Vapor-liquid Equilibrium Research Articles

Application of thermodynamics at different scales to describe the behaviour of fast reacting binary mixtures in vapour-liquid equilibrium

The use of reactive working fluids in thermodynamic cycles is currently being considered as an alternative to inert working fluids, because of the preliminarily attested higher energy-efficiency potential. The current needs to simulate their use in thermodynamic cycles, which may operate in liquid, vapour or vapour-liquid state, are an accurate real-fluid equation of state and ideal gas thermochemical properties of each molecule constituting the mixture, to calculate the equilibrium constant. To this end, the appeal to a multi-scale theoretical methodology is paramount and its definition represents the objective of the present work. This methodology is applied and validated on the system N2O4 ⇌ 2NO2. Firstly, the equations solved for simultaneous two-phase and reaction equilibrium are presented. Secondly, ideal gas thermochemical properties of N2O4 and NO2 are computed at atomic scale by quantum mechanics simulations. Then, to apply the selected cubic equation of state, pure-component properties of the species forming the reactive mixture (critical point coordinates and acentric factor) are required as input. However, these properties are not measurable, since NO2 and N2O4 do not exist in nature as pure components. To get around this difficulty, the methodology relies on molecular Monte Carlo simulations of the pure N2O4 and NO2, as well as on the reactive N2O4 ⇌ 2NO2, enabling the determination of those missing pure-component properties and thus the calculation, on a macroscopic scale, of the reactive mixture properties. Finally, the comparison of calculated mixture properties with available experimental data leads to validate the accuracy of the proposed methodology.

High-pressure carbon dioxide solubility in a deep eutectic solvent (Choline Chloride/MDEA) + sulfolane—Experimental study and thermodynamic modeling using PC-SAFT equation of state

In recent years, releasing post-combustion CO2 into the atmosphere has led to global warming. Air contamination has appeared as a challenge for governments, so several approaches have been used to overcome this issue. So far, physical and chemical solvents have been employed by researchers for CO2 capture. These years deep eutectic solvents (DES) have emerged as an alternative to traditional solvents. In this study, we have investigated a mixture of DES + a physical solvent for the CO2 solubility measurement using a static vapor-liquid equilibrium cell. In this work, the DES was composed of Choline Chloride and MDEA in a molar ratio of 1 to 6 which is blended with sulfolane in weight percentages of 5,10, and 15. We performed the experiments at temperatures of 323.15, 333.15, and 343.15 K and a pressure range of up to 5 MPa. In our previous work, we had already investigated the influence of piperazine on the present DES that led to enhancing CO2 absorption in the mixture, while adding sulfolane to the DES in the present work does not present a positive effect on CO2 solubility in the DES. Enhancing pressure and reducing temperature also led to increasing CO2 solubility. Finally, we modeled the solubility data with the PC-SAFT equation of state. The modeling results were in excellent agreement with the experimental data for DES-CO2, DES-sulfolane-CO2, and DES-piperazine-CO2 systems, so the PC-SAFT EoS successfully estimated the carbon dioxide solubility in the present systems with the absolute average deviation percent of less than unity.

The Influence of Wettability Effect and Adsorption Thickness on Nanoconfined Methane Phase Behavior: Vapor-Liquid Co-Existence Curves and Phase Diagrams

Research interest in the behavior of methane inside nanopores has been growing, driven by the substantial geological reserves of shale gas and coalbed methane. The phase diagram of methane in nanopores differs significantly from its bulk state, influencing its existing form and pertinent physical properties—such as density and viscosity—at specific pressures and temperatures. Currently, there is a lack of effort to understand the nanoconfinement effect on the methane phase diagram; this is a crucial issue that needs urgent attention before delving into other aspects of nanoconfined methane behavior. In this study, we establish a fully coupled model to predict the methane phase diagram across various scales. The model is based on vapor-liquid fugacity equilibrium, considering the shift in critical pressure and temperature induced by pore size shrinkage and adsorption-phase thickness. Notably, our proposed model incorporates the often-overlooked factor of capillary pressure, which is greatly amplified by nanoscale pore size and the presence of the adsorption phase. Additionally, we investigated the impact of surface wettability, correlated to capillary pressure and the shift in critical properties, on the methane phase diagram. Our results indicate that (a) as pore size decreases, the methane phase diagram becomes more vertical, suggesting a transition from a gaseous to a liquid state for some methane molecules, which is contrary to the conventional phase diagram; (b) enhancing surface wettability results in a more vertical phase diagram, with the minimum temperature corresponding to 0 MPa pressure on the phase diagram, increasing by as much as 87.3%; (c) the influence of capillary pressure on the phase diagram is more pronounced under strong wettability conditions compared to weak wettability, and the impact from the shift in critical properties can be neglected when the pore size exceeds 50 nm.

Evaluation of potassium glycinate as a green solvent for direct air capture and modelling its performance in hollow fiber membrane contactors

Current direct air capture (DAC) technology is largely cost-prohibitive for large scale implementation due to the excessive energy required to operate a combined absorption–desorption cycle. As the desorption process consumes much of the supplied energy, there is a demand to find more sustainable sorbent materials that maintain high absorptive capacities yet can be regenerated at lower working temperatures. This work evaluates potassium glycinate (GlyK) as one such alternative absorbent. Through conducting vapor–liquid equilibria and wetted wall column kinetic studies, GlyK is found to have comparable working capacities and liquid mass transfer coefficients to those reported for the industrial standard, monoethanolamine (MEA), yet outperforms it with regards to its distinctly low regeneration temperature. To further understand how GlyK would perform in an industrial scale DAC system, an Aspen Custom Modeler® (ACM) model is developed that integrates the experimentally obtained equilibria and kinetic data with the performance characteristics of a gas-solvent hollow fiber membrane contactor (HFMC). Full-scale simulations show that via implementing a 20°–90 °C absorption–desorption cycle, GlyK can capture up to 83 % of the CO2 in atmospheric air and be 55 % regenerated within a single membrane contactor pass. As these low working temperatures vastly outperform the conventional ∼ 40°–140 °C temperature swing currently implemented in industrial CO2 processing, GlyK is concluded to be a viable and sustainable option for use within energy-efficient DAC technology whereby renewable heat sources can be used.

Thermal stability and vapor-liquid equilibrium of aqueous solutions of choline and tetramethylammonium taurate

The thermal degradation of tetramethylammonium taurate and choline taurate and aqueous solutions of these compounds were examined. The thermal degradation products for each of the solid compounds are identified and the data show that the compounds lose less than 1 % of their mass when heating is below 85 °C for 10 h. However, it is difficult to distinguish between the degradation of the compounds and the loss of strongly retained water. The degradation products of the compounds in aqueous solution are also identified and a degradation pathway is proposed. Additionally, the vapor–liquid equilibrium of the compounds in aqueous solutions was measured and the data was fit to the non-random two-liquid (NRTL) model. The data indicate significant deviations from ideality as described by the activity coefficients of the solutions. The results provide insight into the selection of absorber stripping temperatures, the modeling of absorber columns that utilize aqueous ionic absorber fluids, and how these properties are impacted by different cations.

Separation of n-propanol - n-propyl acetate azeotropic system by extractive distillation with ionic liquids: COSMO-RS prediction, experimental investigation and quantum chemical calculation

During the preparation of n-propyl acetate (NPAC), an azeotropic mixture of NPAC and n-propanol (NPA) will form inevitably, which is difficult to separate by ordinary distillation. In this work, COSMO-RS model was applied to screen appropriate ionic liquids (ILs) to separate the binary azeotrope of NPAC - NPA. 1-decyl-3-methylimidazolium acetate ([DMIM][Ac]), 1-octyl-3-methylimidazolium acetate ([OMIM][Ac]), and 1-hexyl-3-methylimidazolium acetate ([HMIM][Ac]) were selected as entrainers based on solvent capacity and selectivity. The vapor–liquid equilibrium (VLE) data of the binary system (NPA - NPAC) and the ternary system (NPA - NPAC - IL) were measured at atmospheric pressure. The thermodynamic consistency of VLE data was verified by van Ness test and Wisniak's L-W test. The NRTL (non-random two liquids) model was used to correlate the VLE experimental data and obtained good applicability. The experimental results demonstrated that all three ionic liquids can improve the relative volatility of NPAC to NPA, and the separation effect is more obvious with the increase of ionic liquid content. The separation performance order of three ionic liquids follows: [HMIM][Ac] > [OMIM][Ac] > [DMIM][Ac]. Finally, ESP analysis, mutual penetration analysis, and IGMH analysis plus QTAIM topological analysis were used to explore the mechanism of separation. The analysis results indicate that the interaction between ionic liquids and NPA is stronger than that between ionic liquids and NPAC. In addition, the stronger interaction between [DMIM][Ac] and NPA is due to their strong hydrogen bond (HB) interactions.

Molecular Simulation Studies on the Vapor-Liquid Equilibrium of CO2 + 3,3,3-Trifluoropropene (R1243zf) Binary Mixtures.

As fourth-generation refrigerants with great development prospects, hydrofluoroolefins (HFOs) can be mixed with other refrigerants, such as carbon dioxide (CO2), to form refrigerant mixtures with low global warming potential (GWP) and zero ozone depleting potential (ODP) while retaining the advantages of each component. Refrigerants can work together to achieve complementary benefits. Combinations of CO2 and HFOs can strengthen the thermodynamic properties of CO2 while inhibiting the flammability of HFOs. At present, relatively few studies have been conducted on the CO2 + 3,3,3-trifluoropropene (R1243zf) mixture. Besides experimental approaches, molecular simulation has grown in importance as a way to determine thermodynamic and transport properties in recent years. In this study, the Gibbs Ensemble Monte Carlo (GEMC) method was used to simulate the vapor-liquid equilibrium (VLE) properties of the CO2 + R1243zf binary mixture in the temperature range of 273.15 to 313.15 K, in which the three-site rigid TraPPE force field and a fully flexible transferable all-atom force field were selected to describe CO2 and R1243zf, respectively. By comparing the GEMC simulation results with the experimental data, it was found that the average deviation of pressure is 2.33%, the average deviation of liquid phase molar fraction Δx is 0.0099, and the mean deviation of gaseous phase molar fraction Δy is 0.0204. The simulation results accord well with the experimental data and the fitting data of the correlation model in the literature, indicating that the molecular models used for CO2 and R1243zf can reliably predict the VLE properties. Finally, the critical parameters of the mixture at a temperature of 313.15 K were predicted, and the radial distribution functions (RDFs) of pure R1243zf and the mixture at 273.15 K and 3.5 MPa were calculated and analyzed by molecular dynamics (MD) simulation.

In situ adaptive tabulation of vapor-liquid equilibrium solutions for multi-component high-pressure transcritical flows with phase change

Vapor-liquid equilibrium (VLE) is a family of first-principled thermodynamic models for transcritical multiphase flows, which can accurately capture the phase transitions at high-pressure conditions that are difficult to deal with using other models. However, VLE-based computational fluid dynamics (CFD) simulation is computationally very expensive for multi-component systems, which severely limits its applications to real-world systems. In this work, we developed a new ISAT-VLE method based on the in situ adaptive tabulation (ISAT) method to improve the computational efficiency of VLE-based CFD simulation with reduced memory usage. We developed several ISAT-VLE solvers for both fully conservative (FC) and double flux (DF) schemes. New methods are proposed to delete redundant records in the ISAT-VLE table and the ISAT-VLE method performance is further improved. To improve the convergence of the VLE solvers, a modified initial guess for equilibrium constant is also introduced. Simulations of high-pressure transcritical two-phase temporal mixing layers and shock-droplet interaction were conducted using the ISAT-VLE CFD solvers. The simulation results show that the new method obtains a speed-up factor approximately from 10 to 60 and the ISAT errors can be controlled within 1%. The shock-droplet interaction results show that the DF scheme can achieve a higher speed-up factor than the FC scheme. The two sets of simulations exhibit the phase separation at high-pressure conditions. It was found that even at supercritical pressures with respect to each component, the droplet surface could still be in a subcritical two-phase state, because the mixture critical pressure is often significantly higher than each component and hence triggers phase separation. In addition, a shock wave could partially or completely convert the droplet surface from a subcritical two-phase state to a single-phase state by raising temperature and pressure.

Thermodynamics of Liquid Alloys and Vapor–Liquid Equilibrium in the Antimony–Tellurium System

The partial and integral thermodynamic functions of formation and evaporation of antimony-tellurium melts were calculated based on the vapor pressure values of the components in the Sb–Sb2Te3 and Sb2Te3–Te systems. It is shown that integral functions of evaporation enthalpy and entropy insignificantly change in value from the alloy corresponding to the Sb2Te3 composition and slightly decrease in the direction of antimony and tellurium on the state diagram. However, they can be described by a linear dependence in the entire concentration interval of solutions existence within the experiment error. The boundaries of liquid and vapor coexistence fields at atmospheric pressure (101.3 kPa) and in vacuum (0.9 kPa) were calculated based on the partial pressure values of melt components. It is shown that the separation of antimony alloys with tellurium by distillation into elements at atmospheric pressure is difficult because of high boiling temperatures of antimony-based alloys. It would require a significant number of condensate re-evaporation cycles in a vacuum. The results aim at creating the fundamental physical and chemical foundations of the distillation technologies for processing melted chalcogenide systems. The second aim is to issue effective practical recommendations necessary for developing and improving the process of extracting rare metals from polymetallic mattes by vacuum-thermal method.Graphical

Simulation Process for Allyl Alcohol Production via Deoxydehydration of Glycerol

A process for the deoxydehydration (DODH) of glycerol to allyl alcohol in 2-hexanol as solvent was modelled with Aspen Plus. Experimental results for the DODH reaction, the liquid vapour equilibria and the catalytic hydrogenation were employed for the development of the model. The whole process consists of four subsystems: allyl alcohol production (S1), solvent recovery (S2), allyl alcohol purification (S3) and solvent regeneration (S4). Based on the results of the process model, allyl alcohol with 96% yield and a purity of 99.99% with product loss of only 0.2% was obtained. The optimisation of the energy consumption through an integrated heat exchange network resulted in a net primary energy input of 863.5 kW, which corresponded to a carbon footprint of 1.89 kgCO2/kgAllylOH.

Simple and accurate expressions for radial distribution functions of hard disk and hard sphere fluids

Analytical expressions for radial distribution function (RDF) are of critical importance for various applications, such as development of the perturbation theories. Theoretically, RDF expressions for odd-dimensional fluids can be obtained by solving the Percus-Yevick integral equations. But for even-dimensional cases, such as the hard disk (2D) fluid, analytical expressions are infeasible. The only 2D RDF is a heuristic expression which provides acceptable estimations for an intermediate and low density range. In this work, we employ a simple and empirical expression for the 2D RDF and the 3D RDF based on an approach proposed for the 3D RDF. The parameters are determined in such a way that the final RDF expressions are thermodynamically consistent, namely the pressure and the isothermal compressibility constraints are both satisfied. The new RDFs for the 2D and 3D hard spheres are highly accurate for the entire density range up to the first-order phase transition points. The predictions of the first coordination numbers are consistent with simulation results for the 3D fluid. Finally, by using the 2D RDF with a primitive second-order perturbation theory, the pressure-volume-temperature relation and vapor-liquid equilibrium are calculated for the 2D Lennard-Jones fluid. Comparisons with the simulation data show promising results.

Isobaric Vapor-Liquid Equilibrium of Methyl Salicylate + Ethyl Salicylate and Methyl Salicylate + α-Pinene Binary Systems at 20.0 and 50.0 kPa

Gandapura oil, also called wintergreen oil in international trade, is evaluated based on the purity of its methyl salicylate content. Gandapura oil has several impurities including mainly ethyl salicylate and α-pinene, which can lower its quality and price. Indonesian local farmer’s gandapura oil has a low methyl salicylate content of only 82.23%, and appears in a dark red colour instead of clear. The low grade product may have been caused by thermal degradation of compounds within gandapura oil by constant heating during atmospheric distillation at temperature above its thermal threshold. The determination of their vapor-liquid equilibrium data can provide basic data for the separation and purification of methyl salicylate towards its two main impurities in gandapura oil. The vacuum pressure condition was selected to lower the distillation temperature, aiming to reduce the chance of thermal decomposition. The vapor-liquid equilibrium under isobaric conditions in the binary systems of methyl salicylate + ethyl salicylate and methyl salicylate + α-Pinene at 20.0 and 50.0 kPa were measured experimentally using modified Glass Othmer-Still. Gas Chromatography (GC) was utilized to analyze the composition of both the liquid and vapor phases in the samples. The thermodynamic consistency of experimental data was confirmed through the L-W Wisniak method. The experimental results were successfully correlated with Wilson, NRTL, and UNIQUAC models. The average absolute deviations of temperature (AAD T) and vapor phase composition (AAD y) between experimental data and models are less than 0.8058 and 0.0196, respectively for all systems. In terms of quality, all samples collected post-experiment maintained a clear color, suggesting that vacuum pressure distillation effectively prevents the thermal decomposition of compounds in gandapura oil.

Vapor–Liquid Equilibrium in Chemically Equilibrium Systems: The System with Reaction of Ethyl Acetate Synthesis

Vapor–Liquid Equilibrium in Chemically Equilibrium Systems: The System with Reaction of Ethyl Acetate Synthesis

ETHYL ALCOHOL - WATER SEPARATION BY EXTRACTIVE DISTILLATION: SIMULATION USING ASPEN PLUS™ AND EXPERIMENTAL VALIDATION

Dilute ethyl alcohol (ethanol, EtOH) is produced using fermentation (< 20 mass%), but it needs to be further purified because it contains large water content. EtOH forms an azeotrope with water and to separate this azeotrope, advanced separation processes like pressure swing distillation (PSD), azeotropic distillation (AD), and extractive distillation (ED) are employed. In this work, ethylene glycol (EG) was used as an entrainer in extractive distillation. Vapour liquid equilibrium (VLE) data was used to validate the chosen rigorous thermodynamic model. To find a workable range of operating parameters, sensitivity analysis was performed to find out the number of stages (N), feed stage (NF), distillate rate (DR), and reflux ratio (RR). Simulation shows that use of accurate operating parameters and correct entrainer can help to obtain almost pure EtOH (99.89 mole %, 99.92 mass %). In order to validate the theoretical findings from the simulation, experimental investigations in the form of batch and semi - batch distillation runs were conducted. It was seen from these runs that it is indeed possible to obtain EtOH with high purity. It was also verified that EG can be separated and recycled back with high purity with a very high recovery.

Vapor-Liquid Equilibrium Measurement of Systems Containing Glycerol for Separation Process of Glycerol as a By-Product of Biodiesel

The most popular technique to produce biodiesel were uses alcohol as a catalyst to transesterify triglycerides. The biodiesel transesterification process has a by-product in the form of glycerol which has a high selling value. Equilibrium data of glycerol and alcohol mixtures is limited in equilibrium conditions and systems which causes the glycerol purification process may not be designed and operated optimally. This research aims to obtain experimentally isobaric vapor-liquid equilibrium of methanol + glycerol binary system at 31.3, 61.3, and 100.8 kPa. A modified Glass Othmer-Still was utilised to carry out the experiment. Refractometer index type Bausch and Lomb ABBE was used to examine the equilibrium composition of the liquid and vapor phases. Using the L-W thermodynamic consistency test method, the experimental data used in this work were shown to be thermodynamically consistent. The experimental data were correlated well with the Wilson, Non-Random Two Liquid (NRTL), and Universal Quasi-Chemical (UNIQUAC) models with absolute average deviation in temperatures (AADT) and that in vapor compositions (AADy) smaller than 0.3% and 0.2%, respectively. The Universal Chemical Functional Group Activity Coefficient (UNIFAC) in predicting VLE the system studied showed good performance giving AADT and AADy smaller than 7.4% and 0.04%, respectively.

Modeling Henry's law and phase separations of water-NaCl-organic mixtures with solvation and ion-pairing.

Empirical measurements of solution vapor pressure of ternary acetonitrile (MeCN) H2O-NaCl-MeCN mixtures were recorded, with NaCl concentrations ranging from zero to the saturation limit, and MeCN concentrations ranging from zero to an absolute mole fraction of 0.64. After accounting for speciation, the variability of the Henry's law coefficient at vapor-liquid equilibrium (VLE) of MeCN ternary mixtures decreased from 107% to 5.1%. Solute speciation was modeled using a mass action solution model that incorporates solute solvation and ion-pairing phenomena. Two empirically determined equilibrium constants corresponding to solute dissociation and ion pairing were utilized for each solute. When speciation effects were considered, the solid-liquid equilibrium of H2O-NaCl-MeCN mixtures appear to be governed by a simple saturation equilibrium constant that is consistent with the binary H2O-NaCl saturation coefficient. Further, our results indicate that the precipitation of NaCl in the MeCN ternary mixtures was not governed by changes in the dielectric constant. Our model indicates that the compositions of the salt-induced liquid-liquid equilibrium (LLE) boundary of the H2O-NaCl-MeCN mixture correspond to the binary plateau activity of MeCN, a range of concentrations over which the activity remains largely invariant in the binary water-MeCN system. Broader comparisons with other ternary miscible organic solvent (MOS) mixtures suggest that salt-induced liquid-liquid equilibrium exists if: (1) the solution displays a positive deviation from the ideal limits governed by Raoult's law; and (2) the minimum of the mixing free energy profile for the binary water-MOS system is organic-rich. This work is one of the first applications of speciation-based solution models to a ternary system, and the first that includes an organic solute.

Improving the estimation accuracy of confined vapor-liquid equilibria by fine-tuning the pure component parameter in the PC-SAFT equation of state.

We propose a thermodynamic model that combines the Young-Laplace equation and perturbed chain-statistical associating fluid theory (PC-SAFT) equation of state to estimate capillary condensation pressure in microporous and mesoporous sorbents. We adjust the PC-SAFT dispersion-energy parameter when the pore size becomes comparable to the molecular dimension. This modelling framework is applied to diverse systems containing associating and non-associating gases, various sorbents, and a wide range of temperatures. Our simulation results show that under extreme confinement, a higher value of the dispersion-energy parameter (ε) is required. Furthermore, using the experimental saturation pressure data for 18 different associating and non-associating confined fluids, we find that the shift in the PC-SAFT dispersion energy correlates with the ratio of the sorbent mean pore size to the PC-SAFT segment size (rp/σ). By fitting to the capillary condensation data, the relative deviation between the confined and bulk PC-SAFT dispersion energy parameter is only 0.1% at rp/σ = 15; however, this deviation starts to increase exponentially as rp/σ decreases. For a sorbent with large pores, when rp/σ > 15, the capillary condensation pressure results from our model are similar to the predictions from the Kelvin equation. Using a dataset containing 235 saturation pressure data points composed of 18 pure gases and 4 binary mixtures, the overall AARD% from our model is 12.26%, which verifies the good accuracy of our model. Because the mean sorbent pore radius (rp), the PC-SAFT energy parameter (ε), and segment size (σ) are known a priori, our model estimates the corrected energy parameter for small pores and, thus, extends its applicability.

Simulation study of reactive distillation process for synthesis of dimethyl maleate

Abstract Conventional dimethyl maleate (DMM) synthesis relies on the use of sulfuric acid as a catalyst which requires water washing and produces a large amount of wastewater that harms the environment. The use of this method is expensive since it involves numerous processes such as neutralization of sulfuric acid, washing with water, distillation etc. and the yield of dimethyl maleate is not very high. Reactive distillation integrates the two important industrial processes such as reaction and distillation into a single unit which shortens the overall process, reduces capital and operating costs, and maintains the reaction in a forward direction to enhance the conversion of maleic anhydride by continuously removing of the products. In this work, simulation study based on experimental investigation of reactive distillation process for the synthesis of dimethyl maleate was carried out using Aspen Plus V11. DZH strong cation exchange resin was used as catalyst for esterification reaction of maleic anhydride with methanol. A reactive section of column was packed with Katapak SP type packing loaded with DZH catalyst while non-reactive sections consist of wire gauze packing. In order to describe a reactive distillation process for synthesis of dimethyl maleate, RAD-FRAC equilibrium stage model was employed. The NRTL activity model and RK equation of state model were selected to describe vapor-liquid equilibrium of the system. The reliability of the developed simulated model was verified by validating the simulation results with the experimental ones. The effect of various design and operating parameters on the conversion of maleic anhydride and purity of dimethyl maleate has been studied. It was found that the optimal condition for RD, were as follow: total number of theoretical stages 17, rectifying stages 3, reactive stages 7, stripping stages 5, reflux ratio 0.25, operating pressure 0.1 MPa, reboiler duty 250 Cal/Sec, feed mole ratio 1:5. Under optimized condition the water formed as a results of esterification reaction was constantly removed from the reactive section of the column to maintain reaction balance, the conversion of maleic anhydride was 99.95 %, purity of dimethyl maleate achieved was 0.997 and the reactive distillation process was feasible to produce dimethyl maleate without any wastewater.

Vapor-liquid equilibrium measurements of ionic liquid [DEME][TFSI] with different hydrofluorocarbon refrigerants R152a, R32, and R143a

To overcome the shortages of traditional working pairs (LiBr/H2O and NH3/H2O) for absorption-refrigeration systems (ARSs), novel working pairs consisting of low global warming potential (GWP) hydrofluorocarbons difluoroethane (R152a) and difluoromethane (R32) plus low-viscosity ionic liquid N,N‑diethyl-2‑methoxy-N-methylethan-1-aminium bis((trifluoromethyl)sulfonyl)amide ([DEME][TFSI]) are studied. Firstly, solubilities of R152a and R32 in [DEME][TFSI] are measured by the isochoric saturation method in the temperature range of 293 K ∼ 343 K and pressure range of 0.14 MPa ∼ 1.664 MPa with the relative expanded uncertainty of 0.03. A high-GWP hydrofluorocarbon 1,1,1-trifluoroethane (R143a) is involved in the experiment for further comparison. The non-random two-liquid model is used to correlate the vapor-liquid equilibrium data with average absolute relative errors of 0.55 % (R152a), 0.58 % (R32), and 0.94 % (R143a), respectively. [DEME][TFSI] shows its low viscosity and good solubility of hydrofluorocarbons by contrast with conventional ionic liquids. A refrigerant solubility rank order in [DEME][TFSI]: R152a > trans-1,3,3,3-tetrafluoropropene (R1234ze(E)) > R32 > 2,3,3,3-tetrafluoro-1-propene (R1234yf) > R143a is obtained from the comparison. This work provides the possibility to apply low-GWP working pairs R152a/[DEME][TFSI] and R32/[DEME][TFSI] in ARSs.

Force Field for Calculation of the Vapor-Liquid Phase Equilibrium of trans-Decalin

Based on the TraPPE force field, previously unknown values of the parameters of the intermolecular interaction potential of trans-decalin were determined. Parametrization was carried out using experimental data on saturated vapor pressure and density at atmospheric pressure. The found parameters make it possible to adequately describe the boiling and condensation lines of trans-decalin and also predict the critical values of pressure, density, and temperature with satisfactory accuracy. Calculations of vapor-liquid phase equilibrium conditions for a binary CO2—trans-decalin mixture in supercritical conditions for CO2 were carried out. When quantitatively comparing the calculated values with experimental data, an underestimation of pressure at a temperature of 345.4 K by 30% is observed, which decreases to 5% for temperatures up to 525 K.