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Electrochemical Systems01:24

Electrochemical Systems

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Electrochemical systems provide a fascinating insight into the dynamic interplay of charged species within various phases. One notable example is the interaction between a membrane permeable to K⁺ ions but not to Cl⁻ ions, separating an aqueous KCl solution from pure water. As K⁺ ions diffuse through the membrane, they generate net charges on each phase, leading to a potential difference between them.Similarly, when a piece of Zn is immersed in an aqueous ZnSO₄ solution,...
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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...
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Interfacial electrochemical methods focus on the phenomena occurring at the boundary between an electrode and a solution, as opposed to bulk methods that concentrate on the solution's overall properties. These interfacial methods are classified as either static or dynamic based on the presence of a nonzero current in the electrochemical cell and the consistency of analyte concentrations. Static methods, such as potentiometry, measure the cell's potential without any significant current...
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Ionic Association01:28

Ionic Association

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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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Solubility of Ionic Compounds02:55

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Solubility is the measure of the maximum amount of solute that can be dissolved in a given quantity of solvent at a given temperature and pressure. Solubility is usually measured in molarity (M) or moles per liter (mol/L). A compound is termed soluble if it dissolves in water.
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Crystalline solids are divided into four types: molecular, ionic, metallic, and covalent network based on the type of constituent units and their interparticle interactions.
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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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Interactions in the ionic liquid [EMIM][FAP]: a coupled experimental and computational analysis.

Iuliia V Voroshylova1, Filipe Teixeira2, Renata Costa3

  • 1CIQ(UP), Faculdade de Ciências da Universidade do Porto, Departamento de Química e Bioquímica, Rua do Campo Alegre, 4169-007 Porto, Portugal. voroshylova.iuliia@fc.up.pt cmpereir@fc.up.pt and LAQV@REQUIMTE, Faculdade de Ciências, Universidade do Porto, Departamento de Química e Bioquímica, Rua do Campo Alegre, 4169-007 Porto, Portugal. ncordeir@fc.up.pt.

Physical Chemistry Chemical Physics : PCCP
|December 25, 2015
PubMed
Summary

Density functional theory and infrared spectroscopy reveal gas-phase properties of 1-ethyl-3-methylimidazolium tris(perfluoroethyl)trifluorophosphate ([EMIM][FAP]). Conformational analysis and quantum theory of atoms in molecules identify hydrogen bonds and vibrational modes.

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Area of Science:

  • Physical Chemistry
  • Computational Chemistry
  • Spectroscopy

Background:

  • Room temperature ionic liquids (RTILs) are salts that are liquid at ambient temperatures, with applications in various fields.
  • Understanding the gas-phase properties of ionic liquids is crucial for predicting their behavior in different environments.
  • 1-ethyl-3-methylimidazolium tris(perfluoroethyl)trifluorophosphate ([EMIM][FAP]) is an RTIL with unique structural and electronic characteristics.

Purpose of the Study:

  • To investigate the gas-phase electronic and structural properties of the [EMIM][FAP] ionic liquid.
  • To identify plausible conformers of the [EMIM][FAP] ion pairs and their thermodynamic properties.
  • To characterize the electronic density topology and hydrogen bonding within [EMIM][FAP] ion pairs.

Main Methods:

  • Density functional theory (DFT) calculations were employed to study the electronic and structural properties.
  • Conformational analysis was performed to identify stable ion pair conformers.
  • Infrared (IR) spectroscopy was used for experimental validation, and the quantum theory of atoms in molecules (QTAIM) was applied for electronic density analysis.

Main Results:

  • Several plausible conformers of [EMIM][FAP] ion pairs were identified, with their infrared spectra predicted and thermodynamic properties evaluated.
  • QTAIM analysis revealed the electronic density topology and identified potential hydrogen bonds between cations and anions.
  • Excellent agreement between predicted and experimental IR spectra allowed for clear attribution of vibrational modes.

Conclusions:

  • The study successfully characterized the gas-phase properties of [EMIM][FAP], providing insights into its conformational landscape and intermolecular interactions.
  • The combination of DFT and IR spectroscopy proved effective in elucidating the vibrational modes and structural features of the ionic liquid.
  • The findings highlight the contribution of different conformers and anion isomers to the macroscopic properties of [EMIM][FAP].