Dr. Bob's Buzz

Testing Electrochemical Capacitors with CV

Simulating Cyclic Voltammetry

One of the problems that faced early electrochemists interested in current-potential-time relationships in cyclic voltammetry was the complexity of the diffusion equations. Sevcik [ Coll Czech Chem Comm, 13 (1948) 349 ] derived a series approximation for the current-potential curve in CV, but cyclic voltammetry got a big boost as a mechanistic tool from the landmark series of publications by Nicholson and Shain [ Anal Chem, 36 (1964) 706 ].

Nicholson solved the x-dependence of the diffusion equation via Laplace Transforms but was then left with an integral equation for current vs. E. He numerically integrated this equation for various values of sweep rate and kinetic parameters and published ‘working curves’ for others to use without having to repeat the (then) tedious calculations.

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There is a description of potentiostat stability (written by DK Roe) in the Kissinger & Heineman book (

Converting Potentials to Another Reference Electrode

Often we find a potential listed in the literature quoted against a different reference electrode than the one we favor, or we would like to convert the potential to a more commonly used reference electrode for publication. A student emailed me: “My experiments involve measuring the redox potential relative to a saturated Ag/AgCl reference electrode. Read more about Converting Potentials to Another Reference Electrode[…]

Gamry Reference Electrodes

Potentials of Common Reference Electrodes

The following tables give the potentials of several commonly used reference electrodes. Various filling solutions are listed where data was available. Note that the nature and concentration of the filling solution can dramatically change the potential! When you look through the scientific literature, be sure the author has specified the filling solution! If you are Read more about Potentials of Common Reference Electrodes[…]

Quartz Crystal Microbalance

The Basics of a Quartz Crystal Microbalance

This tutorial provides an introduction to the quartz crystal microbalance (QCM), which is an instrument that allows a user to monitor small mass changes on an electrode. The reader is directed to the numerous reviews1 and book chapters2 for a more in-depth description concerning the theory and application of the QCM. A basic understanding of electrical components and concepts is assumed.

The two major points of this document are:

Explanation of the Piezoelectric Effect
Equivalent Circuit Models

The Piezoelectric Effect

QCM Basics

Figure 1. Graphical Representation of Thickness Shear Deformation.

The application of a mechanical strain to certain types of materials (mostly crystals) results in the generation of an electrical potential across that material. Conversely, the application of a potential to the same material results in a mechanical strain (a deformation). Removal of the potential allows the crystal to restore to its original orientation. The igniters on gas grills are a good example of everyday use of the piezoelectric effect. Depressing the button causes the spring-loaded hammer to strike a quartz crystal thereby producing a large potential that discharges across a gap to a metal wire igniting the gas.

Quartz is by far the most widely utilized material for the development of instruments containing oscillators partly due to historical reasons (the first crystals were harvested naturally) and partly due to its commercial availability (synthetically grown nowadays). There are many ways to cut quartz crystals and each cut has a different vibrational mode upon application of a potential. The AT-cut has gained the most use in QCM applications due to its low temperature coefficient at room temperature. This means that small changes in temperature only result in small changes in frequency. It has a vibrational mode of thickness shear deformation as shown below in Figure 1.

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Fitting EIS Data to Equivalent Circuits

“Although the equivalent circuit approach is looked down upon by some, analyzing EIS data by fitting it to equivalent circuit models can be a valid and rewarding approach, particularly in the early stages of an investigation.” When you first begin an electrochemical investigation, very often you may know little or nothing about the process or Read more about Fitting EIS Data to Equivalent Circuits[…]

There is a description of potentiostat stability (written by DK Roe) in the Kissinger & Heineman book (

Potentiostat Stability

Contact Dr Bobs Buzz - Electrochemical Methods

A while ago I received an email from an electrochemist who lamented:

“We have some problems with the 173, which we still prefer to use occasionally  because of its analog nature. … (The) potentiostat goes into oscillations.”

Although the M173 has a reputation for ‘stability’ it has always had problems with oscillation! These problems tend to be most troublesome when the more sensitive current ranges are used and when the cell capacitance is large. PAR had a ‘noise filter’ in their catalog for a long time that was really a ‘stability aid’ more than a ‘noise filter.’ It consisted of a capacitor that was placed between the counter electrode lead and the input jack of the M178 electrometer. This acts as a shunt for the higher frequency, oscillation-producing signals. A capacitor value of 0.01 µF is a good place to start. I think this stands the best chance of stabilizing your system.

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Markup: HTML Tags and Formatting

Headings Header one Header two Header three Header four Header five Header six Blockquotes Single line blockquote: Stay hungry. Stay foolish. Multi line blockquote with a cite reference: People think focus means saying yes to the thing you’ve got to focus on. But that’s not what it means at all. It means saying no to Read more about Markup: HTML Tags and Formatting[…]

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