Linear Sweep Voltammetry

1/31/2014 Linear sweep voltammetry - Wikipedia, the free encyclopedia
Linear sweep voltammetry

From Wikipedia, the free encyclopedia
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. 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.
Contents Linear potential sweep
1 Experimental method
2 Characterization
3 Variations
4 Applications
5 See also
6 References
Experimental method
The experimental setup for linear sweep voltammetry utilizes a potentiostat and a three-electrode setup to deliver a
potential to a solution and monitor its change in current. The three-electrode setup consists of a working electrode,
an auxiliary electrode, and a reference electrode. The potentiostat delivers the potentials through the three-electrode
setup. A potential, E, is delivered through the working electrode. The slope of the potential vs. time graph is called
the scan rate and can range from mV/s to 1,000,000 V/s.[1] At higher scan rates the current is found to increase
which improves the signal to noise ratio. Therefore higher scan rates lead to better signal to noise ratios.
The working electrode is where the oxidation/reduction reactions occur. The equation below gives an example of
an oxidation occurring at the surface of the working electrode. ES is the standard reduction potential of A. As E
approaches ES the current on the surface increases and when E=ES then the concentration of [A] = [A-] at the
surface.[2] As the molecules on the surface of the working electrode or oxidized/reduced they move away from the
surface and new molecules come into contact with the surface of the working electrode. This flow of molecules to
and from the working electrode causes the current.
E_s=0.00V
Oxidation of molecule A at the surface of the working electrode
http://en.wikipedia.org/w/index.php?title=Linear_sweep_voltammetry&printable=yes 1/3
The auxiliary and reference electrode work in unison to balance out the charge added or removed by the working
electrode. The auxiliary electrode balances the working electrode, but in order to know how much potential it has
to add or remove it relies on the reference electrode. The reference electrode has a known reduction potential. The
auxiliary electrode tries to keep the reference electrode at a certain reduction potential and to do this it has to
balance the working electrode.[3]
Characterization
Linear sweep voltammetry can identify unknown species and determine the concentration of solutions. E1/2 can be
used to identify the unknown species while the height of the limiting current can determine the concentration. The
sensitivity of current changes vs. voltage can be increased by increasing the scan rate. Higher potentials per second
result in more oxidation/reduction of a species at the surface of the working electrode.
Variations
For reversible reactions cyclic voltammetry can be used to find information about the forward reaction and the
reverse reaction. Like linear sweep voltammetry, cyclic voltammetry applies a linear potential over time and at a
certain potential the potentiostat will reverse the potential applied and sweep back to the beginning point. Cyclic
voltammetry provides information about the oxidation and reduction reactions.
Applications
While cyclic voltammetry is applicable to most cases where linear sweep voltammetry is used, there are some
instances where linear sweep voltammetry is more useful. In cases where the reaction is irreversible cyclic
voltammetry will not give any additional data that linear sweep voltammetry would give us.[4] In one example,[5]
linear voltammetry was used to examine direct methane production via a biocathode. Since the production of
methane from CO2 is an irreversible reaction, cyclic voltammetry did not present any distinct advantage over linear
sweep voltammetry. This group found that the biocathode produced higher current densities than a plain carbon
cathode and that methane can be produced from a direct electrical current without the need of hydrogen gas.
See also
Cyclic voltammetry
Electroanalytical Methods
Linear Sweep Voltammetry/Cyclic Voltammetry. [Online]
http://www.basinc.com/mans/EC_epsilon/Techniques/CycVolt/cv.html.
[email protected]. Linear Sweep and Cyclic Voltametry: The Principles. Department of Chemical
Engineering and Biotechnology, University of Cambridge. [Online] http://www.ceb.cam.ac.uk/pages/linear-
sweep-and-cyclic-voltametry-the-principles.html.
References
1. ^ Tissue, Brian M. "Linear Sweep Voltammetry" (http://www.files.chem.vt.edu/chem-ed/echem/linsweep.html).
CHP.
2. ^ "Voltammetry" (http://mail.chiangmai.ac.th/~scijjkmn/voltammetry.htm). CHP.
3. ^ Kounaves, Samuel P. Voltammetric Techniques. Handbook of Instrumental Techniques for Analytical Chemistry.
pp. 709–725.
4. ^ "Instrumentation, Pine Research. Linear Sweep Voltammetry"
(http://www.voltammetry.net/pine/aftermath/echem/linear_sweep_voltammetry.). CHP. 2008.
5. ^ Logan, Bruce E. (2009). "Direct Biological Conversion of Electrical Current into Methane by
Electromethanogenesis". Environ. Sci. Technol.: 3953–3958.
Retrieved from "http://en.wikipedia.org/w/index.php?title=Linear_sweep_voltammetry&oldid=589002119"
Categories: Electroanalytical methods
This page was last modified on 3 January 2014 at 17:14.

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1/31/2014 Linear sweep voltammetry - Wikipedia, the free encyclopedia

Linear sweep voltammetry is a

Contents Linear potential sweep

Oxidation of molecule A at the surface of the working electrode

This page was last modified on 3 January 2014 at 17:14.

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