Voltammetry is a category of electroanalytical methods used in analytical chemistry and various industrial processes. In voltammetry, information about an analyte is obtained by measuring the current as the potential is varied.
Three electrodes system
Voltammetry experiments investigate the half cell reactivity of an analyte. Voltammetry is the study of current as a function of applied potential. These curves I = f(E) are called voltammograms. The potential is varied arbitrarily either step by step or continuously, and the actual current value is measured as the dependent variable. The opposite, i.e., amperometry, is also possible but not common. The shape of the curves depends on the speed of potential variation (nature of driving force) and on whether the solution is stirred or quiescent (mass transfer). Most experiments control the potential (volts) of an electrode in contact with the analyte while measuring the resulting current (amperes).
To conduct such an experiment one requires at least two electrodes. The working electrode, which makes contact with the analyte, must apply the desired potential in a controlled way and facilitate the transfer of charge to and from the analyte. A second electrode acts as the other half of the cell. This second electrode must have a known potential with which to gauge the potential of the working electrode, furthermore it must balance the charge added or removed by the working electrode. While this is a viable setup, it has a number of shortcomings. Most significantly, it is extremely difficult for an electrode to maintain a constant potential while passing current to counter redox events at the working electrode.
To solve this problem, the roles of supplying electrons and providing a reference potential are divided between two separate electrodes. The reference electrode is a half cell with a known reduction potential. Its only role is to act as reference in measuring and controlling the working electrode's potential and at no point does it pass any current. The auxiliary electrode passes all the current needed to balance the current observed at the working electrode. To achieve this current, the auxiliary will often swing to extreme potentials at the edges of the solvent window, where it oxidizes or reduces the solvent or supporting electrolyte. These electrodes, the working, reference, and auxiliary make up the modern three electrode system.
There are many systems which have more electrodes, but their design principles are generally the same as the three electrode system. For example, the rotating ring-disk electrode has two distinct and separate working electrodes, a disk and a ring, which can be used to scan or hold potentials independently of each other. Both of these electrodes are balanced by a single reference and auxiliary combination for an overall four electrode design. More complicated experiments may add working electrodes as required and at times reference or auxiliary electrodes.
In practice it can be very important to have a working electrode with known dimensions and surface characteristics. As a result, it is common to clean and polish working electrodes regularly. The auxiliary electrode can be almost anything as long as it doesn't react with the bulk of the analyte solution and conducts well. It is (or was?) common to use mercury as working electrode e.g. DME and HMDE, and also as auxilliary, and the voltammetry method is then known as polarography. The reference is the most complex of the three electrodes; there are a variety of standards used and it is worth investigating elsewhere. For non-aqueous work, IUPAC recommends the use of the ferrocene/ferrocenium couple as an internal standard. In most voltammetry experiments, a bulk electrolyte (also known as a supporting electrolyte) is used to minimize solution resistance. It is possible to run an experiment without a bulk electrolyte, but the added resistance greatly reduces the accuracy of the results. With room temperature ionic liquids, the solvent can act as the electrolyte.
Data analysis requires the consideration of kinetics in addition to thermodynamics, due to the temporal component of voltammetry. Idealized theoretical electrochemical thermodynamic relationships such as the Nernst equation are modeled without a time component. While these models are insufficient alone to describe the dynamic aspects of voltammetry, models like the Tafel equation and Butler-Volmer equation lay the groundwork for the modified voltammetry relationships that relate theory to observed results.
Types of voltammetry
- Linear sweep voltammetry
- Staircase voltammetry
- Squarewave voltammetry
- Cyclic voltammetry - A voltammetric method that can be used to determine diffusion coefficients and half cell reduction potentials.
- Anodic stripping voltammetry - A quantitative, analytical method for trace analysis of metal cations. The analyte is deposited (electroplated) onto the working electrode during a deposition step, and then oxidized during the stripping step. The current is measured during the stripping step.
- Cathodic stripping voltammetry - A quantitative, analytical method for trace analysis of anions. A positive potential is applied, oxidizing the mercury electrode and forming insoluble precipitates of the anions. A negative potential then reduces (strips) the deposited film into solution.
- Adsorptive stripping voltammetry - A quantitative, analytical method for trace analysis. The analyte is deposited simply by adsorption on the electrode surface (i.e., no electrolysis), then electrolyzed to give the analytical signal. Chemically modified electrodes are often used.
- Alternating current voltammetry
- Polarography - a subclass of voltammetry where the working electrode is a dropping mercury electrode (DME), useful for its wide cathodic range and renewable surface.
- Rotated electrode voltammetry - A hydrodynamic technique in which the working electrode, usually a rotating disk electrode (RDE) or rotating ring-disk electrode (RRDE), is rotated at a very high rate. This technique is useful for studying the kinetics and electrochemical reaction mechanism for a half reaction.
- Normal pulse voltammetry
- Differential pulse voltammetry
The beginning of voltammetry was facilitated by the discovery of polarography in 1922 by the Nobel Prize–winning chemist Jaroslav Heyrovský. Early voltammetric techniques had many problems, limiting their viability for everyday use in analytical chemistry. In 1942 Hickling built the first three electrodes potentiostat. The 1960s and 1970s saw many advances in the theory, instrumentation, and the introduction of computer added and controlled systems. These advancements improved sensitivity and created new analytical methods. Industry responded with the production of cheaper potentiostat, electrodes, and cells that could be effectively used in routine analytical work.
Voltammetric sensors A number of voltammetric systems are produced commercially for the determination of specific species that are of interest in industry and research. These devices are sometimes called electrodes but are, in fact, complete voltammetric cells and are better referred to as sensors. These sensors can be employed for the analysis of various organic and inorganic analytes in various matrices.      
The oxygen electrode The determination of dissolved oxygen in a variety of aqueous environments, such as sea water, blood, sewage, effluents from chemical plants, and soils is of tremendous importance to industry, biomedical and environmental research, and clinical medicine. One of the most common and convenient methods for making such measurements is with the Clark oxygen sensor, which was patented by L.C. Clark, Jr. in 1956.
- Electroanalytical method
- Cyclic voltammetry
- Working electrode
- Reference electrode
- Auxiliary electrode
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