Why Is CO<sub>2</sub> So Soluble in Imidazolium-Based Ionic Liquids?

Cadena, Cesar; Anthony, James R.; Shah, Jindal K.; Morrow, Timothy I.; Brennecke, Joan F.; Maginn, Edward J.

doi:10.1021/ja039615x

Cited by 1,412 publications

(1,373 citation statements)

References 29 publications

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“…This scenario also applies to the OCS- [Bmim] [Ac]. It remains to understand why the presence of imidazolium-dithiocarboxylate was not observed in CS 2 …”

Section: Interpretation and Discussionmentioning

confidence: 99%

“…[1][2][3][4][5][6][7][8][9][10][11] In this context, imidazolium acetate based ILs were proposed as systems able to capture comparatively to other ionic liquids, unusual amounts of carbon dioxide. 12,13 A number of investigations by us and others have shown that carbon dioxide dissolved in dried 1-butyl-3-methylimidazolium acetate [Bmim] [Ac] a) Author to whom correspondence should be addressed.…”

Section: Introductionmentioning

confidence: 99%

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Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

Cabaço¹,

Besnard

Chávez

et al. 2014

The Journal of Chemical Physics

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NMR spectroscopy ( 1 H, 13 C, 15 N) shows that carbon disulfide reacts spontaneously with 1-butyl-1-methylpyrrolidinium acetate ([BmPyrro][Ac]) in the liquid phase. It is found that the acetate anions play an important role in conditioning chemical reactions with CS 2 leading, via coupled complex reactions, to the degradation of this molecule to form thioacetate anion (CH 3 COS − ), CO 2 , OCS, and trithiocarbonate (CS 3 2− ). In marked contrast, the cation does not lead to the formation of any adducts allowing to conclude that, at most, its role consists in assisting indirectly these reactions. The choice of the [BmPyrro] + cation in the present study allows disentangling the role of the anion and the cation in the reactions. As a consequence, the ensemble of results already reported on (2), and CO 2 - [Bmim][Ac] (3) systems can be consistently rationalized. It is argued that in system (1) both anion and cation play a role. The CS 2 reacts with the acetate anion leading to the formation of CH 3 COS − , CO 2 , and OCS. After these reactions have proceeded the nascent CO 2 and OCS interact with the cation to form imidazolium-carboxylate ([Bmim] CO 2 ) and imidazoliumthiocarboxylate ([Bmim] COS). The same scenario also applies to system (2). In contrast, in the CO 2 - [Bmim] [Ac] system a concerted cooperative process between the cation, the anion, and the CO 2 molecule takes place. A carbene issued from the cation reacts to form the [Bmim] CO 2 , whereas the proton released by the ring interacts with the anion to produce acetic acid. In all these systems, the formation of adduct resulting from the reaction between the solute molecule and the carbene species originating from the cation is expected. However, this species was only observed in systems (2) and (3). The absence of such an adduct in system (1) has been theoretically investigated using DFT calculations. The values of the energetic barrier of the reactions show that the formation of [Bmim] CS 2 is unfavoured and that the anion offers a competitive reactive channel via an oxygensulphur exchange mechanism with the solute in systems (1) and (2). © 2014 AIP Publishing LLC.

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“…This scenario also applies to the OCS- [Bmim] [Ac]. It remains to understand why the presence of imidazolium-dithiocarboxylate was not observed in CS 2 …”

Section: Interpretation and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

Cabaço¹,

Besnard

Chávez

et al. 2014

The Journal of Chemical Physics

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“…The large entropic effect led to a negative deviation from the ideal solubility that might explain why CO 2 is more soluble in the larger 1-decyl-than in the smaller 1-ethyl-3-methylimidazolium IL`s (Cadena et al, 2004;Anthony et al, 2005).…”

Section: Brazilian Journal Of Chemical Engineeringmentioning

confidence: 99%

Modeling vapor liquid equilibrium of ionic liquids + gas binary systems at high pressure with cubic equations of state

Freitas

Cunico

Aznar

et al. 2013

Braz. J. Chem. Eng.

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-Ionic liquids (IL) have been described as novel environmentally benign solvents because of their remarkable characteristics. Numerous applications of these solvents continue to grow at an exponential rate. In this work, high pressure vapor liquid equilibria for 17 different IL + gas binary systems were modeled at different temperatures with Peng-Robinson (PR) and Soave-Redlich-Kwong (SRK) equations of state, combined with the van der Waals mixing rule with two binary interaction parameters (vdW-2). The experimental data were taken from the literature. The optimum binary interaction parameters were estimated by minimization of an objective function based on the average absolute relative deviation of liquid and vapor phases, using the modified Simplex algorithm. The solubilities of all gases studied in this work decrease as the temperature increases and increase with increasing pressure. The correlated results were highly satisfactory, with average absolute relative deviations of 2.10% and 2.25% for PR-vdW-2 and SRK-vdW-2, respectively.

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“…CO2 can act as both Lewis acid and Lewis base. The CO2 solvation is initiated by some carboxylation reaction at the C2 position of the imidazolium ring [5]. Besides, the ether functionality helps in CO2 capture whereby the lone pair of electrons present on the oxygen atom takes part in nucleophilic attack with the carbon atom on CO2 [4].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and application of 1-(2-cyanoethyl)-3-(3-methoxypropane)imidazolium bromide for CO₂capture

et al. 2017

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Abstract. Amine scrubbing is dominating in carbon dioxide (CO2) capturing technology because of its high affinity towards CO2. However, the drawbacks of amine solvents are its high corrosivity and volatility. Ionic liquids (ILs) have gained a lot of attention in recent years for CO2 capturing and have been proposed to be one of the promising alternative to the conventional solvents. The objective of this research is to design a new imidazolium based ether-nitrile functionalized ionic liquid of low viscosity to improve CO2 capturing. The molecular structure of the ionic liquid were confirmed by 1 H NMR, 13 C NMR and FTIR. The thermal properties; glass transition temperature, thermal decomposition temperature, and their physical properties; water content and density were determined. The solubility of CO2 in the synthesized ionic liquid was measured using pressure drop method. They showed high thermal stability above 200°C and the glass transition temperature was -49.80°C. The CO2 sorption in the newly synthesized IL was 0.08, 0.12, 0.29, 1.01, 2.30 mol of CO2/mol of IL at pressures 1, 5, 10, 15 and 20 bar respectively.

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Why Is CO₂ So Soluble in Imidazolium-Based Ionic Liquids?

Cited by 1,412 publications

References 29 publications

Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

Modeling vapor liquid equilibrium of ionic liquids + gas binary systems at high pressure with cubic equations of state

Synthesis, characterization and application of 1-(2-cyanoethyl)-3-(3-methoxypropane)imidazolium bromide for CO₂capture

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Why Is CO2 So Soluble in Imidazolium-Based Ionic Liquids?

Cited by 1,412 publications

References 29 publications

Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

Modeling vapor liquid equilibrium of ionic liquids + gas binary systems at high pressure with cubic equations of state

Synthesis, characterization and application of 1-(2-cyanoethyl)-3-(3-methoxypropane)imidazolium bromide for CO2capture

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Product

Resources

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Why Is CO₂ So Soluble in Imidazolium-Based Ionic Liquids?

Synthesis, characterization and application of 1-(2-cyanoethyl)-3-(3-methoxypropane)imidazolium bromide for CO₂capture