A.

Electrochemical Cells
1. Defining the cell
The voltammetric methods we have described thus far involve the application of a potential from an external power source to a
working electrode (WE) relative to that of a reference electrode (RE), and the measurement of current that flows as a result of
that applied potential. In most instances, the electrochemical cell in which this process is carried out involves a solid working
electrode immersed in a solution of charged electrolyte along with a reference half-cell of fixed composition.
As was discussed in the Electrochemical thermodynamics section of this module, current passing in the cell as a result of
applied potential can be of two basic types:
1. nonfaradaic, in which a change in the potential at the WE causes a rearrangement of electrolyte charges at each
electrode/solution interface to counter the charge at the electrode surface;
2. faradaic, in which electrons are transferred across the electrode/solution interface to a solution species which is either
oxidized or reduced.
The two-electrode cell shown in Figure 32 is suitable as long as very little current passes during the experiment. This is the
case for very low concentration solutions, or for very small working electrode dimensions (ultramicroelectrodes). In most
practical applications, however, the circuit is designed to include a third electrode called the auxiliary electrode (AE). The
device applying the potential and measuring the current (the potentiostat) electronically isolates the reference electrode so that
little or no current passes through it, while allowing current to pass through the working and auxiliary electrodes. In this way,
the activities of the reference half-cell components and thus the reference potential are prevented from changing during the
experiment (a desirable characteristic!). The potentiostat will be discussed in a later section.

Figure 32

2. Positioning of the electrodes

For the remainder of our discussion, we will consider only the three-electrode electrochemical cell. The primary consideration
for the relative location of the three electrodes in a cell is the minimization of the solution resistance. This is most usually
accomplished by keeping the tips of the three electrodes as close together as feasible, while not interfering with the current
paths between one another. Close approach is especially critical for the reference and working electrodes. The solution
resistance between these electrodes leads to an iR drop that manifests itself as an error in the measured potential difference
between them. In addition, the potentiostat is normally unable to electronically compensate for this resistance, as it can for the
resistance between the reference electrode and the auxiliary electrode. A Luggin capillary arrangement is often employed, in
which the RE is placed inside a tube drawn at the end to a fine capillary allowing very close positioning relative to the WE.
A second important consideration involves the shape and size of the auxiliary electrode relative to the working electrode. The
AE should be at least as large in area as the WE, and positioned symmetrically with respect to the WE so that the current
density and potential experienced along its entire length is constant.

5/13/2021 1 https://chem.libretexts.org/@go/page/61541
In most voltammetric experiments, the three electrodes can be placed together in the same solution. Under certain conditions,
however, either the AE or the RE (or both) may need to be physically isolated from the solution containing the WE. For
example, if the goal of the experiment is the total electrochemical conversion of the bulk electroactive material to product
(bulk electrolysis), products produced at the AE may be detrimental to the reaction occurring at the WE. Other times, small
amounts of leakage of RE components, like Ag+ or even water from a Ag/AgCl reference, may cause undesirable reactions in
the electrolyis solution, especially in experiments that involve non aqueous solvents. These problems can generally be avoided
by the use of a glass frit or Vycor membrane (which allow charge to pass but not mixing of electrolyte) to separate the
compartments of the electrochemical cell.

3. Other considerations
Most experiments require that dissolved oxygen be removed from the cell. Not only is it electrochemically active across the
cathodic potential range, it is very likely to react with products formed by electron transfer. Typically, the solution is sparged
with an inert gas like nitrogen or argon for 5 – 10 minutes prior to the experiment, and a “blanket” of inert gas maintained
above the solution during the experiment.
Cell volumes are quite variable and range from microliters to many mL, depending upon the goal of the experiment. Designs
for cells can be quite simple – a glass vial with a screw cap drilled with holes for each electrode – to quite complex, requiring
significant glass-blowing and/or machining skills. Cells are available from numerous electrochemical suppliers, some with
very specific applications.
Two common cell configurations for quiescent solution voltammetry are shown in Figure 33. On the left, the AE has been
fashioned to be symmetrical to the WE. At right, a cell is shown with RE isolated from the solution containing the WE using a
Luggin capillary. The AE is also isolated in a fritted compartment. Both cells have a fritted sparge tube to allow
deoxygentation of the solution with inert gas.

Figure 33

5/13/2021 2 https://chem.libretexts.org/@go/page/61541