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Color profile: Generic offset separations profile

Peter T. Kissinger, Ph.D., pete@bioanalytical.com and Adrian W. Bott, Ph.D., awb@bioanalytical.com

Bioanalytical Systems, Inc., 2701 Kent Avenue, West Lafayette, Indiana 47906 USA

Electrochemistry for the Non-Electrochemist

This article discusses nine basic concepts in finite current electrochemistry.

1. Electrodes are Surfaces 2. Current is Rate case and where the rate of the
heterogeneous electron transfer
The fundamental process in Current is expressed in amperes; that is, reaction is of interest (e.g., corrosion
electrochemistry is the transfer of coulombs/second. As the word implies, electrochemistry).
electrons between the electrode surface it is a quantitative expression of how As discussed above, the electrode
and molecules in the solution adjacent fast something is happening. The surface area and reactant concentration
to the electrode surface; that is, it is a differential form of Faradays Law affect the current. Other factors that
heterogeneous process, in contrast to affect the current include the
many other measurements (e.g., NMR, temperature and the viscosity of the
UV, etc.) that typically involve solution, and it is important to ensure
homogeneous solutions in three shows that the rate at which electrons that these parameters remain constant
dimensions. Therefore, it is often useful are moved across the electrode-solution so the current is proportional to the
to consider quantities per unit area as interface (i.e., the faradaic current) is reactant concentration. This is
well as per total area. One quantity that directly related to the rate of the particularly important for quantitative
is particularly important in reaction occurring at that interface. analysis.
electrochemical experiments is current Therefore, when we measure the There are some other sources of
(i), and the current/per unit area is faradaic current, we are also measuring current in addition to the faradaic
referred to as current density the rate of a chemical reaction. This is a current due to the analyte; these are
(amps/cm2). Current density is the more unique feature of electrochemistry. collectively referred to as the
fundamental quantity, since it is Most other techniques do not provide an background current. They include the
independent of the electrode surface instantaneous measure of rate. electrolysis of impurities, the
It should be noted that there are electrolysis of the electrolyte, the
area, whereas current is proportional to
multiple steps involved in an electrolysis of the electrode material,
the electrode surface area.
Since current results from a chemical electrochemical reaction, such as the and capacitive (or charging) current.
substance dissolved in the solution electron transfer reaction, transport of The first three are faradaic currents,
adjacent to the electrode surface, it is molecules from the bulk solution to the whereas the last one is a property of the
not surprising that the probability of a electrode surface, and chemical interface between the electrode and the
molecule or ion reacting at the electrode reactions coupled to the electron solution. This interface behaves like an
surface is directly related to the transfer reaction. As with any multi- electrical capacitor in that it can store
concentration. Therefore, current step reaction, the rate of the overall charge, and (to a first approximation) it
density is directly proportional to the reaction is generally determined by the obeys the equation:
concentration, provided the electrode rate of the slowest step (the rate-
reaction does not have unusual features, determining step), and it is important to Q = CV 100

such as adsorption and dimerization. know which step is the rate-determining

(A point of nomenclature: It is step. In analytical electrochemistry of where Q is the charge stored, C is the 95

redundant to say that current flows. dissolved species, this step is typically capacitance (in farads), and V is the
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The word current is sufficient. When the transport of molecules to the potential difference across the interface.
water or a charge flows, we have electrode surface. However, there are An equation for the capacitive current
current.) many instances where this is not the (ic) can be obtained by differentiating
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the above equation: we can see the total amount of various non-aqueous and aqueous
electricity passed (Q - the charge, solutions).
measured in units of coulombs) is When the pH is higher than the pKa,
proportional to the number of moles N an acid will favor its protonated form.
When the applied potential is more
t The total current will therefore be a
of material processed by the
electrochemical reaction. negative than Eo', a redox couple will
summation of currents, including the favor the reduced form R.
faradaic currents for the analyte, the
electrolyte, and the electrode material, 4. Potential Controls the
as well as the capacitive current. All but 5. Potential Controls Rate
Position of the Equilibrium
the first of these currents are generally
undesirable, and attention must be Between O and R There are two important parameters that
given to minimizing their effects. In affect the rate of the heterogeneous
The fundamental reaction in
some cases, the background current can electron transfer reactionthe intrinsic
electrochemistry is the equilibrium
be subtracted from the total current to ability of the molecule to undergo an
between two species (O and R) that are
leave the signal of interest. However, in electron transfer reaction (as reflected
interconverted by the transfer of an
other cases, eliminating the background in the rate constant ks) and the applied
electron:
current is not so easy. In the worst cases, potential. The rate of electron transfer
the background and signal currents are increases exponentially with the
O + e- R
combined in a non-linear manner, applied potential. Therefore, we can
making it impossible to estimate When discussing the effect of the adjust the rate by varying the applied
reliably the background current in the applied potential (E) on this reaction (or potential; for example, if the intrinsic
absence of the sample. Fortunately, redox couple), a useful analogy is the rate of electron transfer for a given
such cases are rare. The capacitive acid-base equilibrium: species is slow, it can be accelerated by
current can be eliminated by operating applying a sufficiently large potential.
the electrode at a fixed potential (i.e., A- + H+ HA Relatively more positive potential will
dV/dt = 0). One application where the speed up oxidations, whereas relatively
background current can be essentially The position of the acid-base more negative potentials will speed up
eliminated is liquid chromatography equilibrium is determined by the reductions. Note that, for example, a
with electrochemical detection concentration of protons (i.e., the pH) relatively more negative potential can
(LC/EC), since a) the fixed potential which can be considered in terms of a still be positive; see #6.
eliminates the capacitive current and b) proton pressure (e.g., increasing the
the background faradaic currents can be proton pressure [decreasing the pH]
precisely measured between peaks, and moves the equilibrium to the right). 6. The Voltammetric Axes
then can be subtracted from the analyte When considering the electron transfer
signal. However, it is important to note equilibrium, we can consider an The most common format for
that the capacitive current will change analogous electron pressure which presenting electrochemical data is a
(even at a fixed potential) if the ionic determines the position of the plot of current vs. potential (i vs. E).
strength or the solvent composition equilibrium between and O and R. The However, it is important to note that
changes the bulk properties of the applied potential is a measure of there are a number of different axis
mobile phase. Such a change can be a electron pressure in the same way that conventions (F1). In the classical (or
transient disturbance; for example, at pH is a measure of proton pressure. polarographic) convention shown in
the solvent front or void volume on In both cases, there is a unique F1, negative potentials are plotted in the
a liquid chromatogram. situation in which the concentration of positive x direction, and cathodic
each form (O and R or A- and HA) is currents (due to reductions) are
equal. This occurs at the positive. In the IUPAC convention,
3. Charge is Amount potential/electron pressure Eo' in the positive potentials are plotted in the 100
former case and in the pH/proton positive x direction, and anodic currents
If we integrate a rate, we obtain an pressure pKa. These values provide a (due to oxidations) are positive. (In 95

amount. From the integrated form of convenient index of the relative strength other conventions, current is plotted
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Faradays Law, of an oxidant/reductant or acid/base. In along the x axis and/or a logarithmic
both cases, the values are medium current scale is used.) It is also vital to
dependent (i.e., they will differ among realize that the potential values are
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quoted relative to a reference potential, the large number of techniques can This falls under the general terminology
the value of which is defined by the intimidate the novice. However, it of spectroelectrochemistry. It ranges
reference electrode; that is, the zero on should be noted that the vast majority of from the UV to the IR and includes
the x-axis is quite arbitrary. Therefore, these are simple combinations of transmission as well as reflection (off
there is no significance in the absolute voltammetry and chronoamperometry. the electrode) methods. Raman
values. Different values of Eo' for a The key experimental variables in a spectroscopy of material adsorbed on
given species under identical conditions given experiment are E, i, and t. Only electrodes is used as well as a variety of
are measured for different reference one of E and i can be varied high vacuum techniques. The latter
electrodes. It should also be noted that independently, and t takes care of itself. require removal of the electrode from
there is no correlation between positive The inverse relationship between time solution (and are well beyond the scope
and negative potentials and oxidations and frequency often plays a role (e.g., of this primer).
and reductions; that is, reductions can high frequency experiments can be used
occur at positive potentials and to look at fast reactions), although data
oxidations can occur at negative from frequency domain experiments 9. The Sound of One Hand
potentials. can be more difficult to interpret. Clapping

While it is obvious once given some

7. Current, Potential and Time 8. Light thought, we should not forget that
electrochemistry with a single electrode
There are only two basic formats for The electrical measures described is like the sound of one hand clapping.
displaying experimental data: current above are not all inclusive to In other words, it is largely
vs. potential (i vs. E - voltammetry), and electrochemical experiments. For meaningless. One needs a minimum of
current vs. time (i vs. t - example, electrode reactions can result two electrodes to light a bulb or to do
chronoamperometry). (Charge plots are in emission of light electrochemistry. If a reduction
obtained by integrating current plots.) (electrochemiluminescence). Likewise, (oxidation) is occurring at the working
Since potential is often related to time light can also influence the rates and electrode, then a second electrode must
by experimental design, i vs. E mechanisms of electrochemical be present and an oxidation (reduction)
experiments also contain some features reactions (photoelectrochemistry). must be occurring there. The two
of the i vs. t experiments. Phenomena of this sort have been electrodes are needed to complete the
For historical reasons, more known since the 19th Century. Finally, circuit (using the language of high
electroanalytical techniques have been light is often used to study school physics).Yes, you can have more
developed than are really needed, and electrochemical reaction mechanisms. than two electrodes. A reference
electrode is often the third electrode, but
F1. it is also possible to have any number of
The classical (or polarographic) convention for plotting voltammetry data. working electrodes, all operating at
different applied potentials in an array.
Needless to say, this is not common.

Conclusion

It has been our intent in this article to

outline nine of the most basic concepts
of electrochemistry, since we have
found that these concepts must be
thoroughly mastered before more
advanced topics can be understood. In 100

our experience, students often become

95
confused about various issues because
these very fundamental ideas are not 75
second nature to them.

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