Squarewave voltammetry
Encyclopedia
Squarewave voltammetry (SWV) is a further improvement of staircase voltammetry
Staircase voltammetry
Staircase voltammetry is a derivative of linear sweep voltammetry. In linear sweep voltammetry the current at a working electrode is measured while the potential between the working electrode and a reference electrode is swept linearly in time...

 which is itself a derivative of linear sweep voltammetry
Linear sweep voltammetry
Linear sweep voltammetry is a voltammetric method where the current at a working electrode is measured while the potential between the working electrode and a reference electrode is swept linearly in time...

. In linear sweep voltammetry the current at a working electrode
Working electrode
The working electrode is the electrode in an electrochemical system on which the reaction of interest is occurring. The working electrode is often used in conjunction with an auxiliary electrode, and a reference electrode in a three electrode system...

 is measured while the potential between the working electrode and a reference electrode
Reference electrode
A reference electrode is an electrode which has a stable and well-known electrode potential. The high stability of the electrode potential is usually reached by employing a redox system with constant concentrations of each participants of the redox reaction.There are many ways reference...

 is swept linearly in time. In squarewave voltammetry, a squarewave is superimposed on the potential staircase sweep. Oxidation or reduction of species is registered as a peak or trough in the current signal at the potential at which the species begins to be oxidized or reduced. In staircase voltammetry the potential sweep is a series of stair steps. The current is measured at the end of each potential change, right before the next, so that the contribution to the current signal from the capacitive charging current is minimized. The differential
Differential
-Mathematics:* Differential comprises multiple related meanings of the word, both in calculus and differential geometry, such as an infinitesimal change in the value of a function* Differential algebra* Differential calculus...

current is then plotted as a function of potential, and the reduction or oxidation of species is measured as a peak or trough. Due to the lesser contribution of capacitative charging current the detection limits for SWV are on the order of nanomolar concentrations.
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