Titration, potentiometric with irreversible electrodes

Another specialized form of potentiometric endpoint detection is the use of dual-polarized electrodes, which consists of two metal pieces of electrode material, usually platinum, through which is imposed a small constant current, usually 2-10 /xA. The scheme of the electric circuit for this kind of titration is presented in Figure 4.1b. The differential potential created by the imposition of the ament is a function of the redox couples present in the titration solution. Examples of the resultant titration curve for three different systems are illustrated in Figure 4.3. In the case of two reversible couples, such as the titration of iron(II) with cerium(IV), curve a results in which there is little potential difference after initiation of the titration up to the equivalence point. Hie titration of arsenic(III) with iodine is representative of an irreversible couple that is titrated with a reversible system. Hence, prior to the equivalence point a large potential difference exists because the passage of current requires decomposition of the solvent for the cathode reaction (Figure 4.3b). Past the equivalence point the potential difference drops to zero because of the presence of both iodine and iodide ion. In contrast, when a reversible couple is titrated with an irreversible couple, the initial potential difference is equal to zero and the large potential difference appears after the equivalence point is reached. 

Nicholson proposed a differential potentiometric tltrator involving two indicator electrodes for the automatic control of processes in industrial plants [35]. As can be seen from Fig. 7.20, the sample and reagent streams are split and led to two half-cells via capillary tubes adjusted to provide slightly different titrated fractions. The potential difference (AE) between the two indicator electrodes Is transmitted to a control and detection system (D) which regulates the flow of titrant in an automatic fashion by means of valve V, thereby maintaining the preselected AE between the two ends of the cell. The speed of titrant addition, reflected by the flow meter (M), is a measure of the sample composition. An evaluation of the instrument carried out by the titration of dichromate with iron(II) revealed that the conditions to be used must be carefully selected. Thus, stable electrode responses are only obtained in the zone where Fe(II) prevails, and not in that where dichromate prevails over the former as the process determining the potential obtained in such a zone is irreversible. This method therefore has limited application in the control of slow reactions. 

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