Conductometric study of binary systems based on ionic liquids and acetonitrile in a wide concentration range

Kalugin, Oleg N.; Voroshylova, Iuliia V.; Riabchunova, Anastasiia V.; Lukinova, E.V.; Chaban, Vitaly V.

doi:10.1016/j.electacta.2013.04.140

Cited by 80 publications

(83 citation statements)

References 56 publications

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“…A survey of literature indicates that most studies report only the specific conductivity data for pure ionic liquids or binary and ternary mixtures of ILs with various solvents at 298.15 K. The conductance studies of dilute solutions of ionic liquids in a wide temperature range allow the determination of the values of association constants and thermodynamic functions of association, which consequently allows the better understanding of the behavior of ILs in various solvents [1][2][3]. This paper is both a continuation and an extension of our and other authors' works on association of imidazolium-based ionic liquids, i.e., [ 4 ] in water [4], 1-propanol [5], N,N-dimethylformamide [6], acetonitrile [7,8], dimethylsulfoxide [9], and methanol [9,10]. Moderate ionic association of ILs occurs in N,N-dimethylformamide, acetonitrile, and methanol, slight in dimethylsulfoxide, whereas it becomes significant in 1-propanol.…”

Section: Introductionmentioning

confidence: 97%

Ionic association and conductance of ionic liquids in dichloromethane at temperatures from 278.15 to 303.15 K

Boruń

Bald

2016

Ionics

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The electrical conductances of very dilute solutions of the ionic liquids 1-ethyl-3-methylimidazolium tetrafluoroborate [emim] [BF 4 ] and 1-butyl-3-methylimidazolium tetrafluoroborate [bmim] [BF 4 ] in the low-permittivity solvent dichloromethane have been measured in the temperature range from 278.15 to 303.15 K at 5 K intervals. The data was analyzed assuming the possible presence of contact (CIP) and solvent-separated (SSIP) ion pairs in the solution on the basis of lcCM model to obtain ionic association constants, K A , and the limiting molar conductivities, Λ o , of these electrolytes. The examined ionic liquids are strongly associated in dichloromethane over the whole temperature range. From the temperature dependence of the limiting molar conductivities, the Eyring's activation enthalpy of charge transport was determined. The thermodynamic functions such as Gibbs energy, entropy, and enthalpy of the process of ion pair formation were calculated from the temperature dependence of the association constants.

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Section: Introductionmentioning

confidence: 97%

Ionic association and conductance of ionic liquids in dichloromethane at temperatures from 278.15 to 303.15 K

Boruń

Bald

2016

Ionics

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“…Use of ILs as supporting electrolytes in traditional solvents has been reported by others. 19,20,37 This has been done to increase conductivity and/or reduce viscosity compared to use of pure ILs. The use of ILs in organic solvents is also particularly useful when traditional electrolytes have limited solubility.…”

Section: Resultsmentioning

confidence: 99%

“…The maximum conductivity of all the mixtures was between the 2-10 mol% IL range which is consistent with the literature on dilute ionic liquid behavior. 19,20,37 The dielectric constants of the solvents used are shown in Table I.…”

Section: Resultsmentioning

confidence: 99%

“…For protic ILs, it has been found that protic solvents such as water separate the ion pairs which would otherwise be in contact with each other, effectively forming a neutral molecule. 22 In the case of aprotic ionic liquids, the addition of aprotic solvents such as chloroform leads to an increase in conductivity characteristic to IL dilution in solvent, 14,19,20 where the solvent increases the ion diffusivity by decreasing the amount of neutral ion clusters and ion pairs. 23 One of the challenges associated with electrochemical systems is the separation of the product from the electrolyte.…”

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confidence: 99%

“…Studies have shown that by diluting the IL in a molecular solvent, the conductivity increases due to increased mobility of the ions in a viscosity-reduced state. 14,19,20 Use of ILs as electrolytes in non-aqueous solvents can improve the conductivity of the system beyond the use of traditional electrolytes because many traditional electrolyte salts suffer from poor solubility in organic solvents. Owing to their strong intermolecular forces such as hydrogen bonding and coulometric attraction, ILs liquids are often limited by poor ion speciation.…”

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confidence: 99%

See 2 more Smart Citations

Ionicity Analysis of Silylamine-Type Reversible Ionic Liquids as a Model Switchable Electrolyte

Jiménez

Jung

Biddinger

2015

J. Electrochem. Soc.

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Separation of the electrochemical product from an electrolyte can add challenges to the overall process. Use of a switchable electrolyte offers the possibility to reduce or eliminate these separation challenges while maintaining high conductivity. Reversible ionic liquids (RevILs) are a type of switchable solvent that could be used as a switchable electrolyte. Switchable solvents are solvents that can have dramatic step-changes in their properties with the introduction of an external stimulus, in this case CO 2 . In order to determine the feasibility of using TEtoxySA-RevIL, which behaves similarly to protic ionic liquids, as an electrolyte an ionicity analysis utilizing binary mixtures of the RevIL and organic solvents were studied to determine the ionic behavior of the system. Both protic and aprotic solvents with a broad range of dielectric constants were used in order to elucidate the ionicity of the RevIL mixtures. When in the pure RevIL state, the conductivity is prohibitively low due to a heightened viscosity and poor ion mobility due to hydrogen bonding and coulometric attraction. We found that in the presence of protic solvents with high dielectric constants the conductivity of the RevIL increased by up to four orders of magnitude and achieved ideal ionicity.

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Imidazolium Salt Ion Pairs in Solution

Stassen

Ludwig

Wulf

et al. 2015

Chemistry A European J

167

151

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The formation, stabilisation and reactivity of contact ion pairs of non-protic imidazolium ionic liquids (ILs) in solution are conceptualized in light of selected experimental evidence as well theoretical calculations reported mainly in the last ten years. Electric conductivity, NMR, ESI-MS and IR data as well as theoretical calculations support not only the formation of contact ion pairs in solution, but also the presence of larger ionic and neutral aggregates even when dissolved in solvents with relatively high dielectric constants, such as acetonitrile and DMSO. The presence of larger imidazolium supramolecular aggregates is favoured at higher salt concentrations in solvents of low dielectric constant for ILs that contain shorter N-alkyl side chains associated with anions of low coordination ability. The stability and reactivity of neutral contact species are also dependent on the nature of the anion, imidazolium substituents, and are more abundant in ILs containing strong coordinating anions, in particular those that can form charge transfer complexes with the imidazolium cation. Finally, some ILs display reactivities as contact ion pairs rather than solvent-separated ions.

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Conductometric study of binary systems based on ionic liquids and acetonitrile in a wide concentration range

Cited by 80 publications

References 56 publications

Ionic association and conductance of ionic liquids in dichloromethane at temperatures from 278.15 to 303.15 K

Ionic association and conductance of ionic liquids in dichloromethane at temperatures from 278.15 to 303.15 K

Ionicity Analysis of Silylamine-Type Reversible Ionic Liquids as a Model Switchable Electrolyte

Imidazolium Salt Ion Pairs in Solution

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