Measurement and modeling of clemastine fumarate (antihistamine drug) solubility in supercritical carbon dioxide

The solubilities of clemastine fumarate in supercritical carbon dioxide (ScCO2) were measured for the first time at temperature (308 to 338 K) and pressure (12 to 27 MPa). The measured solubilities were reported in terms of mole faction (mol/mol total) and it had a range from 1.61 × 10–6 to 9.41 × 10–6. Various models were used to correlate the data. The efficacy of the models was quantified with corrected Akaike’s information criterion (AICc). A new cluster salvation model was derived to correlate the solubility data. The new model was able to correlate the data and deviation was 10.3% in terms of average absolute relative deviation (AARD). Furthermore, the measured solubilities were also correlated with existing K.-W. Chen et al., model, equation of state model and a few other density models. Among density models, Reddy and Garlapati model was observed to be the best model and corresponding AARD was 7.57% (corresponding AICc was − 678.88). The temperature independent Peng–Robinson equation of state was able to correlate the data and AARD was 8.25% (corresponding AICc was − 674.88). Thermodynamic parameters like heats of reaction, sublimation and solvation of clemastine fumarate were calculated and reported.

Measurement and Modeling of Clemastine Fumarate (Antihistamine Drug) Solubility in Supercritical Carbon Dioxide

The solubilities of clemastine fumarate in supercritical carbon dioxide) ScCO2( were measured for the first time at temperature (308 to 338 K) and pressure (12 to 27 MPa). The measured solubilities were reported in terms of mole faction and it is ranged from 1.61 ×10− 6 to 9.41×10− 6. Various models were used to correlate the data. The efficacy of the models was quantified with corrected Akaike’s information criterion (AICc). A new cluster salvation model was derived to correlate the solubility data. The new model was able to correlate the data and deviation was 10.3% in terms of average absolute relative deviation (AARD). Furthermore, the measured solubilities were also correlated with existing K.-W. Chen et al., cluster salvation model, equation of state (EoS) model and few density models. Among density models, Tippana and Garlapati model was observed to be the best model and corresponding AARD% was 7.57 (corresponding AICc is -678.88). The Peng-Robinson equation of state as temperature independent was able to correlate the data and deviation was 8.25% in terms of AARD% (corresponding AICc is -674.88). Moreover, thermodynamic enthalpies of clemastine fumarate were estimated.

Theoretical And Experimental Investigation Of Thermodiffusion (Soret Effect) In A Porous Medium

Thermodiffusion (the Soret effect) is important for the study of compositional variation in hydrocarbon reservoirs. The development of research history, theoretical modeling and applications to multicomponent hydrocarbon mixtures is included in this work. The Firoozabadi model appears to be an appropriate model for thermodiffusion estimation for hydrocarbon mixtures, and it is derived based on the equation of entropy generation rate and four postulates in non-equilibrium thermodynamics. Two equations of state, the Peng-Robinson Equation of State (PR-EoS) and the volume translated Peng Robinson Equation of State (vt-PR-EoS), have been used to estimate the thermodynamic properties of mixtures. In this work, different cases are presented: first, a new thermodiffusion cell designed to perform high pressure measurements in a porous medium has been validated at atmospheric pressure. Two systems were investigated, (1) 1,2,3,4-tetrahydronaphtalene (THN) and n-dodecane (nC12), and (2) isobutylbenzene (IBB) and n-dodecane at 50% of mass fraction. Experimental results revealed an excellent agreement with benchmark values and a good agreement with theoretical data. Second, the thermal expansion and concentration expansion coefficients and the viscosity of mixtures are necessary properties for the determination of the thermodiffusion coefficient. The densities of binaries of nC12, IBB and THN for pressures from 0.1 to 20 MPa and a temperature centred on 25⁰ were measured. By an derivative method, the thermal expansion and concentration expansion coefficients were determined. Viscosities were directly measured using a high pressure high temperature viscometer. Finally, the thermosolutal convections of two ternary mixtures, methane (C1), n-butane (nC4) and n-dodecane (nC12) at a pressure of 35.0 MPa and nC12, THN and IBB at atmospheric pressure, in a porous medium, were investigated over a wide range of permeability. The effect of permeability in the homogeneous and heterogeneous porous media on fluid transport was studied with consideration of thermodiffusion and molecular diffusion. In the analysis of the homogeneous porous medium, it was found that, for permeability below 300 mD, the thermodiffusion for both mixtures was dominant; and above this level, buoyancy convection became the dominant mechanism. Also, the viscosity was found to influence the evaluation of the molecular and thermodiffusion coefficients. In the case of heterogeneous porous medium, the impact of permeability ratio on the composition of the mixture components, velocity in the porous medium and on the separation ratio was investigated. It was found that the heterogeneity of porous medium has a significant influence on the composition of the mixture components.

Theoretical And Experimental Investigation Of Thermodiffusion (Soret Effect) In A Porous Medium

Thermodiffusion (the Soret effect) is important for the study of compositional variation in hydrocarbon reservoirs. The development of research history, theoretical modeling and applications to multicomponent hydrocarbon mixtures is included in this work. The Firoozabadi model appears to be an appropriate model for thermodiffusion estimation for hydrocarbon mixtures, and it is derived based on the equation of entropy generation rate and four postulates in non-equilibrium thermodynamics. Two equations of state, the Peng-Robinson Equation of State (PR-EoS) and the volume translated Peng Robinson Equation of State (vt-PR-EoS), have been used to estimate the thermodynamic properties of mixtures. In this work, different cases are presented: first, a new thermodiffusion cell designed to perform high pressure measurements in a porous medium has been validated at atmospheric pressure. Two systems were investigated, (1) 1,2,3,4-tetrahydronaphtalene (THN) and n-dodecane (nC12), and (2) isobutylbenzene (IBB) and n-dodecane at 50% of mass fraction. Experimental results revealed an excellent agreement with benchmark values and a good agreement with theoretical data. Second, the thermal expansion and concentration expansion coefficients and the viscosity of mixtures are necessary properties for the determination of the thermodiffusion coefficient. The densities of binaries of nC12, IBB and THN for pressures from 0.1 to 20 MPa and a temperature centred on 25⁰ were measured. By an derivative method, the thermal expansion and concentration expansion coefficients were determined. Viscosities were directly measured using a high pressure high temperature viscometer. Finally, the thermosolutal convections of two ternary mixtures, methane (C1), n-butane (nC4) and n-dodecane (nC12) at a pressure of 35.0 MPa and nC12, THN and IBB at atmospheric pressure, in a porous medium, were investigated over a wide range of permeability. The effect of permeability in the homogeneous and heterogeneous porous media on fluid transport was studied with consideration of thermodiffusion and molecular diffusion. In the analysis of the homogeneous porous medium, it was found that, for permeability below 300 mD, the thermodiffusion for both mixtures was dominant; and above this level, buoyancy convection became the dominant mechanism. Also, the viscosity was found to influence the evaluation of the molecular and thermodiffusion coefficients. In the case of heterogeneous porous medium, the impact of permeability ratio on the composition of the mixture components, velocity in the porous medium and on the separation ratio was investigated. It was found that the heterogeneity of porous medium has a significant influence on the composition of the mixture components.

Application of Scalar Filtered Density Function to Turbulent Flows Under Supercritical Condition

The scalar filtered density function (FDF) methodology is extended and employed for large eddy simulation (LES) of turbulent flows under supercritical condition. To describe real-fluid behavior, the extended methodology incorporates the generalized heat and mass diffusion models along with real fluid thermodynamic relations which are derived using the cubic Peng-Robinson equation of state. These models are implemented within the stochastic differential equations comprising the scalar FDF transport. Simulations are conducted of a temporally developing mixing layer under supercritical condition and the results are assessed by comparing with data generated by direct numerical simulation (DNS) of the same layer. The consistency of the proposed FDF methodology is assessed. The LES-FDF predictions are shown to agree favorably with the DNS data and exhibit several key features pertaining to supercritical turbulent flows.

Revisiting Kelvin equation and Peng–Robinson equation of state for accurate modeling of hydrocarbon phase behavior in nano capillaries

The thermodynamics of fluids in confined (capillary) media is different from the bulk conditions due to the effects of the surface tension, wettability, and pore radius as described by the classical Kelvin equation. This study provides experimental data showing the deviation of propane vapour pressures in capillary media from the bulk conditions. Comparisons were also made with the vapour pressures calculated by the Peng–Robinson equation-of-state (PR-EOS). While the propane vapour pressures measured using synthetic capillary medium models (Hele–Shaw cells and microfluidic chips) were comparable with those measured at bulk conditions, the measured vapour pressures in the rock samples (sandstone, limestone, tight sandstone, and shale) were 15% (on average) less than those modelled by PR-EOS.