Journal of Supercritical Fluids, Vol.37, No.1, 63-71, 2006
Binary diffusion coefficients and retention factors for gamma-linolenic acid and its methyl and ethyl esters in supercritical carbon dioxide
Infinite dilution binary diffusion coefficients D-12 and retention factors k for gamma-linolenic acid were measured by chromatographic impulse response technique in supercritical carbon dioxide over the ranges of temperature from 308 to 343 K and pressure from 9 to 30 MPa, together with those for the methyl and ethyl esters at 313 and 343 K and pressures from 8 to 16 MPa. In comparison with literature values for C18 free fatty acids and the esters. the differences in D-12 data were almost indiscernible for each isomer group: alpha- and gamma-linolenic acid, oleic and elaidic acids, oleic and elaidic acid methyl esters, and their ethyl esters. The number of carbon double bonds did not affect the D-12 values significantly. Moreover, the differences in the values between free fatty acid and the ester forms were also small, whereas the D-12 values increased in order of acid to ethyl ester to methyl ester. The validities of the predictive correlations we had proposed such as the D-12/T-CO2 viscosity and the Schmidt number correlation were verified. The retention factor k values for the acid form were much higher than those for the methyl and ethyl esters. The k values were correlated with temperature and CO2 density for each compound, and the solute partial molar volumes were determined from the k-CO2 density correlation. (C) 2005 Elsevier B.V. All rights reserved.
Keywords:carbon dioxide;chromatographic impulse response;diffusion coefficients;ethyl ester;gamma-linolenic acid;methyl ester;retention factor;supercritical