Application Bulletin 280/3 e

Automated water content determination with the 874 OSP

Application Bulletin 280/3 e

Automated water content determination with the 874 Oven

Sample Processor

Branch The methanol loss should therefore be compensated

regularly to avoid too high results.
All branches
Coulometric reagents have a limited water capacity. The
capacity is equivalent to the amount of sulfur dioxide.
Keywords Decreasing sulfur dioxide concentrations (lower than half of
Titration; Karl Fischer titration; coulometric; gas extraction; the initial concentration) lead to longer determination times.
oven technique; automation; 874 Oven Sample Processor; The reagent should be completely replaced. The monitoring
water standard; sodium tartrate of the reagent capacity and the exchange of the reagent can
be done by the titration system and the software.

Summary
Standards
In principle the gas extraction or oven technique can be used
with all types of samples which release the contained water Standards (with different water contents) suitable for the oven
when the samples are heated. The oven technique is technique are commercially available.
essential whenever direct Karl Fischer titration is impossible
because the sample contains interfering components or, due
Carrier gas
to its consistency, is difficult to place in the titration vessel.
The carrier gas transports the released water into the titration
This Application Bulletin shows examples from food,
vessel. In principle it is not important what gas is used.
pharmaceutical, plastics and petrochemical industry to
However, due to oxidation reactions with oxygen, the thermal
describe automated water content determination using the
stability of organic substances at higher temperatures is often
oven technique in combination with coulometric KF titration.
poor, when using dry air as carrier gas. Inert gases, usually
nitrogen, offer more flexibility and reliability.
Instruments For solids with a water content below 1% we recommend a
874 Oven Sample Processor gas flow rate of 50 mL/min. Gas flow rates of up to 100
mL/min can be used for solids with higher water contents.
KF Titrator (coulometric)
Higher flow rates do usually not lead to shorter determination
times.
Electrodes Measurements in liquid samples (oil, fuel, solvents,…) should
Double Pt wire electrode (for coulometry) be carried out using gas flow rates of 80 mL/min or higher.
Generator electrode with or without diaphragm (for Furthermore it is recommended that the inlet needle is
coulometry)* immersed in the sample and the gas is allowed to flow
* For measurements of samples with absolute water contents
through the sample.
< 100 µg, the generator electrode with diaphragm is recommended.

General
Reagents The combination of the oven technique with coulometric Karl
For the coulometric technique, special reagents suitable for Fischer titration is ideal for samples with low water content.
the oven technique are available. Foodstuff, pharmaceutical products, plastics or mineral oil
products can be analyzed fully automated and accurately.
Due to the constant gas flow during measurements, methanol
contained in the reagents evaporates. With the generator In accordance with the gas extraction principle the water is
electrode without diaphragm a decreasing methanol content driven out of the heated sample by a stream of dry carrier gas
can lead to false high results, with recoveries of up to 110%. and transferred to the titration vessel, where the water
content is determined.

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 Application Bulletin 280/3 e
Automated water content determination with the 874 OSP

Preparation empty sample vials are determined. Three replicas of the

blank value determination are recommended. Finally the
Sample
analysis of the water content of the sample takes place.
The sample is thoroughly mixed. Make sure the sample does
Normally a flow rate of the carrier gas (air, nitrogen or a
not change its water content during the mixing. The optimal
different inert gas) of 40 to 60 mL/min is sufficient. The flow
sample size depends on the water content of the sample.
rate can be adjusted up to 150 mL/min to make sure that the
Unfortunately there is no equation describing the relation
gas flow is high enough to transfer the released water as fast
between water content and sample size. But there is a rule of
as possible into the titration vessel. Generally the
thumb: the higher the water content, the smaller the sample
determination time for liquid samples decreases if the gas
size and vice versa. Sample weights that are too low have a
flow is increased. Avoid high gas flow rates when analyzing
negative effect on the measuring accuracy (balance error).
solid samples which could swirl up.
The upper limit for the sample size is defined by the volume
of the sample vial. Theoretically the maximum sample weight The vials for conditioning, system preparation, determination
is also limited by the water capacity of the reagent. Usually of the blank and the sample vials are placed on the rack of
the capacity is approximately 1000 mg H2O per 100 mL the 874 Oven Sample Processor. For coulometric KF
reagent (please contact reagent manufacturer for more titrations, the titration cell is filled with 150 mL of reagent and
information). In other words, with one sample this capacity is then conditioned.
never used.
The absolute amount of water transferred to the titration Temperature gradient
vessel is recommended to be in the range of 300 to 5000 µg.
For samples whose temperature behavior is unknown, a so-
If the absolute amount of water for a sample cannot be
called temperature gradient is run (available temperature
reduced (e.g. smaller sample size …) also larger amounts of
range: 50 to 250 °C). The required method “temp gradient” is
water (> 5000 µg) can be determined using the oven
a preprogrammed method included in the tiamo™ software.
technique. Please be aware that in such cases the
This method uses a heating rate of 2 °C/min to heat up
determination times will increase.
samples from 50 to 250 °C. Figure 1 shows a theoretical
The appropriate amounts of sample are weighed into the temperature gradient where the sample is heated from 50 to
sample vials and the vials are sealed with a septum cap. 250 °C in 100 min.
Previous to usage, the vials and caps should be conditioned
for at least 24 hours at ambient air.
Table 2 on pages 5 and 6 shows recommended sample
weights for a choice of samples.

Instrument and software

The 874 Oven Sample Processor and the KF Titrator are
connected to a PC. The tiamo™ software is started. After the
instruments are recognized and therefore visible in the device
list, the work position for the conditioning vial, the tower
(sample positions) and the shift position are defined. The
tiamo™ software includes several preprogrammed methods
which can be loaded and used with an 874 system. Fig. 1: Diagram showing a theoretical temperature gradient.
Depending on the KF Titrator, the methods need to be
While a temperature gradient is being run it is possible to
adapted with the right instruments. For the analysis of sample
record both, the amount of water released and the drift as a
series, the following sequence of methods is recommended:
function of time (see Fig. 2). The software tiamo™ offers the
• systemprep possibility to correlate the amount of water released and the
• blank value drift with the oven temperature. This allows statements about
• water content the kinetics of the water release as a function of the
temperature.
The method “systemprep” is run once before a sample series.
This makes sure that the system of tubes is purged and ready
for the sample determinations. Afterwards the blank values of

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 Application Bulletin 280/3 e
Automated water content determination with the 874 OSP

However, for sodium tartrate dihydrate the manufacturer

recommends an oven temperature of 160 °C. According to
the temperature gradient in figure 2, an oven temperature of
200°C could be used. The reason for this discrepancy is the
fact that for some samples a heating rate of 2 °C is too high.
In such cases the heating rate may be reduced to find the
optimal oven temperature for the sample analysis. Figure 4
shows the temperature gradient of sodium tartrate dihydrate
using a low heating rate of 0.07 °C/min.

Fig. 2: Temperature gradient (2 °C/min) of sodium tartrate

dihydrate showing the amount of released water and the
associated drift value as a function of the temperature
The temperature gradient of sodium tartrate (Fig. 2) shows
that the surface water and parts of the crystal water are
released starting at 50 °C up to approximately 120 °C. At
120 °C both, the amount of water which is released and the
drift increase again. Up to 140 °C the remaining water of
crystallization is released. After the water of crystallization
has been released, the drift decreases to its basic value of
approximately 10 µg/min. A sign of decomposition is the drift
value, which starts to increase at around 220 °C. Also the
color change of the sodium tartrate after running the Fig. 4: Temperature gradient (0.07 °C/min) of sodium tartrate
temperature gradient suggests decomposition (see figure 3). dihydrate.
A closer look at the drift values between 170 and 220 °C
shows that the drift starts to increase already around 190 °C
(see figure 5). Therefore an oven temperature of 160 °C is
used for the analysis of sodium tartrate dihydrate.

Fig. 3: Sodium tartrate dihydrate before (left) and after (right) Fig. 5: Temperature gradient (0.07 °C/min) of sodium tartrate
running a temperature gradient. dihydrate between 170 and 220 °C.
The temperature curve can be used to determine the optimal Please note that the time to record a temperature gradient
oven temperature for extracting the water from the sample. increases if the heating rate is reduced. The temperature
This temperature should be high enough for the water to be gradient in figure 4 took more than 24 hours to finish.
extracted completely without any decomposition of the
sample. The determination time should be kept as short as
possible. Therefore the oven temperature should be chosen Analysis
as high as possible, but approximately 20 °C below the start Each analysis consists of the following steps:
of decomposition. This procedure works for many different • Conditioning of the complete titration system (titration
samples and can be used for a fast assessment of the oven cell and tubing)
temperature.

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 Application Bulletin 280/3 e
Automated water content determination with the 874 OSP

• Extraction of the water from the sample Water extraction

• Transport of the water into the titration cell The dried carrier gas is passed through the sample vial and
• Karl Fischer titration transfers the released water into the titration cell. The
temperature of the oven can be varied according to the
• Calculation of the result
temperature stability of the sample.
Conditioning It is generally advisable to set an extraction time. During the
Conditioning or titrating the titration cell to dryness is carried extraction time no endpoint is accepted, even if the endpoint
out under stirring in the so-called conditioning position. This criteria are fulfilled. In this way, there is enough time for the
conditioning step must be carried out before every sample to heat up to the defined temperature. We
determination. The oven is heated up to the defined recommend a time of 2 to 5 min.
temperature. After the temperature is reached and the
Karl Fischer titration
titration system is conditioned, the first measurement can
start. For a coulometric Karl Fischer titration a KF reagent which
contains iodide is used. During the determination the iodide
Carrier gas dried with molecular sieve is used to transport the
is oxidized to iodine at the anode of the generator electrode.
released water into the titration cell, where the determination
The iodine is used for the KF reaction. The coulometric
of the water content takes place. By means of a double hollow
technique is an absolute method and there is no titer
needle (figure 6), the gas is led through the sample vial. The
determination required. The endpoint indication is bi-
length of the needle can be adjusted depending on the
voltametric using a double Pt-wire electrode (indicator
sample which is analyzed. Generally it is recommended to
electrode) to which a constant alternating current is applied.
use a short immersion depth of the needle for solid samples
This creates a potential difference (voltage) between the two
(needle holder 6.2049.050). This prevents the needle from
platinum wires. If even very small amounts of free iodine are
being blocked by the sample. In addition swirling of powdery
present, the voltage drops suddenly; which indicates the
samples can be avoided. For liquid samples the needle can
endpoint of the titration.
be immersed in the sample (needle holder 6.2049.040). In
this way the gas flows through the sample, which mixes the Titration sequence
sample and leads to faster extraction of the water. The water content determined by the gas extraction with
subsequent KF titration is made up as follows:

water contentabsolute =
water contentsample + blank value + drift x determination time

During “conditioning” the needle is located in the conditioning

vial, water contained in the system, is removed until a
constant low drift in the range of 1 to 10 µg/min is achieved.
If the automatic drift correction is activated the drift value must
be stable. A stabilizing time can be defined to ensure a stable
drift value. For drift correction, the drift value measured at the
start of the determination is multiplied with the determination
time and subtracted from the found water content at the end
of the determination.
Alternatively the value for drift correction can be determined
using a separate method, which is carried out prior to every
sample series. In a first step, the system is conditioned until
a stable drift is achieved. Depending on the reagent this can
take between approximately 15 min and 2 hours. Then the
consumption of iodine is recorded during 10 min. The
determined mean value is stored and can be used for drift
correction and as stop criterion. It is essential that during the
Fig. 6: Principle of the oven technique in liquid samples
sample series the system drift does not change (e.g.
interfering additives in sample).

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 Application Bulletin 280/3 e
Automated water content determination with the 874 OSP

System preparation means that the whole system is adjusted Stop criterion rel. drift
to the selected conditions. An empty sample vial is treated in Relative stop drift 5 µg/min
exactly the same way as the following samples, but the value
Conditioning Start drift 10 µg/min
is not taken into account. We recommend that this step –
parameters
which is at the same time used for checking that the analysis
Stabilizing time 60 s
system is working properly – is carried out before every new
* 400 mA are used with the generator electrode without diaphragm.
sample series.
The setting auto is chosen for the generator electrode with
Apart from the water in the sample, the sample vial also diaphragm.
contains atmospheric humidity; this makes a blank value
determination necessary. A three-fold determination of the
Troubleshooting
blank value is normally sufficient. The mean value is stored
as a Common Variable and taken into account in the Procedure for poor precision (reproducibility):
calculation of the water content (subtracted). If large sample • Optimize the titration and control parameters.
sizes are used, it might be necessary to correct the blank • Check whether the sample vials are tightly sealed.
value (see KF Application note AN-K-048).
• Drift too high: Switch off the gas flow.
The system preparation and the blank value determination If drift value decreases: Check the needle system,
must be carried out using the same method parameters as transfer tube.
for the analysis of the samples. In order to do this, an empty If drift value does not change: check titration cell,
system preparation vial and three empty blank value vials are septum and/or seals leak, molecular sieve exhausted,
placed on the rack of the 874 Oven Sample Processor and poorly conditioned reagent, ensure thorough mixing.
analyzed before the samples.
• Clean electrodes according to the electrode leaflet.
End of titration • Check the needle system and possibly clean it with
The titration and the gas extraction of the sample is stopped water and methanol. Dry the components afterwards.
as soon as the drift value (amount of water per time) falls • Check the transfer tube and clean it with water and
below a predefined value. Usually the parameter “relative methanol to remove condensates and dirt.
drift” is used to stop a determination. The stop drift is
• KF reagent contaminated/exhausted: change the
calculated by adding the drift at the start of the determination
solution, possibly use a different batch.
and the value entered for the “relative drift”. The endpoint is
reached if the actual drift is smaller than the sum of the two • Check electrical contacts; defective contacts can lead
mentioned values. The higher the chosen value for the to an unstable measuring signal.
“relative drift” the sooner the determination is stopped and the • Check if chosen oven temperature is suitable for
more water remains in the sample. The “relative drift” value sample analysis.
should not be higher than 5 µg/min. If high accuracy is • Balance: too inexact, drafts, temperature equilibrium
required and for small water contents the “relative drift” not reached, sample weight not optimal/too low.
should be reduced (e.g. to 2 µg/min).
• Possibly carry out a qualification of the analysis system.
Please contact Metrohm Service for further information.
Parameters
Table 1: Recommended parameters for the oven technique in
Example applications
combination with coulometry.
The following table 2 provides an overview of samples
Parameter Setting
analyzed by the oven technique. In each case the Karl
General parameters I(pol) 10 µA Fischer water determination was carried out in combination
Generator current 400 mA or with a Coulometer using N2 as a carrier gas (flow rate
auto* 40 mL/min).
Control parameters EP at 50 mV
Dynamics 70 mV
Max. rate Maximum
µg/min
Min. rate 15 µg/min

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 Application Bulletin 280/3 e
Automated water content determination with the 874 OSP

Table 2: Selection of samples which can be analyzed using the Denture cleaner, 70 0.2–1.5 3.8%
oven technique
effervescent
Sample Temp. Sample Water content tablets4
[°C] weight [g] Drugs 140 0.04 6.7%
Foodstuff Lyophilizate 150 0.01 5.0%
Lyophilizate 120 0.06 1.4% Others
Aromas1 100 0.03–0.08 2.5-5.4% Sodium tartrate 160 0.02–0.08 15.5%
Maltodextrin 100 0.03–0.08 4.7-8.8% dihydrate
Lactose 155 0.06 5.2% Potassium 220 0.03 5.6%
monohydrate citrate
Skimmed milk 90 0.06 4.4% monohydrate
powder2 Polyammonium 220 0.03–0.3 1.0-85.0%
Whole milk 90 0.06 3.9% compounds
powder2 Emulsified fat 220 0.03–0.08 85.0%
Sweet whey 90 0.06 4.9% compound
powder2 Formamidosulfo 220 0.2–0.3 < 1.0%
Glucose 90 0.06 8.9% nic acid
monohydrate2 Pigment 100 0.03–0.3 7.9%
Maltose 120 0.06 5.9% Polyol ether 150 0.6–1.3 0.2%
monohydrate3 Dibutene 100– 0.03 250 µg/g
Garlic powder 110 0.2 3.5% 140
Mineral mixtures 110 0.3 6.0-7.0% Lithium cobaltite 100 0.45–1.0 64 µg/g
Plastics Building rubble
Polypropylene 170 3.0 380 µg/g Surface water 50–60 0.3 0.6%
Polyethylene 115 3.0 40 µg/g Bound water 85–140 0.3 1.0%
Olefins 180 3.0 100 µg/g
1
With the 874 Oven Sample Processor the dissolution of the
Polyamide 180 0.3 0.8% sample in KF reagent, which is required in a direct Karl Fischer
Polyoxy- 170 0.3 0.1% titration and which frequently cannot be carried out completely , is
methylene no longer necessary
2
(POM) With the addition of 4 mL methanol as extraction agent (the water
content of the methanol must be determined and included in the
Polystyrene 120 0.05…0.2 200–500 µg/g
blank value).
Refinery products 3
With the addition of 4 mL 1,5-pentandiol, extraction time 600 s
Transformer oil 150 3.0 80 µg/g (the water content of the 1,5-pentandiol must also be determined
Mineral oil 120 1–3 10–100 µg/g and included in the blank value).
4
Above 70 °C the contained carbonate decomposes.
Insulating oil 140 3 5 µg/g
Crude oil 140 2 500-1200
µg/g Reference
Additive 120 0.01…0.03 4.4% • Metrohm Monograph 8.026.5013 - Water Determination
Antimony 50–130 3.0 700 µg/g by Karl Fischer Titration
dialkyl- • AN-K-048 – Sample preparation with the oven
thiocarbamate in technique – relative blank (available on
crude oil www.metrohm.com)
Pharmaceutical products
Collagens 160 0.07–0.4 10.6-9.2%
Author
Competence Center Titration
Metrohm International Headquarters

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