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Coulometric titration generates the standard reagent electrolytically using a constant current, whereas conventional titrations use pre-made standard solutions. The amount of analyte is calculated from the current and time required for titration rather than from solution volume. This eliminates the need for standard solutions and allows use of unstable reagents that cannot be stored.

The galvanostat provides the regulated constant current essential for coulometric titration. It ensures that the working electrode generates the standard reagent at a consistent rate, maintaining 100% current efficiency. This controlled current delivery is critical for accurate calculation of analyte quantity based on the time required to reach the endpoint.

The auxiliary or counter electrode is isolated from the bulk solution to prevent its reaction products from interfering with the titration. Isolation ensures that only the generated reagent from the working electrode reacts with the analyte, maintaining the accuracy and specificity of the measurement throughout the titration process.

Coulometric titration offers high sensitivity through accurate measurement of small electrical quantities, eliminates the need for standard solutions, permits use of unstable reagents, generates small titrant amounts on-demand, avoids sample dilution, and provides more accurate results through pre-titration. It is also adaptable to remote and automatic control, making it ideal for routine analysis.

Endpoints are detected using chemical indicators, potentiometric observations, or amperometric procedures. These methods establish conditions where either the analyte or titrant reacts at an indicator electrode, producing a current proportional to the electro-active substance concentration. The endpoint corresponds to when the generated reagent completely reacts with the analyte.

External reagent generation produces the standard reagent in an isolated generation cell at constant current with 100% efficiency, then delivers it to the titration cell. This approach overcomes limitations of internal generation, such as interference from substances reacting at generator electrodes and difficulties locating equivalence points. It is well-suited for automatic control and determining substances in small amounts.

Coulometric titration requires 100% efficiency in the reagent-generating electrode reaction and a stoichiometric, preferably rapid reaction between the generated reagent and the analyte. These requirements ensure that all electrical charge is converted to reagent and that the titration proceeds predictably, allowing accurate calculation of analyte quantity from current and time measurements.