Amperometric titrations

The main techniques employed in quantitative analysis are based upon (a) the quantitative performance of suitable chemical reactions and either measuring the amount of reagent needed to complete the reaction, or ascertaining the amount of reaction product obtained (b) appropriate electrical measurements (e.g. potentiometry) (c) the measurement of certain optical properties (e.g. absorption spectra). In some cases, a combination of optical or electrical measurements and quantitative chemical reaction (e.g. amperometric titration) may be used. 

In cases where it proves impossible to find a suitable indicator (and this will occur when dealing with strongly coloured solutions) then titration may be possible by an electrometric method such as conductimetric, potentiometric or amperometric titration see Chapters 13-16. In some instances, spectrophotometric titration (Chapter 17) may be feasible. It should also be noted that ifit is possible to work in a non-aqueous solution rather than in water, then acidic and basic properties may be altered according to the solvent chosen, and titrations which are difficult in aqueous solution may then become easy to perform. This procedure is widely used for the analysis of organic materials but is of very limited application with inorganic substances and is discussed in Sections 10.19-10.21. 

A selection of coulometric titrations of different types is collected in Table 14.2. It may be noted that the Karl Fischer method for determining water was first developed as an amperometric titration procedure (Section 16.35), but modern instrumentation treats it as a coulometric procedure with electrolytic generation of I2. The reagents referred to in the table are generated at a platinum cathode unless otherwise indicated in the Notes. 

Amperometry refers to measurement of current under a constant applied voltage and under these conditions it is the concentration of the analyte which determines the magnitude of the current. Such measurements may be used to follow the change in concentration of a given ion during a titration, and thus to fix the end point this procedure is referred to as amperometric titration. 

Titrations can be carried out in cases in which the solubility relations are such that potentiometric or visual indicator methods are unsatisfactory for example, when the reaction product is markedly soluble (precipitation titration) or appreciably hydrolysed (acid-base titration). This is because the readings near the equivalence point have no special significance in amperometric titrations. Readings are recorded in regions where there is excess of titrant, or of reagent, at which points the solubility or hydrolysis is suppressed by the Mass Action effect the point of intersection of these lines gives the equivalence point. 

A number of amperometric titrations can be carried out at dilutions (ca 10-4M) at which many visual or potentiometric titrations no longer yield accurate results. 

TECHNIQUE OF AMPEROMETRIC TITRATIONS WITH THE OROPPING MERCURY ELECTROOE 16.24... 

Both lead ion and dichromate ion yield a diffusion current at an applied potential to a dropping mercury electrode of —1.0 volt against the saturated calomel electrode (S.C.E.). Amperometric titration gives a V-shaped curve [Fig. 16.14 (C)]. The exercise described refers to the determination of lead in lead nitrate the application to the determination of lead in dilute aqueous solutions (10-3 — 10-4lVf) is self-evident. 

It may be noted that it is not always necessary to use a D.M.E. when performing an amperometric titration in some cases a graphite rod may be used. Use of a platinum electrode is considered in Section 16.28. 

EXAMPLES OF AMPEROMETRIC TITRATIONS USING A SINGLE POLARISED ELECTRODE... 

Amperometric titrations involving chelates and chelating agents. J. Dolezal, K. Stulik and J. Zyka, Chelates Anal. Chem., 1972, 3, 57-150 (300). 

A second method which is now probably the most widely used method in the Pediatric Laboratory is to use amperometric titration. In this connection, a constant current flows through the solution. The silver dissolves and reacts stolchlometrlcally with chloride, precipitating silver chloride. When all of the chloride has reacted, there is a sharp increase in conductivity which is read as an end point. This instrument, therefore, measures the amount of time a current flows. Instruments are now available for which 5 microliters can be used routinely, rapidly, titration being of the order of about 20 seconds. 

As a microanalytical tool the method of amperometric titraTion is the most reproducible and is the method of oice for the Laboratory of Neonatology, for the analysis of chloride. 

Hence the slope of the plot of log[S] against log[M] must equal Cs-The concentration [S] of unreacted mercaptan regulator may be determined by amperometric titration with silver nitrate,or the combined sulfur in the polymer may be determined radiochemically using mercaptan containing S, and the unreacted mercaptan concentration [S] calculated by difference. Transfer constants for carbon... 

Polarisation titrations are often referred to as amper-ometric or biamperometric titrations. It is necessary that one of the substances involved in the titration reaction be oxidisable or reducible at the working electrode surface. In general, the polarisation titration method is applicable to oxidation-reduction, precipitation and complex-ation titrations. Relatively few applications involving acid/base titration are found. Amperometric titrations can be applied in the determination of analyte solutions as low as ICE5 M to 10-6 M in concentration. 

For a rotating wire electrode see under amperometric titrations. 

In a wider sense the subject of voltammetric titration would include the polarographic mode as a type of amperometric titration however, we have already treated this in Section 3.3.1.3, because we prefer to use the term voltammetric titration in the strict sense, i.e., for faradaic non-polarographic titration techniques, a survey of which is given in Table 3.3. 

Most successful is a rotating Pt wire microelectrode as illustrated in Fig. 3.75 as a consequence of the rotation, which should be of a constant speed, the steady state is quickly attained and the diffusion layer thickness appreciably reduced, thus raising the limiting current (proportional to the rotation speed to the 1/3 power above 200 rpm140 and 15-20-fold in comparison with a dme) and as a result considerably improving the sensitivity of the amperometric- titration. 

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