Reference electrode

Reference electrode is an electrode which has a stable and well-known electrode potential. The high stability of the electrode potential is usually reached by employing a redox system with constant (buffered or saturated) concentrations of each participants of the redox reaction.

Reference electrodes are used to measure electrochemical potential.

Aqueous Reference Electrodes

Common reference electrodes and potential with respect to the standard hydrogen electrode:

• Standard hydrogen electrode (SHE) (E=0.000V) also known as "normal hydrogen electrode" (NHE)
• Reversible hydrogen electrode (RHE) (E=0.000V + 0.0591*pH)
• Saturated calomel electrode (SCE) (E=+0.242V saturated)
• Copper-copper(II) sulfate electrode (E=-0.314V)
• Silver Chloride Electrode (E=0.225V saturated)
• pH-electrode (in case of pH buffered solutions, see buffer solution)
• Palladium-Hydrogen electrode

• Standard Hydrogen Electrode

  Standard Hydrogen Electrode

• Cu-Cu(II) reference electrode

  Cu-Cu(II) reference electrode

• Ag-AgCl reference electrode

  Ag-AgCl reference electrode

Pseudo-reference electrodes

A pseudo-reference electrode is so named because it does not maintain a constant potential; therefore, by definition, it is not a true reference electrode. However, its potential depends on conditions in a well-defined manner; if the conditions are known, the potential can be calculated and the electrode can be used as for reference potential.

Yttria-stabilized zriconia (YSZ) membrane electrodes were developed with a variety of redox couples, e.g., Ni/NiO. Their potential depends on pH. When the pH value is known, these electrode can be employed as a reference with notable applications at elevated temperatures.

Nonaqueous Reference Electrodes

While it is convenient to compare between solvents to qualitativley compare systems it is not quantitatively meaningful. Much as pK_a are related between solvents, but not the same, so is the case with E°. While the SHE might seem to be a reasonable reference for nonaqueous work as it turns out the platinum is rapidly poisoned by many solvents including acetonitirile causing uncontrolled drifts in potential. Both the SCE and saturated Ag/AgCl are aqueous electrodes based around saturated aqueous solution. While for short periods it may be possible to use such aqueous electrodes as references with nonaqueus solutions the long-term results are not trustworthy. Using aqueous electrodes introduces undefined, variable, and unmeasurable junction potentials to the cell in the form of a liquid-liquid junction as well as different ionic composition between the reference compartment and the rest of the cell. The best argument against using aqueous reference electrodes with nonaqueous systems, as mentioned earlier, is that potentials measured in different solvents are not directly comparable.

Quasi-Reference Electrode Making a quasi-reference electrode (QRE). i) Inserting a piece of Silver wire into concentrated HCl then allow the wire to dry on a chem-wipe. This forms an insoluble layer of AgCl on the surface of the electrode and gives you a Ag/AgCl wire. Repeat dipping every few months or if the QRE starts to drift. ii) Obtain a ‘Vycor’ glass frit (4 mm diameter) and glass tubing of similar diameter. Attach ‘Vycor’ glass frit to the glass tubing with heat shrink Teflon tubing. iii) Rinse then fill the clean glass tube with supporting electrolyte solution and insert Ag/AgCl wire. iv) The Ferrocene (II/III) couple should lie around 400 mV versus this Ag/AgCl QRE in an acetonitrile solution. This potential will varying up to 200 mV with the specific undefined conditions. Thus adding an internal standard such as ferrocene at some point during the experiment is always necassary.

A QRE avoids the issues mentioned above. A QRE with Ferrocene or similar internal standard (Cobaltocene) referenced back to Ferrocene is ideal for nonaqueous work. Since the early 1960s ferrocene has been gaining acceptance as the standard reference for nonaqueous work for a number of reasons. In 1984 IUPAC recommend ferrocene(II/III) as a standard redox couple. The preparation of the QRE electrode is simple allowing a fresh reference to be prepared with each set of experiments. Since QREs are made fresh there is also no concern of improper storage or maintenance of the electrode. QREs are also more affordable than other reference electrodes.

See also

Working electrode

Auxiliary electrode

Further reading

Gritzner, G.; Kuta, J. Pure Appl. Chem. 1984, 56, 461.

Geiger, W.E. Organometallics 2007, 26, 5738-5765

Bard, A.J. & L.R. Faulkner, Electrochemical Methods: Fundamentals and Applications. New York: John Wiley & Sons, 2nd Edition, 2000.

D.J.G. Ives & G.J. Janz, Reference Electrodes, Theory and Practice. New York: Academic Press, 1961.

P. Zanello, Inorganic Electrochemistry: theory, practice and applications. Cambridge: Royal Society of Chemistry, 2003.