Amperometric titration refers to a class of

titration Titration (also known as titrimetry and volumetric analysis) is a common laboratory method of quantitative chemical analysis to determine the concentration of an identified analyte (a substance to be analyzed). A reagent, termed the ''titrant ...

s in which the

equivalence point The equivalence point, or stoichiometric point, of a chemical reaction is the point at which chemically equivalent quantities of reactants have been mixed. For an acid-base reaction the equivalence point is where the moles of acid and the moles o ...

is determined through measurement of the

electric current An electric current is a stream of charged particles, such as electrons or ions, moving through an electrical conductor or space. It is measured as the net rate of flow of electric charge through a surface or into a control volume. The movin ...

produced by the titration reaction. It is a form of

quantitative analysis Quantitative analysis may refer to: * Quantitative research, application of mathematics and statistics in economics and marketing * Quantitative analysis (chemistry), the determination of the absolute or relative abundance of one or more substanc ...

Background

A solution containing the analyte, A, in the presence of some conductive buffer. If an electrolytic potential is applied to the solution through a working electrode, then the measured current depends (in part) on the concentration of the analyte. Measurement of this current can be used to determine the concentration of the analyte directly; this is a form of

amperometry Amperometry in chemistry is detection of ions in a solution based on electric current or changes in electric current. Amperometry is used in electrophysiology to study vesicle release events using a carbon fiber electrode. Unlike patch clamp t ...

. However, the difficulty is that the measured current depends on several other variables, and it is not always possible to control all of them adequately. This limits the precision of direct amperometry. If the potential applied to the working electrode is sufficient to reduce the analyte, then the concentration of analyte close to the working electrode will decrease. More of the analyte will slowly

diffuse Diffusion is the net movement of anything (for example, atoms, ions, molecules, energy) generally from a region of higher concentration to a region of lower concentration. Diffusion is driven by a gradient in Gibbs free energy or chemical p ...

into the volume of solution close to the working electrode, restoring the concentration. If the potential applied to the working electrode is great enough (an

overpotential In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's thermodynamically determined reduction potential and the potential at which the redox event is experimentally observed. The term is directly relat ...

), then the concentration of analyte next to the working electrode will depend entirely on the rate of diffusion. In such a case, the current is said to be ''diffusion limited''. As the analyte is reduced at the working electrode, the concentration of the analyte in the whole solution will very slowly decrease; this depends on the size of the working electrode compared to the volume of the solution. What happens if some other species which reacts with the analyte (the titrant) is added? (For instance, chromate ions can be added to oxidize lead ions.) After a small quantity of the titrant (chromate) is added, the concentration of the analyte (lead) has decreased due to the reaction with chromate. The current from the reduction of lead ion at the working electrode will decrease. The addition is repeated, and the current decreases again. A plot of the current against volume of added titrant will be a straight line. After enough titrant has been added to react completely with the analyte, the excess titrant may itself be reduced at the working electrode. Since this is a different species with different diffusion characteristics (and different

half-reaction A half reaction (or half-cell reaction) is either the oxidation or reduction reaction component of a redox reaction. A half reaction is obtained by considering the change in oxidation states of individual substances involved in the redox reaction. ...

), the slope of current versus added titrant will have a different slope after the equivalence point. This change in slope marks the equivalence point, in the same way that, for instance, the sudden change in pH marks the equivalence point in an

acid–base titration An acid–base titration is a method of quantitative analysis for determining the concentration of an acid or base by exactly neutralizing it with a standard solution of base or acid having known concentration. A pH indicator is used to monito ...

. The electrode potential may also be chosen such that the titrant is reduced, but the analyte is not. In this case, the presence of excess titrant is easily detected by the increase in current above background (charging) current.

Advantages

The chief advantage over direct amperometry is that the magnitude of the measured current is of interest only as an indicator. Thus, factors that are of critical importance to quantitative amperometry, such as the surface area of the working electrode, completely disappear from amperometric titrations. The chief advantage over other types of titration is the selectivity offered by the electrode potential, as well as by the choice of titrant. For instance, lead ion is reduced at a potential of -0.60 V (relative to the saturated calomel electrode), while zinc ions are not; this allows the determination of lead in the presence of zinc. Clearly this advantage depends entirely on the other species present in the sample.

References

* * {{Electroanalytical Electroanalytical methods Titration

Background

Advantages

See also

References