Application Bulletin 77/3 e

Volumetric water content determination according to

Karl Fischer
Tips and tricks for volumetric Karl Fischer titration

Branch amount of sample and diluted KF reagents are used, then the
determination limit is approx. 50 – 100 ppm of water.
All branches
KF titrants do not have a stable titer. Therefore, one of the
minor disadvantages of volumetry is that the titer has to be
Keywords determined on a regular basis. Titer determination is crucial
Titration; Karl Fischer titration; volumetric; KFT; KFV; water to obtain correct results as the titer has a significant influence
content determination; volumetry; ASTM E203 on the calculation of the samples water content.
This Application Bulletin gives an overview of the volumetric
water content determination according to Karl Fischer.
Summary
Amongst others, it describes the handling of electrodes,
In addition to the determination of pH, weighing and acid- samples, and water standards. The described procedures
base titration, the determination of the water content is one of and parameters comply with the ASTM E203.
the most frequently used methods in laboratories worldwide.
Two methods in particular have become dominant in the
market: Instruments
A – Drying methods (drying ovens, infrared balances…)  Titrator with a KFT mode
Various standards mention this method. However, it suffers
from the following disadvantages: Electrodes
 Loss on drying is determined and not necessarily the
Double Pt wire-electrode (indicator electrode for
water content. Apart from water, also other volatile
volumetric Karl Fischer titration)
components of the sample are determined.
 It takes a long time to obtain the results (several hours
in a drying oven). Reagents

B – Titration methods For volumetric KF titration, there is a general distinction

between one- and two-component reagents.
 In contrast to drying, Karl Fischer titration is a specific
method. If no side reactions occur, only water will be A - One-component reagents
determined. The titrant of one-component reagents contains all the
 The method is rapid and normally takes a few minutes reactants necessary for the Karl Fischer reaction. The solvent
only. component is in most cases pure methanol. To improve
solubility of the sample, suitable organic solvents
 The method can be validated and fully documented.
(e.g., chloroform, toluene, …) can be mixed with methanol.
Higher water contents (> 1%) are preferably determined by
B – Two-component reagents
volumetric titration. Volumetry has the advantages that solid
or pasty samples can be introduced directly into the titration The two-component reagents consist of all necessary
vessel. In contrast to coulometry, opening a volumetric reactants as well, but the components are divided in two
titration cell for a short period of time does not falsify the different solutions, the titrant and solvent component.
results. Additionally, volumetry allows carrying out a titration A large variety of KF reagents is available from various
with various suitable organic solvents depending on the manufacturers (e.g., Honeywell, Merck, …).
sample at hand. Additionally, solid and liquid water standards are available.
Of course, it is also possible to determine small amounts of These standards can be used to determine the titer of the
water volumetrically, e.g., in solvents. If an appropriate used titrant or to validate the titration system.

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 Application Bulletin 77/3 e
Volumetric water content determination according to Karl Fischer

Parameters Titer determination

Table 1: Default method parameter for a volumetric KF titration Please refer to AB-424 for a detailed description of a Karl
Parameter Setting Fischer titer determination.
General I(pol) 50 µA
Control parameter EP at 250 mV Sample addition
Titration rate optimal
Sample size
Stop criterion drift
The sample size depends on the water content of the sample
Stop drift 20 µL/min (see tables 3 to 5). In principle, the sample size should be
Titration parameters Titration direction - selected in such a way that the titrant consumption lies
Conditioning Start drift 20 µL/min between 10% and 90% of the buret volume. For a 10 mL
buret, the consumption of titrant should therefore be between
1 and 9 mL.
For most applications, the parameters mentioned in Table 1
are suitable. In addition, the selected sample weight should not be too low.
For recommended sample sizes, see tables 3 to 5. On the
If ketone reagents (methanol free reagents for water content
one hand, the weighing error can be significant, while on the
determination in aldehydes and ketones) or methanol
other hand the sample will no longer be representative. In
deficient reagents are used, then the endpoint, start and stop
cases of high water content, it may be better to use a buret
drift must be adjusted, as those reagents influence the
with a larger volume in order to avoid filling the buret during
reaction rate of the Karl Fischer reaction.
the titration.
If the sample does not dissolve completely in the working
Table 2: Control and titration parameter for ketone reagents
medium, then the selected sample size may be too high and
Parameter Setting exceeds the dissolving capacity of the working medium. This
General I(pol) 20 µA can be avoided by reducing the sample size and using a
Control parameter EP at 500 mV smaller buret or a titrant with a lower water equivalent, e.g.,
2 mg/mL or 1 mg/mL. Despite the lower initial weight, the
Titration rate optimal
titrant consumption will then be in the range of 10 to 90% of
Stop criterion drift
the buret volume.
Stop drift 20 µL/min
Generally when the titrant consumption is low, you should
Titration parameters Titration direction - work with a lower titer (e.g., Titrant 1, Titrant 2), and with a
Conditioning Start drift 20 µL/min high titer when titrant consumption is high (Titrant 5).

Conditioning and drift Table 3: Approximate sample size in [g] for a 5 mL buret
depending on the titer of the titrant and the expected
The titration cell must be dry before the determination start. water content of the sample
Conditioning removes water contained in the reagent and
Expected Titrant 1 Titrant 2 Titrant 5
water on the surfaces of the equipment (inside of titration cell,
water content
electrodes, …). The water content determination of the
sample should only be started once a low and stable drift is 0.5% 0.1-0.9 0.2-1.8 0.5-4.5
reached. 1.0% 0.05-0.45 0.1-0.9 0.25-2.25
A constant drift equal or lower than 10 μL/min is acceptable. 5.0% - 0.02-0.18 0.05-0.45
Lower values are certainly possible. If higher and stable drift 10.0% - - 0.03-0.23
values occur, then the results are normally still good as the 25.0% - - -
drift can be compensated. However, a high drift value can
50.0% - - -
also indicate a leak in the setup (see also section
troubleshooting).

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 Application Bulletin 77/3 e
Volumetric water content determination according to Karl Fischer

Table 4: Approximate sample size in [g] for a 10 mL buret

depending on the titer of the titrant and the expected
water content of the sample

Expected Titrant 1 Titrant 2 Titrant 5

water content
0.5% 0.2-1.8 0.4-3.6 -
1.0% 0.1-0.9 0.2-1.8 0.5-4.5 Fig. 1: OMNIS spoon for paste (6.02711.000)
5.0% 0.02-0.18 0.4-0.36 0.1-0.9
10.0% - 0.02-0.18 0.05-0.45 The sample can be weighed directly on the spoon and the
25.0% - - 0.02-0.18 spoon can be left in the titration cell until the end of the
50.0% - - 0.02-0.09 titration.

Solid samples
Table 5: Approximate sample size in [g] for a 20 mL buret To add solid samples, the septum stopper of the titration cell
depending on the titer of the titrant and the expected
is removed. The sample can then be added using a weighing
water content of the sample
boat (see figure 2), a weighing paper or any other suitable
Expected Titrant 1 Titrant 2 Titrant 5 tool.
water content
0.5% 0.4-3.6 - -
1.0% 0.2-1.8 0.4-3.6 -
5.0% 0.04-0.36 0.8-0.72 0.2-1.8
10.0% 0.02-0.18 0.04-0.36 0.1-0.9
25.0% - 0.02-0.14 0.04-0.36
50.0% - - 0.02-0.18

Liquid samples Fig. 2: Glass weighing boat (6.2412.000) for addition of solid
samples
Liquid samples are usually added with the aid of a syringe.
Either a syringe with a long needle is used with the needle To avoid any influence of atmospheric moisture on the
being immersed beneath the surface of the reagent during results, the sample should only be exposed to the ambient air
injection or a short needle can be used, with the last drop as short as possible and added as quickly as possible before
being drawn back into the needle. The best way of the titration cell is closed again quickly.
determining the actual sample weight is by weighing the
syringe before and after injection.
Tips and tricks
Volatile or low-viscosity samples should be refrigerated
Reagent exchange
before the sample is taken, in order to prevent handling
losses. In contrast, the syringe itself should not be directly In the following cases, the reagent should be exchanged:
refrigerated as this could cause the formation of condensate.  When the titration vessel is too full.
For the same reason aspirating air into a syringe that has  When the capacity of the reagent is exhausted
been cooled by taking up a refrigerated sample should be (unstable drift values).
avoided.
 If the drift is too high and shaking the cell does not
Highly viscous samples can be warmed to lower their result in any improvement.
viscosity, but the syringe must also be warmed. The same
 If a two-phase mixture is formed in the titration vessel.
goal (lower viscosity) can be reached by dilution with a
suitable solvent. In this case, the water content of the solvent  If the sample does not dissolve anymore in the solvent.
must be determined and deducted as a blank value
correction. Alternatively, viscous samples can be added
using a spoon for paste (figure 1).

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 Application Bulletin 77/3 e
Volumetric water content determination according to Karl Fischer

Indicator electrode 9. Enter the injected sample weight in the software.

The two Pt wires of the indicator electrode should be as Repeat steps the required number of times. If the complete
parallel to one another as possible. Check on insertion. content of an ampoule has been injected, the needle can be
Cleaning filled with fresh standard (same batch). In this case, the
needle does not need to be rinsed again. Start directly with
The indicator electrode can be cleaned by rising it with
step 4.
methanol or ethanol. Please make sure that the ethanol does
not contain any ketone additives, as ketones cause side There are two possibilities to add liquid standard. It can be
reactions with KF reagents. injected with the tip of the needle above the reagent level.
Then, the last drop must be aspirated back into the syringe.
If rinsing does not help, the indicator electrode can be
Otherwise, it is wiped off at the septum and might not be
carefully cleaned with an abrasive cleansing agent (e.g.,
determined although the weight of it is taken into account.
aluminum oxide (6.2802.000 Polishing Set) or toothpaste).
Care should be taken not to bend the two Pt wires during the If the needle is long enough, it can be immersed in the
cleaning. After cleaning, it should be rinsed with methanol or reagent directly. In this case, there is no last drop and the
ethanol. Please make sure that the ethanol does not contain needle can be pulled out of the titration vessel without
any ketone additives. aspirating back any liquid.

Dry all parts thoroughly after cleaning. If the parts are dried in Solid water standard
a drying oven, take care that the temperature does not 1. Place the weighing spoon on the balance and tare the
exceed 70 °C (plastic components!). balance. Weigh an appropriate amount of solid
Storage standard. Tare the balance again.
The indicator electrode can either be stored dry or directly in 2. Start the titration, quickly remove the stopper with
the titration cell immersed in the Karl Fischer reagent. septum, add the solid standard and put the stopper
back. When adding the standard, take care that no
standard sticks to the electrode or the walls of the
Handling of standard titration vessel. In case parts of the solid standard are
Liquid water standard not dissolved in the reagent, gently swirl the titration
vessel to wash down the standard.
1. Open the ampoule containing the standard as
recommended by the manufacturer. 3. After the addition of the standard, place the weighing
spoon on the balance again.
2. Aspirate approximately 1 mL of the standard into the
syringe. 4. Enter the sample weight in the software.
3. Take the tip of the needle out of the liquid and pull back Repeat steps the required number of times.
the plunger to the maximal volume. Sway the syringe to Pure water
rinse it with standard. Then eject the standard into the
By weight
waste.
1. An insulin syringe is filled with water. Due to the very
4. Aspirate the remaining content of the ampoule into the
small amounts of pure water added for the titer
needle (in case air is aspirated, eject the air out of the
determination, we recommend to use a very thin
syringe).
needle. This helps to add small sample sizes.
5. Remove excess liquid from the outside of the needle
2. After filling the syringe, place the syringe on a balance
with a paper tissue.
and tare the balance.
6. Place the needle on a balance and tare the balance.
3. Then start the titration and inject an appropriate amount
7. Then start the determination and inject a suitable of water through the septum into the titration vessel.
amount of standard (see table in AB-424) through the Aspirate the last drop back into the syringe.
septum into the titration vessel. Do not inject the whole
4. Then pull out the needle and place the syringe on the
content of the syringe! Please take care that the
balance again.
standard is injected into the reagent and not onto the
electrode or the wall of the titration vessel. This leads to 5. Enter the sample weight in the software.
unreproducible results. Repeat steps 2 to 5 at least three times.
8. After injecting the standard, place the syringe again on
the balance.

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 Application Bulletin 77/3 e
Volumetric water content determination according to Karl Fischer

By volume Results are widely scattered

1. A microliter syringe is filled with an appropriate volume  Inhomogeneous sample? Poor reproducibility of sample
of water. Make sure there are no air bubbles in the addition?
syringe. Air bubbles will falsify the result.  Drift unstable.
2. After filling the syringe, start the titration and inject the
Titration times too long
content of the syringe through the septum into the
titration vessel.  Wait until drift during conditioning becomes stable.

3. Enter the added volume in the software.  Amount of water in sample aliquot too large

Repeat steps the required number of times.  Set stop drift higher.
 Set control range smaller.
 Set maximal titration rate faster.
Troubleshooting

Drift too high

Literature
 Depots containing water in the titration vessel  shake
titration cell.  Metrohm Monograph
Water determination by Karl Fischer Titration.
 Reagent exhausted or contaminated  exchange
8.026.5003
reagent.
 Metrohm Application Bulletin AB-280 – Automatic water
 Moisture penetrating into titration cell:
content determination using gas extraction
 Molecular sieve exhausted?
 Metrohm Application Bulletin AB-407 – Automated
 Septum pierced? volumetric Karl Fischer titration
 Seals not OK?  Metrohm Application Bulletin AB-417 – Automated
 Sample matrix consumes iodine. Change reagent more volumetric Karl Fischer titration including sample
often. preparation
 When working with Oven/Oven Sample Processor:  Metrohm Application Bulletin AB-418 – Utilization of the
 Molecular sieve of Oven/Oven Sample Polytron PT 1300 D (Metrohm version)
Processor exhausted?  Metrohm Application Bulletin AB-424 – Titer
 Gas flow too high? determination in volumetric Karl Fischer titration

 Allow to run overnight.

 Screw seals tight? Date

Drift unstable March 2019

 Poor stirring  Stir in such a way, that mixing is

efficient, but without the formation of air bubbles. Author
 Reset the control parameters to standard values. Competence Center Titration
Result too high Metrohm International Headquarters
 Titration cell not properly conditioned  shake and wait
until drift has stabilized.
 Sample contains substances that are oxidized.
 Set stop drift higher.

Result too low

 Stop drift too high.
 Minimal titration rate too slow.
 Sample releases iodine.

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