Thermodynamics Research Center / ThermoML | Journal of Chemical Thermodynamics

ABSTRACT

An apparatus based on a microwave re-entrant cavity resonator, originally built for accurate measurements of the dielectric permittivity of natural gas mixtures, was refurbished and extensively characterised. This was done to enable the future investigation of phase equilibria and (p, q, T, x) behaviour of fluid mixtures utilizing the present experimental technique. Vacuum resonance frequencies and Q-factors of the resonator s modes were modelled using both analytic and finite element methods, and found to compare well with experimental values. The finite element models helped to identify two whispering gallery-type modes not previously reported for such cavity geometries. The models also predict distributions of the electric and magnetic fields in the re-entrant cavity resonator useful for identifying regions in the cavity more sensitive to the presence of a liquid. Following the resonator s characterisation, its ability to measure dew points was tested using a gravimetrically prepared (0.2501 argon + 0.7499 carbon dioxide) mixture over the temperature range from (252 to 280) K at pressures from (2.8 to 6.9) MPa. The combined expanded uncertainty with a level of confidence of approximately 95% (k = 2) in dew-point temperature and pressure ranged between (0.025 and 0.044) K and from (0.009 to 0.015) MPa, respectively. We compared the experimental dew-point pressures with the recently developed multiparameter equation of state optimised for combustion gases (EOS-CG), showing relative deviations in the range of (0.044 to 0.479)%. In contrast, relative deviations of up to 4% from the GERG-2008 equation of state and two different implementations of the Peng-Robinson equation were observed, although these models are not optimised for dew point calculations of carbon dioxide rich mixtures.