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Ion-Exchange Chromatography01:09

Ion-Exchange Chromatography

Ion-exchange chromatography, or IEC, is a technique for separating ions based on their affinity for the stationary phase. The stationary phase is a cross-linked polymer resin with covalently attached ionic functional groups. The functional groups can be either positively charged (cation exchangers) or negatively charged (anion exchangers). A cation exchanger consists of a polymeric anion and active cations, while an anion exchanger is a polymeric cation with active anions. The choice of...
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Basicity of Heterocyclic Aromatic Amines

Heterocyclic amines, where the N atom is a part of an alicyclic system, are similar in basicity to alkylamines. Interestingly, the heterocyclic amine having a nitrogen atom as part of an aromatic ring has much less basicity than its corresponding alicyclic counterpart. For this reason, as presented in Figure 1, piperidine (pKb = 2.8) is significantly more basic than pyridine (pKb = 8.8).
Ionic Crystal Structures02:42

Ionic Crystal Structures

Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
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Atoms and molecules interact through bonds (or forces): intramolecular and intermolecular. The forces are electrostatic as they arise from interactions (attractive or repulsive) between charged species (permanent, partial, or temporary charges) and exist with varying strengths between ions, polar, nonpolar, and neutral molecules. The different types of intermolecular forces are ion–dipole, dipole–dipole, hydrogen bonds, and dispersion; among these, dipole–dipole, hydrogen bonds, and dispersion...
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The ionic association is the association of oppositely charged ions in an electrolyte solution to form ion pairs. Bjerrum defined ion pairs as two oppositely charged ions whose electrostatic attraction exceeds the thermal energy of the system, typically expressed as 2kT. Electrostatic attraction depends on ionic charge, separation distance, and the dielectric constant of the medium. Thermal energy, represented by kT, reflects the tendency of ions to move independently due to molecular motion.

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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
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Published on: March 24, 2018

Charge trapping in imidazolium ionic liquids.

Ilya A Shkrob1, James F Wishart

  • 1Chemistry Division, Argonne National Laboratory, 9700 S. Cass Ave, Argonne, Illinois 60439, USA. shkrob@anl.gov

The Journal of Physical Chemistry. B
|March 28, 2009
PubMed
Summary

Ionic liquids (ILs) exposed to radiation form stable radical ions, not neutral radicals. This finding impacts understanding of ILs in applications like photovoltaics and solvent extraction.

Area of Science:

  • Physical Chemistry
  • Materials Science
  • Radiochemistry

Background:

  • Room-temperature ionic liquids (ILs) are versatile solvents with applications in photovoltaics and solvent extraction.
  • Exposure to ionizing radiation necessitates understanding ILs' radiation and photochemistry.
  • Previous studies suggested radical formation from ionized ILs.

Purpose of the Study:

  • To investigate the nature of charge-trapped species in ionized 1,3-dialkylimidazolium ionic liquids.
  • To elucidate the reaction pathways of different anions upon ionization.
  • To determine the implications of charge localization on secondary chemistry in ILs.

Main Methods:

  • Computational chemistry methods.
  • Electron spin resonance (ESR) spectroscopy.

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  • Transient absorption spectroscopy.

    • Main Results:

    • Electron localization in imidazolium ILs forms a gauche dimer radical cation with an elongated C(2)-C(2) bond, absorbing in the NIR and visible regions.
    • Amide anions like dicyanamide form dimer radical anions via three-electron N-N bonding, while bis(triflyl)amide is sterically hindered.
    • Bis(oxalato)borate anions undergo CO(2) elimination pathways.
    • Primary charges in ILs preferentially localize as radical ions, not neutral radicals.

    Conclusions:

    • Ionized ILs exhibit a tendency to form radical ions, influencing their secondary chemistry.
    • The identified dimer radical cation species explains observed ESR spectra and optical absorption.
    • Understanding these radical ion pathways is crucial for optimizing ILs in radiation-exposed applications.