Since I started working at Metrohm more than 15 years ago, I have received many questions about Karl Fischer titration. Some of those questions have been asked repeatedly from several people in different locations around the world. Therefore, I have chosen 20 of the most frequent questions received over the years concerning Karl Fischer equipment and arranged them into three categories: instrument preparation and handling, titration troubleshooting, and the oven technique. Part 1 discusses instrument preparation and handling, and Part 2 covers the other two topics.
Summary of questions in the FAQ (click to go directly to each question):
- How can I check if the electrode is working correctly?
- How long can an electrode be stored in KF reagent?
- Can the molecular sieve be dried and reused, or should it be replaced?
- How long does conditioning normally take?
- When conditioning, many bubbles form in the coulometric titration cell with a very high drift, also when using fresh reagent. What could be the reason for this effect?
- What is the best frequency to clean the Karl Fischer equipment?
- How do I clean the Karl Fischer equipment?
- Is it also possible to use a cleaning agent like «CIF» or toothpaste to clean the double Pt electrode?
- How do I clean a generator electrode with a diaphragm?
Instrument preparation and handling
I recommend carrying out a volumetric or coulometric Karl Fischer titration using a certified water standard as sample. In volumetry, you can carry out a threefold titer determination followed by a determination of a different standard. Then, you can calculate the recovery of the water content determination of the standard.
To check a coulometric system, carry out a threefold determination with a certified water standard and calculate the recovery. If the recovery is between 97–103%, this indicated that the system, including the electrode, is working fine.
The color of the working medium is an additional indicator as to whether the indication is working properly.
Pale yellow is perfect, whereas dark yellow or even pale brown suggests indication problems. If this happens, then the indicator electrode should be cleaned.
Check out questions 7 and 8 for tips on the cleaning of the indicator electrode.
Karl Fischer electrodes are made from glass and platinum. Therefore, the KF reagent does not affect the electrode. It can be stored in reagent as long as you want.
The molecular sieve can of course be dried and reused. I recommend drying it for at least 24 hours at a temperature between 200–300 °C. Afterwards, let it cool down in a desiccator and then transfer it into a glass bottle with an airtight seal for storage.
Conditioning of a freshly filled titration vessel normally takes around 2–4 minutes for volumetry, depending on the reaction speed (type of reagent), and around 15–30 minutes for coulometry. In combination with an oven, it might take a bit longer to reach a stable drift owing to the constant gas flow. I recommend stabilizing the entire oven system for at least 1 hour before the first titration.
Between single measurements in the same working medium, conditioning takes approximately 1–2 minutes. Take care that the original drift level is reached again.
At the anode, the generator electrode produces iodine from the iodide-containing reagent. The bubbles you see at the cathode are the result of the reduction of H+ ions to hydrogen gas.
After opening the titration cell or after filling it with fresh reagent, the conditioning step removes any moisture brought into the system, avoiding a bias in the water content determination of the sample. Removing the water results in an increased drift level. During conditioning, the aforementioned H2 is generated. The gas bubbles are therefore completely normal and not a cause for concern. Generally, the following rule applies: The more moisture present in the titration vessel, the higher the drift value will be, and the more hydrogen will form.
There is no strict rule as to when you should clean the KF equipment. The cleaning intervals strongly depend on the type and the amount of sample added to the titration cell. Poor solubility and contamination of the indicator electrode (deposition layer on its surface) or memory effects due to large amounts of sample can be good reasons for cleaning the equipment.
The drift can be a good indicator as well. In case you observe higher and unstable drift values, I would recommend cleaning the titration cell or at least refilling the working medium.
For a mounted titration vessel, it can be as simple as rinsing with alcohol. For an intense cleaning, the vessel should be removed from the titrator. Water, solvents like methanol, or cleaning agents are fine to clean the KF equipment. Even concentrated nitric acid can be used as an oxidizing agent, e.g., in case of contaminated indicator electrodes or coulometric generator electrodes.
All of these options are fine, but keep in mind that the last cleaning step should always be rinsing with alcohol followed by proper drying in a drying oven or with a hair dryer at max. 50 °C to remove as much adherent water as possible.
You should never use ketones (e.g., acetone) to clean Karl Fischer equipment, as they react with methanol. This reaction releases water. If there are still traces of ketones left in the titration cell after cleaning, they will react with the methanol in the KF reagent and might cause the drift to be too high to start any titration.
8. Is it also possible to use a cleaning agent like «CIF» or toothpaste to clean the double Pt electrode?
Normally, rinsing with alcoholic solvents and polishing with paper tissue should be enough to clean the indicator electrode. You may also use detergents, toothpaste, or the polishing set offered by Metrohm. Just make sure that you rinse the electrode properly after the cleaning process to remove all traces of your chosen cleaning agent before using the electrode again.
Cleaning instructions can also be found in our video about metal and KF electrode maintenance:
After removing the generator electrode from the titration vessel, dispose the catholyte solution, then rinse the electrode with water. Place the generator electrode upright (e.g., in an Erlenmeyer flask) and cover the connector with the protection cap to prevent corrosion. Fill the generator electrode with some milliliters of concentrated nitric acid, and let the acid flow through the diaphragm. Then fill the cathode compartment with water, and again allow the liquid to flow through the diaphragm. Repeat the rinsing step with water several times to make sure that all traces of nitric acid are washed out of the diaphragm.
Please note that the nitric acid treatment can be left out if the level of contamination does not require it.
Finally, pour some methanol into the generator electrode to remove the water. Repeat this step a few times to remove all traces of water. The last step is properly drying the electrode in a drying oven or with a hair dryer at max. 50 °C. After this cleaning procedure, the electrode is as good as new and can be used again for titrations.
In Part 2, I cover the topics of KF titration troubleshooting and the Karl Fischer oven technique. You can click below to go there directly.