Journal of Solution Chemistry

, Volume 21, Issue 1, pp 49–65 | Cite as

Thermodynamics of liquid mixtures containing n-alkanes and strongly polar components: VE and C P E of mixtures with either pyridine or piperidine

  • A. Lainez
  • M. M. Rodrigo
  • Emmerich Wilhelm
  • J. -P. E. Grolier


Excess molar volumes V E and excess molar heat capacities C P /E at constant pressure have been obtained, as a function of mole fraction x1, for several binary liquid mixtures belonging either to series I: pyridine+n-alkane (ClH2l+2), with l=7, 10, 14, 16, or series II: piperidine+n-alkane, with l=7, 8, 10, 12, 14. The instruments used were a vibrating-tube densimeter and a Picker flow microcalorimeter, respectively. V E of pyridine+n-heptane shows a S-shaped composition dependence with a small negative part in the region rich in pyridine (x1>0.90). All the other systems show positive V E only. The excess volumes increase with increasing chain length l of the n-alkane. The excess molar heat capacities of the mixtures belonging to series II are all negative, except for a small positive part for piperidine+n-heptane in the region rich in piperidine (x1>0.87). The C P /E at the respective minima, C P /E (x1,min), become more negative with increasing l, and the x1,min values range from about 0.26 (l=7) to 0.39 (l=14). Most interestingly, mixtures of series I exhibit curves of C P /E against x1 with two minima and one maximum, the so-called W-shape curves.

Key words

Excess heat capacity W-shapedCPE excess volume pyridine piperidine n-alkanes polar solvent 


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  1. 1.
    A. Inglese, E. Wilhelm, and J.-P. E. Grolier,37 th Annual Calorimetry Conference, No. 54 (Snowbird, Utah, 1982).Google Scholar
  2. 2.
    J.-P. E. Grolier, A. Inglese, and E. Wilhelm,J. Chem. Thermodyn. 16, 67 (1984).Google Scholar
  3. 3.
    E. Wilhelm,Thermochimica Acta 94, 47 (1985).Google Scholar
  4. 4.
    E. Wilhelm,Thermochimica Acta 162, 43 (1990).Google Scholar
  5. 5.
    M. E. Saint-Victor and D. Patterson,Fluid Phase Equil. 35, 237 (1987).Google Scholar
  6. 6.
    H. Kalali, F. Kohler, and P. Svejda,Monatsh. Chem. 118, 1 (1987).Google Scholar
  7. 7.
    A. Lainez, G. Roux-Desgranges, J.-P. E. Grolier, and E. Wilhelm,Fluid Phase Equil. 20, 47 (1985).Google Scholar
  8. 8.
    A. Lainez, E. Wilhelm, G. Roux-Desgranges, and J.-P. E. Grolier,J. Chem. Thermodyn.17, 1153 (1985).Google Scholar
  9. 9.
    E. Wilhelm, A. Lainez, and J.-P. E. Grolier,Fluid Phase Equil. 49, 233 (1989).Google Scholar
  10. 10.
    A. Lainez, M. M. Rodrigo, A. H. Roux, J.-P. E. Grolier, and E. Wilhelm,Calorim. Anal. Therm. 16, 153 (1985).Google Scholar
  11. 11.
    E. Wilhelm, A. H. Roux, G. Roux-Desgranges, M. M. Rodrigo, A. Lainez, and J.-P. E. Grolier,Calorim. Anal. Therm. 17, 12 (1986).Google Scholar
  12. 12.
    H. Kalali, F. Kohler, and P. Svejda,Fluid Phase Equil. 20, 75 (1985).Google Scholar
  13. 13.
    E. Wilhelm, A. Lainez, M. M. Rodrigo, A. H. Roux, and J.-P. E. Grolier,Calorim. Anal. Therm. 19, C20.1 (1988).Google Scholar
  14. 14.
    E. Wilhelm,Calorim. Anal. Therm. 20/21, 413 (1990).Google Scholar
  15. 15.
    E. A. Guggenheim,Mixtures (Clarendon Press, Oxford, 1952).Google Scholar
  16. 16.
    R. G. Rubio, M. Cáceres, R. M. Masegosa, L. Andreolli-Ball, M. Costas, and D. Patterson,Ber. Bunsenges. Phys. Chem. 93, 48 (1989).Google Scholar
  17. 17.
    L. Andreolli-Ball, M. Costas, D. Patterson, R. G. Rubio, M. Cáceres, and R. M. Masegosa,Ber. Bunsenges. Phys. Chem. 93, 882 (1989).Google Scholar
  18. 18.
    A. B. Bathia and D. E. Thornton,Phys. Rev. B 2, 3004 (1970).Google Scholar
  19. 19.
    J. S. Rowlinson and F. L. Swinton,Liquids and Liquid Mixtures, 3rd edn., (McGraw-Hill, New York, 1982).Google Scholar
  20. 20.
    A. J. Treszczanowicz, D. Patterson, G. C. Benson, and T. Kasprzycka-Guttman,Fluid Phase Equil. 50, 235 (1989).Google Scholar
  21. 21.
    T. Kasprzycka-Guttman and H. Kurcinska,J. Solution Chem. 18, 727 (1989).Google Scholar
  22. 22.
    R. K. Nigam, P. P. Singh, S. Aggarwal, and S. P. Sharma,Fluid Phase Equil. 16, 25 (1984).Google Scholar
  23. 23.
    B. Kowalski, A. Boniecka, and A. Orszagh,Pol. J. Chem. 52, 1079 (1978).Google Scholar
  24. 24.
    M. Woycicka,Pure Appl. Chem. 2, 147 (1961).Google Scholar
  25. 25.(a)
    T. Kasprzycka-Guttman and H. Wilczura,J. Thermal Anal. 35, 2441 (1989);Google Scholar
  26. 25.(b)
    —,Thermochimica Acta 158, 1 (1990).Google Scholar
  27. 26.
    R. K. Nigam and S. Aggarwal,Fluid Phase Equil. 26, 181 (1986).Google Scholar
  28. 27.
    E. G. Konakbaeva,Int. DATA Ser., Sel. Data Mixtures Ser. A 50, 51 (1985).Google Scholar
  29. 28.
    H. Wilczura, T. Kasprzycka-Guttman, and S. Randzio,Bull. Pol. Acad. Sci. Chem. 34, 483 (1987).Google Scholar
  30. 29.
    T. Kasprzycka-Guttman and I. Chojnacka,J. Chem. Thermodyn. 21, 721 (1989).Google Scholar
  31. 30.(a)
    M.-A. Michou-Saucet, J. Jose, and C. Michou-Saucet,Thermochimica Acta 102, 271 (1986);Google Scholar
  32. 30.(b)
    M.-A. Michou-Saucet, J. Jose, and C. Michou-Saucet,Int. Data Ser., Sel. Data Mixtures, Ser. A 140–145 (1986).Google Scholar
  33. 31.
    E. G. Konakbaeva,Int. Data Ser., Sel. Data Mixtures, Ser. A 41 (1985).Google Scholar
  34. 32.
    A. Ait-Kaci and H. V. Kehiaian,Int. Data Ser., Sel. Data Mixtures, Ser. A 42, 43 (1985).Google Scholar
  35. 33.
    S. Warycha and J. H. Rytting,J. Solution Chem. 13, 589 (1984).Google Scholar
  36. 34.
    Z. Maczynska,Int. Data Ser., Sel. Data Mixtures, Ser. A, 104–115 (1980).Google Scholar
  37. 35.
    J.-P. Herbeuval, M.-L. Gaulard, and P. Boule,J. Chim. Phys. 71, 326 (1974).Google Scholar
  38. 36.
    R. E. Cornish, R. C. Archibald, E. A. Murphy, and H. M. Evans,Ind. Eng. Chem. 26, 397 (1934).Google Scholar
  39. 37.
    A. W. Francis,Ind. Eng. Chem. 36, 764 (1944).Google Scholar
  40. 38.
    A. Kreglewski,Rocz. Chem. 31, 1001 (1957).Google Scholar
  41. 39.
    E. Brunner,J. Chem. Thermodyn. 19, 823 (1987).Google Scholar
  42. 40.
    IUPAC,Pure Appl. Chem. 58, 1677 (1986).Google Scholar
  43. 41.
    J.-P. E. Grolier, E. Wilhelm, and M. H. Hamedi,Ber. Bunsenges. Phys. Chem. 82, 1282 (1978).Google Scholar
  44. 42.
    G. S. Kell,J. Chem. Eng. Data 20, 97 (1975).Google Scholar
  45. 43.
    J. L. Fortier, G. C. Benson, and P. Picker,J. Chem. Thermodyn. 8, 289 (1976).Google Scholar
  46. 44.
    J. L. Fortier and G. C. Benson,J. Chem. Thermodyn. 8, 411 (1976).Google Scholar
  47. 45.
    E. Wilhelm, J.-P. E. Grolier, and M. H. Karbalai Ghassemi,Ber. Bunsenges. Phys. Chem. 81, 925 (1977).Google Scholar
  48. 46.
    J. A. Riddick and W. B. Bunger,Organic Solvents, 3rd edn., (Wiley, New York, 1970).Google Scholar
  49. 47.
    V. T. Lam, P. Picker, D. Patterson, and P. Tancrede,J. Chem. Soc. Faraday Trans. II 70, 1465 (1974).Google Scholar
  50. 48.
    J. Weclawski,Fluid Phase Equil. 12, 155 (1983).Google Scholar
  51. 49.
    J. Timmermans,Physico-Chemical Constants of Pure Organic Compounds (Elsevier, New York, 1965).Google Scholar
  52. 50.
    E. A. Moelwyn-Hughes and P. L. Thorpe,Proc. Roy. Soc. London (A) 278, 574 (1964).Google Scholar
  53. 51.
    K. Nakanishi, H. Wada, and H. Touhara,J. Chem. Thermodyn. 7, 1125 (1975).Google Scholar
  54. 52.
    Selected Values of Physical, and Thermodynamic Properties of Hydrocarbons, and Related Compounds, American Petroleum Institute, Research Project 44, (Carnegie Press, Pittsburgh, Pa, 1953).Google Scholar
  55. 53.
    TRC Thermodynamic Tables: Hydrocarbons, 1986. Data sheets d-1011, andd-1014 (June 30, 1973) Texas A&M University, College Station Texas.Google Scholar
  56. 54.
    A. J. Treszczanowicz and G. C. Benson,J. Chem. Thermodyn. 12, 173 (1980).Google Scholar
  57. 55.
    D. L. Camin and F. D. Rossini,J. Phys. Chem. 59, 1173 (1955).Google Scholar
  58. 56.
    TRC Thermodynamic Tables: Non Hydrocarbons, 1986, p. 9410. Texas A&M University, College Station Texas.Google Scholar
  59. 57.
    J. F. Messerly, S. S. Todd, H. L. Finke, W. D. Good, and B. E. Gammon,J. Chem. Thermodyn. 20, 209 (1988).Google Scholar
  60. 58.
    J.-P. E. Grolier, A. Inglese, A. H. Roux, and E. Wilhelm,Ber. Bunsenges. Phys. Chem. 85, 768 (1981).Google Scholar
  61. 59.
    J. F. Messerly, G. B. Guthrie, S. S. Todd, and H. L. Finke,J. Chem. Eng. Data 12, 338 (1967).Google Scholar
  62. 60.
    A. H. Roux, J.-P. E. Grolier, A. Inglese, and E. Wilhelm,Ber. Bunsenges. Phys. Chem. 88, 986 (1984).Google Scholar
  63. 61.
    J.-P. E. Grolier and G. C. Benson,Can. J. Chem. 62, 949 (1984).Google Scholar
  64. 62.
    D. Ambrose,NPL Report Chem. 107 (1980).Google Scholar
  65. 63.
    R. C. Reid, J. P. Prausnitz, and T. K. Sherwood,The Properties of Gases and Liquids, 3rd edn., (McGraw, New York, 1977).Google Scholar
  66. 64.
    R. D. Nelson, Jr., D. R. Lide, Jr., and A. A. Maryott,Selected Values of Electric Dipole Moments for Molecules in the Gas Phase,NSRDS-NBS 10 (National Bureau of Standards, Washington, D. C., 1967).Google Scholar
  67. 65.
    V. M. Rao and R. Kewley,Can. J. Chem. 50, 955 (1972).Google Scholar
  68. 66.
    G. O. Sorensen, L. Mahler, and N. Rastrup-Andersen,J. Molecular Struct. 20, 119 (1974).Google Scholar
  69. 67.
    J. E. Parkin, P. J. Buckley, and C. C. Costain,J. Molecular Spectr. 89, 465 (1981).Google Scholar
  70. 68.
    R. N. Joarder and M. Silbert,Chem. Phys. 95, 357 (1985).Google Scholar
  71. 69.
    S. Malanowski, R. Patz, M. T. Rätzsch, and C. Wohlfarth,Fluid Phase Equil. 3, 291 (1979).Google Scholar
  72. 70.
    P. P. Singh and S. P. Sharma,Thermochimica Acta 88, 467 (1985).Google Scholar
  73. 71.
    W. Brzostowski,J. Chim. Phys. 66, 314 (1969).Google Scholar
  74. 72.
    R. Smets and P. Huyskens,Bull. Soc. Chim. France 173 (1978).Google Scholar
  75. 73.(a)
    W. Woycicki and K. W. Sadowska,Bull. Acad. Pol. Sci., Ser. Sci. Chim. 16, 365 (1968);Google Scholar
  76. 73.(b)
    W. Woycicki and K. W. Sadowska,Int. Data Ser., Sel. Data Mixtures, Ser. A, 33 (1975).Google Scholar
  77. 74.
    A. Lainez, M. M. Rodrigo, J.-P. E. Grolier, and E. Wilhelm, unpublished results.Google Scholar

Copyright information

© Plenum Publishing Corporation 1992

Authors and Affiliations

  • A. Lainez
    • 1
  • M. M. Rodrigo
    • 2
  • Emmerich Wilhelm
    • 3
  • J. -P. E. Grolier
    • 4
  1. 1.Departamento de Química Física, Facultad de C.C. QuímicasUniversidad ComplutenseMadridSpain
  2. 2.Departamento de Química FísicaUniversidad de Alcalá de HenaresMadridSpain
  3. 3.Institut für Physikalische ChemieUniversität WienWienAustria
  4. 4.Laboratoire de Thermodynamique et Cinétique ChimiqueUniversité Blaise PascalAubièreFrance

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