. Chem. Phys. 20 969 (1952).

    Article  CAS  Google Scholar 

  86. Kubo, M., Sci. Papers Phys. Chem. Res., 29 169 (1936).

    Google Scholar 

  87. Thiebault, J.M., Rivail, J.L., Grefe, J.L., J.Chem.Soc.Farad.II, 72 2024 (1976).

    Article  Google Scholar 

  88. Deul, R., Thesis, Karlsruhe 1984.

    Google Scholar 

  89. Franks, F.: Water — A comprehensive Treatise, Wiley, London 1973

    Google Scholar 

  90. Francesconi, A.Z., Franck, E.U., Lentz, H., Ber. Bunsenges. Phys. Chem. 79 897 (1975).

    Google Scholar 

  91. Buckingham, A.D., Raab,R.E., J.Chem. Soc. 5511 (1961).

    Google Scholar 

  92. Kratochwill, A., Weidner, J.U., Zimmermann, H., Ber. Bunsenges. Phys. Chem. 77 408 (1973).

    Google Scholar 

  93. Bertagnolli, H., Ber. Bunsenges. Phys. Chem. 81 739 (1977).

    CAS  Google Scholar 

  94. Arnold, R., Yarwood, J., Price, T.E., Mol. Phys. 48 451 (1983).

    Article  Google Scholar 

  95. DiGiacomo, A., Smyth, C.P., J. Am. Chem. Soc. 77, 774 (1955).

    Article  CAS  Google Scholar 

  96. Kong, C.L., Larson, J.W., J. Chem. Phys. 55, 3051 (1971).

    Article  CAS  Google Scholar 

  97. Kielich, S. im Dielectric and Related Molecular Processes, Davis, M. ed., The Chemical Society, London, 1972, p. 192.

    Google Scholar 

  98. J.R. van Wazer, C.S. Ewig, J. Am. Chem. Soc. 108, 4354 (1986).

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Bremen, Leobener Str., D-2800, Bremen 33, Germany

    W. Schröer, D. Labrenz & C. Rybarsch

Authors
  1. W. Schröer
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. D. Labrenz
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. C. Rybarsch
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. Fakultät für Chemie, Universität Bielefeld, Bielefeld, Germany

    Th. Dorfmüller

Rights and permissions

Reprints and permissions

Copyright information

© 1989 Kluwer Academic Publishers

About this chapter

Cite this chapter

Schröer, W., Labrenz, D., Rybarsch, C. (1989). Dielectric Polarization of Fluids Comprising Rigid Dipoles and Molecules with Internal Rotational Degrees of Freedom. In: Dorfmüller, T. (eds) Reactive and Flexible Molecules in Liquids. NATO ASI Series, vol 291. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-1043-0_8

Download citation

  • DOI: https://doi.org/10.1007/978-94-009-1043-0_8

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-6961-8

  • Online ISBN: 978-94-009-1043-0

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation