Elucidation of inorganic reaction mechanisms in ionic liquids: the important role of solvent donor and acceptor properties

Schmeisser, Matthias; Eldik, Rudi van

doi:10.1039/c4dt01239a

Cited by 23 publications

(13 citation statements)

References 126 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Therefore, the dependence of cellulose dissolution in ILs on the solvatochromic parameters of Equation (2) (or Equation (3)) is related to which ion is being varied. This conclusion is in line with the high (Gutmann) acceptor numbers (related to SA) and donor numbers (related to SB) of ILs [56]; with cellulose dissolution in ILs [57], and results of theoretical calculations [58]. We now discuss some representative examples of cellulose dissolution in pure ILs.…”

Section: Pure Ionic Liquids As Cellulose Solventssupporting

confidence: 77%

Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

et al. 2019

View full text Add to dashboard Cite

This review is focused on assessment of solvents for cellulose dissolution and the mechanism of regeneration of the dissolved biopolymer. The solvents of interest are imidazole-based ionic liquids, quaternary ammonium electrolytes, salts of super-bases, and their binary mixtures with molecular solvents. We briefly discuss the mechanism of cellulose dissolution and address the strategies for assessing solvent efficiency, as inferred from its physico-chemical properties. In addition to the favorable effect of lower cellulose solution rheology, microscopic solvent/solution properties, including empirical polarity, Lewis acidity, Lewis basicity, and dipolarity/polarizability are determinants of cellulose dissolution. We discuss how these microscopic properties are calculated from the UV-Vis spectra of solvatochromic probes, and their use to explain the observed solvent efficiency order. We dwell briefly on use of other techniques, in particular NMR and theoretical calculations for the same purpose. Once dissolved, cellulose is either regenerated in different physical shapes, or derivatized under homogeneous conditions. We discuss the mechanism of, and the steps involved in cellulose regeneration, via formation of mini-sheets, association into "mini-crystals", and convergence into larger crystalline and amorphous regions. We discuss the use of different techniques, including FTIR, X-ray diffraction, and theoretical calculations to probe the forces involved in cellulose regeneration.

show abstract

Section: Pure Ionic Liquids As Cellulose Solventssupporting

confidence: 77%

Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

et al. 2019

View full text Add to dashboard Cite

show abstract

“…Dicyanamide (DCA) ILs are good nonaqueous solvents of transition metal salts because of the ligand ability of DCA anion as a Lewis base (Simons et al, 2014 ). Most of the metal chlorides are insoluble in tetrafluoroborate, hexafluorophosphate, and bis(trifluoromethylsulfonyl)imide ILs, but well dissolved into DCA ILs due to the high complexing ability of DCA anion (Schmeissera and Eldik, 2014 ). Furthermore, the structure of DCA anion is much easier to be oxidize by fuming nitric acid, which can be used as new hypergolic propellants.…”

Section: Introductionmentioning

confidence: 99%

Viscosity, Conductivity, and Electrochemical Property of Dicyanamide Ionic Liquids

et al. 2018

View full text Add to dashboard Cite

The instructive structure-property relationships of ionic liquids (ILs) can be put to task-specific design of new functionalized ILs. The dicyanamide (DCA) ILs are typical CHN type ILs which are halogen free, chemical stable, low-viscous, and fuel-rich. The transport properties of DCA ionic liquids are significant for their applications as solvents, electrolytes, and hypergolic propellants. This work systematically investigates several important transport properties of four DCA ILs ([C4mim][N(CN)2], [C4m2im][N(CN)2], N4442[N(CN)2], and N8444[N(CN)2]) including viscosity, conductivity, and electrochemical property at different temperatures. The melting points, temperature-dependent viscosities and conductivities reveal the structure-activity relationship of four DCA ILs. From the Walden plots, the imidazolium cations exhibit stronger cation–anion attraction than the ammonium cations. DCA ILs have relatively high values of electrochemical windows (EWs), which indicates that the DCA ILs are potential candidates for electrolytes in electrochemical applications. The cyclic voltammograms of Eu(III) in these DCA ILs at GC working electrode at various temperatures 303–333 K consists of quasi-reversible waves. The electrochemical properties of the DCA ILs are also dominated by the cationic structures. The current intensity (ip), the diffusion coefficients (Do), the charge transfer rate constants (ks) of Eu(III) in DCA ILs all increased with the molar conductivities increased. The cationic structure-transport property relationships of DCA ILs were constructed for designing novel functionalized ILs to fulfill specific demands.

show abstract

“…A rigorous examination suggests that the difference in the behavior of the different alkyl groups attached to the cationic ring in their solutions depends on the solvent properties. The significant solvent properties for these solvents taken from the literature are tabulated in Table S12. For the [EMIM][BF 4 ]‐ethyl‐substituted solvent systems, a permutation of α , β , and π * is effective to representing the

H_{I L}^{E, \infty}

values as shown by;

…”

Section: Resultsmentioning

confidence: 99%

Structural Elucidation of the Binary Mixtures of [EMIM][BF₄] and [BMIM][BF₄] in Ethyl‐Substituted Solvents by Isothermal Titration Calorimeter

Jain

Kumar

2018

ChemistrySelect

View full text Add to dashboard Cite

In order to address the issue whether both ionic liquids and solvents influence the enthalpy of their solutions, highly accurate excess partial molar enthalpy, HILE values have been measured using Isothermal Titration Calorimeter (ITC). Therefore, thermodynamic behavior has been observed in the mixtures containing ionic liquids. It essentially depends on the molecular structure of the constituents of the mixture. The hydrogen bonding between ionic liquids and ethyl‐substituted solvents (2‐ethoxyethanol, ethylene glycol, diethylamine, ethyl acetate and N,N‐ diethylacetamide) may lead to strong ion‐solvent interactions. In the present study, an effort has been made to quantify various interactions between ionic liquid and solvent, based on the HILE values. Linear solvation free relation shows dependence of limiting excess partial molar enthalpies, HILboldE,∞ upon the solvent properties. Structural orientation of solvent molecules and ionic liquids also described by the HILboldE,∞ values. The ion‐ion, ion‐solvent interactions have also been investigated in terms of the enthalpic interaction parameters, HIL-ILE and relative apparent molar enthalpy, φL of ionic liquid‐ethyl‐substituted solvent systems.

show abstract

Elucidation of inorganic reaction mechanisms in ionic liquids: the important role of solvent donor and acceptor properties

Abstract: Solvent donor and acceptor properties play an important role in the elucidation of inorganic reaction mechanisms studied in ionic liquids.

Cited by 23 publications

References 126 publications

Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

Viscosity, Conductivity, and Electrochemical Property of Dicyanamide Ionic Liquids

Structural Elucidation of the Binary Mixtures of [EMIM][BF₄] and [BMIM][BF₄] in Ethyl‐Substituted Solvents by Isothermal Titration Calorimeter

Contact Info

Product

Resources

About

Elucidation of inorganic reaction mechanisms in ionic liquids: the important role of solvent donor and acceptor properties

Abstract: Solvent donor and acceptor properties play an important role in the elucidation of inorganic reaction mechanisms studied in ionic liquids.

Cited by 23 publications

References 126 publications

Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

Viscosity, Conductivity, and Electrochemical Property of Dicyanamide Ionic Liquids

Structural Elucidation of the Binary Mixtures of [EMIM][BF4] and [BMIM][BF4] in Ethyl‐Substituted Solvents by Isothermal Titration Calorimeter

Contact Info

Product

Resources

About

Structural Elucidation of the Binary Mixtures of [EMIM][BF₄] and [BMIM][BF₄] in Ethyl‐Substituted Solvents by Isothermal Titration Calorimeter