Kinetic model for the hydrolysis of lignocellulosic biomass in the ionic liquid, 1-ethyl-3-methyl-imidazolium chloride†

The kinetics of the acid-catalysed hydrolysis of cellobiose in the ionic liquid 1-ethyl-3-methylimidazolium chloride, [C(2)mim]Cl, was studied as a model for general lignocellulosic biomass hydrolysis in ionic liquid systems. The results show that the rate of the two competing reactions, polysaccharide hydrolysis and sugar decomposition, vary with acid strength, and that for acids with an aqueous pK(a) below approximately zero, the hydrolysis reaction is significantly faster than the degradation of glucose, thus allowing hydrolysis to be performed with a high selectivity in glucose. In tests with soluble cellulose, hemicellulose (xylan), and lignocellulosic biomass (Miscanthus grass), comparable hydrolysis rates were observed with bond scission occurring randomly along the biopolymer chains, in contrast to end-group hydrolysis observed with aqueous acids.

Designing ionic liquids with boron cluster anions: alkylpyridinium and imidazolium [nido-C(2)B(9)H(11)] and [closo-CB(11)H(12)] carborane salts

A range of new alkylpyridinium and imidazolium carborane salts with [nido-C2B9H12](-), [closo-CB11H12](-), and [RC2B11H11](-) (R = methyl or butyl) anions have been prepared and characterized by physical and thermal methods, including the solid state structures of five of the salts determined by single crystal X-ray diffraction. The tendency of the salts to form low-melting ionic liquids has been assessed; all the salts studied with [nido-C2B9H12](-) anions melted below 100 degrees C and, significantly, have melting points that are 25-85 degrees C lower than those of the corresponding [closo-CB11H12](-) analogs, demonstrating that a wider range of boron-rich ionic liquid materials can be readily accessed.

Designing ionic liquids: Imidazolium melts with inert carborane anions

A new class of low-melting N,N'-dialkylimidazolium salts has been prepared with carborane counterions, some of the most inert and least nucleophilic anions presently known. The cations and anions have been systematically varied with combinations of 1-ethyl-3-methyl-(EMIM+), 1-octyl-3-methyl-(OMIM+), 1-ethyl-2,3-dimethyl- (EDMIM+), and 1-butyl-2,3-dimethyl- (BDMIM+) imidazolium cations and CB11H12-CB11H6Cl6-, and CB11H6Br6- carborane anions to elucidate the factors which affect their melting points. From trends in melting points, which range from 156 degrees C down to 45 degrees C, it is clear that the alkylation pattern on the imidazolium cation is the main determinant of melting point and that packing inefficiency of the cation is the intrinsic cause of low melting points. C-Alkylation of the anion can also contribute to low melting points by the introduction of a further packing inefficiency. Nine of the thirteen salts have been the subject of X-ray crystal structural determination. Notably, crystallographic disorder of the cation is observed in all but one of these salts. It is the most direct evidence to date that packing inefficiency is the major reason unsymmetrical N,N'-dialkylimidazolium salts can be liquids at room temperature.

Crystal structures of imidazolium bis(trifluoromethanesulfonyl)imide 'ionic liquid' salts: the first organic salt with a cis-TFSI anion conformation

Crystal structures of two examples of an important class of ionic liquids, 1,3-dimethylimidazolium and 1,2,3-triethylimidazolium bis(trifluoromethanesulfonyl)imide have been characterized by single crystal X-ray diffraction. The anion in the 1,3-dimethylimidazolium example (mp 22 degreesC), adopts an unusual cis-geometry constrained by bifurcated cation-anion C-H...O hydrogen-bonds from the imidazolium cation to the anion resulting in the formation of fluorous layers within the solid-state structure. In contrast, in the 1,2,3-triethylimidazolium salt (mp 57 degreesC), the ions are discretely packed with only weak C-H...O contacts between the ions close to the van der Waals separation distances, and with the anion adopting the twisted conformation observed for all other examples from the limited set of organic bis( trifluoromethanesulfonyl) imide crystal structures. The structures are discussed in terms of the favorable physical properties that bis(trifluoromethanesulfonyl) imide anions impart in ionic liquids.

Influence of the anion on the electrodeposition of cobalt from imidazolium ionic liquids

Cyclic voltammetry and absorption spectrophotometry were used to examine the complex formation of cobalt (II) in the ionic liquids 1-butyl-3-methylimidazolium chloride ([C(4)mim] Cl) and 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide ([C(4)mim][Tf2N]). In [C(4)mim]Cl, cobalt(II) is complexed as [CoCl4](2-) at CoCl2 concentrations less than 33 mol %. Cyclic voltammograms show that cobalt cannot be electrodeposited at these concentrations. However, cobalt metal can be electrodeposited at CoCl2 concentrations above the threshold concentration of 33 mol %. In the ionic liquid [C(4)mim][Tf2N] there is no threshold CoCl2 concentration for electrodeposition due to the absence of [CoCl4](2-). (C) 2007 The Electrochemical Society.

Purification of imidazolium ionic liquids for spectroscopic applications

Ionic liquids are often contaminated by colored impurities. These impurities can be problematic for spectroscopic studies or for monitoring organic reactions by UV/Vis spectroscopy. The effect of different purification methods on the optical quality of colored ionic liquids was studied and compared. Yellowish ionic liquids can partially be decolorized by treatment with active charcoal or by recrystallization. Our experiments show column liquid chromatography is not always a good technique to prepare spectrograde imidazolium halide ionic liquids. Colorless and UV-transparent ionic liquids were synthesized by a method that can exclude the need for further purification steps. (c) 2005 Elsevier B.V. All rights reserved.

Photostability of a highly luminescent europium beta-diketonate complex in imidazolium ionic liquids

A high quantum yield and an enhanced photostability was found for a europium(III) tetrakis(2-thenoyltrifluoroacetonate) complex after dissolving the complex in a weakly-coordinating imidazolium ionic liquid.

Intense near-infrared luminescence of anhydrous lanthanide(III) iodides in an imidazolium ionic liquid

Anhydrous neodymium(III) iodide and erbium(Ill) iodide were dissolved in carefully dried batches of the ionic liquid 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(12)mim][Tf2N]. Provided that the ionic liquid had a low water content, intense near-infrared emission could be observed for both the neodymium(III) ion and for the erbium(III) ion. Luminescence lifetimes have been measured, and the quantum yield of the neodymium(III) sample has been measured. Exposure of the hygroscopic samples to atmospheric moisture conditions caused a rapid decrease of the luminescence intensities. (C) 2004 Elsevier B.V. All rights reserved.

Interfacial tensions of imidazolium-based ionic liquids with water and n-alkanes

The interfacial tension of the liquid-liquid phase boundary of several 1,3-dialkyl imidazolium based ionic liquids, namely, 1,3-dimethylimidazolium bis{(trifluoromethyl)sulfonyl}imide [C(1)mim][NTf2], 1-ethyl-3-methylimidazoliurn bis{(trifluoromethyl)sulfonyl}imide [C(2)mim][NTf2], 1-butyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide [C(4)mim][NTf2], 1-hexyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide [C(6)mim][NTf2], 1-octyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide [C(8)mim][NTf2], 1-butyl-3-methylimidazolium trifluoromethylsulfonate [C(4)mim][CF3SO3], and 1-butyl-3-methylimidazolium trifluoroacetate [C(4)mim][CF3COO] with water and with the n-alkanes, n-hexane, n-octane and n-decane, has been measured using the pendant drop method as a function of temperature from 293 to 323 K. The experimental interfacial tension data were correlated using the ionic liquid parachor estimation method and a mutual solubility model. The influence of the cation and anion of ionic liquids and also of alkyl chain length of n-alkanes on interfacial tension is discussed. It has also been demonstrated that the interfacial tension data estimated by the correlation methods are in good agreement with the experimental data. (C) 2010 Elsevier B.V. All rights reserved.

Aggregation behavior in water of new imidazolium and pyrrolidinium alkycarboxylates protic ionic liquids

A novel class of anionic surfactants was prepared through the neutralization of pyrrolidine or imidazole by alkylcarboxylic acids. The compounds, namely the pyrrolidinium alkylcarboxylates ([Pyrr][CnH2n+1COO]) and imidazolium alkylcarboxylates ([Im][CnH2n+1COO]), were obtained as ionic liquids at room temperature. Their aggregation behavior has been examined as a function of the alkyl chain length (from n = 5 to 8) by surface tensiometry and conductivity. Decreases in the critical micelle concentration (cmc) were obtained, for both studied PIL families, when increasing the anionic alkyl chain length (n). Surprisingly, a large effect of the alkyl chain length was observed on the minimum surface area per surfactant molecule (Amin) and, hence the maximum surface excess concentration (Gmax) when the counterion was the pyrrolidinium cation. This unusual comportment has been interpreted in term of a balance between van der Waals and coulombic interactions. Conductimetric measurements permit determination of the degree of ionization of the micelle (a) and the molar conductivity (?M) of these surfactants as a function of n. The molar conductivities at infinite dilution in water (?8) of the [Pyrr]+ and [Im]+ cations have been then determined by using the classical Kohlraush equation. Observed change in the physicochemical, surface, and micellar properties of these new protonic ionic liquid surfactants can be linked to the nature of the cation. By comparison with classical anionic surfactants having inorganic counterions, pyrrolidinium alkylcarboxylates and imidazolium alkylcarboxylates exhibit a higher ability to aggregate in aqueous solution, demonstrating their potential applicability as surfactant.

Volumetric Properties, Viscosities, and Isobaric Heat Capacities of Imidazolium Octanoate Protic Ionic Liquid in Molecular Solvents

Densities (F), viscosities (?), and isobaric heat molar capacities (Cp) of binary mixtures containing imidazolium octanoate, [Im][C7CO2], a protic ionic liquid (PIL), with four molecular solvents, water, acetonitrile, ethanol, and 1-octanol, are determined as a function of temperature from (298.15 to 323.15) K and within the whole composition range at atmospheric pressure. Excess molar volumes, VE, excess molar heat capacities, Cp E, and the deviation from additivity rules of viscosities, ??, of imidazolium octanoate solutions were then deduced from the experimental results, as well as apparent molar volumes, Vfi, and partial molar volumes, V j m,i. Results are discussed according to the nature of the interaction between the PIL and the molecules and the effect of temperature. The excess Gibbs energies of activation of viscous flow (?G*E) for these systems were then calculated at 298.15 K. The excess isobaric heat capacities, Cp E, of binary ([Im][C7CO2] + solvent) systems, depend also of the nature of the molecular solvent in mixture. The excess properties were then correlated, at each temperature, as a function of composition by a Redlich-Kister-type equation. Finally results have been discussed in terms of molecular interactions and molecular structures in these binary mixtures, and thermodynamic properties of investigated binary mixtures were then compared to literature values together to investigate the impact of the nature of the solvent on these reported properties.

Reaction of elemental chalcogens with imidazolium acetates to yield imidazole-2-chalcogenones: direct evidence for ionic liquids as proto-carbenes

Mechanistic analysis of the reaction between elemental sulfur or selenium and 1,3-dialkylimidazolium acetate ionic liquids, in the absence of an external base or solvent, affords evidence for the equilibrium presence of carbene species in these ionic liquids. It demonstrates the potential to control, through anion selection, the concentration of carbene in stable ionic liquids.