Appendix VIII B. Amperometric and Potentiomeric Titrations

In amperometric titration the end-point is determined by following the variation of the current measured between 2 electrodes (either one indicator electrode and one reference electrode or 2 indicator electrodes) immersed in the solution to be examined and maintained at a constant potential difference as a function of the quantity of titrant added.

The potential of the measuring electrode is sufficient to ensure a diffusion current for the electroactive substance.

Apparatus The apparatus comprises an adjustable voltage source and a sensitive microammeter; the detection system generally consists of an indicator electrode (for example, a platinum electrode, a dropping-mercury electrode, a rotating-disc electrode or a carbon electrode) and a reference electrode (for example, a calomel electrode or a silver-silver chloride electrode).

A three-electrode apparatus is sometimes used, consisting of an indicator electrode, a reference electrode and a polarised auxiliary electrode.

Method Set the potential of the indicator electrode as prescribed and plot a graph of the initial current and the values obtained during the titration as functions of the quantity of titrant added. Add the titrant in not fewer than 3 successive quantities equal to a total of about 80 per cent of the theoretical volume corresponding to the presumed equivalence point. The 3 values must fall on a straight line. Continue adding the titrant beyond the presumed equivalence point in not fewer than 3 successive quantities. The values obtained must fall on a straight line. The point of intersection of the 2 lines represents the end-point of the titration.

For amperometric titration with 2 indicator electrodes, the whole titration curve is recorded and used to determine the end-point.

In a potentiometric titration the end-point of the titration is determined by following the variation of the potential difference between 2 electrodes (either one indicator electrode and one reference electrode or 2 indicator electrodes) immersed in the solution to be examined as a function of the quantity of titrant added.

The potential is usually measured at zero or practically zero current.

Apparatus The apparatus used (a simple potentiometer or electronic device) comprises a voltmeter allowing readings to the nearest millivolt.

The indicator electrode to be used depends on the substance to be determined and may be a glass or metal electrode (for example, platinum, gold, silver or mercury). The reference electrode is generally a calomel or a silver-silver chloride electrode.

For acid-base titrations and unless otherwise prescribed, a glass-calomel or glass-silver-silver chloride electrode combination is used.

Method The solvent mixture is neutralised, if necessary, before dissolution of the substance to be examined. Plot a graph of the variation of potential difference as a function of the quantity of the titrant added, continuing the addition of the titrant beyond the presumed equivalence point. The end-point corresponds to a sharp variation of potential difference.

Dissolve the prescribed quantity of the substance to be examined in 50 mL of dilute hydrochloric acid R or in another prescribed solvent and add 3 g of potassium bromide R. Cool in ice-water and titrate by slowly adding 0.1 M sodium nitrite with constant stirring.

Determine the end-point electrometrically or by the use of the prescribed indicator.