Polymer Bulletin

, Volume 63, Issue 4, pp 547–563

Thermodynamic characterization of poly (caprolactonediol) by inverse gas chromatography


  • T. V. M. Sreekanth
    • Department of ChemistrySri Venkateswara University
  • S. Ramanaiah
    • Department of ChemistrySri Venkateswara University
  • P. Reddi Rani
    • Department of ChemistrySri Venkateswara University
    • Department of ChemistrySri Venkateswara University
Original Paper

DOI: 10.1007/s00289-009-0105-4

Cite this article as:
Sreekanth, T.V.M., Ramanaiah, S., Reddi Rani, P. et al. Polym. Bull. (2009) 63: 547. doi:10.1007/s00289-009-0105-4


Specific retention volumes, Vg0, were determined for 21 solute probes on poly (caprolactonediol) (PCLD) in the temperature range 323.15–403.15 K by inverse gas chromatography. The retention diagrams drawn between ln Vg0 versus 1/T are linear for all the solutes since PCLD with ten repeating units in its chain behaving like a non polymeric material under the conditions applied. The stationary phase with melting temperature ~321 K is in the liquid state in the GC column over the temperature range studied and hence found to be suitable to determine infinite dilution partial molar thermodynamic properties of mixing for solutes on PCLD. The Vg0 values have been used to calculate weight fraction activity coefficients Ω and Flory–Huggins interaction parameters, χ12. The average partial molar enthalpy of solution, \( \overline{\Updelta H}_{1}^{S} , \) and partial molar enthalpy of mixing, \( \overline{\Updelta H}_{1}^{\infty } , \) are calculated using Vg0 and Ω respectively. The average molar enthalpy of vaporization ΔH1V for solutes have been calculated using \( \overline{\Updelta H}_{1}^{\infty } \) and \( \overline{\Updelta H}_{1}^{S} \) values and compared with the literature values at 363.15 K which is the average column temperature. The partial molar entropy of mixing, \( \overline{\Updelta S}_{1}^{\infty } \)calculated at 363.15 K are in good correlation with the average \( \overline{\Updelta H}_{1}^{\infty } \)values. The total solubility parameter due to Guillet and the Hansen solubility parameters (HSP) are calculated for PCLD using χ12 values. In the present work the Hansen solubility parameters have been calculated using a new method following the Hansen theory and Huang method with less weight on polar and hydrogen bonding components. The errors in the solubility HSP are lower and the correlation coefficients are better in both the methods compared to unweighted three dimensional model.


Poly (caprolactonediol)Inverse gas chromatographyThermodynamic propertiesHansen solubility parameters

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© Springer-Verlag 2009