Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

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

  • 83 Accesses

  • 52 Citations

Abstract

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. VE 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 VE 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.

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

References

  1. 1.

    A. Inglese, E. Wilhelm, and J.-P. E. Grolier,37 th Annual Calorimetry Conference, No. 54 (Snowbird, Utah, 1982).

  2. 2.

    J.-P. E. Grolier, A. Inglese, and E. Wilhelm,J. Chem. Thermodyn. 16, 67 (1984).

  3. 3.

    E. Wilhelm,Thermochimica Acta 94, 47 (1985).

  4. 4.

    E. Wilhelm,Thermochimica Acta 162, 43 (1990).

  5. 5.

    M. E. Saint-Victor and D. Patterson,Fluid Phase Equil. 35, 237 (1987).

  6. 6.

    H. Kalali, F. Kohler, and P. Svejda,Monatsh. Chem. 118, 1 (1987).

  7. 7.

    A. Lainez, G. Roux-Desgranges, J.-P. E. Grolier, and E. Wilhelm,Fluid Phase Equil. 20, 47 (1985).

  8. 8.

    A. Lainez, E. Wilhelm, G. Roux-Desgranges, and J.-P. E. Grolier,J. Chem. Thermodyn.17, 1153 (1985).

  9. 9.

    E. Wilhelm, A. Lainez, and J.-P. E. Grolier,Fluid Phase Equil. 49, 233 (1989).

  10. 10.

    A. Lainez, M. M. Rodrigo, A. H. Roux, J.-P. E. Grolier, and E. Wilhelm,Calorim. Anal. Therm. 16, 153 (1985).

  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).

  12. 12.

    H. Kalali, F. Kohler, and P. Svejda,Fluid Phase Equil. 20, 75 (1985).

  13. 13.

    E. Wilhelm, A. Lainez, M. M. Rodrigo, A. H. Roux, and J.-P. E. Grolier,Calorim. Anal. Therm. 19, C20.1 (1988).

  14. 14.

    E. Wilhelm,Calorim. Anal. Therm. 20/21, 413 (1990).

  15. 15.

    E. A. Guggenheim,Mixtures (Clarendon Press, Oxford, 1952).

  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).

  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).

  18. 18.

    A. B. Bathia and D. E. Thornton,Phys. Rev. B 2, 3004 (1970).

  19. 19.

    J. S. Rowlinson and F. L. Swinton,Liquids and Liquid Mixtures, 3rd edn., (McGraw-Hill, New York, 1982).

  20. 20.

    A. J. Treszczanowicz, D. Patterson, G. C. Benson, and T. Kasprzycka-Guttman,Fluid Phase Equil. 50, 235 (1989).

  21. 21.

    T. Kasprzycka-Guttman and H. Kurcinska,J. Solution Chem. 18, 727 (1989).

  22. 22.

    R. K. Nigam, P. P. Singh, S. Aggarwal, and S. P. Sharma,Fluid Phase Equil. 16, 25 (1984).

  23. 23.

    B. Kowalski, A. Boniecka, and A. Orszagh,Pol. J. Chem. 52, 1079 (1978).

  24. 24.

    M. Woycicka,Pure Appl. Chem. 2, 147 (1961).

  25. 25.(a)

    T. Kasprzycka-Guttman and H. Wilczura,J. Thermal Anal. 35, 2441 (1989);

  26. 25.(b)

    —,Thermochimica Acta 158, 1 (1990).

  27. 26.

    R. K. Nigam and S. Aggarwal,Fluid Phase Equil. 26, 181 (1986).

  28. 27.

    E. G. Konakbaeva,Int. DATA Ser., Sel. Data Mixtures Ser. A 50, 51 (1985).

  29. 28.

    H. Wilczura, T. Kasprzycka-Guttman, and S. Randzio,Bull. Pol. Acad. Sci. Chem. 34, 483 (1987).

  30. 29.

    T. Kasprzycka-Guttman and I. Chojnacka,J. Chem. Thermodyn. 21, 721 (1989).

  31. 30.(a)

    M.-A. Michou-Saucet, J. Jose, and C. Michou-Saucet,Thermochimica Acta 102, 271 (1986);

  32. 30.(b)

    M.-A. Michou-Saucet, J. Jose, and C. Michou-Saucet,Int. Data Ser., Sel. Data Mixtures, Ser. A 140–145 (1986).

  33. 31.

    E. G. Konakbaeva,Int. Data Ser., Sel. Data Mixtures, Ser. A 41 (1985).

  34. 32.

    A. Ait-Kaci and H. V. Kehiaian,Int. Data Ser., Sel. Data Mixtures, Ser. A 42, 43 (1985).

  35. 33.

    S. Warycha and J. H. Rytting,J. Solution Chem. 13, 589 (1984).

  36. 34.

    Z. Maczynska,Int. Data Ser., Sel. Data Mixtures, Ser. A, 104–115 (1980).

  37. 35.

    J.-P. Herbeuval, M.-L. Gaulard, and P. Boule,J. Chim. Phys. 71, 326 (1974).

  38. 36.

    R. E. Cornish, R. C. Archibald, E. A. Murphy, and H. M. Evans,Ind. Eng. Chem. 26, 397 (1934).

  39. 37.

    A. W. Francis,Ind. Eng. Chem. 36, 764 (1944).

  40. 38.

    A. Kreglewski,Rocz. Chem. 31, 1001 (1957).

  41. 39.

    E. Brunner,J. Chem. Thermodyn. 19, 823 (1987).

  42. 40.

    IUPAC,Pure Appl. Chem. 58, 1677 (1986).

  43. 41.

    J.-P. E. Grolier, E. Wilhelm, and M. H. Hamedi,Ber. Bunsenges. Phys. Chem. 82, 1282 (1978).

  44. 42.

    G. S. Kell,J. Chem. Eng. Data 20, 97 (1975).

  45. 43.

    J. L. Fortier, G. C. Benson, and P. Picker,J. Chem. Thermodyn. 8, 289 (1976).

  46. 44.

    J. L. Fortier and G. C. Benson,J. Chem. Thermodyn. 8, 411 (1976).

  47. 45.

    E. Wilhelm, J.-P. E. Grolier, and M. H. Karbalai Ghassemi,Ber. Bunsenges. Phys. Chem. 81, 925 (1977).

  48. 46.

    J. A. Riddick and W. B. Bunger,Organic Solvents, 3rd edn., (Wiley, New York, 1970).

  49. 47.

    V. T. Lam, P. Picker, D. Patterson, and P. Tancrede,J. Chem. Soc. Faraday Trans. II 70, 1465 (1974).

  50. 48.

    J. Weclawski,Fluid Phase Equil. 12, 155 (1983).

  51. 49.

    J. Timmermans,Physico-Chemical Constants of Pure Organic Compounds (Elsevier, New York, 1965).

  52. 50.

    E. A. Moelwyn-Hughes and P. L. Thorpe,Proc. Roy. Soc. London (A) 278, 574 (1964).

  53. 51.

    K. Nakanishi, H. Wada, and H. Touhara,J. Chem. Thermodyn. 7, 1125 (1975).

  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).

  55. 53.

    TRC Thermodynamic Tables: Hydrocarbons, 1986. Data sheets d-1011, andd-1014 (June 30, 1973) Texas A&M University, College Station Texas.

  56. 54.

    A. J. Treszczanowicz and G. C. Benson,J. Chem. Thermodyn. 12, 173 (1980).

  57. 55.

    D. L. Camin and F. D. Rossini,J. Phys. Chem. 59, 1173 (1955).

  58. 56.

    TRC Thermodynamic Tables: Non Hydrocarbons, 1986, p. 9410. Texas A&M University, College Station Texas.

  59. 57.

    J. F. Messerly, S. S. Todd, H. L. Finke, W. D. Good, and B. E. Gammon,J. Chem. Thermodyn. 20, 209 (1988).

  60. 58.

    J.-P. E. Grolier, A. Inglese, A. H. Roux, and E. Wilhelm,Ber. Bunsenges. Phys. Chem. 85, 768 (1981).

  61. 59.

    J. F. Messerly, G. B. Guthrie, S. S. Todd, and H. L. Finke,J. Chem. Eng. Data 12, 338 (1967).

  62. 60.

    A. H. Roux, J.-P. E. Grolier, A. Inglese, and E. Wilhelm,Ber. Bunsenges. Phys. Chem. 88, 986 (1984).

  63. 61.

    J.-P. E. Grolier and G. C. Benson,Can. J. Chem. 62, 949 (1984).

  64. 62.

    D. Ambrose,NPL Report Chem. 107 (1980).

  65. 63.

    R. C. Reid, J. P. Prausnitz, and T. K. Sherwood,The Properties of Gases and Liquids, 3rd edn., (McGraw, New York, 1977).

  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).

  67. 65.

    V. M. Rao and R. Kewley,Can. J. Chem. 50, 955 (1972).

  68. 66.

    G. O. Sorensen, L. Mahler, and N. Rastrup-Andersen,J. Molecular Struct. 20, 119 (1974).

  69. 67.

    J. E. Parkin, P. J. Buckley, and C. C. Costain,J. Molecular Spectr. 89, 465 (1981).

  70. 68.

    R. N. Joarder and M. Silbert,Chem. Phys. 95, 357 (1985).

  71. 69.

    S. Malanowski, R. Patz, M. T. Rätzsch, and C. Wohlfarth,Fluid Phase Equil. 3, 291 (1979).

  72. 70.

    P. P. Singh and S. P. Sharma,Thermochimica Acta 88, 467 (1985).

  73. 71.

    W. Brzostowski,J. Chim. Phys. 66, 314 (1969).

  74. 72.

    R. Smets and P. Huyskens,Bull. Soc. Chim. France 173 (1978).

  75. 73.(a)

    W. Woycicki and K. W. Sadowska,Bull. Acad. Pol. Sci., Ser. Sci. Chim. 16, 365 (1968);

  76. 73.(b)

    W. Woycicki and K. W. Sadowska,Int. Data Ser., Sel. Data Mixtures, Ser. A, 33 (1975).

  77. 74.

    A. Lainez, M. M. Rodrigo, J.-P. E. Grolier, and E. Wilhelm, unpublished results.

Download references

Author information

Additional information

Dedicated to Professor A. Néckel on the occasion of his 65th birthday. Communicated in part at the XVIIèmes Journées de Calorimétrie, d'Analyse Thermique et de Thermodynamique Chimique, Ferrara, Italy, 27–30 October, 1986.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Lainez, A., Rodrigo, M.M., Wilhelm, E. et al. Thermodynamics of liquid mixtures containing n-alkanes and strongly polar components: VE and C P E of mixtures with either pyridine or piperidine. J Solution Chem 21, 49–65 (1992). https://doi.org/10.1007/BF00648980

Download citation

Key words

  • Excess heat capacity
  • W-shapedC P E
  • excess volume
  • pyridine
  • piperidine
  • n-alkanes
  • polar solvent