Auxiliary electrodeIn electrochemistry, the auxiliary electrode, often also called the counter electrode, is an electrode used in a three-electrode electrochemical cell for voltammetric analysis or other reactions in which an electric current is expected to flow. The auxiliary electrode is distinct from the reference electrode, which establishes the electrical potential against which other potentials may be measured, and the working electrode, at which the cell reaction takes place.
Electrochemical reaction mechanismIn electrochemistry, an electrochemical reaction mechanism is the step-by-step sequence of elementary steps, involving at least one outer-sphere electron transfer, by which an overall electrochemical reaction occurs. Elementary steps like proton coupled electron transfer and the movement of electrons between an electrode and substrate are special to electrochemical processes.
Hydrodynamic voltammetryIn analytical chemistry, hydrodynamic voltammetry is a form of voltammetry in which the analyte solution flows relative to a working electrode. In many voltammetry techniques, the solution is intentionally left still to allow diffusion-controlled mass transfer. When a solution is made to flow, through stirring or some other physical mechanism, it is very important to the technique to achieve a very controlled flux or mass transfer in order to obtain predictable results.
PolarographyPolarography is a type of voltammetry where the working electrode is a dropping mercury electrode (DME) or a static mercury drop electrode (SMDE), which are useful for their wide cathodic ranges and renewable surfaces. It was invented in 1922 by Czech chemist Jaroslav Heyrovský, for which he won the Nobel prize in 1959. The main advantages of mercury as electrode material are as follows: 1) a large voltage window: ca. from +0.2 V to -1.8 V vs reversible hydrogen electrode (RHE).
Reference electrodeA reference electrode is an electrode that has a stable and well-known electrode potential. The overall chemical reaction taking place in a cell is made up of two independent half-reactions, which describe chemical changes at the two electrodes. To focus on the reaction at the working electrode, the reference electrode is standardized with constant (buffered or saturated) concentrations of each participant of the redox reaction. There are many ways reference electrodes are used.
Nernst equationIn electrochemistry, the Nernst equation is a chemical thermodynamical relationship that permits the calculation of the reduction potential of a reaction (half-cell or full cell reaction) from the standard electrode potential, absolute temperature, the number of electrons involved in the redox reaction, and activities (often approximated by concentrations) of the chemical species undergoing reduction and oxidation respectively. It was named after Walther Nernst, a German physical chemist who formulated the equation.
Cottrell equationIn electrochemistry, the Cottrell equation describes the change in electric current with respect to time in a controlled potential experiment, such as chronoamperometry. Specifically it describes the current response when the potential is a step function in time. It was derived by Frederick Gardner Cottrell in 1903. For a simple redox event, such as the ferrocene/ferrocenium couple, the current measured depends on the rate at which the analyte diffuses to the electrode. That is, the current is said to be "diffusion controlled".
OverpotentialIn 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 related to a cell's voltage efficiency. In an electrolytic cell the existence of overpotential implies that the cell requires more energy than thermodynamically expected to drive a reaction. In a galvanic cell the existence of overpotential means less energy is recovered than thermodynamics predicts.
