ABSTRACT
This study reviews available van der Waals- and Platteeuw-based hydrate models considering multiple occupancy of cavities. Small guest molecules, such as hydrogen and nitrogen, are known to occupy lattice cavities multiple times. This phenomenon has a significant impact on hydrate stability and thermodynamic properties of the hydrate phase. The objective of this work is to provide a comprehensive overview and required correlations for the implementation of a computationally sufficient cluster model that considers up to five guest molecules per cavity. Two methodologies for cluster size estimation are evaluated by existing nitrogen hydrate models showing accurate results for phase equilibria calculations. Furthermore, a preliminary hydrogen hydrate model is introduced and compared with the results of other theoretical studies, indicating that double occupancy of small sII cavities is improbable and four-molecule clusters are predominant in large sII cavities for pressures above 300 MPa. This work lays the foundation for further exploration and optimization of hydrate-based technologies for small guest molecules, e.g., storage and transportation, emphasizing their role in the future landscape of sustainable energy solutions.
ABSTRACT
An empirical fundamental equation of state in terms of the Helmholtz energy for tetrahydrofuran is presented. In the validity range from the triple-point temperature up to 550 K and pressures up to 600 MPa, the equation of state enables the calculation of all thermodynamic properties in the liquid, vapor, and super-critical regions including saturation states. Based on an extensive literature review, experimental data are represented within their experimental uncertainty. In the homogeneous liquid phase at atmospheric pressure, the uncertainty in density is 0.015 %, speed of sound is represented with an uncertainty of 0.03 %, and isobaric heat capacity has an uncertainty of 0.4 %. Isobaric heat capacities in the homogeneous vapor phase are described with an uncertainty of 0.2 %. Higher uncertainties occur above atmospheric pressure for all homogeneous properties. Depending on the temperature range, vapor pressure can be calculated with an uncertainty from 0.02 % to 3 %. The extrapolation behavior is evaluated, showing reasonable extrapolation behavior towards extreme conditions. Supplementary Information: The online version contains supplementary material available at 10.1007/s10765-023-03258-3.
ABSTRACT
One of the major challenges during polarimetric determination of glucose concentration is the spectral superposition with other optically active molecules, especially proteins like albumin. Since each of those substances has a characteristic optical rotatory dispersion (ORD), we developed a broadband polarimeter setup to distinguish between glucose and albumin. A partial least squares (PLS) regression with 5 components was applied to the polarimeter signal in the wavelength range of 380 - 680 nm . To verify the efficacy of the proposed method, different glucose levels of 0 - 500 mg/dl were spiked with varying albumin concentrations up to 1000 mg/dl . A standard error of prediction of ± 16.0 mg/dl was achieved compared to ± 128.3 mg/dl using a two-wavelength system with 532 nm and 635 nm under the same conditions.
ABSTRACT
Polarimetric determination of glucose is known to be strongly affected by scattering in turbid media. Other effects like fluctuations of light source emission and sample absorption also deteriorate glucose predictability. This work presents a measurement setup using a real-time data processing method to address these problems. The approach uses the frequency-dependent intensity components created when the polarization of the incident light is periodically modulated by a Faraday rotator. The efficacy of the proposed method was verified experimentally for a glucose range of 0 - 500 mg/dl. It was shown that the approach reduces the prediction errors in slightly turbid media from 35.7 mg/dl down to 1.17 mg/dl. In a similar way, the glucose predictability for fluctuating light source emission was improved from ±16.16 mg/dl to ±1 mg/dl and for varying sample absorbance from ±15.69 mg/dl to ±1.23 mg/dl, respectively. Therefore, considerable improvement of robustness and reproducibility of glucose determination was demonstrated.
