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Solubility Equilibria03:07

Solubility Equilibria

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Solubility equilibria are established when the dissolution and precipitation of a solute species occur at equal rates. These equilibria underlie many natural and technological processes, ranging from tooth decay to water purification. An understanding of the factors affecting compound solubility is, therefore, essential to the effective management of these processes. This section applies previously introduced equilibrium concepts and tools to systems involving dissolution and precipitation.
The...
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Solubility03:00

Solubility

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Solution, Solubility, and Solubility Equilibrium
A solution is a homogeneous mixture composed of a solvent, the major component, and a solute, the minor component. The physical state of a solution—solid, liquid, or gas—is typically the same as that of the solvent. Solute concentrations are often described with qualitative terms such as dilute (of relatively low concentration) and concentrated (of relatively high concentration).
In a solution, the solute particles (molecules,...
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Solubility Equilibria: Overview01:09

Solubility Equilibria: Overview

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When a substance such as sodium chloride is added to water, it dissolves, forming an aqueous solution. The extent of dissolution is called solubility. The process of dissolution can exist in equilibrium, just like other chemical processes. Solubility equilibria are also called precipitation equilibria because the process of solubility can be reversible. The reverse of the solubility process is called precipitation.
Solubility is important in biological and environmental processes. A notable...
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Aqueous Solutions and Heats of Hydration02:42

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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.
When ionic compounds dissolve in water, the ions in the solid separate and disperse uniformly throughout the solution because water molecules surround and solvate the ions, reducing the strong electrostatic forces between them. This process...
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Chemical and Solubility Equilibria02:21

Chemical and Solubility Equilibria

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The free energy change associated with dissolving a solute in a liter of solvent is called the free energy of a solution, ΔGsolution. The overall ΔGsolution is expressed as the balance of ΔGinteraction against the always-favorable free-energy of mixing, ΔGmixing. Solution formation is favorable if  ΔGsolution is less than zero, whereas it is unfavorable if ΔGsolution is greater than zero. In short, for a solution to form and complete dissolution to take place,...
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Common Ion Effect03:24

Common Ion Effect

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Compared with pure water, the solubility of an ionic compound is less in aqueous solutions containing a common ion (one also produced by dissolution of the ionic compound). This is an example of a phenomenon known as the common ion effect, which is a consequence of the law of mass action that may be explained using Le Châtelier’s principle. Consider the dissolution of silver iodide:
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Pentaglyme-K salt binary mixtures: phase behavior, solvate structures, and physicochemical properties.

Toshihiko Mandai1, Seiji Tsuzuki, Kazuhide Ueno

  • 1Department of Chemistry and Biotechnology, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan. mandi@chalmers.se mwatanab@ynu.ac.jp.

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Binary mixtures of potassium salts and pentaglyme form stable equimolar complexes. These solvate structures, characterized by X-ray crystallography and Raman spectroscopy, influence their properties as ionic liquids.

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Physical Chemistry

Background:

  • Understanding the behavior of electrolyte solutions is crucial for developing advanced energy storage systems.
  • Pentaglyme (G5) is a glyme solvent known for its ability to solvate cations.
  • Potassium (K) salts with various anions are investigated for their potential in electrochemical applications.

Purpose of the Study:

  • To prepare and characterize binary mixtures of potassium salts (KX) and pentaglyme (G5).
  • To investigate the formation of equimolar complexes and their structural properties in crystalline and molten states.
  • To evaluate the physicochemical properties and classify the resulting systems as solvate ionic liquids.

Main Methods:

  • Preparation and characterization of binary mixtures with varying salt concentrations and anions (TFSA-, TfO-, NfO-, PF6-, SCN-).
  • Phase diagram analysis and thermal stability studies.
  • Single-crystal X-ray crystallography to determine solvate structures.
  • Temperature-dependent Raman spectroscopy to elucidate molten state structures.
  • Physicochemical property evaluation, including Walden plots.

Main Results:

  • Phase diagrams and thermal stability indicate the formation of equimolar K(G5)X complexes.
  • X-ray crystallography reveals that G5 coordinates to K+ similarly to 18-crown-6 ether, irrespective of the anion.
  • Raman spectroscopy shows a breakdown of crystalline solvate structures upon melting, with stability dependent on ion-ion interactions.
  • Walden plots confirm the ionic nature of the molten equimolar complexes.
  • Systems were classified into good and poor solvate ionic liquids based on structural characteristics and dissociativity.

Conclusions:

  • Equimolar complexes of K+ and G5 form stable solvates when ion-dipole interactions dominate over ion-ion interactions.
  • The coordination of G5 to K+ is consistent across different anions in the crystalline state.
  • The prepared K(G5)X mixtures represent potential solvate ionic liquids with tunable properties.