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Karl Fischer Over Titration and 7 things you should know about it
Posted by Hank Levi on Wed, May 02, 2012 @ 05:30 PM
We have all seen it. Were running a test to see how much moisture is in our sample when inexplicably the liquid inside the Karl
Fischer vessel starts to turn from a normal light-yellow color to a dark burnt-red looking color. Sometimes the titrator screen will
inform us of the problem with a digital readout stating the dreaded
OVER-TITRATION!

Sometimes the digital readout says nothing at all. In either case the operator knows something has gone wrong because the Karl
Fischer Titrator is no longer giving moisture results. A panic to figure out the problem and get testing underway again becomes
the immediate priority.
But where do you start?
As it turns out over-titration is probably one of the top 2 or 3 complaints or issues we hear about from operators. So
what is causing this problem to occur? How can we determine the source of this problem, fix it, and more importantly how can we
avoid it?

This is a critical question for operators and managers working in a production or QC environment who are concerned with keeping
their Karl Fischer Titrator 100% in-service, day-in and day-out. Having the ability to identify the problem correctly so appropriate
measures can be taken quickly is very important.

So how do we approach the problem of over-titration? By knowing the facts. Having a clear understanding of the process
can help operators correct the problem faster when time is of the essence.
Important facts you should know about over-titration:
Karl Fischer Over Titration and 7 things you should know about it http://info.scientificgear.com/bid/125207/Karl-Fischer-Over-Titration-an...
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Over-titration is a state where there is more iodine present in the vessel than water (general definition). 1.
When over-titration occurs the vessel will become very dark as a result of the abundance of iodine present inside the
vessel.
2.
The reagent inside the vessel should normally have a light-yellow color absent a very dark sample such as oil. 3.
The Karl Fischer Titrator always attempts to maintain an equilibrium where only enough iodine is introduced to counter and
neutralize the water present inside the vessel.
4.
During a single titration test there should only be enough iodine introduced to counter and neutralize the amount of water
present inside the titration vessel during that test no more, no less.
5.
Any incident that interferes with the final amount of iodine introduced during the titration test can lead to dis-equilibrium and
result in more iodine being introduced than necessary.
6.
Important facts you should know about Karl Fischer Titrator Glassware:
The Karl Fischer Vessel and Glassware is composed of the following
Vessel (coulometric and volumetric) 1.
Generator Electrode (coulometric only) - The Generator Electrode is a precision electrode designed to deliver an
electrical current inside the vessel to the reagent causing the reagent to produce iodine
2.
Titration nozzle (volumetric only) - The titration nozzle delivers precise amounts of iodine (composite or titrant) via a
burette driven mechanism using a piston
3.
Detector Electrode (coulometric and volumetric) - The detector electrode has a sole purpose and probably the
most important role in continuously monitoring and determining the conductivity levels within the titration vessel.
4.
1.
So what are the causes that can lead to over-titration?
A damaged Detector Electrode
A "Tricked" or "Fooled" Detector Electrode (no joke)

Since coulometric and volumetric Karl Fischer Titrators handle the delivery of iodine differently its worth describing the two
methods separately.
A Word About Coulometric Karl Fischer Titration:
In a coulometric system the reagent is a complete system where it is designed to release iodine when the generator electrode
delivers an electrical current to it. So what causes the generator electrode to deliver too much current causing the over
production of iodine? Another way to say it is, who or what is telling the generator electrode to continue to generate a current
when its not needed?

The detector electrode! So why would the detector electrode do this?
Without getting into too much of the electronics the detector electrode is
designed to detect conductivity in the vessel. Depending on the amount of
conductivity detected the detector electrode will send a message to the titrator
telling it to continue producing a current - enough to release the appropriate
amount of iodine to counter and neutralize the water present in the vessel. As
long as this process is working during a titration an eventual endpoint will be found
and a result will be produced.
So its really a problem of misinformation. If the Karl Fischer Titrator is not
getting the right information from the detector electrode then over-titration is
possible.
The problems we see that can effect the proper functioning of the detector electrode
include:
The electrode cable. If the cable becomes cracked or breaks it can
cause a situation where the message to the titrator is to continue producing
a current continually. In this case the vessel will become very dark and in most cases the titrator will not even know it is
in an over-titration state. The generator electrode will simply continue to produce a current, turning the vessel very dark.
There will be no other warning or notice from the titrator for the operator to see.
1.
Cracked electrode. Sometimes mishandling or even a stirrer bar bouncing around inside the vessel can cause a tiny
crack near the bottom of the detector electrode that cannot be seen with the naked eye. These cracks can allow small
amounts of reagent inside the electrode enough where errors in detection will begin to occur. What ensues is an unstable
drift that jumps around giving the titrator a misreading. The jumping around and unstable drift may be picked up by the
titrator and an error stating OVER TITRATION may be seen on the screen of the titrator.
2.
Cable connectors. Sometimes the connectors on the titrator itself can become dirty, wet and corroded. Also, some 3.
Karl Fischer Over Titration and 7 things you should know about it http://info.scientificgear.com/bid/125207/Karl-Fischer-Over-Titration-an...
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electrodes use multi-plug designs that can also become dirty, wet and corroded. These connectors if not clean and dry
can lead to a similar misreading similar to a cracked electrode where the drift begins to jump around and become
unstable. The titrator may also state that there is OVER TITRATION when this occurs.
A "Tricked" or "Fooled" Detector Electrode you say?
If its determined that the problem is not the detector electrode then we need to look at the stirring action inside
the vessel. If the iodine being released is not mixing well because the stirrer is off or set too low, then the
detector electrode will not realize there is iodine already released inside the vessel. This will cause the detector
electrode to continue telling the titrator to produce more current via the generator electrode up to the point
where the detector electrode senses a reduction in the conductivity level inside the vessel. Conductivity only
reduces as the iodine interacts with the water. So it is important for the detector electrode to sense the true and
most accurate mix or state of iodine and water during the titration process. If it does not know the true state of
the mix it will be fooled into telling the titrator to keep going causing OVER TITRATION.
A Word About Volumetric Karl Fischer Titration:

In a volumetric system the reagent setup is different where a composite or titrant is
introduced via a burette piston through a titration nozzle. The amount of composite or
titrant delivered is based upon the commands of the titrator. The command from the
titrator to the burette and piston that push out the iodine through the titration nozzle is,
yes, given by the detector electrode. For the purposes of this discussion the
difference between the coulometric and volumetric setup is that the delivery of iodine
is different. But the same problem can occur where the iodine does not mix well and
therefore trick the detector electrode in to thinking there is not enough iodine present
inside the vessel to counter and neutralize the water. Since both coulometric and
volumetric Karl Fischer Titrators use detector electrodes the problems mentioned
earlier about the detector electrode will hold true with volumetric titrators also.


7 Thoughts (DOs and DON'Ts) on Problem Solving and Prevention:
1. Dont abuse the detector electrode! Be very careful with the detector electrode and do not handle it unnecessarily. Small
bumps (clanks) here and there can lead to a crack. Do you really need to remove the detector electrode from the vessel all the
time?
2. Dont turn up the titrators stirrer speed to high. This will only cause the
stirrer bar to bounce around uncontrollably and possibly hit and damage the
detector electrode (crack).
3. Do inspect all connections and connectors on the detector electrode
cable and Karl Fischer Titrator to ensure they are dry and clean.
4. Do be careful with the detector electrode cable. Try not to bend it
unnecessarily.
5. Do make sure there is enough stirring action inside the vessel to mix the
iodine around effectively. A small vortex should be visible. But not too fast
to cause the stir bar to bounce around.
6. Do introduce some moisture - Sometimes when you are in an
over-titration situation and the vessel is already very dark you can introduce
a little moisture to bring the vessel back to equilibrium. This sometimes
works and immediately the vessel turns from a dark burnt-red color to a
light-yellow.
7. Do have a spare detector electrode on hand. This little electrode
seems to get over looked but plays a huge role inside the Karl Fischer
Titrator vessel.
Tags: Karl Fischer Titration, Titration, Moisture Testing, Karl Fischer, Parts Per Million, PPM, Karl Fisher, Karl Fisher
Water Standards, Karl Fisher Reagents, Karl Fisher Titrator, Karl Fischer Titrators, Karl Fischer Water standards,
Volumetric Karl Fischer Titration, Reagents, Karl Fischer Generator Electrode Repair, Repair Inner Burette for Karl
Fischer, Karl Fischer Titrator, Electrode, coulometric Karl Fischer
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