Sorption Thermodynamics of CO2, H2O, and CH3OH in a Glassy Polyetherimide: A Molecular Perspective

Mensitieri, Giuseppe; Scherillo, Giuseppe; Manna, Pietro La; Musto, Pellegrino

doi:10.3390/membranes9020023

Cited by 17 publications

(9 citation statements)

References 74 publications

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“…Our group has already performed several investigations focused on sorption thermodynamics of low molecular weight compounds in glassy polymers where modeling of the thermodynamic behavior of the systems was combined with the wealth of information provided by vibrational spectroscopy and gravimetric measurements. − In all the systems considered, the results of vibrational spectroscopy were used to tailor the structure of the thermodynamic model used to interpret sorption thermodynamics. In particular, the interpretation of experimental sorption isotherms was performed using a statistical thermodynamics approach consisting of the so-called nonequilibrium theory for glassy polymers with nonrandom hydrogen bonding, NETGP-NRHB.…”

Section: Introductionmentioning

confidence: 99%

Weak Interactions between Poly(ether imide) and Carbon Dioxide: A Multiscale Investigation Combining Experiments, Theory, and Simulations

et al. 2022

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This contribution aims at an understanding, at a molecular scale, of the state of CO2 molecules absorbed in glassy poly(ether imide) (PEI). This issue has been challenged by combining different approaches that tackle the problem from both the experimental and the theoretical viewpoints and providing a comprehensive physicochemical picture. In situ FTIR spectroscopy and gravimetry were exploited to gather relevant experimental information, while molecular dynamics (MD), density functional theory (DFT), and statistical thermodynamics approaches were used to model the behavior of the binary system at different scales. Based on the findings of FTIR spectroscopy and on DFT and MD calculations, it was determined that, among the possible interaction configurations, some are prevailing. In particular, the carbon atom of carbon dioxide molecules establishes relatively weak interactions prevalently with the carbonyl groups of PEI. A quantitative estimate of such interaction has been provided by MD calculations. The system was also analyzed using a lattice fluid model, specifically developed to deal with sorption of low molecular weight compounds in glassy polymers, that is rooted on statistical thermodynamics, determining the values of the isosteric heat of sorption and carbon-dioxide–polymer interaction energy. Finally, experimental data of CO2–PEI mutual diffusivity have been interpreted using a semiempirical theoretical model accounting for the effects of the penetrant concentration, of energy barriers associated with the occurrence of an effective diffusive jump, and of a thermodynamic factor.

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Section: Introductionmentioning

confidence: 99%

Weak Interactions between Poly(ether imide) and Carbon Dioxide: A Multiscale Investigation Combining Experiments, Theory, and Simulations

et al. 2022

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“…Here, we use the NETGP-NRHB ,− approach to model the two-phase equilibrium, at fixed P and T , between a polymer–penetrant mixture in a nonequilibrium (glassy) state and a homogeneous multicomponent penetrant fluid phase of assigned composition, in which the polymer is assumed to be not soluble. This is better identified as a pseudoequilibrium (PE) condition since it concerns the solubility of penetrants within an out-of-equilibrium glassy polymer at a temperature that is well below the glass-to-rubber transition temperature, T g , of the polymer–penetrant mixture.…”

Section: Theoretical Backgroundmentioning

confidence: 99%

“…Following this approach, the NRHB model has also been extended to describe the sorption pseudoequilibrium (PE) of the phase between the gaseous or liquid mixtures of low-molecular-weight compounds and an amorphous nonequilibrium glassy polymer–penetrant mixture. − This extension of the NRHB model, referred to in the following as NETGP-NRHB, has been successfully implemented to model the solubility of water in several glassy polymers, showing a good predictive capability of the amount of both the cross and self-HB interactions established within the system. − …”

Section: Introductionmentioning

confidence: 99%

Predictive Approach for the Solubility and Permeability of Binary Gas Mixtures in Glassy Polymers Based on an NETGP-NRHB Model

Baldanza

Loianno

Mensitieri

et al. 2022

Ind. Eng. Chem. Res.

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The NETGP-NRHB lattice-fluid model describes the sorption thermodynamics of penetrants in amorphous polymer−penetrant mixtures locked in an out-of-equilibrium "glassy" state. It accounts for the nonrandom distribution of mean-field contacts and voids and for the possible occurrence of specific interactions. In this contribution, we assess the suitability of the NETGP-NRHB model to interpret the sorption thermodynamics of binary penetrant mixtures in glassy polymers. Moreover, adopting the gradients of NETGP-NRHB penetrant chemical potentials as driving forces for their diffusive fluxes, a self-consistent framework is proposed to predict the permeability of light gas binary mixtures in glassy polymer membranes once all of the model parameters are obtained by nonlinear regression of data of the corresponding binary and pure component subsystems. This approach is validated against solubility data of CO 2 /CH 4 and CO 2 /C 2 H 4 mixtures in glassy amorphous poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and poly(methyl methacrylate) (PMMA), respectively, and permeability data of CO 2 /CH 4 mixtures in three glassy amorphous polymer membranes (PAr, PSf, PH); all of the data are taken from the literature. In particular, solubility data are investigated up to a CH 4 partial pressure of 15 atm at a fixed CO 2 partial pressure equal to 5.1 atm for the system CO 2 /CH 4 /PPO and up to a CO 2 partial pressure of 4 atm at a fixed C 2 H 4 partial pressure equal to 2.09 atm for the system CO 2 /C 2 H 4 /PMMA. Permeability data are investigated at a fixed upstream molar concentration of the binary gas mixture equal to 0.5 by changing the total pressure up to 18 atm for the systems CO 2 /CH 4 /PAr and CO 2 /CH 4 /PSf and up to 14 atm for the system CO 2 /CH 4 /PH; the downstream total pressure is equal to 0 atm for all of the systems. All of the experimental sets of data are obtained at 35 °C. Solubility and permeability predictions for the ternary systems compare very well with all experimental literature data without additional parameters besides those required for the corresponding binary subsystems.

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“…Molecular dynamics simulation is a method of ab initio calculations that requires few parameters and does not rely on the bias caused by experimentally fitted parameters. Therefore, it is used to predict the dynamics and thermodynamic properties of the mixture, 8 vapor‐liquid equilibrium, 9 etc. Chaban 10 investigated the vapor‐liquid equilibrium process of ionic liquid‐acetone mixtures by molecular dynamics (MD) simulations and performed a detailed analysis of the thermodynamic and kinetic properties.…”

Section: Introductionmentioning

confidence: 99%

Research progress on the formation mechanism of azeotrope and its separation process in microwave field

Zeng

Jia

et al. 2021

J of Chemical Tech & Biotech

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In the process of petrochemical, coal chemical, and pharmaceutical industries, a large amount of azeotrope is usually produced. The traditional method of separating azeotrope consumes a lot of energy. Therefore, it is of great significance to develop a low energy consumption and high efficiency method of separating azeotrope to achieve economic benefits and reduce energy consumption. The use of microwave fields for enhanced distillation processes to separate azeotrope is currently of great interest. In this paper, the mechanism of azeotropic formation is reviewed from three aspects: experimental studies, quantum chemical calculations and molecular simulations, and the influence of cluster structure on azeotropic formation is analyzed. Then the paper discusses the experimental study of microwave‐enhanced distillation process to separate azeotrope and the molecular simulation process, and the mechanism of microwave‐assisted azeotropic separation and the feasibility of industrialization are analyzed. © 2021 Society of Chemical Industry (SCI).

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Sorption Thermodynamics of CO2, H2O, and CH3OH in a Glassy Polyetherimide: A Molecular Perspective

Cited by 17 publications

References 74 publications

Weak Interactions between Poly(ether imide) and Carbon Dioxide: A Multiscale Investigation Combining Experiments, Theory, and Simulations

Weak Interactions between Poly(ether imide) and Carbon Dioxide: A Multiscale Investigation Combining Experiments, Theory, and Simulations

Predictive Approach for the Solubility and Permeability of Binary Gas Mixtures in Glassy Polymers Based on an NETGP-NRHB Model

Research progress on the formation mechanism of azeotrope and its separation process in microwave field

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