Reference Electrode - Nonaqueous Reference Electrodes

Nonaqueous Reference Electrodes

While it is convenient to compare between solvents to qualitatively 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 acetonitrile 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 nonaqueous 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.

A Quasi-Reference Electrode (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, and in 1984, IUPAC recommended ferrocene (II/III) as a standard redox couple. The preparation of the QRE electrode is simple, allowing for a fresh reference to be prepared with each set of experiments. Since QREs are made fresh, there is also no concern with improper storage or maintenance of the electrode. QREs are also more affordable than other reference electrodes.

To make a quasi-reference electrode (QRE):

1. Insert 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.
2. 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.
3. Rinse then fill the clean glass tube with supporting electrolyte solution and insert Ag/AgCl wire.
4. 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 necessary.