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Related Concept Videos

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.
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...
Ionic Strength: Effects on Chemical Equilibria01:19

Ionic Strength: Effects on Chemical Equilibria

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.
In this solution, the primary cation—the calcium...
Common Ion Effect03:24

Common Ion Effect

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:
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...
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.
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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Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
16:24

Controlling the Size, Shape and Stability of Supramolecular Polymers in Water

Published on: August 2, 2012

Hydration control in molecular salts through counterion selection.

Henry A Holleb1, Natalie E Pridmore1, Amy V Hall1

  • 1Department of Chemistry, Durham University, Durham, UK.

Nature Communications
|June 18, 2026
PubMed
Summary

Counterion charge localization is key to predicting molecular salt hydrates. Localized charge promotes hydrate formation, while delocalized charge suppresses it, enabling tunable control over solid-state hydration.

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Area of Science:

  • Solid-state chemistry
  • Crystallization science
  • Materials science

Background:

  • Predicting molecular salt hydrate formation is crucial for material stability and performance.
  • Existing methods lack a clear determinant for hydrate formation.
  • Hydration impacts industrial material properties.

Purpose of the Study:

  • Identify key factors governing hydrate formation in molecular salts.
  • Develop a predictive framework for controlling solid-state hydration.
  • Establish a link between molecular electrostatics and crystallization outcomes.

Main Methods:

  • Analysis of over 31,000 crystal structures.
  • Electron density calculations.
  • Experimental validation using salts of 4-aminoacetanilide and the ΔpKa rule.

Main Results:

  • Counterion charge localization is identified as the primary determinant of hydrate formation.
  • Delocalized counterion charge suppresses hydrate formation.
  • Localized charge promotes hydrate formation, allowing tunable control (from ~80% to <10%).

Conclusions:

  • A predictive framework for hydrate formation based on counterion charge localization is established.
  • Rational control of hydration in molecular salts is achievable through counterion selection.
  • Molecular electrostatics directly influence crystallization outcomes, enabling tailored material design.