Gas-sensing electrodes are designed to monitor dissolved gases.

Typically they consist of an

internal ion-selective electrode of one of the designs previously described (usually a glass
electrode), which has a second, gas-permeable membrane wrapped around the membrane of the
internal electrode. Between the membranes is an electrolyte solution containing ions that
correspond to a reaction product of the analyte gas. For example, an ammonia-selective electrode
can be constructed by using an internal glass pH electrode and an ammonium chloride solution
between the membranes. The ammonia from the sample diffuses into the ammonium chloride
solution between the membranes and partially dissociates in the aqueous solution to form
ammonium ions and hydroxide ions. The internal pH electrode responds to the altered pH of the
solution caused by the formation of hydroxide ions.

Biomembrane electrodes are similar in design to gas-sensing electrodes. The outer permeable
membrane is used to hold a gel between the two membranes. The gel contains an enzyme that
selectively catalyzes the reaction of the analyte. The internal ion-selective electrode is chosen to
respond to one of the products of the catalyzed reaction. Internal pH electrodes are commonly
used.

Electrogravimetry
Electrogravimetry was briefly described above as an interference removal technique. This
method employs two or three electrodes, just as in voltammetry. Either a constant current or a
constant potential is applied to the preweighed working electrode. The working electrode
corresponds to the indicator electrode in voltammetry and most other electroanalytical methods.
A solid product of the electrochemical reaction of the analyte coats the electrode during
application of the electric current or potential. After the assayed substance has been completely
removed from the solution by the electrochemical reaction, the working electrode is removed,
rinsed, dried, and weighed. The increased mass of the electrode due to the presence of the
reaction product is used to calculate the initial concentration of the analyte.

Assays done by using constant-current electrogravimetry can be completed more rapidly

(typically 30 minutes per assay) than assays done by using constant-potential electrogravimetry
(typically one hour per assay), but the constant-current assays are subject to more interferences.
If only one component in the solution can react to form a deposit on the electrode, constant-
current electrogravimetry is the preferred method. In constant-potential electrogravimetry the
potential at the working electrode is controlled so that only a single electrochemical reaction can
occur. The applied potential corresponds to the potential on the plateau of a voltammetric wave
of the assayed material.

Coulometry
This technique is similar to electrogravimetry in that it can be used in the constant-current or in
the constant-potential modes. It differs from electrogravimetry, however, in that the total
quantity of electricity (coulombs) required to cause the analyte to completely react is measured
rather than the mass of the electrochemical reaction product. It is not necessary for the reaction
product to deposit on the electrode in order to perform a coulometric assay; however, it is
necessary that the current that flows through the electrode be ultimately used for a single
electrochemical reaction. This requirement can be met in constant-current coulometry by using
the current to perform a coulometric titration. In a coulometric titration, the current generates a
titrant that chemically reacts with the analyte. By keeping the precursor to the titrant in excess, it
is possible to ensure that all of the current is used to form the chemical reactant. Because the
electrochemically formed titrant reacts completely with the analyte, it is possible to perform a
quantitative analysis. Constant-potential coulometry is not subject to the effects of interferences,
because the potential of the working electrode is controlled at a value at which only a single
electrochemical reaction can occur.

Auxiliary electrode
From Wikipedia, the free encyclopedia

Jump to navigation Jump to search

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.[1][2][3] 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.

In a two-electrode system, either a known current or potential is applied between the working
and auxiliary electrodes and the other variable may be measured. The auxiliary electrode
functions as a cathode whenever the working electrode is operating as an anode and vice versa.
The auxiliary electrode often has a surface area much larger than that of the working electrode to
ensure that the half-reaction occurring at the auxiliary electrode can occur fast enough so as not
to limit the process at the working electrode.

When a three electrode cell is used to perform electroanalytical chemistry, the auxiliary
electrode, along with the working electrode, provides circuit over which current is either applied
or measured. Here, the potential of the auxiliary electrode is usually not measured and is adjusted
so as to balance the reaction occurring at the working electrode. This configuration allows the
potential of the working electrode to be measured against a known reference electrode without
compromising the stability of that reference electrode by passing current over it.

The auxiliary electrode may be isolated from the working electrode using a glass frit. Such
isolation prevents any byproducts generated at the auxiliary electrode from contaminating the
main test solution: for example, if a reduction is being performed at the working electrode in
aqueous solution, oxygen may be evolved from the auxiliary electrode. Such isolation is crucial
during the bulk electrolysis of a species which exhibits reversible redox behavior.

Auxiliary electrodes are often fabricated from electrochemically inert materials such as gold,
platinum, or carbon.