Reliability of binary diffusion coefficients determined from tailing response curves measured by the Taylor dispersion method in the near critical region

Two kinds of tracer response measurements, by the Taylor dispersion method using a stainless-steel diffusion column and the chromatographic impulse response (CIR) method using a polymer-coated diffusion column, were carried out by using the curve fitting to determine infinite-dilution binary diffusion coefficients of vitamin K3 (2-methylnaphthalene-1,4-dione), as a medium polar compound, in supercritical CO2 at 308.2 K and pressures from 7.75 to 31.00 MPa. The response curves in the Taylor dispersion method showed more significantly tailing closer to the critical point, whereas those did not at conditions away from the critical point. However, the CIR method provided the response curves almost without tailing over an entire range of pressure studied. Consequently, in the CIR method the response curves were accurately reproduced with the determined values of two parameters, binary diffusion coefficient and retention factor. The determined values of diffusion coefficients showed a little slow-down in the near critical region. In the Taylor dispersion method, however, the response curves with tailing were poorly reproduced with the determined values of diffusion coefficients, which apparently led to a steep-down in the near critical region.