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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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The process of surrounding a solute with solvent is called solvation. It involves evenly distributing the solute within the solvent. The rule of thumb for determining a solvent for a given compound is that like dissolves like. A good solvent has molecular characteristics similar to those of the compound to be dissolved. For example, polar solutions dissolve polar solutes, and apolar solvents dissolve apolar solutes. A polar solvent is a solvent that has a high dielectric constant (ϵ ≥ 15); an...
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Some compounds produce hydroxide ions when dissolved by chemically reacting with water molecules. In all cases, these compounds react only partially and so are classified as weak bases. These types of compounds are also abundant in nature and important commodities in various technologies. For example, global production of the weak base ammonia is typically well over 100 metric tons annually, being widely used as an agricultural fertilizer, a raw material for chemical synthesis of other...
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Solubility Equilibria: Ionic Product of Water01:16

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Pure water is a weak electrolyte; only a small amount ionizes into hydrogen and hydroxide ions. At any given temperature, the concentration of undissociated water is almost constant, so the ionic product of water is the product of the hydrogen and hydroxide ion concentrations, denoted as Kw. The square root of Kw gives the individual ion concentrations.
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Quantification of Hydrogen Concentrations in Surface and Interface Layers and Bulk Materials through Depth Profiling with Nuclear Reaction Analysis
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Kinetic Approach for Assessing Absolute Hydrogen Potential (pHabs) across Diverse Solvents.

Abel Tetteh Sika-Nartey1, Junfeng Guo1, William Thomas Broomhead1

  • 1Department of Chemical Engineering and Applied Chemistry, University of Toronto, Toronto M5S 3E5, Ontario, Canada.

The Journal of Physical Chemistry. A
|June 30, 2026
PubMed
Summary

Quantifying proton (H+) potential in diverse solvents is challenging. This study introduces a framework using phenol-d6 substitution to measure absolute hydrogen potential (pHabs), enabling prediction of proton reactivity in catalysis.

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Area of Science:

  • Physical Chemistry
  • Catalysis
  • Solvent Effects

Background:

  • Proton (H+) chemical potential governs catalytic reactivity but is difficult to quantify in nonaqueous and mixed solvents.
  • Existing methods struggle to accurately assess proton behavior across a wide range of solvent polarities and solvation properties.

Purpose of the Study:

  • To develop a robust framework for determining the absolute hydrogen potential (pHabs) in various solvent systems.
  • To establish a reliable method for predicting proton reactivity in thermal catalysis based on solvent properties.

Main Methods:

  • Utilized the electrophilic C-D/C-H substitution of phenol-d6 as a kinetic probe to measure proton reactivity.
  • Categorized solvents based on their ability to solvate and stabilize sulfuric acid (H2SO4) and its conjugate base (HSO4-).
  • Measured reaction rate constants at dilute H2SO4 concentrations and normalized them to 1 mol L-1.

Main Results:

  • A log-linear correlation was observed between normalized substitution rate constants and the solvent-modulated chemical potential of H+ across ~20 pHabs units.
  • This correlation revealed a >37,000,000-fold variation in normalized rate constants at 333 K.
  • Estimated pHabs values for nonaqueous and aqueous systems showed good agreement with existing pKa measurements for H2SO4 in methanol.

Conclusions:

  • The developed framework provides a reliable method for assessing absolute hydrogen potential (pHabs) across diverse solvent environments.
  • This approach enables accurate prediction of proton reactivity, crucial for advancing thermal catalysis research.
  • Understanding solvent effects on proton behavior is key to designing efficient catalytic processes.