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Related Concept Videos

Theory of Strong Electrolytes01:23

Theory of Strong Electrolytes

The interionic forces of the strong electrolytes depend on the solvent's dielectric constant, which is the ability of a solvent to store electrical energy, based on its polarizability. and the solution's concentration. In high-dielectric solvents and in dilute solutions, weak electrostatic forces keep ions apart. However, in low-dielectric solvents or concentrated solutions, stronger interionic forces may cause ions to pair up as ionic doublets despite being fully ionized. The theory of strong...
Ionic Strength: Overview01:12

Ionic Strength: Overview

The ionic strength of a solution is a quantitative way of expressing the total electrolyte concentration of a solution. This concept was first introduced in 1921 by two American physical chemists, Gilbert N. Lewis and Merle Randall, while describing the activity coefficient of strong electrolytes. During the calculation of ionic strength (I or μ), all the cations and anions are considered. However, the concentration (c) of an ion with a greater charge number (z) has a greater contribution to...
Ionic Association01:28

Ionic Association

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.
Aqueous Solutions and Heats of Hydration02:42

Aqueous Solutions and Heats of Hydration

Water and other polar molecules are attracted to ions. The electrostatic attraction between an ion and a molecule with a dipole is called an ion-dipole attraction. These attractions play an important role in the dissolution of ionic compounds in water.
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Electrolytes: van't Hoff Factor03:08

Electrolytes: van't Hoff Factor

Colligative Properties of ElectrolytesThe colligative properties of a solution depend only on the number, not on the identity, of solute species dissolved. The concentration terms in the equations for various colligative properties (freezing point depression, boiling point elevation, osmotic pressure) pertain to all solute species present in the solution. Nonelectrolytes dissolve physically without dissociation or any other accompanying process. Each molecule that dissolves yields one dissolved...
Intermolecular Forces03:13

Intermolecular Forces

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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Synthesis of Ionic Liquid Based Electrolytes, Assembly of Li-ion Batteries, and Measurements of Performance at High Temperature
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Published on: December 20, 2016

Comparison of interionic/intermolecular vibrational dynamics between ionic liquids and concentrated electrolyte

Tomotsumi Fujisawa1, Keiko Nishikawa, Hideaki Shirota

  • 1Department of Nanomaterial Science, Graduate School of Advanced Integration Science, Chiba University, 1-33 Yayoi, Inage-ku, Chiba 263-8522, Japan.

The Journal of Chemical Physics
|January 12, 2010
PubMed
Summary

This study compares vibrational dynamics in ionic liquids (ILs) and concentrated electrolyte solutions using advanced spectroscopy. Concentrated electrolytes show stronger interionic interactions than ILs due to cation and solvent effects on anion conformation.

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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding

Published on: March 24, 2018

Area of Science:

  • Physical Chemistry
  • Spectroscopy
  • Materials Science

Background:

  • Ionic liquids (ILs) and concentrated electrolyte solutions exhibit complex interionic/intermolecular vibrational dynamics.
  • Understanding these dynamics is crucial for designing advanced materials and electrochemical systems.
  • Femtosecond optically heterodyne-detected Raman-induced Kerr effect (HOKE) spectroscopy provides insights into ultrafast molecular motions.

Purpose of the Study:

  • To compare the interionic/intermolecular vibrational dynamics of ILs and concentrated electrolyte solutions.
  • To investigate the influence of cations and solvents on the vibrational spectra and molecular interactions.
  • To elucidate the conformational changes of the bis(trifluoromethanesulfonyl)amide ([NTf(2)](-)) anion in different environments.

Main Methods:

  • Femtosecond optically heterodyne-detected Raman-induced Kerr effect (HOKE) spectroscopy was employed.
  • Measurements were performed on ILs with 1-butyl-3-methylimidazolium, 1-butylpyridinium, N-butyl-N,N,N-triethylammonium, and 1-butyl-1-methylpyrrolidinium cations and the [NTf(2)](-) anion.
  • Control samples included Li[NTf(2)] solutions in water, methanol, propylene carbonate, and poly(ethylene glycol).

Main Results:

  • HOKE transients revealed intra- and interionic/intermolecular vibrational dynamics followed by slow relaxation in both ILs and electrolyte solutions.
  • Fourier transform Kerr spectra showed differences in the [NTf(2)](-) anion's intraionic bands (280-350 cm(-1)) between ILs and electrolyte solutions, attributed to conformational changes (cisoid/transoid equilibrium).
  • Low-frequency spectra (0-200 cm(-1)) displayed unique features related to cation type and solvent, with aromatic ILs showing librational motion around 100 cm(-1) and a common interionic motion near 20 cm(-1).

Conclusions:

  • The stabilization of the cisoid form of the [NTf(2)](-) anion by Li(+) and dipolar solvents alters its conformational equilibrium in electrolyte solutions compared to ILs.
  • Non-aromatic ILs show spectral similarities to propylene carbonate and poly(ethylene glycol) solutions, enabling direct comparison.
  • Concentrated electrolyte solutions exhibit stronger interionic/intermolecular interactions than ILs, as indicated by spectral analysis.