Mole Fraction Research Articles

Experimental analysis and modeling of aprepitant (an antiemetic drug for chemotherapy) solubility in subcritical water with/without co-solvent

This action described the experimental equilibrium solubility of aprepitant (APT), an antiemetic drug for chemotherapy, in subcritical water (SW) with/without ethanol as co-solvent, acquired through a static method between 298.15 and 393.15 K and 0–15 % (w/w) of ethanol and the constant pressure of 10 bar. The mole fraction of APT was obtained in the range of 0.39×10−4 to 9.10×10−4 while its mole fraction by cosolvent varied from 0.75×10−4 to 22.98×10−4. The obtained results represented the significant effect of solvent temperature on the solubility of APT. For both studied systems, the solubility data was successfully correlated with two well-known semi-empirical temperature-based models, namely the linear and modified Apelblat models. Results from applying statistical criteria exhibited that the modified Apelblat model had the highest accordance with experimental data. Finally, using the obtained correlation results, the apparent thermodynamic analysis including enthalpy, entropy, and Gibbs free energy of dissolution for APT dissolved in SW was obtained.

Aggregation in Deep Eutectic Solvents (DESs): Formation of Polar DES-in-Nonpolar DES Microemulsions.

The versatility of environmentally benign and inexpensive deep eutectic solvents (DESs) lies in their widely varying physicochemical properties. Depending on its constituents, a DES may be highly polar or nonpolar in nature. This offers an enticing possibility of formation of novel nonaqueous microemulsions (MEs). Evidence of the presence of polar DES-in-nonpolar DES MEs is presented with reline (formed by mixing choline chloride and urea in 1 : 2 mol ratio) as the polar DES forming the ME pools, Thy : DA [formed by mixing thymol (Thy) and n-decanoic acid (DA) in 1 : 1 mol ratio] nonpolar DES as the bulk oil phase and nonionic surfactant Brij-35 as the emulsifying agent. While only sparingly miscible in Thy : DA, as high as 2.5 M reline can be solubilized in this DES in the presence of 100 mM Brij-35; reline loading (w Rel = [reline]/[Brij-35]) as high as 25 can be achieved. The ternary phase diagram of the Thy : DA/Brij-35/reline system reveals a clear and transparent single-phase region where MEs may be forming. Dynamic light scattering confirms the presence of MEs of 2-10 nm size. Even as up to 2.5 M (ca. 0.35 mole fraction) reline, whose dynamic viscosity (η) and electrical conductivity (κ) are very high, is added to 100 mM Brij-35 solution of Thy : DA, the η and κ values of the solution increase insignificantly, thus conforming to the formation of MEs in the solution. Fourier transform infrared (FTIR) absorbance spectra and fluorescence probe responses further indicate that reline is not dispersed in the medium but rather forms polar pools of the MEs. These novel nonaqueous polar DES-in-nonpolar DES MEs will not only expand the application potential of DESs but also offer a new class of organized media with widespread potential.

Experimental and numerical study on the influence of N2/H2 on the laminar combustion characteristics of syngas premixed flames

This paper primarily analyzes the influence of N2 and H2 content on the laminar combustion characteristics of low calorific value syngas, using a constant-volume combustion bomb to measure the laminar combustion velocity (SL) of the fuel and compare it with five commonly used mechanisms. The study reveals that higher N2 content significantly reduces the SL of CO/CH4/CO2 mixed fuels, primarily due to a general decrease in the mole fractions of key intermediates and net reaction rates. Increasing H2 content leads to an increase in the SL of CO/CH4/CO2/N2 mixed fuels. The thermal effect becomes increasingly prominent with the elevation of H2 content, while the proportion of thermal effect initially decreases and subsequently increases as the equivalence ratio rises. With the increase in N2 content, the mole fraction of NO experiences a significant decrease, and the rate of decline in thermal NO production is even faster. Conversely, with the increase in H2 content, the rate of rise in non-thermal NO generation is faster, and the mole fraction of NO tends to increase.

Using metal oxide gas sensors to estimate the emission rates and locations of methane leaks in an industrial site: assessment with controlled methane releases

Abstract. Fugitive methane (CH4) emissions occur in the whole chain of oil and gas production, including from extraction, transportation, storage, and distribution. Such emissions are usually detected and quantified by conducting surveys as close as possible to the source location. However, these surveys are labour-intensive, are costly, and fail to not provide continuous emissions monitoring. The deployment of permanent sensor networks in the vicinity of industrial CH4 emitting facilities would overcome the limitations of surveys by providing accurate emission estimates, thanks to continuous sampling of emission plumes. Yet high-precision instruments are too costly to deploy in such networks. Low-cost sensors using a metal oxide semiconductor (MOS) are presented as a cheap alternative for such deployments due to their compact dimensions and to their sensitivity to CH4. In this study, we demonstrate the ability of two types of MOS sensors (TGS 2611-C00 and TGS 2611-E00) manufactured by Figaro® to reconstruct a CH4 signal, as measured by a high-precision reference gas analyser, during a 7 d controlled release campaign conducted by TotalEnergies® in autumn 2019 near Pau, France. We propose a baseline voltage correction linked to atmospheric CH4 background variations per instrument based on an iterative comparison of neighbouring observations, i.e. data points. Two CH4 mole fraction reconstruction models were compared: multilayer perceptron (MLP) and second-degree polynomial. Emission estimates were then computed using an inversion approach based on the adjoint of a Gaussian dispersion model. Despite obtaining emission estimates comparable with those obtained using high-precision instruments (average emission rate error of 25 % and average location error of 9.5 m), the application of these emission estimates is limited to adequate environmental conditions. Emission estimates are also influenced by model errors in the inversion process.

Effects of equivalent ratio and initial temperature on the explosion characteristics of ethanol, acetone, and ethyl acetate

In this paper, the effects of equivalence ratio (0.8–2.0) and temperature (30°C–120°C) on ethanol, acetone, and, ethyl acetate vapors explosion characteristics through experimental and numerical studies were investigated. The explosion overpressure and flame propagation velocity were recorded through the pressure transducer and high-speed camera. The results showed that the flame propagation velocity, peak explosion overpressure, and peak growth rate of explosion overpressure increased first and then decreased with the increase of equivalence ratio. The cracks on the flame surface enhanced with the increase of the equivalence ratio. As the initial temperature increased, peak explosion overpressure, the flame propagation velocity, and peak growth rate of explosion overpressure gradually increased. The sensitivity analysis of laminar burning velocity indicated that with the change of equivalence ratio and initial temperature, the shared elementary reactions that increased the reactivity were H + O2 <=> O + OH, HCO + M <=> H + CO + M, and CO + OH <=> CO2 + H, and the shared elementary reaction that reduced the reactivity was H + OH + M <=> H2O + M. The main factor affecting laminar burning velocity was the mole fraction of H and OH radicals.

Synchrotron vacuum ultraviolet photoionization mass spectrometry and modeling study of iso-octane low temperature oxidation at varied pressures

Because of its excellent anti-knock properties, iso-octane has been selected as the main component of gasoline surrogates, and a thorough understanding of its low temperature oxidation process is essential for the development of kinetic models. Although iso-octane has been studied for decades, a comprehensive understanding of its low temperature oxidation chemistry has not been realized, and kinetic models were not well developed. In this work, the previously developed, variable pressure jet-stirred reactor-synchrotron vacuum ultraviolet photoionization mass spectrometry system was used to study the low temperature oxidation of iso-octane at five bar, with an initial fuel mole fraction of 0.01, residence time of 2 s, and equivalence ratio of 0.25. Dozens of oxidation intermediates were qualitatively and quantitatively analyzed, helping to reveal the low temperature oxidation reaction processes of iso-octane and examine the kinetic models. Comparing iso-octane studies at high pressure in the literature, a highly detailed species pool was probed, which included H2O2, carbonyl acids, alkyl hydroperoxides, and keto-hydroperoxides (KHP). By combining the atmospheric pressure data in the literature, the recently developed model of iso-octane low temperature oxidation was examined. Further improvement of the kinetic model was achieved by carefully tuning the reaction rate constant of the KHP decomposition. Finally, according to the variation of mole fraction of products at different pressures, the pressure effects on key reaction pathways were discussed, and the selectivity of products at varied pressure conditions clarified.

Upgrading low-concentration oxygen-bearing coal bed methane by dual-reflux vacuum swing adsorption

Fugitive methane (CH4) is a typical by-product of mining processes, which is commonly known as coal bed methane (CBM) or coal mine gas (CMG). The capture of these CH4 gases can simultaneously avoid greenhouse gas emissions and provide extra energy benefits. However, the explosion risk of low-concentration CBM (CH4 molar fraction ≤ 30%) requires strictly safe operating protocols to conduct the capture process. Dual reflux vacuum swing adsorption (DR-VSA) is a promising candidate with a vacuum operating condition which can lower the explosion risk and simultaneously reach CH4 enrichment and O2 removal targets in product and effluent streams. Herein, a low-concentration oxygen-bearing CBM (20% CH4, 16% O2 and 64% N2) can be upgraded to 69.7 mol% in the product gas while ensuring an effluent concentration of 2.5 mol% by the DR-VSA cycle using ionic liquidic zeolites (ILZ) as the adsorbents. A rigorous safety analysis has been conducted to investigate the explosion risk in the adsorption column and product tank, suggesting that the DR-VSA process is a safe technology for upgrading low-concentration oxygen-bearing methane.

Experimental and theoretical study of multiple active site-functionalized Spirulina residue-based porous carbon as an economical adsorbent for NH3 and SO2 adsorption: Micro- and macro-mechanistic investigations

Here, we successfully synthesized a cost-effective (7.88 USD/kg) multi-active site (CuCl2, CuO and KCl) functionalized Spirulina residue-based porous carbon (MMBC). This innovative synthesis method utilizes Spirulina residue, a sustainable and low-cost biomass source, making the production of MMBC economically viable and environmentally friendly. Under ambient conditions, MMBC exhibits competitive adsorption capacities for NH3 and SO2 compared to other adsorbents, reaching 3.01 mmol/g (i.e., 51.26 mg/g) and 0.70 mmol/g (i.e., 44.85 mg/g), respectively, and tolerable recoverability. These values are significant improvements over many existing adsorbents, highlighting MMBC's efficiency in removing toxic industrial chemicals (TICs). Additionally, even at low molar fractions of NH3 or SO2, such as 0.001, MMBC demonstrates significant ideal adsorption solution theory (IAST) selectivity for NH3/N2 and SO2/N2, with values of 12.02 and 4.19, respectively. This high selectivity at low concentrations underscores MMBC's potential for applications in environments with trace amounts of pollutants. Furthermore, extensive research has been conducted in this study to elucidate the microscopic and macroscopic adsorption mechanisms of NH3 and SO2 on MMBC. Specifically, investigations in statistical physics models and statistical thermodynamics reveal that the adsorption of NH3 and SO2 on MMBC adhere to a non-aggregative, multilayer, multi-anchorage, and spontaneous exothermic physicochemical behavior. And the adsorption orientation occurs either horizontally or both horizontally and non-horizontally, contingent upon the system and temperature. These findings provide a deeper understanding of the adsorption processes and provide innovative insights into the adsorption mechanisms at the molecular level and at the macroscopic scale. Besides, the material characterization results reveal that the above adsorption process involves both physical interactions (pore diffusion and van der Waals forces) and chemical interactions (CuCl2 with NH3, CuO and KCl with SO2), indicating a physicochemical adsorption mechanism. This dual mechanism of adsorption offers a comprehensive explanation of the high performance of MMBC. In summary, this study developed a cost-effective Spirulina residue-based adsorbent, exhibiting high removal efficiency and selectivity for TICs, and providing deep insights into adsorption mechanisms. The innovative use of Spirulina residue addresses waste management issues and promotes the development of sustainable materials in the field of environmental remediation, contributing to cleaner production.

Comparisons of Greenhouse Gas Observation Satellite Performances Over Seoul Using a Portable Ground‐Based Spectrometer

AbstractSatellites provide global coverage for monitoring atmospheric greenhouse gases, crucial for understanding global climate dynamics. However, their temporal and spatial resolutions fall short in detecting urban‐scale variations. To enhance satellite reliability over urban areas, this study presents the first comprehensive analysis of long‐term observations of column‐averaged dry air mole fractions of CO2, CH4, and CO (XCO2, XCH4, XCO) using two ground‐based fourier transform infrared spectrometers, EM27/SUNs, in a megacity. With over 2 years of observations, our study shows that EM27/SUN measurements can effectively capture the daily and seasonal variability of XCO2, XCH4, and XCO over Seoul, a megacity with complex topography and various emission sources. In addition, we use the advantage of having multiple greenhouse gas satellites targeting Seoul to compare with the EM27/SUNs. Our study highlights the importance of EM27/SUN observations in Seoul to identify the need for improvements in satellites to monitor greenhouse gas behaviors and emissions in urban areas.

Modeling and simulation of laser-ignited Al-PTFE reactive material in vacuum

Despite extensive investigations elucidating the initial response behavior of aluminized polytetrafluoroethylene (Al-PTFE) under atmospheric pressure, research on their response in lean-oxygen environments pertinent to propulsion and explosion scenarios is still lacking. This paper theoretically analyzes the multi-physical processes of laser-ignited Al-PTFE, identifying the initial response, main chemical reaction paths, and gas-phase product flow mechanisms. A dynamic reaction model of Al-PTFE considering material moving front, chemical reactions, gas-phase product dynamics, and variations in thermophysical properties, was developed. The robust coupling scheme in the model addresses nonlinear equations and fluid-solid coupling boundary conditions. Validation was achieved by comparing the ablation depth and plume number density field calculated by the model with the experimental results in the literature. The model reveals a positive correlation between laser fluence and both temperature growth rate and ablation depth of Al-PTFE, with the effects mainly observed in the full width at half maximum (FWHM) of the pulsed laser due to the thermal decomposition of the PTFE matrix. Simulations of the equilibrium constants and molar fractions of 19 components in the Al-PTFE ablation plume within the temperature range of 2000 K to 30,000 K at 0.001 Pa indicate that the equilibrium constants for dissociative reactions exceed those for ionization reactions, primarily in the early plume formation stages. Analysis of kinetic parameters and ambient pressure effects shows that during laser ablation, the maximum temperature of the plume initially appears near the ablation surface, shifting to the front, where the maximum velocity is always located. An elliptical shock wave forms due to adiabatic expansion of the plume, creating a cavity inside the plume. Lower ambient pressure increases plume expansion velocity, temperature, and size.

Electrical characteristics of Si0.7Ge0.3/Si heterostructure-based n-type GAA MOSFETs

Electrical characteristics of Si0.7Ge0.3/Si heterostructure-based n-type gate-all-around MOSFETs (GAA MOSFETs) are reported in this work through experimental and numerical simulation data. N-type GAA MOSFETs of varying lengths (60 nm to 160 nm) and widths (20 nm to 42 nm) are fabricated and measured to extract key electrical parameters like ON current, ON-to-OFF current ratio, threshold voltage, DIBL, and subthreshold swing. Moreover, the influence of tensile strain on carrier transport parameters in the buried Si layer is examined in this work. The Ge mole fraction in SiGe is raised from 0.2 to 0.3, and the corresponding changes in XX-stress, and current density are analyzed using a TCAD simulator. The performance of the proposed device has also been compared with unstrained SiGe/Si, all Si, and SiGe-based GAA MOSFETs.

Thermo physical and spectroscopic properties of binary liquid mixtures at various temperatures and correlation with the Jouyban–Acree model (propargyl alcohol, ethanoic acid, propanoic acid and butanoic acid)

ABSTRACT A thorough investigation into binary mixtures of propargyl alcohol and various carboxylic acids (ethanoic, propanoic and butanoic) was conducted. Measurements of density (ρ), speed of sound (u) and viscosity (η) were meticulously performed across the entire range of mole fractions at temperatures (303.15 K−313.15 K) and atmospheric pressure (0.1 MPa). These data were used to calculate key thermodynamic and transport properties, including excess molar volume, excess isentropic compressibility, deviation in viscosity and excess Gibbs free energy of activation for viscous flow. The partial molar properties and infinite dilution molar partial properties were also determined for each binary system. Trends and behaviours were interpreted within the framework of intermolecular interactions, focusing on complex formation and specific chemical forces. The PFP theory and Jouyban–Acree model were critically applied, with confidence in the findings supported by FTIR studies.

Experiment and simulation assessment of supercritical underground coal gasification in deep coal seam

To explain the impact of geological and process factors on underground coal gasification in deep coal seam (>2200 m) and promote the efficient and clean extraction and conversion of coal, this study employs the orthogonal experimental design method to investigate the impact of CO2 coefficient (0–1), moisture content (30–80 wt%), calcite content (0–10 wt%), albite content (0–10 wt%), kaolinite content (0–20 wt%), reaction temperature (550–650 °C), and reaction pressure (23–27 MPa) on the characteristics of coal underground gasification under supercritical H2O/CO2 conditions. Furthermore, range analysis and variance analysis are utilized to determine the degree of influence of each factor and the interaction between factors. Finally, the Gibbs free energy minimization method is used to conduct a thermodynamic equilibrium analysis of coal supercritical H2O/CO2 gasification at high temperatures (750–1000 °C). The results indicate that the three most significant factors affecting the process of coal supercritical H2O/CO2 gasification are the CO2 coefficient, moisture content, and reaction temperature. The maximum carbon gasification efficiency at 650 °C in experimental cases and 1000 °C in simulation cases is 22.2% and 88.1%, respectively. Although the addition of CO2 at lower temperatures reduces the carbon gasification efficiency, at high temperatures (>900 °C), a higher initial CO2 concentration increases the carbon gasification efficiency. The addition of CO2 under conditions of low moisture content increases the mole fraction of H2, but reduces it under conditions of high moisture content (≥70 wt%). Among the three minerals, calcite has the most significant influence on the gasification process.

Analyses of Jet Buoyant Flow in a Multicompartment Containment Using an Open-Source Solver

Hydrogen mixing and distribution in a nuclear power plant containment during a postulated severe accident is a phenomenon with high safety relevance for current and advanced light water reactors. The Organisation for Economic Co-operation and Development (OECD)/Nuclear Energy Agency (NEA) SESAR Thermal-Hydraulics (SETH) project was carried out to generate experimental data on basic containment phenomena with the required instrumentation to assess computational fluid dynamics (CFD) and lumped parameter codes. In this paper, we analyze the PANDA SETH Test 16 of the OECD/NEA SETH project using containmentFOAM, which is a tailored open-source CFD code package for containment analysis developed at Forschungszentrum Jülich GmbH based on OpenFOAM.® SETH Test 16 addressed steam-air mixture transport driven by jets and plumes in the multicompartment PANDA facility (two vessels and an interconnecting pipe) at the Paul Scherrer Institut in Switzerland. Steam as a wall plume was injected at 0.040 kg/s and 140°C in vessel 1, which was initially filled with dry air at 108°C. The steam-air mixture was vented out from the top of vessel 2. The system pressure was constant at 1.3 bar for the whole test duration (4000 s). To simulate SETH Test 16, the k-ω shear stress transport turbulence model was adopted with the generalized gradient diffusive hypothesis buoyancy turbulence model. The simulation represented the experimental phenomenology reasonably well. The trends for the calculated temperature distribution were similar to those of the experiments and only yielded a slight discrepancy of about 2.7%. In addition, the distribution of the steam molar fraction was well predicted above the injection tube in vessel 1. However, below the injection tube in vessel 1, some discrepancies between the simulations and the experimental results were observed. These may have been caused by the higher turbulent mass diffusivity in the physical model and the challenge of the mesh resolution in the middle region of vessel 1.

Thermal radiation at high-temperature and high-pressure conditions: Validation of HITEMP-2010 for carbon dioxide

Line-by-line models based on spectroscopic databases are powerful tools for the generation of accurate gas absorption spectra but still require validation for high-temperature and high-pressure conditions. Therefore, this study carried out spectral transmissivity measurements of CO2/N2 mixtures at temperatures of approximately 773K and 1273K and pressures between 1bar and 60bar. The measurement data was obtained in a spectral range from 1900cm−1 to 6600cm−1 at a spectral resolution of 1cm−1 and was compared with line-by-line predictions. The comparisons show that the absorption spectra of CO2 can be predicted for high-temperature and high-pressure conditions with good accuracy if the line-by-line calculations are performed using modified line profiles and the HITEMP-2010 database. In comparison with standard line-shape functions, both the Voigt line-shape function combined with the cut-off criterion of Alberti et al. (Combust. Flame 162 (2015) 597–612) and the Price line-shape function modified with one of the two ξ corrections of Westlye et al. (J. Quant. Spectrosc. Radiat. Transfer 302 (2023) 108555; J. Quant. Spectrosc. Radiat. Transfer 280 (2022) 108089) provided significantly superior predictions. However, deficiencies of the cut-off criterion of Alberti et al. become clear in the transmissivity predictions of the right wings of the 4.3µm band and the 2.7µm band. The Price line-shape function combined with the first ξ correction of Westlye et al. was able to overcome these erroneous predictions of the wings, while the Price line-shape function modified with the second ξ correction of Westlye et al. only proved superior for gas mixtures with 20% CO2 and 80% N2 (in mole fractions).

Thermophysical properties of Ni-Ti melts measured by electromagnetic levitation method using static magnetic field

The normal spectral emissivity, molar heat capacity at constant pressure, and thermal conductivity of Ni-Ti melts were measured during electromagnetic levitation under a static magnetic field. The emissivity and heat capacity of the Ni-Ti melts were measured under a 3 T static magnetic field. The temperature range for the emissivity measurements was 1240–1839 K, and the temperature range for the heat capacity measurements ranged was 1223–1851 K. The emissivity and heat capacity of the Ni-Ti melts, except for the Ni mole fractions (xNi) of 0 and 0.25, showed without temperature dependence within the experimental temperature range. Furthermore, the heat capacity was larger than the ideal solution over the whole range of compositions. The emissivity of the Ni-Ti melts was discussed based on the Drude model. The temperature dependence of thermodynamic functions, such as enthalpy of mixing, excess entropy, and excess Gibbs energy, were calculated using excess heat capacity. The thermal conductivity of Ni-Ti melts was measured under a static magnetic field of 10 T. The temperature range for the thermal conductivity measurements was 1177–1900 K. The thermal conductivities of the Ni-Ti melts increased with increasing temperature, exhibited a local minimum for xNi = 0.75, and were higher than those calculated using the Wiedemann–Franz laws. This difference in thermal conductivity was discussed by considering the contribution of atomic vibrations.

Comprehensive Utilization of Fossil Energy: Fabrication of Fire-Retardant Building Materials from Waste Plastic

As one of the most common fossil derivatives, plastics are widely used for their exceptional chemical stability, low density, and ease of processing. In recent years, there has been a significant increase in the production of waste plastics, coupled with a low recycling rate, resulting in serious environmental pollution. To enhance the use of waste plastics, this research synthesized flame-retardant materials from hypercrosslinked polystyrene with different molar fractions of flame retardants. Waste polystyrene foam was used as the raw material, while aniline, triphenylphosphine, and melamine were employed as flame-retardant additives. The flame-retardant additives were successfully doped into the porous skeleton structure of hypercrosslinked polystyrene through a chemical reaction or physical mixing to achieve in situ flame retardancy, and the materials were shaped by a phenolic resin prepolymer. Then, the samples were characterized in detail, and the results indicate that the addition of a flame retardant enhances the flame retardancy of the material. In addition, the material has excellent thermal insulation performance, with a minimum thermal conductivity of 0.04176 W/(m·K).

One-dimensional dynamic model of a PEM fuel cell for analyzing through-plane species distribution and irreversible losses under various operating conditions

This study develops a one-dimensional dynamic model of a proton-exchange membrane fuel cell (PEMFC), using species mole fractions as shared variables to examine through-plane water and oxygen distribution. During dynamic operation, the species mole fraction difference between the cathode channel/cathode gas distribution media (cCH/cGDM) interface and the cGDM/cathode catalyst layer (cGDM/cCL) interface varies with current density. When relative humidity (RH) changes from 20 % to 90 % at 1 A/cm2, the water mole fraction difference between cCH/cGDM and cGDM/cCL increases by 33.21 %, while the oxygen mole fraction difference increases by only 3.29 %. Current density step changes cause overshoot and undershoot behavior in the water mole fraction, affecting membrane water content, especially at low RH, where it remains low and sensitive to current and temperature changes. Beyond 50 % RH, membrane water content stabilizes, with fluctuations mainly observed on the anode side. The impact of species distribution on irreversible losses was then examined.Furthermore, oxygen transport resistance increases with operating pressure, while oxygen molecular diffusion remains stable. Conversely, rising temperatures substantially improve oxygen molecular diffusion. An analysis of FC loss profiles under various temperatures (333.15K–363.15K) and RH (0%–100 %) at constant loads (0.2&1 A/cm2) shows the model's capability in determining optimized operating conditions for PEMFCs.

Adsorption and Diffusion Properties of Gas in Nanopores of Kerogen: Insights from Grand Canonical Monte Carlo and Molecular Dynamics Simulations

Investigating the adsorption and diffusion processes of shale gas within the nanopores of kerogen is essential for comprehending the presence of shale gas in organic matter of shale. In this study, an organic nanoporous structure was constructed based on the unit structure of Longmaxi shale kerogen. Grand canonical Monte Carlo and molecular dynamics simulation methods were employed to explore the adsorption and diffusion mechanisms of pure CH4, CO2, and N2, as well as their binary mixtures with varying mole fractions. The results revealed that the physical adsorption characteristics of CH4, CO2, and N2 gases on kerogen adhered to the Langmuir adsorption law. The quantity of adsorbed gas molecules increased with rising pressure but decreased with increasing temperature. The variation in the heat of adsorption was also analyzed. Under identical temperature and pressure conditions, the adsorption of CH4 increased with higher mole fractions of CH4, whereas it decreased with greater mole fractions of CO2 and N2. Notably, CO2 molecules exhibited a robust interaction with kerogen molecules compared to the adsorption properties of CH4 and N2. Furthermore, the self-diffusion coefficient of gas within kerogen nanopores gradually decreased with increasing pressure or decreasing temperature. The diffusion capacity of gas molecules followed the descending order N2 > CH4 > CO2 under the same pressure and temperature conditions.

Thermophysical properties of binary mixtures of pentyl acetate with butanol at 298.15 K to 318.15 K: PFP theory, FTB model, and Graph theoretical approach

The measured density (ρ) and refractive index (nD) of binary pentyl acetate (1) + isomers of butanol (2) mixtures were reported at T = 298.15 K to 318.15 K and at 0.1 MPa pressure. Using the experimental ρ, u and nD data, excess molar volume (VmE), excess ultrasonic speed (uE), excess isentropic compressibility (κSE), and excess refractive index (nDE) were calculated and correlated with the Redlich–Kister (RK) equation. The findings suggest that the behavior of a mixture is affected by intermolecular interactions (cohesive forces such as dipole–dipole, H–bonding, dispersive force) and structural aspects of the molecules. The Prigogine–Flory–Patterson (PFP) theory, Flory–Treszczanowicz–Benson (FTB) model, and Graph theoretical approach (GTA) accurately analyzed the VmE values. Both the FTB model and PFP theory predicted the VmE curves not only successfully but also accurately represented their shape and magnitude except GTA at a lower mole fraction of pentyl acetate (xA<0.2). The positive values of VmE values were observed for binary mixtures across all temperatures. The intermolecular interactions were also corroborated by uE, κSE and nDE.