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Karl Fischer Titration essentials: Verification of linearity

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 Conclusions and the τT data indicates how quickly it References
[1] M. Johnson, Dairy Pipeline (12(1)),
Heating modifies the texture of a cheese, occurs. Measuring the SP sheds light on
2000:1-5.
and the original microstructure is altered the interplay among the meltability, vis- [2] M.-T. Frölich-Wyder et al., Dairy Sci.
during the complex softening process. SP cosity, and stretchiness of the cheese in a Technol. (89), 2009:463-483.
[3] R.Kapoor, L.E. Metzger, CRFSFS (7),
data indicates the temperature at which phenomenological way.
Expert tips

2008:194-214.
this thermally-induced event takes place
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Karl Fischer Titration essentials:

Verification of linearity
Water content, an important quality control parameter, is analyzed by Karl Fischer titration
to determine water in the sample. In some cases, samples are insoluble or release water
slowly making it necessary to use an oven to vaporize the water present. To ensure the
accuracy of the KF titrator-oven coupled system, it is necessary to verify its linearity.

Dr. C. A. De Caro

Knowledge of water content is a decisive
factor, affecting the quality and proper-
ties of products in a multitude of indus-
tries. Water plays a role in the stability
of drugs, the taste of food, as well as the
protective properties of lubricants. Karl
16
14
Figure 1:
12
Measured water content (%)
Fischer (KF) titration has long been the
method of choice for the determination
of water content due to its short analy-
sis time, accuracy and repeatability, its
selectivity to water and its broad concen-
tration range.
y = 0.9861 x 0.0355
KF Volumeter
For a successful KF titration, water must
be released completely from the sample
matrix. This is commonly achieved by
external extraction or dissolution and
the aid of auxiliary solvents. However,
when samples lead to side reactions with
the Karl Fischer reagents, or the water
release is too slow, the water must first
be extracted into the gas phase using a
suitable Karl Fischer oven. The resulting
water vapor is transferred to the titration
cell by means of an inert gas flow, and

Plot of the mea-

sured water content is ready for titration. In this article we
of 1%, 5.55% and 10
describe an analytical system consisting
15.66% water stan-
dards versus nomi- 8 of a KF titrator in combination with a KF
nal water content. oven autosampler.
This plot shows
6
ideal linearity with
a slope close to 1. KF Titrator-Oven Autosampler
The linear fit has 4
a slope of 0.9861, coupled system
showing excellent 2 For reliable results the complete analyti-
agreement between
the nominal and cal system – KF titrator and a KF Oven
0
determined water
0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00
autosampler – must be tested. In short,
content in the KF
titrator-oven
the accuracy and precision of the water
Certified water standard (%)
system. content determination is verified by

16 METTLER TOLEDO UserCom 22

measuring a known amount of water, in
the form of a water standard, in the ana-
lytical system.
In a first step the titrator is tested without
the oven. The liquid water standards are
injected directly into the titration cell.
The second step proceeds with the com-
plete system. The KF oven autosampler
is connected to the titrator and tested by
heating solid certified water standards.
The evaporated water is determined in
the titrator.
Some samples exhibit a broad water
content range. For example, plastics
and polymers can have a range of 1%
to 10%. In this case, it is important to
verify the linearity of the complete sys-
tem by measuring solid standards that
cover the whole measuring range. As a
rule, KF oven autosamplers are tested
with commercially available water stan-
dards, 1%, 5.55% and 15.66%. Plotting the
results obtained, as a function of the cer-
tified content, illustrates the linearity of
a system with increasing water content.
Sometimes the deviation between the
certified values of the standard and the
titration results lies outside the tolerance
range, as given by the manufacturer and
the user SOP. This calls for a repeat veri-
fication of the KF titrator-oven coupled
system with certified water standards, as
well as for the verification of the method
parameters for water evaporation, name-
ly temperature and the heating time.
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Table 1:
Analytical System Solid water Titration
Ready-to-use titra-
standard Application tion applications
C30S Compact KF Coulometer and 1% M315 for performance
InMotion KF Oven Autosampler verification of the
5.55% M500 KF titrator-oven au-
15.66% M689 tosampler.
V30S Compact KF Volumeter and 1% M680
InMotion KF Oven Autosampler 5.55% M312
15.66% M688
Verification of linearity oven has reached a stable temperature.
The linearity of the KF titrator-oven Then a blank value of the glass vials is
autosampler can be verified with the measured, followed directly by the deter-
titration applications developed for this mination of the water content of the cer-
purpose (Table 1). These applications are tified standards.
ready-to-use performance verification
methods that can also be used as tem- A suitable heating time and temperature
plates for the development of individual is selected according to the solid water
application methods. standard being measured. Air is used
as a carrier gas in order to transfer the
The linearity of the results, as measured evaporated moisture from the heated
with a V30S Compact KF Volumeter vial into the titration cell. Accuracy and
connected to an InMotion KF Oven reproducibility can be improved further
Autosampler, has been verified with 1%, by first drying the glass vials in a drying
5.55% and 15.66% KF solid water stan- oven overnight and then placing them in
dards, respectively (Figure 1). a desiccator to cool down to room tem-
perature.
Running the solid water
standard analysis Conclusion
Depending on the water content and on The reliability of KF analyses depends on
the KF technique used – coulometry the linearity of the titrator-oven autos-
(traces of water) or volumetry (larger ampler system. Linearity is verified with
amounts of water) – a suitable amount the aid of suitable solid water standards.
of water standard is weighed into the The predefined methods on the titrator
glass vial sealed with a screw cap. The help you choose the correct measurement
vial is placed onto the sample rack and procedure for each standard. To fulfil
the corresponding method is started. In data integrity requirements of quality
a first step a pre-titration is run until the management the procedure can be auto-
instrument is placed on standby and the mated with LabX® PC software.
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