Densities of two methane-rich binary mixtures were measured in the homogeneous liquid and the supercritical region at temperatures between (100 and 160) K using a low-temperature single-sinker magnetic-suspension densimeter. For each mixture, four isotherms were studied over the pressure range from (0.3 to 10.8) MPa. Molar compositions of the gravimetrically prepared methane-rich binary mixtures were approximately 0.01 butane and 0.02 isopentane, respectively, with the balance being methane. The relative expanded combined uncertainty (k = 2) of the experimental densities was estimated to be in the range of (0.02 to 0.06) %. Due to a supercritical liquefaction procedure and the integration of a special VLE-cell, it was possible to measure densities in the homogeneous liquid phase without changing the composition of the liquefied mixture. Based on the supercritical liquefaction procedure, a new time-saving measurement procedure was developed and applied. Moreover, saturated-liquid densities were determined by extrapolation of the experimental single-phase liquid densities to the vapor pressure calculated with an equation of state (EOS); here, the relative expanded combined uncertainty (k = 2) is less than 0.05 % in most cases. The new experimental results were compared with the GERG-2008 equation of state, the EOS-LNG and the enhanced revised Klosek and McKinley (ERKM) method.

Densities of two synthetic biomethane-like mixtures were measured in the homogeneous liquid phase and the supercritical region using a low-temperature single-sinker magnetic-suspension densimeter. Both mixtures consist of methane, nitrogen, hydrogen and oxygen, whereas the second mixture additionally contains carbon dioxide. For the first mixture, four isotherms from (100 to 160) K were studied over the pressure range from (1.5 to 6.6) MPa. The second mixture was investigated along three isotherms from (140 to 180) K at pressures of (2.6 to 9.0) MPa, where only the densities at 180 K are usable due to solidification of the carbon dioxide at the lower temperatures. The relative expanded combined uncertainty (k = 2) of the experimental densities was estimated to be in the range of (0.022 to 0.027)  % for the first mixture and (0.046 to 0.054)  % for the second mixture, respectively. Due to a supercritical liquefaction procedure and the integration of a special VLE-cell, densities in the homogeneous liquid phase could be measured without changing the composition of the liquefied mixture. Moreover, saturated-liquid densities were determined by extrapolation of the experimental single-phase liquid densities to the vapor pressure, which was determined experimentally for the mixture without carbon dioxide and calculated with an equation of state (EOS) for the mixture containing carbon dioxide. The relative expanded combined uncertainty (k = 2) of the saturated-liquid densities is less than 0.08 % in most cases. The new experimental results were compared with the GERG-2008 equation of state; the deviations are less than 0.17 %.

Exact knowledge of natural gas composition is essential in custody transfer to determine the energy content of the delivery. However, for liquefied natural gas (LNG), a reliable composition determination is difficult. Here, we describe the design of a laboratory‐scale reference liquefier that enables the validation and calibration of optical spectroscopy sensors by providing them with a sample of metrologically traceable composition. Hence, it is crucial to avoid fractionation of the sample during liquefaction. This is realized by supercritical liquefaction of a reference gas mixture in conjunction with a special vapor–liquid‐equilibrium (VLE) cell. As this is a demanding high‐pressure application, low‐pressure condensation as liquefaction method was also assessed. Through experimental investigations and VLE calculations, preservation of the composition of the produced liquid sample during condensation was studied. We conclude that under optimized conditions, validation, and calibration measurements of optical sensors can be performed on condensed liquids, which, however, needs further confirmation.

Densities of an air-like binary mixture (0.2094 oxygen + 0.7906 nitrogen, mole fractions) were measured along six isotherms over the temperature range from 100 K to 298.15 K at pressures up to 8.0 MPa, using a low-temperature single-sinker magnetic suspension densimeter. The measurements were carried out at T = (100, 115, and 130) K in the homogeneous gas and liquid region, and at T = (145, 220, and 298.15) K in the supercritical region (critical temperature TC = 132.35 K); in total, we present results for 52 (T, p) state points. The relative expanded combined uncertainty (k = 2) of the experimental densities was estimated to be between 0.03 % and 0.13 %, except for four values near the critical point. The largest error is caused by the magnetic suspension coupling in combination with the mixture component oxygen, which is strongly paramagnetic; the resulting force transmission error is up to 1.1 %. However, this error can be corrected with a proven correction model to an uncertainty contribution in density of less than 0.044 %. Due to a supercritical liquefaction procedure and the integration of a special VLE-cell, it was possible to measure densities in the homogeneous liquid phase without changing the composition of the liquefied mixture. Moreover, saturated liquid and saturated vapor densities were determined at T = (100, 115, and 130) K by extrapolation of the experimental single-phase densities to the saturation pressure. The new experimental results were compared with the mixture model of Lemmon et al. for the system (nitrogen + argon + oxygen) and the GERG-2008 equation of state.