Reaction between Diiodide Anion Radicals in Ionic Liquids

Takahashi, Kenji; Sakai, S.; Tezuka, Hiroaki; Hiejima, Yusuke; Katsumura, Yosuke; Watanabe, Masayoshi

doi:10.1021/jp0671087

Cited by 46 publications

(43 citation statements)

References 46 publications

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“…Many studies, both in electrochemistry and in chemistry to a general sense, have been undertaken to understand the differences in the kinetics in these solvents. 4,[15][16][17][18][19][20][21] Accelerations of the reaction rates, 17,19,22 as well as lower or identical kinetics were equally highlighted. 18,[23][24][25][26] The present work aims to extend our observations on the influence of ionic liquids on the kinetics of dimerization of ion radicals, underlining the ILs' complex solvation effects with respect to the molecular electrolyte.…”

Section: Introductionmentioning

confidence: 99%

Dimerization of ion radicals in ionic liquids. An example of favourable “Coulombic” solvation

André

Hapiot

Lagrost

2010

Phys. Chem. Chem. Phys.

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The irreversible dimerization of the acetophenone radical anion, chosen as an example of a carbon-carbon coupling reaction between two charged species, was investigated in a series of 1,3-dialkylimidazolium and 1,2,3-trialkylimidazolium ionic liquids. Indeed, such ion dimerizations which display slow kinetics despite small activation energies, are controlled by a subtle competition between bond formation, Coulombic repulsion and solvation. The effects of viscosity, "polarity" and ionic solvation on the reactivity of the radical anions were examined. The dimerization rate constants were demonstrated to be only weakly affected by the high viscosity of the medium or its apparent polarity. When the acetophenone radical anion is "solvated" in imidazolium-based ionic liquids, a strong interaction between the negatively-charged intermediates and the imidazolium cation occurs. The ensuing charge stabilization allows a fast dimerization step in all the ionic liquids used. The kinetic effect is even enhanced in the 1,3-dialkylimidazolium salts as compared to the 1,2,3-trialkylimidazolium ones because the interaction between the radical anions and the 1,3-dialkylimidazolium cations are stronger, probably due to the formation of H-bond. The reactivity of the ion radical is demonstrated not only to be mainly dominated by electrostatic interactions, but also that the nature of the ionic liquid cations with respect to that of the ion radical is a major factor that affects the reaction kinetics.

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Section: Introductionmentioning

confidence: 99%

Dimerization of ion radicals in ionic liquids. An example of favourable “Coulombic” solvation

André

Hapiot

Lagrost

2010

Phys. Chem. Chem. Phys.

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“…These exciting results yielded materials with conductivities as high as 10 −2 S cm −1 . The use of pure ionic liquids in lithium batteries, dye sensitized solar cells, and fuel cells is being explored 15–21. When commercial applications require dimensional stability, amorphous linear polymers are problematic because they have a tendency to flow at high temperatures.…”

Section: Introductionmentioning

confidence: 99%

Thermal analysis and ionic conductivity of ionic liquid containing composites with different crosslinkers

Sterner

Rosol

Gross

et al. 2009

J of Applied Polymer Sci

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Conductive polymer composites were synthesized by the polymerization of methylmethacrylate in the presence of ionic liquid solvents. These composites were characterized by attenuated total reflectance infrared spectroscopy, differential scanning calorimetry, and dynamic mechanical analysis. AC impedance measurements were performed on these composites as a function of ionic liquid type, ionic liquid concentration, crosslinker density, and molecular weight between crosslinks at various temperatures. 1-Butyl-3-methylimidazolium thiocyanate produced composites with a greater conductivity than 1-ethyl-3-methylimidazolium trifluoromethanesulfonimide, despite having a higher viscosity. The viscosity of the virgin ionic liquid could not be used to predict the order of ionic conductivity for composites made from these ionic liquids. The effect of crosslink density within the range of 0-0.6 mmol crosslinking agent per gram of monomer was studied. Composites with 25% ionic liquid (w/w) appeared to have an optimum crosslink density for maximum ionic conductivity. In the range of crosslink densities studied, composites with greater ionic liquid concentration exhibited no significant effect of crosslink density on ionic conductivity. This could be due to the fact that the difference in crosslink density did not effectively change the T g of these composites. The composite with the lowest theoretical molecular weight between crosslinks had the lowest ionic conductivity. This could be due to restriction of ion movement at this molecular weight between crosslinks. The composite with the highest molecular weight between crosslinks had comparable ionic conductivity to an uncrosslinked composite. This study showed that these materials have ionic conductivities practical for advanced energy applications over a wide range of morphologies with dimensional stability.

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“…A production process of I − 3 originates from the CTTS reaction, namely, atomic iodine produced by I − + hν → I + e solv reacts with I − to form I − 2 (I + I − → I − 2 ) and it is followed by I − 2 + I − 2 → I − 3 + I − . 33) Another production mechanism of I − 3 is the plasma irradiation. The production of I − 3 is observed in a KI-starch solution irradiated with an atmospheric-pressure plasma jet.…”

Section: Scavenger Produced In Tmpa-tfsi/ki Solutionmentioning

confidence: 99%

Reactivity of solvated electrons in ionic liquid interacting with low-pressure plasmas

Inagaki

Sasaki

2020

Jpn. J. Appl. Phys.

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We employed the charge transfer to solvent (CTTS) transition to examine the reactivity of solvated electrons in ionic liquid interacting with plasmas. A dye laser pulse at 225 nm was injected into N,N,N-trimethyl-N-propylammonium bis (trifluoromethylsulfonyl) imide with the addition of potassium iodide, which was irradiated with low-pressure plasmas, and the reaction frequency of solvated electrons produced by the CTTS transition was measured by optical absorption spectroscopy. It was observed that the reaction frequency of solvated electrons was enhanced by the plasma irradiation. The enhanced reaction frequency was more remarkable by the irradiation of a nitrogen plasma than argon and oxygen plasmas. In addition, a higher reaction frequency was observed at a closer distance from the plasma-liquid interface. The UV-vis absorbance spectrum of the ionic liquid was changed by the plasma irradiation, indicating the production of unknown species which had a high reaction frequency with solvated electrons in the ionic liquid.

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Reaction between Diiodide Anion Radicals in Ionic Liquids

Cited by 46 publications

References 46 publications

Dimerization of ion radicals in ionic liquids. An example of favourable “Coulombic” solvation

Dimerization of ion radicals in ionic liquids. An example of favourable “Coulombic” solvation

Thermal analysis and ionic conductivity of ionic liquid containing composites with different crosslinkers

Reactivity of solvated electrons in ionic liquid interacting with low-pressure plasmas

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