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Concentration dependence of ionic hydration numbers.

Yizhak Marcus1

  • 1Institute of Chemistry, The Hebrew University of Jerusalem , Jerusalem 91904, Israel.

The Journal of Physical Chemistry. B
|August 15, 2014
PubMed
Summary
This summary is machine-generated.

Hydration numbers of aqueous electrolytes decrease with concentration, approaching ion adsorption site limits. Ultrasound-derived hydration numbers are inaccurate at infinite dilution.

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Area of Science:

  • Physical Chemistry
  • Solution Chemistry

Background:

  • Understanding ion-solvation is crucial in aqueous electrolyte solutions.
  • Hydration numbers quantify the extent of water molecules interacting with ions.

Purpose of the Study:

  • To calculate hydration numbers for 23 aqueous electrolyte solutions using isothermal compressibility data.
  • To investigate the concentration dependence of hydration numbers.
  • To compare hydration numbers derived from different compressibility methods.

Main Methods:

  • Utilized literature data on isothermal compressibility of 23 aqueous electrolyte solutions at 25 °C.
  • Calculated hydration numbers based on isothermal compressibility.
  • Compared results with hydration numbers derived from isentropic compressibility (ultrasound speed).
  • Referenced the Brunauer-Emmett-Teller (BET) method for adsorption site determination.

Main Results:

  • Hydration numbers diminish significantly as electrolyte concentration increases.
  • The high-concentration limit of hydration numbers approximates the number of water adsorption sites on ions.
  • Hydration numbers derived from ultrasound speed (isentropic compressibility) are excessively large at infinite dilution and deemed invalid.

Conclusions:

  • Isothermal compressibility provides a valid method for determining hydration numbers in aqueous electrolytes.
  • Hydration number concentration dependence reflects changes in ion-solvation shells.
  • Isentropic compressibility measurements are not suitable for accurate hydration number determination, especially at low concentrations.