Coulometric titrations are a form of titrimetric analysis where the reagent is generated electrically, and its amount is evaluated based on current and generating time. The electron serves as the standard reagent. The procedure is similar to conventional titrations, such as endpoint detection.

The fundamental requirements for coulometric titrations are (1) 100% efficiency in the reagent-generating electrode reaction and (2) a stoichiometric and preferably rapid reaction between the generated reagent and the determined substance. The reagent can be generated directly within the test solution or externally in a separate solution.

Coulometric titrimetry offers several advantages, including high sensitivity due to the accurate measurement of small quantities of electricity. Moreover, it does not require standard solutions, can utilize unstable reagents, allows the generation of small amounts of titrants, avoids sample dilution, provides more accurate results through pre-titration, and is adaptable to remote and automatic control.

Coulometric titrators require a constant current source and an integrator to measure the product of current and time. The titration cell typically consists of a beaker, generator, auxiliary, and indicator electrodes.

General procedures for coulometric titrations involve setting up the electrolysis cell with generator and indicator electrodes, charging the cell with the test solution, adjusting the current, and allowing the reaction to proceed. The endpoint of the titration is evaluated based on the current change during titration. The auxiliary or counter electrode, which completes the electrical circuit, remains isolated from the bulk solution to prevent contamination. The reagent is sometimes generated externally before being added to the titration vessel.

Endpoints in coulometric titrations can be detected using chemical indicators, potentiometric observations, or amperometric procedures. These methods rely on establishing conditions that cause either the substance being determined or the titrant to react at an indicator electrode, producing a current proportional to the concentration of the electro-active substance.

Limitations of coulometric titration with the internal generation of the titrant include the presence of substances that may react at the generator electrodes and difficulties locating the equivalence point by amperometric methods for macro-scale samples. These limitations can be overcome by externally generating the reagent at a constant current with 100% efficiency in an external generator cell, which is then delivered to the titration cell. Despite its minor disadvantage of diluting the titration cell contents, this procedure is well-suited for automatic control and determination of substances present in small amounts.