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
Article

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. 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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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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