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Home  Blog  The Significance of Half-Wave Potential in Cyclic Voltammetry

The Significance of Half-Wave Potential

in Cyclic Voltammetry
 CADENCE PCB SOLUTIONS

Key Takeaways

The half-wave potential in cyclic voltammetry is like a fingerprint for specific

electrochemical reactions.

The half-wave potential can be easily seen by looking at the center point between two
peaks in a cyclic voltammetry sweep curve.

The half-wave potential can be examined visually on a graph, or it can be extracted from
voltage measurements using a simple peak finding algorithm.

Electrochemical measurements are needed for battery design, industrial monitoring, and
scientific research.
Electrochemistry is all around us and it’s responsible for many of the things that make
modern life possible. Whether you’re designing batteries, charging systems, monitoring
systems, or just a potentiostat, you should know what the half-wave potential is and why it is
important. In fact, the half-wave potential will tell you some important information about your
electrochemical reaction, especially in complex reactions involving multiple reactants and
products.
If you need to use cyclic voltammetry for design and analysis, the half-wave potential is just
one of many things to examine in a cyclic voltammetry sweep. When automating monitoring
or measurement activities, or when you’re designing a testing system, pay attention to the
nature of the reaction so that your system can get the most accurate measurements. Here’s
what you need to know about the half-wave potential and how to design your
electrochemical system for measurement and testing.

What is Half-Wave Potential?

The half-wave potential can be seen in a cyclic voltammetry plot. When scanning the
potential applied to an electrochemical cell, the current from the reaction will follow two
different curves, depending on the scan direction. As the applied potential is scanned, the
current will reach a peak value and then fall back to low saturation value at extreme
potentials. The half-wave potential is located right between the two peak potential values in a
back-and-forth cyclic voltammetry sweep curve. This is shown in the graph below; the two
red lines show the peak potential values, and the dashed purple line shows the half-wave
potential.

Cyclic voltammogram showing the half-wave potential in a back-and-forth potential sweep

The image above is shown using the US convention, i.e., Ep1 corresponds to oxidation at the
anode and Ep2 corresponds to reduction at the cathode. When the applied potential is equal
to the half-wave potential, the total current is equal to one-half the diffusion current in the
solution. The above potential values on the x-axis are measured with respect to some
reference. Textbooks most commonly quote these values with respect to a standard calomel
electrode (SCE), although Ag/AgCl or standard hydrogen electrodes (SHE) are also used as
references.
There are many textbooks that contain lists of half-wave potentials for various reactions.
These reactions are normally specified under particular conditions. In general, the half-wave
potential and the current are affected by the following factors in an electrochemical cell:
 Supporting electrolyte: The species and concentration will affect the half-wave potential.

Environmental conditions: Temperature will determine the rate constant for the reaction,
which will also influence the half-wave potential.

Reactants/products: The half-wave potential and the measured current are proportional
to the type of reactants and products, concentration in the cell, and the electrochemical
reaction order.

Valence states and chemical structure: These two factors will also influence the half-
wave potential measured in the cell.

Because of these factors, half-wave potential measurements in electrochemical cells can be

used to determine specific analyte concentrations, reaction rates, and valence states by
comparing the measurements with some well-known reference. It’s important to understand
exactly what is being measured in these applications as part of designing an electrochemical
system.

Designing for Current Measurements in Electrochemical

Monitoring
When monitoring an electrochemical cell, the relevant quantity to be measured is the total
current flowing in the cell. This imposes some particular design requirements for these
systems:

Low current measurement

Controllable potential source

Additional input terminal for a reference electrode

ADC required for quantifying measured current

Temperature measurement for correcting or comparing with values at STP

MCU for controlling system components and implementing a simple peak-finding

algorithm

Data storage in memory (Flash or RAM)

In this type of modern electrochemical measurement system, everything can be controlled

with the microcontroller, which could also interface with a keypad or touch screen for
displaying data. These systems can also be designed to connect to a computer through a
GPIB connection, where data can be displayed on a graph in real-time. The main task of this
system is to collect a current measurement, which can be done with an op-amp circuit.
Current Measurement Setup
The block diagram below shows the measurement setup used to collect current from the
electrochemical cell. This simple circuit uses a basic op-amp and BJT, and it can be used in a
standard 3-electrode cell.
 Current measurement circuit for an electrochemical cell in cyclic voltammetry
This amplification stage will accept current from the cell and output a voltage that can be
read with an ADC. The above circuit could be improved by adding additional filtration on the
electrode terminals.
Electrical Simulations
Before you complete your PCB layout for your monitoring or measurement system, it helps to
build out standard circuit models for electrochemical cells and use these in a circuit
simulator. The goal in using a circuit simulator during design is to assess signal behavior and
the potential/current measurements one would expect to see in the cell. In addition, you can
see the real current that would reach your measurement amplifier input, which will help you
optimize your amplifier stage for accurate cell impedance measurements.

When you’re designing a system to measure the half-wave potential of an electrochemical

cell, you’ll need the best PCB design and analysis software to support your electronics. The
Allegro PCB Designer application from Cadence includes a complete set of PCB design and
layout features that integrate with simulation and modeling tools. You’ll have a complete set
of design features for building and optimizing your next electrochemical system.

If you’re looking to learn more about how Cadence has the solution for you, talk to us and our
team of experts.

About the Author

Cadence PCB solutions is a complete front to back design tool to enable fast and efficient product creation.
Cadence enables users accurately shorten design cycles to hand off to manufacturing through modern, IPC-
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