Fluid Phase Equilibria, Vol.194, 1169-1178, 2002
Measurements of binary diffusion coefficients for some low volatile compounds in supercritical carbon dioxide by input-output response technique with two diffusion columns connected in series
Binary diffusion coefficients (D-12) for low volatile compounds such as Vitamin K-3. ubiquinone (UQ-10), alpha-tocopherol, beta-carotene, and phenol in supercritical carbon dioxide were measured by the Taylor dispersion method with two columns connected in series: a poly(ethylene glycol) (PEG) coated capillary column followed by a stainless steel uncoated capillary column. at 313.15 K and pressures from 9 to 30 MPa. The tracer species dissolved with a common organic solvent such as hexane or chloroform was injected to the diffusion column as a delta shot through an ordinary HPLC injector. The response curve measured at the exit of the first column, coated with PEG. was regarded as an input signal, and that measured at the exit of the second column made of the uncoated stainless steel tubing as the output signal. The tracer species and the organic solvent were separated during flowing in the first column. The output response signal was calculated from the input signal and the inverse Laplace transform of the transfer function through the convolution integral. The D-12 values were determined by fitting the calculated output curve to that measured experimentally. The measured D-12 values were fully consistent with those measured with the PEG coated capillary column for one point measurement reported [Ind. Eng. Chem. Res. 39 (2000) 4462]. This two-point measurements with the two columns were adequate for measuring D-12 values for low volatile compounds in supercritical fluids.
Keywords:experimental method;diffusion coefficient;vitamins;carbon dioxide;Taylor dispersion;curve fitting