(245b) Speed of Sound and Density of (Carbon Dioxide + Nonane) and (Carbon Dioxide + Methylbenzene) at Temperatures between (283 and 473) K and Pressures up to 390 Mpa
AIChE Annual Meeting
2018
2018 AIChE Annual Meeting
Engineering Sciences and Fundamentals
Thermodynamic and Transport Properties Under Pressure
Monday, October 29, 2018 - 3:54pm to 4:18pm
Densities were measured using a vibrating U-tube denimeter which was carefully calibrated over the full working ranges of temperature and pressure using helium and water as the reference fluids. Validation measurements carried out on the pure substances verify the uncertainty analysis.
The speed of sound was measured using a dual-path pulse-echo apparatus operating at a frequency of 5 MHz. The difference between the lengths of the two acoustic paths at a reference temperature and pressure was obtained by calibration with water. The pathlength difference at other conditions was calculated from the known thermal expansivity and compressibility of the fused-quartz spacer tubes.
Mixtures were prepared gravimetrically in a variable-volume cell. They were then compressed to a pressure above their bubble point and homogenized prior to filling the apparatus. Thereafter, the mixture in the variable volume cell was always maintained in the single-phase region. However, flashing occurred when the mixture was initially introduced into the measurement apparatus. Therefore, the sound-speed apparatus was equipped with a re-circulation pump to permit homogenization in situ. The density apparatus, having a small hold-up volume, was instead flushed under pressure to expel the initial fluid charge.
The experimental results are used to examine the predictive capability of several leading thermodynamic models, including the Predictive Peng-Robinson (PPR-78) equation of state [1], a version of the Statistical Associating Fluid Theory for potentials of the Mie form (SAFT-γ Mie) [2] and the GERG-2008 equation of state [3]. The first two of these are group contribution approaches and can be applied to complex multi-component systems. The GERG model was developed primarily for natural gas systems but can be applied to liquid and super-critical mixtures. PPR-78 and SAFT-γ Mie both give a good account of the literature vapor-liquid equilibrium data and predict the densities to within (2 to 4) %. However, SAFT-γ Mie is much more accurate for derivative properties and is the only one capable of describing the sound-speed data. The GERG-2008 model is the most accurate for the pure substances but perform poorly for the mixtures, probably because it lacks binary-specific departure functions for these systems.
References
- Jaubert J-N, Privat R. Relationship between the binary interaction parameters (kij) of the Peng-Robinson and those of the Soave-Redlich-Kwong equations of state: Application to the definition of the PR2SRK model. Fluid Phase Equilib. 2010;295:26-37
- Dufal S, Papaioannou V, Sadeqzadeh M, Pogiatzis T, Chremos A, Adjiman CS, et al. Prediction of Thermodynamic Properties and Phase Behavior of Fluids and Mixtures with the SAFT-gamma Mie Group-Contribution Equation of State. J Chem Eng Data. 2014;59:3272-88
- Kunz O, Wagner W. The GERG-2008 wide-range equation of state for natural gases and other mixtures: an expansion of GERG-2004. J Chem Eng Data. 2012;57:3032â91.
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