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Related Concept Videos

Ions as Acids and Bases02:54

Ions as Acids and Bases

Salts with Acidic Ions
Salts are ionic compounds composed of cations and anions, either of which may be capable of undergoing an acid or base ionization reaction with water. Aqueous salt solutions, therefore, may be acidic, basic, or neutral, depending on the relative acid-base strengths of the salt’s constituent ions. For example, dissolving the ammonium chloride in water results in its dissociation, as described by the equation:
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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Ion Exchange01:17

Ion Exchange

Ion exchange chromatography separates charged molecules from a solution by reversibly exchanging them with mobile, or 'active', ions associated with the oppositely charged stationary phase. This method can be used to separate ions, soften and deionize water, and purify solutions. The polymers comprising the ion-exchange column are high-molecular-weight and chemically stable polymers, crosslinked to be porous and essentially insoluble. They are also functionalized with either acidic or basic...
Titration in Nonaqueous Solvents01:16

Titration in Nonaqueous Solvents

Most acid-base titrations are performed in an aqueous medium. In aqueous titrations, water competes with weaker acids or bases for proton donation or acceptance, leading to ambiguous endpoints in the titration curve. Water also affects the partial ionization of weak acids or bases. For example, water accepts a proton from acetic acid to form hydronium and acetate ions. The hydronium ion formed is a stronger acid than acetic acid, and the acetate ion is a stronger base than water. As a result,...
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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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Anions dramatically enhance proton transfer through aqueous interfaces.

Himanshu Mishra1, Shinichi Enami, Robert J Nielsen

  • 1Ronald and Maxine Linde Center for Global Environmental Science, Materials Science, and Materials and Process Simulation Center, California Institute of Technology, Pasadena, CA 91125, USA.

Proceedings of the National Academy of Sciences of the United States of America
|June 13, 2012
PubMed
Summary

Proton transfer across water surfaces is slow unless ions are present. Anions lower the energy barrier, facilitating nitric acid dissociation at aqueous interfaces.

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Area of Science:

  • Physical Chemistry
  • Surface Science
  • Chemical Physics

Background:

  • Proton transfer (PT) is crucial in chemistry and biology.
  • Interfacial PT differs significantly from PT in bulk water.

Purpose of the Study:

  • To investigate the dissociation of gas-phase nitric acid (HNO3) at aqueous interfaces.
  • To elucidate the role of ions and electrostatic effects in interfacial PT.

Main Methods:

  • In situ monitoring of aqueous jet surfaces using online electrospray ionization mass spectrometry.
  • Exposure of water surfaces to nitric acid gas beams.
  • Quantum mechanical calculations to model dissociation barriers.

Main Results:

  • Gas-phase HNO3 does not dissociate on pure water surfaces; ions are required.
  • HNO3 dissociation significantly increases with > 30-μM inert electrolyte concentrations.
  • Anions lower the energy barrier for HNO3 dissociation at water cluster surfaces.

Conclusions:

  • Interfacial PT is counterintuitively slow at water-hydrophobe boundaries.
  • Electrostatic interactions with anions are critical for facilitating PT at interfaces.
  • Results provide mechanistic insights into ion-mediated interfacial proton transfer.