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Voltammetry Plotting Conventions

Last Updated: 4/24/19 by Support

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  1. Plotting Conventions

1Plotting Conventions

The two streams of data recorded during a voltammetry experiment are the potential vs. time and the current vs. time.  Rather than plot these two streams separately (Fig 3. bottom-left), it is more common to plot current vs. potential (Fig 3. top).  Such a plot is called a voltammogram.
Although most electroanalytical researchers agree that current should be plotted along the vertical axis and potential should be plotted along the horizontal axis, there is no widespread agreement as to the orientation (direction) for each axis.  Some researchers plot positive (anodic, oxidizing) potentials toward the right while others plot negative (cathodic, reducing) potential toward the right (as per classical polarography tradition).  Furthermore, some researchers plot anodic (oxidizing) current upward along the vertical axis, while others plot cathodic (reducing) current in the upward direction.
This means there are four possible conventions for plotting a voltammogram, and one should always take a moment to ascertain the orientation of the axes before interpreting a voltammogram.  Fortunately, of the four possible ways to plot a voltammogram, only two are commonly used.  The older tradition (based on classical polarography) plots cathodic current upwards along the vertical axis and negative (cathodic, reducing) potentials toward the right along the horizontal axis.  A complex voltammogram involving four different limiting currents (Fig 4. Left) illustrates this convention, which is sometimes called the “North American” convention.
two popular voltammogram plotting conventions

Fig 4. two popular voltammogram plotting conventions

The same data may be plotted using the “European” convention (Fig 4. Right).  This convention plots anodic currents upward along the vertical axis and more positive (anodic, oxidizing) potentials to the right along the horizontal axis.  The European convention is more readily understood by those outside the electroanalytical research community (because positive values are plotted to the right along the horizontal axis).  Further, IUPAC specifies to use the "European" convention for electrochemical data.
The European convention is used throughout the remainder of this document.  Note that this choice also implies a mathematical sign convention for the current.  Specifically, positive current values are considered anodic, and negative current values are considered cathodic in this document.  This sign convention is somewhat arbitrary, and electrochemical data processing software available from various manufacturers may or may not use this sign convention.
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