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Related Concept Videos

Ionic Strength: Effects on Chemical Equilibria01:19

Ionic Strength: Effects on Chemical Equilibria

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The addition of an inert ionic compound increases the solubility of a sparingly soluble salt. For example, adding potassium nitrate to a saturated solution of calcium sulfate significantly enhances the solubility of calcium sulfate. Le Châtelier's principle cannot predict this shift in the equilibrium. Instead, this could be explained in terms of changes in the effective concentration of the ions in solution in the presence of added inert salt.
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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...
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Colligative Properties of Electrolytes
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Solubility Equilibria: Overview01:09

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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.
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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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Solvating Effects02:12

Solvating Effects

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An understanding of the solvating effect helps rationalize the relation between solvation and acidity of the compound. In addition, this also explains the relative stability of conjugate bases for compounds with different pKa values. This lesson details, in-depth, the principle of solvating effects. The strength of an acid and the stability of its corresponding conjugate base are determined using pKa values. This observed relationship is a consequence of solvation, which is the interaction...
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Generation and Control of Electrohydrodynamic Flows in Aqueous Electrolyte Solutions
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Extended Stability Window in Water-in-Salt Electrolytes: Understanding the Origins.

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  • 1Department of Mechanical and Process Engineering, ETH Zurich, 8092 Zurich, Switzerland.

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Water-in-salt electrolytes enhance aqueous energy storage voltage stability. Sluggish water transport, not just reduced water activity, significantly slows hydrogen evolution reactions, widening the stability window.

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Area of Science:

  • Electrochemistry
  • Materials Science
  • Computational Chemistry

Background:

  • Water-in-salt electrolytes offer wider voltage stability for aqueous energy storage.
  • This enhanced stability is often linked to solid electrolyte interphase (SEI) formation or reduced water activity.

Purpose of the Study:

  • Investigate alternative mechanisms beyond SEI and water activity influencing stability in water-in-salt electrolytes.
  • Quantify the impact of water activity, local pH, and transport limitations on the hydrogen evolution reaction (HER).

Main Methods:

  • Electrochemical measurements on platinum electrodes.
  • Molecular Dynamics (MD) simulations.
  • Density Functional Theory (DFT) calculations.

Main Results:

  • HER kinetics significantly slow with increasing electrolyte concentration (1-17 molal NaClO4).
  • A linear correlation observed between decreased surface water coverage and HER exchange current density.
  • MD simulations show sluggish water transport in the double layer limits HER, extending the stability window.

Conclusions:

  • Sluggish water transport is a key factor, not bulk water activity, in enhancing water-in-salt electrolyte stability.
  • Disrupted hydrogen bonding and transport limitations kinetically hinder HER, widening the electrochemical stability window.
  • Alternative mechanisms beyond SEI formation are crucial for understanding high-voltage aqueous energy storage.