Introduction to electrochemistry

The investigation of electroactive microorganisms affords an appropriate measurement system. To perform highly sensitive measurements we used a Potentiostat. For the understanding of the mode of operation of a Potentiostat it is necessary to define a few basic principles of electrochemistry. The following definitions come from (Harnisch, F. & Freguia, 2012):

• Anode:
  The electrode where an oxidation takes place.


• Cathode:
  The electrode where a reduction takes place.


• Current:
  The flow of electric charge.


• Capacitive Current:
  The current related to the change in the electrode surface charge, not related to an oxidation/ reduction reaction.


• Faradaic Current:
  The current generated from the oxidation (positive current) of reduction (negative current) of chemical spezies.


• Charge q [C]:
  Cumulative current flow (1C= 1A x 1s). Values can be determined by the integration of current-time curves.


• Formal Potential E^f [V]:
  Replaces the standard potential when the activities of the species involved and of the side-reactions are unknown or too complex. It is the favoured value for reactions that take place in a biological environment.


• Peak Current:
  The maximum current at the working electrode in a voltammetric measurement.


• Peak Potential:
  The potential of the working electrode at which the peak current in a voltammetric measurement is obtained.


• Potentiostat:
  An electronic amplifier that controls the potential drop between an electrode (the WE) and the electrolyte solution; it usally constitutes a reference electode (RE) as a sensing component and a counter electrode (CE) for balancing the current flow.


• Reference electrode (RE):
  A non-polarizable (stable) electrode with a fixed potential that sets or measures the potential of the WE.


• Working electrode:
  An electrode at which a given electrochemical reaction of interest is examined; its potential is controlled versus the RE in a three-electrode system.


• Scan rate [mV s^-1]:
  The speed of potential change per unit of time in a voltammetric experiment.

The Potentiostat

A potentiostat is an electronic control and measuring device for the study of electrochemical phenomenons. The instrument controls the voltage difference between a working electrode (WE) and a reference electrode (RE). Therefore the prevailling potential of the WE is sensed in respect of the RE. The potential control and set to a constant value is implemented by injecting current into the cell through a counter electrode (CE). (Gamry Instruments)
The fundamental principle is shown in figure 1.

Figure 1: Principle of the circuit for potentiostatic measurements with a four electrode set up.

The potential difference between WE ad RE is measured at the entrance of the regulatory circuit (actual current) and compared to a target voltage. There are two modes of operation for the target voltage. It can be held constant by the 2 V DC-circuit or operated with a variable voltage, set by a function generator. If there occures a difference between actual current and target voltage the regulatory circuit automatically sets the wanted current by sending an electric current into the electrobiochemical reactor system.
Thus the set up ensures that the measured potential at the WE is held constant at the wanted potential. The current i gets isolated by the resistor R. The set up allows it to vary the target voltage and enables the execution of linear increasing target voltages. This mode of operation allows the recording of a current-voltage chart by an oszilloscope that can be displayed and analyzed on a computer. (Hamann et al.,2007)

Cyclic voltammetry

Cyclic voltammetric measurements requires a three electrode setup composed of a reference electrode, a counter electrode and a working electrode attached to a working and optionally to a working sense lead. Those three electrode setups are especially suitable for electrochemical measurements because only the potential changes at the working electrode are measured. Any variances at the counter electrode are not considered and are totally independent of the measurement. This makes it possible to monitor specific reaction with a maximum of precision.(Gamry Instruments)
Therefore cyclic voltammetry can be used to study oxidative and reductive reactions of chemical compounds. Thereby a linearly proceeding potential referred to the reference electrode is applied to the working electrode up to a specific value. Afterwards the potential returns linearly to the initial value again. If the potential has reached the starting value one cycle is completed. During one measurement several cycles can be performed. The scan rate can be derived from the gradient of the curve.(Harnisch, F. & Freguia, 2012)
The course of potential during the measurement is shown in figure 1.
Due to the applied potential the compound which should be analyzed runs through an oxidation-reduction cycle and a current-voltage chart is plotted (figure 2).Therefore there is nearly no current flow in the initial phase of the linearly proceeding potential except the capacitive current. By reaching a certain potential the current flow increases up to the faradaic current where the chemical compound gets oxidized. The resulting peak current indicates the peak potential which is needed to oxidize the compound. If the potential begins to return linearly back to the initial value the compound gets reduced again at a specific potential, the peak potential which is needed to reduce the compound. If both current peaks are measurable the chemical compound is reversible oxidable and reducible (figure 2).(Harnisch, F. & Freguia, 2012)

Chronoamperometry

References

• Harnisch, F. & Freguia, S., 2012. A Basic Tutorial on Cyclic Voltammetry for the investigation of Electroactive Microbial Biofilms. In: Chemistry – An Asian Journal, 7 (3), pp. 466–475.

• Gamry Instruments: Potentiostat fundamentals

• Hamann, Carl H., Hamnett, Andrew, Vielstich, Wolf (2007): Electrochemistry. 2. edition. Weinheim: Wiley-VCH

• Gamry Instruments: Two-, Three-, and Four-Electrode Experiments