Molecular Simulation of the Thermophysical Properties of N-Functionalized Alkylimidazoles

Turner, C. Heath; Cooper, Alex; Zhang, Zhongtao; Shannon, Matthew S.; Bara, Jason E.

doi:10.1021/jp3029787

Cited by 26 publications

(36 citation statements)

References 34 publications

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“…[32,33] More interestingly, these simulations also provide deep insight into the formation of cavities or "free volume" at the nano-level, which is a useful metric for understanding the solubility of CO 2 and solubility selectivity for CO 2 /CH 4 . [32,33] More interestingly, these simulations also provide deep insight into the formation of cavities or "free volume" at the nano-level, which is a useful metric for understanding the solubility of CO 2 and solubility selectivity for CO 2 /CH 4 .…”

Section: Experimental and Computational Resultsmentioning

confidence: 98%

Imidazole-Based Solvents and Membranes for CO₂ Capture Applications

et al. 2014

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Imidazoles present a tunable, versatile and economical platform for the development of novel liquid solvents and polymer membranes for CO 2 capture. An overview of our studies in this area is presented, with emphasis on characterization of structure-property relationships in imidazole-based materials through both experimental and computational studies. To this end, a growing library of systematically varied imidazole compounds has been synthesized using only commercial available starting materials and straightforward reactions. Using this library of compounds, we have sought to understand and develop predictive models for thermophysical properties relating to process design, including: density, viscosity, vapor pressure, pK a and CO 2 absorption capacity. Furthermore, we have discovered that imidazoles are stable in the presence of SO 2 and can form reversible 1:1 adducts, which can be beneficial as SO 2 is typically present at ppm levels alongside CO 2 in flue gas from coal-fired power plants.

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Section: Experimental and Computational Resultsmentioning

confidence: 98%

Imidazole-Based Solvents and Membranes for CO₂ Capture Applications

et al. 2014

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“…Force field parameters for [C 4 mim]-[Tf 2 N] ILs were taken from Lopez et al, 44,45 and parameters for NMP molecules were extracted from Aparicio et al 46 The TraPPE 47 force field for CO 2 and CH 4 was used on the basis of previous experience of others modeling gas adsorption in ILs. 1,27,48 The Lorentz−Berthelot mixing rules were used for cross-term interactions.…”

Section: Simulation Detailsmentioning

confidence: 99%

“…Ionic liquids, generally defined as organic salts with melting-point temperatures <100 °C, are potential solvents for gas-separation processes. − They have demonstrated high selectivity for CO 2 − versus CH 4 , , and this makes ILs promising for applications in natural gas sweetening and precombustion CO 2 capture. In addition, the energy required for solvent recovery in ILs can be reduced by the physical absorption mechanism.…”

Section: Introductionmentioning

confidence: 99%

Molecular Simulation of Ionic Polyimides and Composites with Ionic Liquids as Gas-Separation Membranes

et al. 2017

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Polyimides are at the forefront of advanced membrane materials for CO capture and gas-purification processes. Recently, ionic polyimides (i-PIs) have been reported as a new class of condensation polymers that combine structural components of both ionic liquids (ILs) and polyimides through covalent linkages. In this study, we report CO and CH adsorption and structural analyses of an i-PI and an i-PI + IL composite containing [Cmim][TfN]. The combination of molecular dynamics (MD) and grand canonical Monte Carlo (GCMC) simulations is used to compute the gas solubility and the adsorption performance with respect to the density, fractional free volume (FFV), and surface area of the materials. Our results highlight the polymer relaxation process and its correlation to the gas solubility. In particular, the surface area can provide meaningful guidance with respect to the gas solubility, and it tends to be a more sensitive indicator of the adsorption behavior versus only considering the system density and FFV. For instance, as the polymer continues to relax, the density, FFV, and pore-size distribution remain constant while the surface area can continue to increase, enabling more adsorption. Structural analyses are also conducted to identify the nature of the gas adsorption once the ionic liquid is added to the polymer. The presence of the IL significantly displaces the CO molecules from the ligand nitrogen sites in the neat i-PI to the imidazolium rings in the i-PI + IL composite. However, the CH molecules move from the imidazolium ring sites in the neat i-PI to the ligand nitrogen atoms in the i-PI + IL composite. These molecular details can provide critical information for the experimental design of highly selective i-PI materials as well as provide additional guidance for the interpretation of the simulated adsorption systems.

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“…In the family of N-functionalized imidazoles, most research efforts have focused on understanding the properties of N-alkylimidazole compounds with linear/straight chains including density [20,21], viscosity [22], vapor pressure [23][24][25][26], heat capacity [27], and pK a [28]. However, the properties of N-alkylimidazoles with branched or cycloalkyl functional groups have been rarely studied, although the synthesis of such compounds is no more difficult or expensive than the linear alkyl counterparts.…”

Section: Introductionmentioning

confidence: 99%

Experimental and Computational Study of the Properties of Imidazole Compounds with Branched and Cycloalkyl Substituents

Qian

Mileski

Irvin

et al. 2022

Liquids

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N-functionalized imidazole compounds with linear alkyl groups have been widely utilized precursors for imidazolium ionic liquids (ILs) while the effects of branched and cycloalkyl substituents on properties of imidazole compounds have not been studied; however, such compounds are just as synthetically accessible as those with linear alkyl groups. In this work, two fundamental properties, density and viscosity, of selected N-functionalized imidazoles bearing iso-propyl, iso-butyl, sec-butyl methylcyclopropyl, cyclopentyl, and methylcyclohexyl groups have been measured in the temperature range of 293.15–353.15 K for the guidance of molecular design for future applications. A linear and parabolic model were used for temperature-density correlation while temperature dependence of viscosity was summarized using the Andrade Equation and the Vogel-Fulcher-Tammann equation. In addition to experimental data, density, viscosity, vapor pressure and vaporization of enthalpies of target imidazole compounds were predicted using COSMOtherm calculations and compared with experimental data. It was found that the calculated densities were quite close to the experimental data, while viscosity data, obtained from COSMOtherm, underestimated experimental measurements and a scaling factor provided agreement with experiments. Predictions of vapor pressure were relatively reliable at low temperature, although the difference between experiment and prediction tended to expand with increasing temperature. Variances of vaporization enthalpies were small upon temperature change and a maximum error of ~12.3% was observed for all compounds studied.

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Molecular Simulation of the Thermophysical Properties of N-Functionalized Alkylimidazoles

Cited by 26 publications

References 34 publications

Imidazole-Based Solvents and Membranes for CO₂ Capture Applications

Imidazole-Based Solvents and Membranes for CO₂ Capture Applications

Molecular Simulation of Ionic Polyimides and Composites with Ionic Liquids as Gas-Separation Membranes

Experimental and Computational Study of the Properties of Imidazole Compounds with Branched and Cycloalkyl Substituents

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Molecular Simulation of the Thermophysical Properties of N-Functionalized Alkylimidazoles

Cited by 26 publications

References 34 publications

Imidazole-Based Solvents and Membranes for CO2 Capture Applications

Imidazole-Based Solvents and Membranes for CO2 Capture Applications

Molecular Simulation of Ionic Polyimides and Composites with Ionic Liquids as Gas-Separation Membranes

Experimental and Computational Study of the Properties of Imidazole Compounds with Branched and Cycloalkyl Substituents

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Imidazole-Based Solvents and Membranes for CO₂ Capture Applications

Imidazole-Based Solvents and Membranes for CO₂ Capture Applications