Study of Imidazolium And Pyrrolidinium Ionic Liquids By Ion Mobility Spectrometry And Electrospray Ionization Mass Spectrometry

Nousiainen, Marjaana; Tolstogouzov, A.; Holopainen, Sanna; Jänis, Janne; Sillanpää, Mika

doi:10.1002/rcm.5143

Cited by 4 publications

(2 citation statements)

References 19 publications

(31 reference statements)

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“…A variety of mass spectrometric techniques were used to investigate the nature of the gas phase produced from ionic liquids under a wide range of experimental conditions. 27,29,33,[47][48][49][50][51][52][53][54] Although several vaporization experiments on BMImNTf 2 were presented in the literature based on mass spectrometric measurements 33,[47][48][49]51,53 no thermodynamic study was done under equilibrium conditions, the only exception being a paper by Tolstogouzov, 48 where a Knudsen molecular source was used. Here we present a KEMS study of the BMImNTf 2 vaporization aimed at gaining more information on the vaporization behavior of this compound under equilibrium conditions and at measuring an independent value of the vaporization enthalpy.…”

Section: Kems Experimentsmentioning

confidence: 99%

Vaporization of the prototypical ionic liquid BMImNTf2 under equilibrium conditions: a multitechnique study

Brunetti

Ciccioli

Gigli

et al. 2014

Phys. Chem. Chem. Phys.

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The vaporization behaviour and thermodynamics of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethyl)sulfonylimide (BMImNTf2) were studied by combining the Knudsen Effusion Mass Loss (KEML) and Knudsen Effusion Mass Spectrometry (KEMS) techniques. KEML studies were carried out in a large temperature range (398-567) K by using effusion orifices with 0.3, 1, and 3 mm diameters. The vapor pressures so measured revealed no kinetically hindered vaporization effects and provided second-law vaporization enthalpies at the mean experimental temperatures in close agreement with literature. By exploiting the large temperature range covered, the heat capacity change associated with vaporization was estimated, resulting in a value of -66.8 J K(-1) mol(-1), much lower than that predicted from calorimetric measurements on the liquid phase and theoretical calculations on the gas phase. The conversion of the high temperature vaporization enthalpy to 298 K was discussed and the value Δ(l)(g)H(m)(298 K) = (128.6 ± 1.3) kJ mol(-1) assessed on the basis of data from literature and present work. Vapor pressure data were also processed by the third-law procedure using different estimations for the auxiliary thermal functions, and a Δ(l)(g)H(m)(298 K) consistent with the assessed value was obtained, although the overall agreement is sensitive to the accuracy of heat capacity data. KEMS measurements were carried out in the lower temperature range (393-467) K and showed that the largely prevailing ion species is BMIm(+), supporting the common view of BMImNTf2 vaporizing as individual, neutral ion pairs also under equilibrium conditions. By monitoring the mass spectrometric signal of this ion as a function of temperature, a second-law Δ(l)(g)H(m)(298 K) of 129.4 ± 7.3 kJ mol(-1) was obtained, well consistent with KEML and literature results. Finally, by combining KEML and KEMS measurements, the electron impact ionization cross section of BMIm(+) was estimated.

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Section: Kems Experimentsmentioning

confidence: 99%

Vaporization of the prototypical ionic liquid BMImNTf2 under equilibrium conditions: a multitechnique study

Brunetti

Ciccioli

Gigli

et al. 2014

Phys. Chem. Chem. Phys.

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“…Note that the ESI + MS spectra of neat imidazolium and pyrrolidinium ILs treated at 220 °C for 5 h exhibited only fragments resulting from the cleavage of the hydrocarbon chain, and no species resulting from alkyl chain redistribution. 64 Here the redistribution showed a chemical evolution of the nature of the cation ring occurring at constant weight.…”

Section: Liquid Phase Analysismentioning

confidence: 87%

Targeting adequate thermal stability and fire safety in selecting ionic liquid-based electrolytes for energy storage

Chancelier

Diallo

Santini

et al. 2014

Phys. Chem. Chem. Phys.

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The energy storage market relating to lithium based systems regularly grows in size and expands in terms of a portfolio of energy and power demanding applications. Thus safety focused research must more than ever accompany related technological breakthroughs regarding performance of cells, resulting in intensive research on the chemistry and materials science to design more reliable batteries. Formulating electrolyte solutions with nonvolatile and hardly flammable ionic liquids instead of actual carbonate mixtures could be safer. However, few definitions of thermal stability of electrolytes based on ionic liquids have been reported in the case of abuse conditions (fire, shortcut, overcharge or overdischarge). This work investigates thermal stability up to combustion of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C1C4Im][NTf2]) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([PYR14][NTf2]) ionic liquids, and their corresponding electrolytes containing lithium bis(trifluoromethanesulfonyl)imide LiNTf2. Their possible routes of degradation during thermal abuse testings were investigated by thermodynamic studies under several experimental conditions. Their behaviours under fire were also tested, including the analysis of emitted compounds.

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Mass spectral evaluation of column bleeding for imidazolium-based ionic liquids as GC liquid phases

Шашков

Sidelnikov

2012

Anal Bioanal Chem

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Mass spectra were obtained to evaluate the use of numerous single-cation and dicationic ionic liquids as stationary liquid phases in GC/MS at high temperature. Background mass spectra and product ion mass spectra of several ions in the background spectrum were obtained. Fragmentation mechanisms were propounded, including the detailed fragmentation pathway of the 1,2-dimethyl-3-propylimidazole cation. The relation between temperature and the main signals in the mass spectra of ILs was studied.

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Study of Imidazolium And Pyrrolidinium Ionic Liquids By Ion Mobility Spectrometry And Electrospray Ionization Mass Spectrometry

Cited by 4 publications

References 19 publications

Vaporization of the prototypical ionic liquid BMImNTf2 under equilibrium conditions: a multitechnique study

Vaporization of the prototypical ionic liquid BMImNTf2 under equilibrium conditions: a multitechnique study

Targeting adequate thermal stability and fire safety in selecting ionic liquid-based electrolytes for energy storage

Mass spectral evaluation of column bleeding for imidazolium-based ionic liquids as GC liquid phases

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