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Autoprotolysis constants by coulometric titration.

S Głab¹, A Hulanicki

¹Department of Chemistry, University of Warsaw, Poland.

|March 1, 1981

Summary

This study presents a coulometric titration method for determining autoprotolysis constants in solvents like water and alcohols. The technique utilizes coulometrically generated base for accurate measurements, offering improved results with a single-compartment cell.

Area of Science:

Electrochemistry
Physical Chemistry
Analytical Chemistry

Background:

Autoprotolysis constants are crucial for understanding solvent properties and acid-base behavior.
Accurate determination of these constants is essential for various chemical applications.
Existing methods may have limitations in precision or applicability across different solvents.

Purpose of the Study:

To develop and validate a precise procedure for evaluating autoprotolysis constants.
To compare the efficacy of single-compartment versus two-compartment cells in coulometric titrations.
To determine autoprotolysis constants for ethylene glycol, methanol, and water using the described method.

Main Methods:

Titration of a strong acid with coulometrically generated strong base.

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Utilizing a two-compartment electrochemical cell for general applicability.

Employing a single-compartment cell with a silver auxiliary electrode for potentially higher accuracy, particularly in bromide-containing solutions.

Main Results:

The procedure successfully determined autoprotolysis constants in ethylene glycol, methanol, and water.
Results obtained were in reasonable agreement with existing literature values.
The single-compartment cell approach demonstrated potential for reducing errors associated with diaphragm diffusion.

Conclusions:

Coulometric generation of base provides a reliable method for autoprotolysis constant determination.
The choice of cell design (single vs. two-compartment) can impact measurement accuracy.
The validated method offers a valuable tool for characterizing solvent autoionization.