Extending reversed-flow chromatographic methods for the measurement of diffusion coefficients to higher temperatures

A reversed-flow gas-chromatography (RF-GC) apparatus for the measurement of binary diffusion coefficients is described and utilized to measure the binary diffusion coefficients for several systems at temperatures from (300 to 723) K. Hydrocarbons are detected using flame ionization detection, and inert species can be detected by thermal conductivity. The present apparatus has been utilized to measure diffusion coefficients at substantially higher temperatures than previous RF-GC work. Characterization of the new apparatus was accomplished by comparing measured binary diffusion coefficients of dilute argon in helium to established reference values. Further diffusion coefficient measurements for dilute helium in argon and dilute nitrogen in helium (using thermal conductivity detection) and dilute methane in helium (using flame ionization detection) were performed and found to be in excellent agreement with literature values. The measurement of these well-established diffusion coefficients has shown that specific experimental conditions are required for accurate diffusion measurements using this technique, particularly at higher temperatures. Numerical simulations of the diffusion experiments are presented to demonstrate that artifacts of the analysis procedure must be specifically identified to ensure accuracy, particularly at higher temperatures.

► Apparatus for RF-GC determination of binary diffusion coefficients for T = (300–723) K. ► Binary diffusion coefficients for He–Ar, He–N2, and He–CH4 at T = (300–723) K. ► Uncertainties in binary diffusion coefficient measurements by RF-GC. ► Simulations of long-time curvature of RF-GC spectra and associated uncertainties.