KF Chemicals

METTLER TOLEDO TItrators
Toluene
OIL
Glue
Karl Fischer Applications

Chemicals, Solvents, Petroleum Products, Plastics
Karl Fischer Water Content Determination
in Chemicals, Solvents, Petroleum Products and Plastics
Contents 1. Introduction 4
2. Inorganic raw materials 5
3. Organic raw materials 9
4. Solvents 15
5. Petroleum products 21
6. Plastics and adhesives 27
7. Medicines (pharmaceuticals) 31
8. Dyes and agrochemicals 35
9. Detergents and surfactants 38
10. Silk, wool, cellulose, paper and wood 40
11. Building materials and minerals 42
12. Index of reagents and suppliers 44
13. KF reagent hazards and waste disposal tips 46
14. Sample Index 47
References Fischer, K., Angew. Chem. 48, 394 (1935)

Mitchell Jr., J. and Smith, D.M., „Aquametry“ Part III, Second edition,
John Wiley and Sons, Inc., New York, 1980
Riedel-de Haën, HYDRANAL® Manual
Fifth edition, 1988
Scholz, E., Karl Fischer Titration,
Springer Verlag, Berlin, 1984
Wieland, G., Wasserbestimmung durch Karl-Fischer-Titration,
GIT Verlag GmbH, Darmstadt, 1985
METTLER, Karl Fischer Applications 3

1. Introduction
The quality and often the usability of many raw materials, intermediates and sub-
stances necessary for the manufacturing of high-grade products frequently de-
pend decisively on the water content. Securing and optimizing the product quality
thus necessitates regular control of the water content.
Karl Fischer titration, being efficient, rapid and accurate, is the most important
method for determining water contents. Thanks to its selectivity, the method fulfills
todays requirements. The traditional drying oven technique, in contrast, has
many systematic errors, is inefficient and slow.
The method developed by Karl Fischer, in which water is titrated in the presence
of sulfur dioxide and an organic base [1], was improved significantly by
E. Eberius, J.C. Verhoef and E. Scholz [2].
2 H20 + S02 + I2 —> H2S04 + 2 Hl [1]
H20 + I2 + S02 + CH30H + 3 RN —> [RNH]S04CH3 + 2 [RNH]I [2]
In an initial reaction, sulfur dioxide, methanol and the base have recently been
shown to react to form methyl sulfite [RNH]SO3CH3.
The pyridine used initially by Karl Fischer has been replaced by more suitable
amines. Several companies supply pyridine-free Karl Fischer reagents with a
constant titer.
Microprocessor controlled METTLER DL18 and DL35 Karl Fischer titrators as well
as METTLER DL37 KF Coulometer allow water contents to be determined rapidly,
easily and reproducibly. The DL35 and DL18 are recommended for water con-
tents ranging from ppm to 100%, whereas the DL37 is useful for trace moisture
content determinations.
Karl Fischer titration allows the quantification of freely available water which has
been brought into solution prior to the titration using an appropriate method.
Gases and liquids are generally easily dissolved in methanol, the usual solvent
for Karl Fischer titration.
Solids, however, may contain water as water of crystallization, occluded water or
as adherent moisture. For this reason, sample preparation is most important for
the analysis. A total water content determination requires that the sample be com-
pletely dissolved. Should this not be possible in methanol, it may be necessary to
add decanol, chloroform, formamide or other solvents. In certain instances titra-
tion at elevated temperatures, at the boiling point, or after external extraction may
be helpful.
For thermally stable products, such as polymers, evaporation of the moisture in a
drying oven (METTLER DO302 or DO337) and transferring the vapor into the
titration cell by a dry purge gas is recommended.
The differential availability of the water may be used to selectively quantify only
the adherent moisture (for plastics, for instance). It is, however, necessary to pre-
vent the rediffusion of more water.
Undesirable side reactions of the KF reagents, such as esterification or bisulfite
addition, may be prevented by the proper selection of reactant composition and
measurement conditions.
4 METTLER, Karl Fischer Applications

2. Inorganic raw materials
General comments Salts

Salts can contain water in the following ways: water of crystallization, in-
cluded water and adherent moisture.
In order to quantify water of crystallization and included water, the sample
must be dissolved completely. Methanol is usually a suitable solvent.
Some substances may require the addition of formamide, or titration at ele-
vated temperatures. For substances that dissolve slowly, finely crushing the
sample may be helpful.
When determining only the adherent moisture, dissolution of the substance
and diffusion of other water into the titration must be prevented. For this
reason, a high proportion of chloroform is used in the solvent.
Acids and bases

These must be neutralized prior to the titration. Imidazole or pyridine are
used for acids, benzoic acid or salicylic acid for bases.
Strong acids also tend to undergo esterification, whereby water is formed
(for example highly concentrated acids such as gaseous HCl or H2SO4
96%).
The following inorganic compounds react with Karl Fischer reagents in a

side reaction which leads to an incorrect water content:
peroxides, oxides, hydroxides, carbonates, hydrogen carbonates, disulfites,
nitrites, sulfites, thiosulfates, hydrazine and derivatives, iron(III) salts,
copper(I) salts, tin(II) salts, silanols, arsenites, arsenates, selenites, tellu-
rites and boron compounds.
For these compounds a direct KF titration is not suitable. The moisture from
thermally stable compounds should be evaporated in a drying oven and
the moisture transferred into the titration cell with a dry purge gas. External
extraction may also be used; however, the sample must be insoluble in the
extraction solvent.
References: ISO 3699-1976 Anhydrous Hydrogen Fluoride for Industrial Use – Determi-
nation of Water Content – Karl Fischer Method
ISO/DIS 7105 Liquified Anhydrous Ammonia for Industrial Use – Determina-
tion of Water Content – Karl Fischer Method
Bryant, W.M.D. and Mitchell, J., Analytical Procedures Employing Karl
Fischer Reagent (Determination of Water of Hydration in Salts in Inorganic
Oxides and Related Components), J. Am. Chem. Soc. 63, 2924-2930
(1941)

Applications: Inorganic raw materials
A) Volumetric determination using DL35
Sample Weight Result RSD Titrant Method
g n % % Solvent
CaCl2 • 2H2O 0.1 6 26.4 0.46 Composite 5 Sample input: weighing boat
30 mL methanol Stir time: 50 s
Phosphoric acid 0.15 6 13.7 0.5 Titrant 5 Sample input: syringe with needle
30 mL solvent Stir time: none
20 mL buffer
Sulfuric acid 0.1 6 4.63 1.4 Titrant 5 Sample input: syringe with needle
approx. 96% 30 mL solvent Stir time: none
20 mL buffer
Sodium 1.7 6 0.443 3.2 Composite 2 Evaporate moisture with drying oven
carbonate 40 mL methanol DO302: 250 °C, 200 mL N2/min
Stir time: 700 s
Calcium oxide 1.5 5 0.227 10.9 Composite 2 Evaporate moisture with drying oven
40 mL methanol DO302: 250 °C, 200 mL N2/min
Stir time: 600 s
Aluminum oxide 1.3 6 0.148 2.2 Titrant 2NH Sample input: weighing boat
30 mL solvent Stir time: 300 s
Reagents:
Titrant 2NH: two component reagent HYDRANAL® Titrant 2NH, Riedel No. 34811 (titrant)
Titrant 5: two component reagent HYDRANAL® Titrant 5, Riedel No. 34801 (titrant)
Solvent: two component reagent HYDRANAL® Solvent, Riedel No. 34800 (solvent)
Composite 2: one component reagent HYDRANAL® Composite 2, Riedel No. 34806 (titrant)
Buffer: buffer 5mmol acid/mL HYDRANAL® Buffer, Riedel No. 34804
B) Coulometric determination using DL37

Sample Weight Result RSD Reagents Method
g n % %
Magnesium 0.07 5 4.6 2.4 100 mL Coulomat A Evaporate moisture with drying oven
oxide 5 mL Coulomat C DO337: 250 °C, 200 mL air/min
Titration time: 400 s
Sodium chloride 1.0 5 0.0360 4.2 100 mL Coulomat A Evaporate moisture with drying oven
5 mL Coulomat C DO337: 300 °C, 200 mL air/min
Lithium chloride 1.0 5 0.7088 3.4 100 mL Coulomat A Evaporate moisture with drying oven
Aluminum 3.0 6 0.0212 3.4 100 mL Coulomat A Evaporate moisture with drying oven
powder 5 mL Coulomat C DO337: 280 °C, 200 mL air/min
Titration parameters for titrations with drying oven DO337:
Adjustment: control gain: 5; switch-off criterium: fixed titration time
automatic drift determination, manual titration start
Reagents:
Coulomat A: anode reagent HYDRANAL® Coulomat A, Riedel No. 34807
Coulomat C: cathode reagent HYDRANAL® Coulomat C, Riedel No. 34808

Comments concerning applications using DL35
Calcium chloride The sample is slightly hygroscopic. All 6 samples could be titrated in the
indicated amount of solvent.
Phosphoric acid The direct titration is unproblematic. The sample must be neutralized with a
base (such as imidazole), otherwise the endpoint will be sluggish.
Sulfuric acid The sample is hygroscopic. The plastic syringe must be discarded after
approx. 96% 3 samples, as the acid will attack it.
Neutralization of the sample with a base (i.e., imidazole) is necessary.
Sodium carbonate Carbonate reduces iodine to give iodide, which results in an erroneously
high water content.
Na2CO3 + I2 + SO2 + CH3OH –> 2NaI + CO2 + HSO4CH3
For this reason the drying oven is used.
An external extraction with methanol results in values that are too high,
since sodium carbonate is slightly soluble in methanol.
Calcium oxide The KF solutions are always weakly acidic, thus they may react with oxides
in a reaction that produces water. CaO + 2 HI –> CaI2 + H2O
This is why use of the drying oven is recommended.
An external extraction with methanol results in elevated values, as traces of
calcium oxide will dissolve in methanol.
Aluminum oxide Aluminum oxide is not basic enough to react with the KF solution. Direct
titration is possible. The sample is highly hygroscopic, thus contact with the
ambient is to be held at a minimum.
The sample releases water slowly, therefore it is necessary to stir for
5 minutes.
Many inorganic salts have low water contents and are thermally stable.
For this reason a coulometric determination using a drying oven is an ideal
method.
Magnesium oxide The high water content necessitates a small sample. This in turn requires
that the sample be homogeneous in order to get reproducible results.
Sodium chloride, The coulometric determination using the drying oven is unproblematic.
lithium chloride,
aluminum powder

Karl Fischer Titration
Water Content Determination of Inorganic Solids
Sample: 3 g Aluminum powder
Preparation: Method:
Heat sample in a crucible, evaporate
the moisture and transfer the vapor into
the titration cell by a dry purge gas.
Oven temperature: 280 °C
Purge gas: 200 mL air/minute
Sample Input:
Fill sample from weighing boat through
connection piece into the crucible.
Cathode Solution:
5 mL Catholyte
(HYDRANAL® Coulomat C No. 34808)
Anode Solution:
100 mL Anolyte
(HYDRANAL® Coulomat A No. 34807)
Comments:
Titration time: 15 minutes Result und Statistics:
The time required for evaporation of the
water is preferably entered as a fixed
titration time (parameter L.Time).
See the operating instructions of the
drying oven for instructions regarding
its use.
Application:
Chemical industry
Instruments:
METTLER DL37 KF Coulometer
Drying oven METTLER DO337
A. Aichert, Application Laboratory, Nov. 1990

3. Organic Raw Materials
General comments Hydrocarbons, halogenated hydrocarbons, alcohols, esters and ether

The water content determination of these substances is unproblematic.
Adding propanol or chloroform increases the solubility of long chained
compounds. Double bonds rarely cause problems.
These compounds generally contain little water, thus coulometry is particu-
larly recommended. Halogenated hydrocarbons may contain active
chlorine from the production process. The active chlorine oxidizes iodide to
iodine (resulting in an erroneously low water content).
Phenols
For most phenols the water content determination is unproblematic. In
some cases salicylic acid may need to be added as a buffer. Some phenols
have been shown to have a high post-consumption (for example, amino-
phenol).
Aldehydes and ketones

These compounds react with methanol to produce acetals and ketals re-
spectively. Water is produced in the reactions. These side reactions may be
suppressed by using methanol-free titrants and solvents. Special reagents
for the water content determination of aldehydes and ketones are available.
Bisulfite addition is a further side reaction which aldehydes will undergo.
This reaction consumes water and starts as soon as the sample is added to
the solvent containing sulfur dioxide. The titration must thus be started im-
mediately to circumvent the bisufite addition.
Organic acids
Strongly acidic organic acids should be neutralized to keep the pH value in
the proper range for a KF titration.
Nitrogen compounds
Strongly basic amines are neutralized with benzoic acid. The solubility of
higher amines needs to be improved by adding chloroform.
A few amines titrated with methanol as the solvent show an unstable end-
point (such as aniline, toluidine, aminophenol), probably due to a side
reaction. This can be eliminated by using a methanol-free solvent.
The water content determination of hydroxylamine, hydrazine and hydra-
zine salts is difficult. Their oxidation by iodine results in erroneously high
water contents.
Sulfur compounds
The determination of these compounds is unproblematic. Exceptions are
mercaptans and thiols. These are oxidized by iodine, resulting in errone-
ously high water contents.
References Scholz, E., Wasserbestimmung in Carbonsäuren,

Fresenius Z. Anal. Chem. 312, 423-426 (1982)
Scholz, E., Titration of Aldehydes and Ketones
Anal. Chem. 57, 2965-2971 (1985)
Scholz, E., Wasserbestimmung in Phenolen
Fresenius Z. Anal. Chem. 330, 8, 694-697 (1988)

Applications: Organic raw materials
g n % % Solvent
4-Chlorotoluene 2.5 8 0.0089 2.3 Composite 2 Input: syringe with needle
30 mL methanol Stir time: none
Benzyl alcohol 2.5 7 0.137 0.57 Composite 2 Input: syringe with needle
2-Nitrophenol 2.0 6 0.0549 1.9 Titrant 2NH Crush sample in mortar
30 mL solvent Input: weighing boat
10 mL buffer Stir time: 30 s
Acetophenone 2.0 8 0.524 0.41 Composite 5K Input: syringe with needle
30 mL Stir time: none
Working medium K
Benzaldehyde 1.0 8 0.168 0.32 Composite 5K Input: syringe with needle
Working medium K Start titration immediately
Salicylic acid 1.0 6 0.0140 0.8 Composite 2 External dissolution in methanol:
30 mL methanol dissolve 30 g in 60 mL MeOH,
Input: 3 ml aliquot with syringe
Oxalic acid 0.06 6 27.9 0.43 Titrant 5 Input: weighing boat
20 mL buffer
Methyl benzoate 3.0 6 0.0083 2.8 Composite 1 Input: syringe with needle
Urea 2.0 6 0.123 4.4 Composite 2 Input: weighing boat
n-Butylamine 0.5 7 1.12 0.4 Titrant 2NH Input: syringe with needle
4 g benzoic acid
Aniline 2.5 6 0.0819 2.7 Composite 5K Input: syringe with needle
Working medium K
5 g salicylic acid
Reagents:
Composite 5K: one component reagent HYDRANAL® Composite 5K, Riedel No. 34816
(Titrant for aldehydes and ketones)
Working medium K: one component reagent HYDRANAL® Working Medium K, Riedel No. 34817
(Solvent for aldehydes and ketones)
Buffer: buffer 5mmol acid/mL HYDRANAL® Buffer, Riedel No. 34804

Comments concerning applications with DL35
4-Chlorotoluene, The direct titration is unproblematic. A titrant with a low concentration

benzyl alcohol (2 mg H2O/mL) is used due to the low water content.
2-Nitrophenol The sample crushed in the mortar dissolves easily in the solvent. Without a
buffer an elevated post-consumption is observed.
Acetophenone Ketones react with methanol to give ketals and water. To prevent this, a
methanol-free titrant and solvent are used.
The solvent should be changed after 4 samples.
Benzaldehyde Aldehydes react with methanol to form an acetal and water. To prevent this,
a methanol-free titrant and solvent should be used. A further side reaction is
bisulfite addition, which consumes water. For this reason the titration is
started immediately after injecting the sample. The weight is entered on the
titrator after the titration.
The solvent must be replaced after each sample. When performing several
titrations in the same solvent a decrease in the determined water content is
observed.
Salicylic acid Finely pulverized salicylic acid may become electrostatically charged,
causing problems during transfer of the sample into the titration cell. The
titration cell remains open for different lengths of time. This may lead to
considerable scatter of the results when titrating small quantities of water.
For this reason, external dissolution in methanol is used. This solution must
be analyzed immediately, as an increasing amount of water (i.e., 250 ppm
after 24 h) is determined after the solution has been standing for some time
(over 3 hours). The cause is a slow esterification of the acid.
Oxalic acid The solvent is to be replaced after 2 samples as its buffering capacity will
be exhausted.
Methyl benzoate The direct titration is straightforward. Due to the low water content, a titrant
with the concentration of 1 mg H2O/ml was used.
Urea As urea is slightly soluble in methanol, the solvent must be replaced after
each sample.
n-Butylamine The endpoint is sluggish in spite of the neutralization with benzoic acid.
The results are too high and poorly reproducible. Decreasing the switch-off
delay to 7 seconds allows reliable and reproducible results to be obtained.
Aniline No stable endpoint could be achieved using methanol as the solvent. Using
a methanol-free solvent eliminates this problem. Neutralizing the aniline
with salicylic acid is necessary, otherwise the endpoint will be sluggish.

Applications: Organic raw materials
g n ppm %
Naphtaline 0.1 6 35.0 10.2 100 mL Coulomat A external dissolution in MeOH:
5 mL Coulomat C dissolve 0.4 g in 25 mL MeOH
Input: 5 mL aliquot with syringe
Stir/Titration time: 0/40 s
4-Chlorotoluene 0.8 6 30.7 1.7 100 mL Coulomat A Input: syringe with needle
dried (1) 5 mL Coulomat C Stir/Titration time: 0/40 s
Benzylalcohol 0.4 6 1273 0.16 100 mL Coulomat A Input: syringe with needle
Phenol 1.0 6 173.7 1.8 100 mL Coulomat A external dissolution in MeOH:
5 mL Coulomat C dissolve 17 g in 60 mL MeOH
Acetophenone 0.3 6 2830 0.46 100 mL Coulomat AK Input: syringe with needle
dried (1) 5 mL Coulomat CK Stir/Titration time: 0/120 s
Benzaldehyde 0.4 6 242.6 0.9 100 mL Coulomat AK Input: syringe with needle
Salicylic acid 0.4 6 115.8 2.9 100 mL Coulomat A external dissolution in MeOH:
(titrate immediately)
Methyl- 0.9 6 49.1 2.0 100 mL Coulomat A Input: syringe with needle
benzoate 5 mL Coulomat C Stir/Titration time: 0/120 s
dried (1)
Benzamide 0.3 6 117.5 3.6 100 mL Coulomat A External dissolution in MeOH:
n-Butylamine 0.2 6 1.14% 0.8 100 mL Coulomat A Input: syringe with needle
20 g benzoic acid Stir/Titration time: 0/200 s
5 mL Coulomat C
Aniline 0.1 1 No result 100 mL Coulomat AK Input: syringe with needle
20 g benzoic acid
5 mL Coulomat CK
Standard titration parameters for all titrations:
Adjustment: control gain: 5 switch-off criterium: End level 0.1 µg/s (0.1 µg H2O/s above drift value)
automatic drift determination, automatic titration start
(1) Dried over molecular sieve 3Å
Reagents:
Coulomat AK: anode reagent HYDRANAL® Coulomat AK, Riedel No.34820
Coulomat CK: cathode reagent HYDRANAL® Coulomat CK, Riedel No.34821

Comments concerning the applications with DL37
Naphtaline A small weigh-in is needed, as napthaline is poorly soluble in methanol.

The coulometric determination with external dissolution is unproblematic.
4-Chlorotoluene, The coulometric determination is straightforward.

benzyl alcohol,
methyl benzoate
Phenol Phenol is first dissolved externally in methanol.
Acetophenone Ketones react with methanol to form a ketal and water. To prevent this, a
methanol-free anolyte and catholyte are used.
With these reagents the titration of acetophenone is straightforward and
gives reproducible results.
Benzaldehyde Aldehydes react with methanol to give an acetal and water. To circumvent
this, methanol-free anolyte and catholyte solutions are used. A further side
reaction is bisulfite addition, a process in which water is consumed.
The titration is started using AUTOSTART immediately after sample addition.
The sample weight is entered on the DL37 during or after the titration.
Salicylic acid and Salicylic acid and benzamide are dissolved in methanol and the external
benzamide solution is then titrated. The salicylic acid solution must be analyzed imme-
diately, since the water content increases upon standing for over 3 hours
(for example, 250 ppm after 24 hours). The slow esterification of the acid
is the cause.
n-Butylamine This is titrated coulometrically by adding benzoic acid. The determined

values tend to increase within the series, resulting in a decreasing repro-
ducibility.
Aniline Aniline will not give a stable endpoint using methanol as the solvent. Even
after using methanol-free reagents and after neutralizing the aniline with
salicylic acid, a coulometric titration proved to be impossible (no endpoint).

Karl Fischer Titratrion
Water Content Determination of Organic Solids
Sample: 0.3 g Phenol
17 g phenol are dissolved in 47 g
methanol in a bottle sealed with a sep-
tum. 1 mL aliquots of the solution are
taken with a syringe for the titration.
Determine the water content of the me-
thanol and enter this as Parameter A.
Sample Input:
Syringe with needle
(such as ME-71482)
Catholyte:
5 mL Catholyte
(HYDRANAL® Coulomat C, No. 34808)
Anolyte:
100 mL Anolyte
(HYDRANAL® Coulomat A, No. 34807)
Result and Statistics:
Comments:
Titration time: 70 seconds
For the coulometric water content de-
termination of solids, an external ex-
traction or external dissolution must be
used. Adding solids directly into the
titration cell by opening the stopper
results in erroneously high water con-
tents (variance greater than 50%).
The DL37 has special calculation for-
mulas for external extraction and exter-
nal dissolution. The parameters are:
A water content of the solvent
(ppm)
B total solvent amount (g)
WtO amount of sample dissolved in B
solvent
Net Aliquot amount (g)
Application:
Chemistry, plastics, pharmaceuticals
Instruments:

4. Solvents
Toluene
General comments Hydrocarbons, halogenated hydrocarbons, alcohols, esters and ether

The water content determination of these substances is unproblematic.
Adding propanol or chloroform increases the solubility of long chained
compounds. Double bonds rarely cause problems.
These compounds generally contain little water, thus coulometry is particu-
larly recommended. Halogenated hydrocarbons may contain active
chlorine from the production process. The active chlorine oxidizes iodide to
iodine (resulting in an erroneously low water content).
Phenols
For most phenols the water content determination is unproblematic. In
some cases salicylic acid may need to be added as a buffer. Some phenols
have been shown to have a high post-consumption (for example, amino-
phenol).
Aldehydes and ketones

These compounds react with methanol and produce acetals and ketals,
respectively. Water is produced in the reactions. These side reactions may
be suppressed by using methanol-free titrants and solvents. Special rea-
gents for the water content determination of aldehydes and ketones are
available.
Bisulfite addition is a further side reaction which aldehydes will undergo.
This reaction consumes water and starts as soon as the sample is added to
the solvent containing sulfur dioxide. The titration must thus be started im-
mediately to prevent the bisulfite addition.
Organic acids
Strongly acidic organic acids should be neutralized to keep the pH value in
the proper range for a KF titration.
Nitrogen compounds
Nitrogen-containing solvents such as amides (i.e., dimethylformamide),
nitro compounds (such as nitrobenzene), and nitriles (acetonitrile) are un-
problematic.
References Scholz, E., Titration of Aldehydes and Ketones

Anal. Chem. 57, 2965-2971 (1985)
ISSN 0192-2971, ASTM Standard, D-1364-87, 1987
Test method for water in volatile solvents (Karl Fischer Titration)

Applications: Solvents
g n % % Solvent
Toluene 3.0 6 0.0144 0.37 Composite 2 Input: syringe with needle
Cyclohexene 2.5 7 0.0080 1.5 Composite 1 Input: syringe with needle
iso-Amyl alcohol 2.0 6 0.141 0.25 Composite 2 Input: syringe with needle
Ethylen glycol 2.0 6 0.651 0.24 Composite 2 Input: syringe with needle
Methylene 3.0 6 0.0115 1.2 Composite 2 Input: syringe with needle
chloride 30 mLmethanol Stir time: 60 s
Diethylether 1.5 6 0.0553 0.40 Composite 2 Input: syringe with needle
Acetone 3.0 7 0.0128 0.48 Composite 5K Input: syringe with needle
Working medium K
Isobutylmethyl- 1.5 6 0.145 0.39 Composite 5K Input: syringe with needle
ketone (IBMK) 30 mL Stir time: none
Working medium K
Formaldehyde 0.04 6 52.0 0.58 Titrant 5 Input: syringe with needle
20 mL buffer
Acetaldehyde 1.3 6 0.0337 4.2 Composite 5K Cool sample to 0 °C
30 mL Input: syringe with needle
Working medium K Titrate immediately
Acetic acid 1.0 6 0.263 0.24 Titrant 2NH Input: syringe with needle
20 mL buffer
Dimethylforma- 1.5 7 0.0867 0.36 Titrant 2NH Input: syringe with needle
mide (DMF) 20 mL solvent Stir time: none
20 mL buffer
Acetonitrile 3.0 7 0.0128 2.3 Composite 2 Input: syringe with needle
Reagents:
Composite 5K: one component reagent HYDRANAL® Composite 5K, Riedel No. 34816
(Titrant for aldehydes and ketones)
Working medium K: one component reagent HYDRANAL® Working Medium K, Riedel No. 34817
(Solvent for aldehydes and ketones)
Buffer: buffer 5 mmol acid/mL HYDRANAL® Buffer, Riedel No. 34804

Toluene, isoamyl- The direct titration is straightforward. Since the water content of these com-
alcohol, ethyleneglycol, pounds is low, a titrant with 2 mg H2O/mL is used.
methylene chloride,
diethylether
Cyclohexene A diluted titrant with a concentration of 1 mg H2O/mL is used to determine

the low water content of 80 ppm.
To achieve a good reproducibility of 1.5% RSD, the following points are
important:
– Condition syringe well with the sample
– Replace the solvent after each 3 samples
(The result using titrant 2 mg H2O/mL: RSD = 2.7% for 6 samples, sample
weight 2 g)
Acetone, Ketones react with methanol generating a ketal and water. Methanol-free
Isobutylmethylketone solvents and titrants must be used to prevent this.
Formaldehyde Formaldehyde will not react with methanol to form an acetal, thus metha-
nol-containing reagents may be used.
The total water content cannot be determined by titrating at room tempera-
ture, as a part of the water is bound as paraformaldehyde.
Even at 50 °C, not all the water will be released (theoretical water content
= 55.8%).
Acetaldehyde Acetaldehyde boils at 15 °C. To simplify sample input with a syringe, cool
the sample to approx. 0 °C.
Acetal formation can be detected by the high post-comsumption, even
though methanol-free reagents were used. Reducing the switch-off delay to
7 seconds reduces the titration time and increases the reproducibility.
Additionally, the sample size was selected to be as small as possible and
was kept constant. The solvent was also renewed after each sample. Bisul-
fite addition occurs as a further side reaction. Water is consumed in this
reaction. To circumvent this problem, the titration is started immediately
after sample addition. The sample weight is entered on the titrator after the
titration.
Acetic acid Acetic acid has a slight tendency to esterify. Thus it is necessary to add a
buffer.
Dimethylformamide The Karl Fischer titration of DMF is straightforward. This is expected to be

true for amides of other carboxylic acids as well.
Acetonitrile The water content determination of acetonitrile is unproblematic.

Applications: Solvents
g n ppm %
Toluene 3.0 6 4.8 9.8 100 mL Coulomat A Input: syringe with needle
n-Hexane 1.0 6 10.5 7.2 100 mL Coulomat A Input: syringe with needle
Sample 1 dried (1) 5 mL Coulomat C Stir/Titration time: 0/36 s
n-Hexane 2.0 8 4.6 9.1 100 mL Anolyte Input: syringe with needle
Sample 2 dried (1) 5 mL Catholyte Stir/Titration time: 0/50 s
Cyclohexene 0.8 6 78.8 1.2 100 mL Coulomat A Input: syringe with needle
5 mL Coulomat C Stir/Titration time: 0/70 s
Isopropyl 0.2 6 787.6 0.31 100 mL Coulomat A Input: syringe with needle
alcohol 5 mL Coulomat C Stir/Titration time: 0/40 s
Ethylene 0.4 6 6541 0.56 100 mL Coulomat A Input: syringe with needle
glycol 5 mL Coulomat C Stir/Titration time: 0/440 s
Ethylene chloride 0.6 6 38.2 3.2 100 mL Coulomat A Input: syringe with needle
Diethylether 0.5 6 40.0 4.0 100 mL Coulomat A Input: syringe with needle
Acetaldehyde 0.5 1 no result 100 mL Coulomat AK Cool sample to 0 °C
5 mL Coulomat CK Input: syringe with needle
Acetone 0.7 6 118.0 0.68 100 mL Coulomat AK Input: syringe with needle
Isobutyl- 0.4 6 717.0 0.18 100 mL Coulomat AK Input: syringe with needle
methylketone 5 mL Coulomat CK Stir/Titration time: 0/100 s
dried (1)
Ethyl acetate 0.5 6 34.9 1.2 100 mL Coulomat A Input: syringe with needle
Dimethyl- 0.4 6 347.3 1.0 100 mL Coulomat A Input: syringe with needle
formamide 5 mL Coulomat C Stir/Titration time: 0/60 s
dried (1)
Adjustment: control gain: 5; switch-off criterium: End level 0.1: µg/s (0.1 µg H2O/s above drift value)
For toluene and n-hexane sample II:
control gain: 3; switch-off criterium: End level 0.05: µg/s (0.05 µg H2O/s above drift value)
(1) Dried over molecular sieve 3 Å
Reagents:
Coulomat AK: anode reagent HYDRANAL® Coulomat AK, Riedel No. 34820
Coulomat CK: cathode reagent HYDRANAL® Coulomat CK, Riedel No. 34821
Anolyte: anode reagent KF reagent for coulometric water content determination, MERCK No. 9255
Catholyte: cathode reagent KF reagent for coulometric water content determination, MERCK No. 9255

Dryed solvents contain little water, sometimes only traces, thus KF coulo-
metry is particularly recommended.
Toluene and n-hexane Toluene and n-hexane sample II were dried for 24 hours over 3 Å molecu-
lar sieve.
n-Hexane sample I was dried for 1 hour over 3 Å molecular sieve.
These examples show that the METTLER DL37 KF coulometer allows repro-
ducible results to be obtained even for trace amounts of water
(i.e., 4.6 ppm ± 0.4 ppm).
Cyclohexene, isopropa- The coulometric titration of these samples is straightforward.

nol, ethylene glycol,
ethylene chloride,
diethylether,
ethyl acetate
Acetone, Ketones react with methanol, generating ketals and water. To prevent this,
isobutylmethylketone a methanol-free anolyte and catholyte are used.
Acetaldehyde The boiling point of acetaldehyde is 15 °C. To simplify sample input with a
syringe, the sample should be cooled to approximately 0 °C.
In spite of the use of methanol-free reagents, acetal formation proceeds at a
rate that makes the coulometric water content determination impossible.
Dimethylformamide This compound is easily analyzed by KF coulometry. This is to be expected

for other acid amides as well.
These examples show that the METTLER DL37 KF Coulometer provides

reliable and exact values even in the trace water range, such as
4.6 ppm ± 0.4 ppm.

Water Content Determination of Solvents
Sample: 2 g n-hexane dried over molecular sieve 3Å
Keep sample in a septum flask.
Sample Input:
Syringe with needle (i.e., ME-71482)
Catholyte:
5 mL Catholyte
(KF reagent for coulometric water
determination, MERCK No. 9255)
Anolyte:
100 mL Anolyte
(KF reagent for coulometric water
determination, MERCK No. 9255)
Comments: Results und Statistics:

Titration time: 50 seconds
Samples with low moisture contents in
the ppm range should be stored in
septum flasks. These samples are ge-
nerally hygroscopic, thus the original
water content is considerably altered
and falsified by any contact with the
ambient (open flask, sample transfer,
etc.).
When removing the sample, the pres-
sure loss should be compensated with
dried air only.
Application:
Chemistry, petroleum products,
polymers, pharmaceuticals
Instruments:

5. Petroleum Products
OIL
General Comments Mineral oils

Mineral oils can be completely dissolved only in the presence of chloro-
form. The chloroform may be replaced by 1-decanol or the special solvent
for oils and fats when analyzing light mineral oil products (i.e, benzene,
kerosine, diesel oil or heating oil). Crude oils, some of which contain tarry
components, are best dissolved in a methanol/chloroform/toluene mixture.
Motor oils contain additives that may interfere with the KF titration (such as
ketones, keto acids, zinc-dialkyl-dithiophosphates, calcium or magnesium
sulfonates). In this case the drying oven can be used. The temperature
should be adjusted to 120–140 °C, as the additives may decompose.
Mineral oils have low moisture contents (frequently less than 100 ppm).
For these samples, KF coulometry is particularly suitable. Crude oils con-
tain insoluble impurities that may clog the diaphragm. The drying oven is
best used for these samples.
Silicon oils
The solubility of silicon oils must be improved by the addition of chloroform
or 1-decanol.
Fats
Some fats are not rendered soluble even after adding chloroform. In these
cases, external extraction in pure chloroform or use of the drying oven
(temperature 120–140 °C) have proven useful.
Parafins and waxes

Waxes and parafins may be titrated directly at 50 °C in a mixture of
methanol/chloroform. The determination using the drying oven is a further
possibility.
Tar and coal

Tarry products can be dissolved by adding toluene or xylene. The drying
oven can also be used for tar and coal.
References ISO/DIS 5381, Flüssige Petroleum Produkte – Wasserbestimmung nach

Karl Fischer
DIN 51777 Teil I, Test von Mineralöl, Kohlenwasserstoffen und Lösungs-
mittlen, Wasserbestimmung nach Karl Fischer. Direkte Methode.
ASTM-Standard, D-4377-88, 1988
Test method for water in crude oils (Karl Fischer Titration)

Applications: Petroleum products
g n % % Solvent
Gasoline 2.5 6 0.0710 0.26 Titrant U 9233 Input: syringe with needle
unleaded 50 mL LM F 9230 Stir time: 30 s
Diesel oil 5.0 6 0.0069 2.1 Titrant 2NH Input: syringe with needle
20 mL 1-decanol
Petroleum 4.5 6 0.0077 0.72 Titrant 2NH Input: syringe with needle
20 mL 1-decanol
Motor oil 2.5 6 0.0721 13.4 Composite 2 Evaporate moisture with drying oven
Stir time: 600 s
Motor oil 0.3 6 0.2261 0.94 Titrant 2NH Input: syringe with needle
30 mL chloroform
Motor oil 2.5 6 0.0842 9.9 Composite 2 Evaporate moisture with drying oven
used 40 mL methanol DO302: 140 °C, 200 mL N2/min
Stir time: 600 s
Silicon oil 4.0 9 0.0097 0.56 Titrant 2NH Input: syringe with needle
20 mL 1-decanol
Crude oil 2.0 5 0.0206 2.9 Titrant 2NH Input: syringe with needle
30 mL chloroform
multi- 0.2 5 0.338 0.88 Titrant 2NH External solution:
purpose 40 mL solvent 3 g in 80 g chloroform,
grease 20 min at RT
Ski wax 1.5 7 0.0417 1.3 Composite 2 Melt sample at 50 °C
25 mL methanol Input: syringe with needle (warm)
25 mL toluene Stir time: none
Shoe polish 2.0 5 0.0219 4.9 Composite 2 Melt sample at 50 °C
25 mL methanol Input: syringe with needle (warm)
25 mL toluene Stir time: none
Reagents:
Titrant U 9233: two component reagent Titrant U 5 mg H2O/mL, MERCK No. 9233
LM F 9230: two component reagent Solvent F (fats and oils), MERCK No. 9230

Comments concerning the applications using DL35
Gasoline, diesel oil, The solubility was improved by using 1-decanol or the special solvent for
petroleum oils and fats instead of chloroform.
Motor oil Motor oil contains additives to improve its usability. These are zinc-dialkyl-
dithiophosphate, calcium sulfonate and magnesium sulfonate. New motor
oils contain 5–7% of these additives.
Motor oil may be titrated by adding chloroform; however, the resultant
values are too high due to side reactions with the additives.
Reliable values can be obtained by evaporating the moisture in a drying
oven at 140 °C and transferring the vapor into the titration cell with a dry
purge gas. At higher temperatures the additives will decompose, which will
also cause errors. The sample is injected through a septum directly into the
crucible using a syringe. The weight is determined by back-weighing.
Silicon oil 1-Decanol must be added to the solvent to completely dissolve the sample.
After 3 samples the solvent should be replaced, as its dissolving capacity
will be exhausted.
Crude oil The sample can be dissolved completely only by adding chloroform to the
solvent. 1-Decanol no longer suffices. Replace solvent after each sample,
as its dissolving capacity is quickly exhausted.
Multi-purpose grease This fat is incompletely soluble even after adding chloroform. For this rea-
son an external extraction with chloroform was used.
A determination using the drying oven at 180 °C is a further possibility.
At higher temperatures, however, the sample will polymerize.
Ski wax, shoe polish The sample is melted in a sealed flask at approximately 50 °C. A pre-
warmed syringe is used for sample input. The syringe may be warmed
using a hair dryer for instance. This procedure is necessary as the sample
will solidify immediately in a cold syringe.
The addition of toluene and heating the titration solution to approx. 30 °C
results in a suspension which can easily be titrated. The solvent must be
replaced after 3 samples, otherwise the sample will begin to precipitate.
This will cover the electrode.
The titration solution was kept at 30–35 °C using a thermostatable titration
beaker (ME-23976) with a circulating water bath.

Applications: Petroleum products
g n ppm %
Gasoline 0.6 13 769.3 0.5 100 mL Coulomat A Input: syringe with needle
super 5 mL Coulomat C Stir/Titration time: 0/50 s
Kerosene 2.5 7 36.1 1.4 100 mL Coulomat A Input: syringe with needle
(flight benzene) 5 mL Coulomat C Stir/Titration time: 0/75 s
Petroleum dried 0.5 6 43.4 2.5 100 mL Coulomat A Input: syringe with needle
with molecular sieve 5 mL Coulomat C Stir/Titration time: 0/30 s
Hydraulic oil 0.5 6 579.8 2.0 70 mL Coulomat A Input: syringe with needle
30 mL chloroform Stir/Titration time: 0/180 s
5 mL Coulomat C
Turbine oil 3.0 3 33.5 1.0 70 mL Coulomat A Input: syringe with needle
30 mL chloroform Stir/Titration time: 0/180 s
5 mL Coulomat C
Transformer 10.0 5 30.4 1.9 100 mL Coulomat A Input: syringe with needle
oil 5 mL Coulomat C Stir/Titration time: 0 / 180 s
Brake fluid 0.3 7 1081.2 0.38 100 mL Anolyte Input: syringe with needle
5 mL Catholyte Stir/Titration time: 0/210 s
Silicon oil 0.5 6 103.5 1.7 100 mL Coulomat A Input: syringe with needle
Paraffin 3.0 6 31.0 15.9 100 mL Coulomat A Evaporate moisture with drying oven
granulate 5 mL Coulomat C DO337: 150 °C, 200 mL air/min
Crude oil 3.0 5 202.0 6.6 100 mL Coulomat A Evaporate moisture with drying oven
Soot 0.8 5 3582.7 1.5 100 mL Anolyte Evaporate moisture with drying oven
5 mL Catholyte DO337: 200 °C, 200 mL N2/min
Adjustment: control gain: 5; switch-off criterium: End level 0.1µg/s (0.1 µg H2O/s above drift value)
Titration parameters for titrations using DO337 drying oven:
Adjustment: control gain: 5; switch-off criterium: fixed titration time and End level 0.05 µg/s
Reagents:
Coulomat A: anode reagent HYDRANAL© Coulomat A, Riedel No. 34807
Coulomat C: cathode reagent HYDRANAL© Coulomat C Riedel No. 34808

Mineral oil products have low moisture contents, sometimes only traces,
thus KF coulometry can be particularly recommended.
Gasoline, kerosine, Coulomat A contains chloroform, thus these samples can be titrated without
petroleum adding chloroform. After 2–3 samples the dissolving capacity of the solvent
is exhausted and an emulsion results. Even in this condition, correct and
reproducible results can be obtained by coulometric titration.
Turbine and Adding chloroform to these oils gives an emulsion which can be titrated
hydraulic oil directly. The emulsive quality of these heavy oils is not as good as that of
gasoline or petroleum. The titration time is longer and the reproducibility
poorer.
These oils can also be titrated using the drying oven: the moisture is evapo-
rated at 130 °C and the vapor transferred into the titration cell using a dry
purge gas.
Transformer oil This oil can be titrated directly as an emulsion. The rather low moisture
content requires a higher sample weight.
Silicon oil Silicon oil can be titrated directly as an emulsion without adding chloro-
form. The emulsive quality is very good. The titration time is short, the
reproducibility high.
Paraffin This can be dissolved only in a chloroform/methanol mixture at approx.

50 °C. Coulometric determinations at elevated temperatures, however, are
not possible due to limits imposed by the DL37. For this reason the drying
oven is used.
When air is used as the purge gas, the drying temperature may not exceed
180 °C. At 200 °C the product begins to oxidize after only 10 minutes.
The oxidation process releases water. The poor reproducibility is primarily
caused by the inhomogeneity of the sample granules.
Crude oil Crude oil contains insoluble contaminants that can clog the diaphragm.
Thus the drying oven is the method of choice. The sample input of the
crude oil is best achieved by injecting the oil through a septum directly into
the crucible. Weight determination by back-weighing.
A direct titration with chloroform addition gives erroneous results:
– the sample is merely emulsified and the water released only partially
– moisture content too low
(mean from 6 samples = 128.9 ppm, RSD = 0.7%)
– black deposit in the titration cell, cell must be cleaned
Soot The coulometric determination using the drying oven is straightforward.

A direct determination using volumetric KF titration (DL35) by adding for-
mamide or chloroform gives results that are too low, as the soot dissolves
incompletely and the water is only partially released.

Water Content Determination of Mineral Oil
Sample: 2 g Crude oil
Preparation:
Keep sample in a septum flask
Sample Input:
Syringe with needle (e.g., ME-71482)
Titrant:
KF titrant, 2 mg H2O/mL
(HYDRANAL® Titrant 2NH No. 34811)
Solvent:
20 mL KF solvent
(HYDRANAL® Solvent, No. 34800)
30 mL chloroform
Comments:
Stir time: 60 seconds
Results und Statistics:
Samples with moisture contents in the
ppm range should be stored in septum
flasks. The samples are generally hy-
groscopic. The original moisture con-
tent is rapidly and significantly altered
by any contact with the ambient (ope-
ning the flask, transferring the sample,
etc.).
After removing the sample from the
flask, the pressure difference should be
compensated with dry air only.
A three-hole adaptor (ME-23982) is
recommended for the sample input
using a syringe.
Replace the solvent after 2 samples, as
the dissolving capacity is exhausted.
Titrations of incompletely dissolved
samples (such as emulsions) give lo-
wer results.
Application:
Petrochemical industry
Instruments:
METTLER DL35 Karl Fischer Titrator
Electrode DM 142
Matrix printer Epson LX-800
A. Aichert, Application Laboratory, Dez. 1990

6. Plastics and Adhesives
Glue
General comments Plastics

Water is usually occluded in plastics. It is released very slowly and incom-
pletely by diffusion. Most plastics are not soluble in a KF solvent or solvent
mixture. Therefore the moisture is usually evaporated in a drying oven,
then the vapor is driven into the titration cell using a dry purge gas. External
extraction in methanol, if necessary at 50°C, is also possible.
Plastics have low moisture contents (often less than 100 ppm), so that KF
coulometry is especially recommendable.
Ion exchanger
Ion exchange resins are insoluble in organic solvents. For this reason, the
drying oven is used to evaporate the moisture. The vapor is driven into the
KF cell using a dry purge gas.
Adhesives
The water content of adhesives can be determined directly. In some cases
chloroform may be necessary to completely dissolve the sample.
References Muroi, K., Determination of Water in Plastic Materials by Karl Fischer

Method, Bunseki Kagaku 11, 351 (1962)
Praeger, K. and Dinse, H.D., Experiences in the Determination of Small
Amounts of Water in Polyethylene and Polyamide
Faserforsch. Textiltechn. 21, 37-38 (1970)
DIN 53715 Wasserbestimmung von pulverförmigen Kunststoffen nach Karl
Fischer
ASTM Designation: D 789-81 Standard Specification for Nylon Injection
Molding and Extrusion Materials
Sharma, H.D. and Subrramanian, N., Determination of Water in Ion-
Exchange Resins by Karl Fischer
Anal. Chem. 41, 2063-2064 (1969)
Anal. Chem. 42, 1278-1290 (1970)
van Acker, P., de Cote, F. and Hoste, J., Determination of Water in Strong
Base Anion-Exchange Resins by the Karl Fischer Titration
Anal. Chim. Acta. 73, 198-203 (1974)

Applications: Plastics and Adhesives
g n % % Solvent
Polyethylene 3.0 6 0.0068 6.9 ReAquant 3.5 Evaporate moisture with drying oven
granules 40 mL solvent Sprint DO337: 280 °C, 200 mL N2/min
Stir time: 600 s
Polyamide 2.0 6 0.5547 0.67 Composite 5 Evaporate moisture with drying oven
granules 40 mL methanol DO302: 190 °C, 200 mL N2/min
Stir time: 900 s
Epoxy resin 0.05 5 0.258 2.6 Titrant 2NH Input: syringe with needle
fluid 20 mL solvent Stir time: 60 s
20 mL chloroform
Glue stick 0.05 6 46.3 0.94 Composite 5 Input: spatula
20 mL methanol Stir time: 100 s
20 mL chloroform
All-purpose glue 0.2 7 1.28 2.2 Titrant 2NH Input: tube with needle
Cyanoacryl glue 30 mL solvent Stir time: 60 s
Rubber 0.1 6 0.287 5.3 Titrant 2NH External dissolution:
cement 10 mL solvent 4 g in 85 g chloroform; 10 min. RT
30 mL chloroform Input: 1 mL aliquot with syringe
Reagents:
ReAquant 3.5: two component reagent ReAquant ® 3.5 mg H2O/mL, J.T.Baker No. 8842 (titrant)
Solvent Sprint: two component reagent ReAquant ® Solvent Sprint, J.T.Baker No. 8855 (solvent)

g n ppm %
Polyethylene 2.0 6 68.7 8.2 100 mL Coulomat A Evaporate moisture with drying oven
granules 5 mL Coulomat C DO337: 180 °C 200 mL air/min
Polypropylene 2.0 6 148.3 5.4 100 mL Coulomat A Evaporate moisture with drying oven
Polystyrene 2.0 6 322.2 2.4 100 mL Coulomat A Evaporate moisture with drying oven
PVC foil 0.1 6 638.1 2.2 100 mL Coulomat A Evaporate moisture with drying oven
5 mL Coulomat C DO337: 150 °C 200 mL air/min
Standard titration parameters for titrations with drying oven DO337:
Adjustment: control gain: 5; (for PVC foil: control gain: 3)
switch-off criterium: fixed titration time and End level 0.05 µg/s
Reagents:

Polyethylene The sample melts and, once cooled, sticks to the weighing boat. Line the
weighing boat with aluminum foil to facilitate sample removal.
Due to the low moisture content, the drift must be determined prior to each
sample to ensure a good reproducibility.
Polyamide The use of too high temperatures for polyamides may result in a continual
condensation reaction which frees water and artificially elevates the water
content. For this reason, the sample was first tested at 120°C for 2 hours;
result: 0.5445%. The temperature was then elevated to 190°C and the
time drastically reduced; result: 0.5547%.
Epoxy resin (fluid) Chloroform was added to the solvent to competely dissolve the sample.
After 4 samples the solvent should be replaced, as its dissolving capacity
will be exhausted.
Glue stick Chloroform must be added to the solvent to ensure that the sample dis-
solves completely. All 6 samples can be titrated in the same solvent.
All-purpose glue The end of the tube was fitted with an injection needle with a large inner
(cyanoacryl glue) diameter (1.2 mm) for the sample input.
Rubber cement As the sample is poorly soluble in the solvent/chloroform mixture, it was
externally dissolved in chloroform.
A solvent/chloroform mixture must be used for titration of the solution. The
rubber precipitates in pure solvent and will cover the electrode.
The solvent must be replaced and the electrode cleaned (deposit on the
electrode) after each titration.
Polyethylene, When air is used as the carrier gas, the oven temperature may not exceed
polypropylene, 180 °C. At 220 °C the polyethylene and polypropylene will oxidize in a
polystyrene process that generates water.
The cooled sample will stick to the weighing boat. Line boat with alumi-
num foil to facilitate sample removal.
PVC foil The foil is cut into approximately 3 cm2 pieces. These will fit easily into the
drying oven crucible. The sample should not touch the inner wall of the
drying oven, as the PVC will stick to it.

Water Content Determination of Plastics
Sample: 3 g Polyethylene granulate
Preparation:
Place sample in drying oven. Evapo-
rate moisture and transfer the vapor
into the titration cell with a dry purge
gas.
Oven temperature: 280 °C
Purge gas stream: 200 mL N2/min
Sample input:
Weighing boat
Titrant:
KF titrant 3.5 mg H2O/mL
(ReAquant® Titrant, J.T. Baker
No. 8842)
Solvent: Results und Statistics:

40 mL KF solvent
(ReAquant® Solvent, J.T. Baker
No. 8855)
Comments:
Stir time: 600 s
METTLER method No. 50
The sample melts and, once cooled,
will stick to the weighing boat. Line
weighing boat with aluminum foil to
facilitate sample removal.
Application:
Polymer industry
Instruments:
METTLER DL35 Karl Fischer Titrator
Electrode DM142
Drying oven METTLER DO302
Matrix printer Epson LX-800
A. Aichert, Application Laboratory, Dez. 1990

7. Medicines (Pharmaceuticals)
General comments In the pharmaceutical industry, moisture contents of active substances, the
raw materials required to synthesize these, and the final products them-
selves are determined.
Raw materials
The raw materials used by the pharmaceutical industry are organic and
inorganic raw materials as well as solvents. The moisture content determi-
nations of these products are described in Chapters 2–4.
Active substances
The pharmaceutically active substances are generally organic or inorganic
compounds which are soluble in methanol. These can usually be titrated
unproblematically. Aldehydes, ketones and some amides require the use of
methanol-free reagents, as their esterification reactions lead to incorrectly
high water contents.
Lyophilized substrates
Injectable substances are sometimes delivered as dried substrates, to pro-
long the usability of active substances. Here the residual water content is a
crucial factor. This water content will be around 100 µg H2O per ampule.
Tablets
Tablets may contain substances that will react with KF reagents in side
reactions. This is the case for magnesium and aluminum hydroxides, for
example. Both compounds are used as antacids.
Ointments, oils, suppositories

The solubility of oils and ointments may be improved by adding chloroform
or 1-decanol. The USP XXI recommends a mixture of carbon tetrachloride :
chloroform : methanol 2:2:1 for ointments. Suppositories can be dissolved
by adding chloroform and elevating the temperature.
References Cachet, T. and Hoogmartens, J., Determination of water in erythromycin by

Karl Fischer titration, J. Pharm. Biomed. Anal. ISSN 0731-7085; 6,5,461-
472 (1988)
Müller, M., Determination of water in erythromycin by Karl Fischer titration,
Dtsch. Apoth. Ztg. ISSN 0011-9857; 127, 41, 2034-2036 (1987)
Use of a simple Karl Fischer apparatus for water determination in lyophil-
ized radiopharmaceutical kits, Appl. Radiot. Isot. ISSN 0883-2889; 38,
11, 992-993 (1987)
Lindquist, J., Determination of water in penicillins using Karl Fischer
reagents, J. Pharm. Biomed. Anal. ISSN 0731-7085; 2,1,37-44, 1984

Applications: Medicines
g n % % Solvent
Aspirin 0.2 6 1.53 1.9 Titrant U 9233 Crush sample
30 mL LM 9241 Input: weighing boat
Stir time: 600 s
Antibiotics 0.2 6 4.56 1.0 Titrant U 9233 Input: weighing boat
dry 30 mL LM K 9221 Stir time: 300 s
2 drops Triton X100 Stir rapidly
Antibiotics 0.03 6 95.8 0.24 Titrant U 9233 Input: syringe with needle
suspension 30 mL LM 9241 Stir time: none
Disinfectant 1.0 6 0.0620 1.5 Titrant 2NH Input: weighing boat
powder 30 mL solvent Stir time: 120 s
Cough drops 0.1 6 6.25 0.13 Titrant U 9233 Input: syringe with needle
30 mL LM 9241 Stir time: none
Valerian 0.1 6 29.3 0.14 Titrant 9258 Input: syringe with needle
essence 30 mL methanol Stir time: none
Chamomile 0.03 6 43.2 0.12 Titrant 9258 Input: syringe with needle
extract 30 mL methanol Stir time: none
Tonic 0.05 6 57.0 0.26 Titrant U 9233 Input: syringe with needle
25 mL LM 9241 Stir time: none
15 mL formamide
Gel for 0.7 6 42.3 0.51 Titrant U 9233 Input: syringe with needle
sprains and 30 mL LM 9241 Stir time: 30 s
infections
Ointment 0.03 5 71.2 0.74 Titrant U 9233 Input: syringe with needle
base 40 mL LM F 9230 Stir time: 30 s
Ointment 0.03 5 54.7 0.40 Titrant U 9233 Input: syringe with needle
for burns 40 mL LM F 9230 Stir time: 60 s
Suppository 1.0 6 0.0023 13.3 Titrant 2NH Input: with tweezers
15 mL toluene Titrate at 50 °C
Reagents:
Titrant 9243: two component reagent Titrant 5 mg H2O/mL, MERCK No. 9243
Titrant U 9233: two copmponent reagent Titrant U 5 mg H2O/mL, MERCK No. 9233
LM 9241: two component reagent Solvent, MERCK No. 9241
LM K 9221: two component reagent Solvent K (for ketones and aldehydes), MERCK No. 9221
LM F 9230: two component reagent Solvent F (for fats and oils), MERCK No. 9230
Titrant 9258 one component reagent Titrant 5 mg H2O/mL, MERCK No. 9258

Aspirin The finely crushed sample does not dissolve completely. To ensure the
complete release of all water, stir for 10 minutes.
Antibiotics (dry) This sample is not dense and is poorly wettable with the solvent. Lumps
form which contain undissolved substances. Lump formation can be
avoided by adding a detergent (Triton X100) and by stirring vigorously.
The sample will then dissolve completely.
An elevated post-consumption can be observed when using regular sol-
vents. This effect can be eliminated by using a methanol-free solvent.
Antibiotics (suspension) The direct titration is straightforward.
Disinfectant powder This powder is insoluble in the KF solvent. A direct titration as a suspension
is possible. Even with a stir time of only 2 minutes, no post-consumption
takes place, thus the water has been completely released.
Chamomile extract, Titrate directly.

couph drops and
valerian extract
Tonic When using the normal solvent of the two component reagent as well as
methanol, a gel drop forms which immediately deposits itself on the
platinum point of the electrode. This results in an over-titration. By adding
formamide this effect can be avoided.
Gels, ointments These samples are filled into the back end of a syringe for the sample input.
No needle is used due to the sample consistency.
The gel dissolves in the solvent of the two component reagent.
The complete dissolution of fat-based ointments requires the addition of
chloroform, 1-decanol or the special solvent for fats and oils.
Suppositories One complete suppository is used for each titration. (The weight is constant:
1.0 g). In the solvent/toluene mixture the suppositories dissolve (melt)
completely at 50 °C. The solvent must be replaced after 2–3 samples, as
the samples no longer dissolve completely. This leads to a decrease in the
reproducibility.

Applications: Medicines
g n ppm %
Massage oil 0.3 6 1059 0.21 100 mL Coulomat A Input: syringe with needle
Eucalyptus 0.1 6 1267 0.39 100 mL Coulomat A Input: syringe with needle
oil 5 mL Coulomat C Stir/Titration time: 0/100 s
Titration parameters:
Adjustment: control gain: 5; switch-off criterium: End level 0.1 µg/s (0.1 µg H2O/s above drift value)
Sample Lot No. Flask Result Reagents Method

µg H2O
Lyophilized 2BOA 1 771.3 100 mL Coulomat A Dissolve in septum flask with
Plasma 2 699.3 5 mL Coulomat C 5 mL titrated Coulomat A
3 759.2 Input: syringe with needle
4 665.7 Stir/Titration time: 0/150 s
RRO5 1 720.7
2 648.7
3 729.3
4 619.1
Titration parameters:
Adjustment: control gain: 2; switch-off criterium: End level 0.1 µg/s (0.1 µg H2O/s above drift value)
Reagents:
Eucalyptus and The direct titration is unproblematic. The addition of chloroform is unneces-
massage oils sary.
Lyophilized plasma An external dissolution of the lyophilisate is not recommendable due to the
low moisture content. The correction factor for the solvent blank is too high
compared to the water content of the sample. Therefore, the following
procedure is used: approximately 5 mL anolyte are removed from the ano-
lyte space of the titration cell with a plastic syringe. This is filled back into
the titration cell. The syringe is rinsed in this manner until it is dry. Then
5 mL anolyte are taken up in the syringe and injected through a septum
into the sample flask. The lyophilisate is suspended by shaking the flask
(5 minutes in the sonicator). The entire suspension is then pulled back into
the syringe, injected into the titration cell, and the water content is deter-
mined.
The pressure compensation for sample removal must be achieved using
dry air.

8. Dyes and Agrochemicals
General Comments Dyes

A large number of dyes are soluble in methanol; these can be titrated easily.
Insoluble dyes, such as pigments, can be titrated directly as a suspension.
Using this procedure, only the adherent moisture will be determined.
A direct titration of water-based dispersion paints and lacquers can also be
undertaken. When titrating lacquers, care must be taken in the choice of a
solvent. Ketones or reactive amines require the use of a methanol-free sol-
vent to prevent interferences caused by side reactions with the KF reagents.
Agrochemicals
Agrochemicals are supplied in solution (with organic solvents), water-
based suspensions or as powders.
Unpolar solvents are generally used for the solution; thus, the samples can
be completely dissolved only by adding chloroform or 1-decanol. The
moisture content of these is low so that the coulometric method is feasible.
The water-based suspensions are best titrated using a direct volumetric
titration.
Powders rarely dissolve in most KF solvents. Suspensions of these powders
allow the determination of the adherent moisture only.
References ASTM D 4017-81 Standard Test Method for Water in Paints and Paint
Materials by Karl Fischer Method

Applications: Dyes and agrochemicals
g n % % Solvent
Optical 0.3 6 3.87 0.76 Titrant 9258 Input: weighing boat
brightener 30 mL methanol Stir time: 300 s
Wool dye 0.25 6 10.99 0.14 Titrant 9258 Input: weighing boat
Orange R 40 mL methanol Stir time: 30 s
Reactive dye 0.3 6 5.24 0.42 Titrant 9258 Input: weighing boat
scarlett F-3G 40 mL methanol Stir time: 60 s
Indicator dye 0.6 6 0.928 1.0 Titrant 9258 Input: weighing boat
methanile yellow 40 mL methanol Stir time: 120 s
Dispersion 0.3 6 6.91 0.22 ReAquant 5 Input: weighing boat
dye olive 30 mL solvent Sprint Stir time: 300 s
25 mL formamide
Acrylic paint 0.05 6 54.3 0.47 Titrant U 9233 External solution:
water based 25 mL LM 9241 3.6 g in 20 mL formamide
15 mL formamide Input: 1 mL aliquot with syringe
Synthetic 1.5 6 0.0906 3.4 Titrant U 9233 Input: syringe with needle
enamel 20 mL LM 9241 Stir time: none
20 mL toluene
Insecticide 2.0 6 0.0977 0.56 Titrant 60626 Input: syringe with needle
biological 30 mL LM 60625 Stir time: none
20 mL 1-decanol
Insecticide 2.0 6 0.1461 0.21 Titrant 60626 Input: syringe with needle
Diazinon 30 mL LM 60625 Stir time: none
10 mL 1-decanol
Rose fungicide 0.03 6 58.3 0.25 Titrant 60626 Input: syringe with needle
watery emulsion 30 mL LM 60625 Stir time: none
Herbicide 1.0 6 1.20 0.49 Titrant U 9233 Input: weighing boat
powder 30 mL LM 9241 Stir time: 180 s
Insecticide 1.0 6 0.273 2.6 Titrant 60626 Input: weighing boat
ant killer 30 mL LM 60625 Stir time: 180 s
Reagents:
Titrant 9258: one component reagent Titrant 5 mg H2O/mL, MERCK No. 9258
Titrant 60625: two component reagent Titrant 5 mg H2O/mL, FLUKA No.60626
LM 60625: two component reagent Solvent, FLUKA No. 60625
ReAquant 5: two component reagent ReAquant® 5 mg H2O/mL, J.T. Baker No. 8844 (titrant)
Solvent Sprint: two component reagent ReAquant® Solvent Sprint, J.T. Baker No. 8855 (solvent)

g n ppm %
Rose fungicide 0.5 6 828.6 0.36 100 mL Anolyte Input: syringe with needle
solution 5 mL Catholyte Stir/Titration time: 0/90 s
Titration parameters for the titration:
Adjustment: control gain: 3; switch-off criterium: End level: 0.1 µg/s
Reagents:
Comments concerning the applications
Optical brightener This sample is not soluble in KF solvents; it can, however, be suspended.
A direct titration with a 5-minutes stir time in methanol is possible. After
2 samples, the solvent should be replaced and the electrode cleaned (forms
deposit).
Wool, reactive and These samples are easily dissolved in methanol. The dissolving capacity of
indicator dyes the solvent is limited; replace the solvent after 3–4 samples.
Dispersion dye This sample is insoluble in KF solvents. It can be titrated directly as a

suspension by adding formamide. In pure methanol the water is released
slowly and incompletely (result: 6.6% with 30 minutes titration time).
Acrylic paint A direct titration in a formamide/solvent mixture results in the sample stick-
ing to titration cell and electrode, and is not a feasible alternative. The
sample is dissolved in pure formamide and this solution is added to the
formamide/solvent mixture. The resulting emulsion can be titrated straight-
forwardly (slightly increased post-consumption). Replace the solvent after
2 samples.
Synthetic enamel The sample is added to a prepared toluene/solvent mixture. The resulting
fine emulsion can be titrated unproblematically (slightly increased post-
consumption). Replace solvent after 2 titrations.
Insecticide and rose These samples (active agent plus solvent) are soluble only in the presence
fungicide (solutions) of 1-decanol. If an emulsion is prepared, somewhat lower values will result.
Due to the low moisture content, a coulometric determination is a further
possibility.
Rose fungicide The direct tiration is unproblematic.

(water-based emulsion)
Insecticide and These samples are insoluble in KF solvents. A direct titration is possible with
herbicide a 3-minutes stir time. (No elevated post-consumption). After 3 samples
have been titrated, the water content values decrease (replace solvent).

9. Detergents and Surfactants
General comments For these products, which are solids, liquids or pastes, a direct KF titration
can easily be undertaken.
Detergents containing hydroxide or perborate result in elevated water
content values, as these compounds undergo a side reaction with the KF
reagent.
References ISO 4317-1977 Surface-Active Agents – Determination of Water – Karl

Fischer Method
Laundry detergent This detergent contains perborate, which reacts with the KF reagent in a
side reaction. For this reason the moisture is evaporated in the drying
oven at 150 °C and the vapor is transferred to the titration cell by a dry
purge gas.
Detergent for fine These detergents contain neither hydroxides nor perborates. They can be
washables titrated directly.
Cleaner, dish detergent, These samples dissolve in the solvent. The direct titration is straightforward.
soft soap Caution: beware of the water dissolving capacity of the KF solvent (replace
solvent after 3–4 samples).
Fabric softener, These emulsions can be titrated directly without encountering problems.
impregnation agent
Non-ionic-surfactant The direct titration is straightforward. The coulometric determination can

be used for samples with a low moisture content.

Applications Detergents and Surfactants
g n % % Solvent
Laundry 0.1 6 13.7 2.3 ReAquant 5 Evaporate moisture with drying oven
detergent 30 mL solvent DO302: 150 °C, 200 mL N2/min
Stir time: 1200 s
Detergent for 0.2 6 6.13 1.2 ReAquant 5 Input:weighing boat
fine washables 30 mL solvent Stir time: 500 s
30–60 °C
Liquid 0.03 6 81.7 0.60 ReAquant 5 Input: syringe with needle
detergent 30 mL solvent Stir time: none
Cleaner 0.03 5 73.9 0.25 ReAquant 5 Input: syringe with needle
liquid 30 mL solvent Stir time: none
Dish detergent 0.03 6 73.0 0.39 ReAquant 5 Input: syringe with needle
liquid 30 mL solvent Stir time: none
Soft soap 0.03 6 76.4 1.3 ReAquant 5 Input: syringe with needle
Fabric softener 0.03 6 84.3 0.37 ReAquant 5 Input: syringe with needle
cocentrate 30 mL solvent Stir time: none
Impregnation 0.03 6 61.4 0.32 ReAquant 5 Input: syringe with needle
agent 30 mL solvent Stir time: 120 s
non-ionic 2.0 6 0.160 0.84 ReAquant 3.5 Input: syringe with needle
surfactant 30 mL solvent Stir time: none
alkylphenylpoly-
ethyleneglycol
Reagents:
ReAquant 5: two component reagent ReAquant ® 5 mg H2O/mL, J.T. Baker No. 8844 (titrant)
ReAquant 3.5: two component reagent ReAquant ® 3.5 mg H2O/mL, J.T. Baker No. 8842 (titrant)
Solvent: two component reagent ReAquant ® Solvent Sprint, J.T. Baker No. 8855 (solvent)

g n ppm %
Non-ionic 0.25 6 718.4 0.58 100 mL Anolyte Input: syringe with needle
surfactant 5 mL Catholyte Stir/Titration time: 0/90 s
nonyl phenyl-
ethylene glycol
Titration parameters for all titrations:
Adjustment: control gain: 3; switch-off criterium: End level: 0.1 mg/s
Reagents:

10. Silk, Wool, Cellulose, Paper and Wood
General comments Wool and cellulose

Wool and cellulose release water easily. Since these products are insol-
uble in KF solvents, an external extraction must be performed. Methanol is
the usual solvent for the extraction. The drying oven can also be used.
Paper
A low moisture content is a criterium of the quality, especially for insula-
tion paper. The KF determination is usually performed by external extrac-
tion in methanol or in a methanol/chloroform mixture. If the drying oven is
to be used, the temperature should be adjusted to 105–130 °C.
Wood
The KF moisture determination of wood can be achieved using either an
external extraction in methanol, or the drying oven in the 105–130 °C
temperature range.
References ASTM D 1348-61 Standard Test Method for Moisture in Cellulose

Fujino, H. and Muroi, K., Determination of Water Content in Electric Insu-
lation Papers by Karl Fischer Method, Bunseki Kagaku 30, 624 (1981)
Comments concerning the applications with DL35
Wood Wood releases water slowly. A direct titration is not possible. Thus the
moisture is evaporated in the drying oven at 140 °C and the vapor is
transferred into the KF titration cell using dry nitrogen as the purge gas.
At higher temperatures the wood slowly darkens (decomposes slowly),
which leads to an increase in the water content.
Wool and silk An external extraction is the method of choice for samples of this nature.
Cellulose powder The finely crushed cellulose powder releases water reluctantly. A direct
titration can be performed with a 15-minutes stir time, with the sample
suspended in the KF solvent.

Applications: Silk, wool, cellulose, paper, wood
g n % % Solvent
Wood (pine) 0.5 6 8.28 0.70 Titrant 9258 Evaporate moisture in drying oven
Stir time: 900 s
Virgin wool 0.08 6 9.84 0.24 Titrant U 9233 External extraction.
30 mL LM 9241 2.1 g in 52 g methanol, 1 h at RT
Silk 0.07 6 6.83 0.35 Titrant U 9233 External extraction:
30 mL LM 9241 1.1 g in 42 g methanol, 1 h at RT
Cellulose 0.2 6 4.23 0.66 Titrant U 9233 Input: weighing boat
powder 30 mL LM 9241 Stir time: 15 minutes
Reagents:

g n ppm %
Copying paper 0.03 6 4.88 1.0 100 mL Coulomat A Evaporate moisture with drying oven
white 5 mL Coulomat C DO337: 140 °C, 200 mL air/min
Copying paper 0.06 6 4.98 0.51 100 mL Coulomat A Evaporate moisture with drying oven
recycled 5 mL Coulomat C DO337: 140 °C, 200 mL air/min
Newspaper 0.04 6 7.04 0.53 100 mL Coulomat A Evaporate moisture with drying oven
Insulation 0.05 6 6.41 0.6 100 mL Coulomat A Evaporate moisture with drying oven
paper 5 mL Coulomat C DO337: 140 °C, 200 mL air/min
Titration parameters for titrations using DO337 drying oven
Adjustment: control gain: 5; switch-off criterium: fixed titration time and End level 0.05 µg/s
automatic drift determination,manual titration start
Reagents:
Comments concerning applications with DL37

The paper samples are cut into pieces of approx. 4–8 cm2. These are placed in the drying oven
sample crucible with tweezers.
The paper should be stored in a closed container under constant conditions. Ambient conditions
(humidity) influence the samples moisture contents considerably.

11. Building Materials and Minerals
General Comments Most minerals and building materials such as cement, plaster of paris and
lime cannot be titrated directly, as the water is chemically bound. A further
hindrance is that oxides or carbonates will undergo a side reaction with
the KF reagents. For these reasons, the water is evaporated in the drying
oven and the vapor then transferred into the KF cell by a dry purge gas.
Zeolites
Zeolites are silicates with a three-dimensional structure composed of SiO4
and AlO4 molecules with characteristically dimensioned canals and hol-
low spaces. These occur naturally; most, however, are synthetic. They are
used as molecular sieves (for the partitioning of small molecules such as
H2O, NH3, H2S, etc.), ion exchangers (for cations), boiling chips, cata-
lysts (for gas-phase reactions) and as detergents. The zeolites tightly bind
water in the spaces. Water is released stepwise at successively higher
temperatures. The release is complete at 300–350 °C.
References Lindner, B. and Rudert, V., Verbesserte Methode zur Bestimmung von ge-
bundenem Wasser in Mineralien, Gesteinen und anderen Feststoffen,
Rechenberg, W., Bestimmung des Wassergehaltes in Zement,
Zement-Kalk-Gips 29, 512-516 (1976)
Farzaneh, A. and Troll, G., Quantitative Methode zur Bestimmung von
Wasser in Mineralien, Gesteinen und anderen Feststoffen,

Applications: Building Materials and Minerals
g n % % Solvent
Plaster of 0.5 6 6.04 0.5 Titrant 9258 Evaporate moisture with drying oven
paris 40 mL methanol DO302: 300 °C, 200 mL, N2/min
Stir time: 600 s
Knifing filler 0.5 5 5.49 1.2 Titrant 9258 Evaporate moisture with drying oven
40 mL methanol DO302: 300 °C, 200 mL, N2/min
Stir time: 900 s
Zeolite S90 0.3 6 12.4 0.43 Titrant 9258 Evaporate moisture with drying oven
ground 40 mL methanol DO302: 300 °C, 200 mL, N2/min
Stir time: 600 s
Reagent:

g n ppm %
Cement 0.4 6 0.820 2.2 100 mL Anolyte Evaporate moisture with drying oven
5 mL Catholyte DO337: 300 °C, 200 mL, N2/min
Titration parameters for titrations with DO337 drying oven:
Adjustment: control gain: 5; switch-off criterium: fixed titration time or End level 0.05 µg/s
Reagents:

Plaster of paris Plaster releases the water slowly. A direct titration of the suspension in
solvent is still possible though. After a stir time of 25 minutes, nearly the
same moisture content (5.8 %) was determined using this method as
was obtained with the drying oven (6.0 %).
Knifing filler The filler binds water tightly. The water is not released completely in a di-
rect titration (result of a direct titration with a 75-minutes stir time: 2.4%).
Due to the tight binding of the water, the sample must be heated to 300 °C
for 15 minutes in the drying oven.
Zeolite Zeolite releases water completely at temperatures higher than 300 °C.
Drying temperature: 300 °C, drying time: 10 minutes.
Cement Cement contains CaO which reacts with the KF reagent. Therefore the
moisture is evaporated in the drying oven at 300 °C and the vapor is
transferred into the titration cell using a dry purge gas. The coulometric
method is used due to the low moisture content.

12. Index of Reagents
Reagent Riedel-de Haën E. MERCK Fluka AG J.T. Baker Ericsen/GFS

(all pyridine-free) HYDRANAL®
Two-component reagent
Titrant 5 mg H2O/mL 34801 9243 60626 8844 1604
Titrant 3,5 mg H2O/mL — — — 8842 —
Titrant 2 mg H2O/mL 34811 — — — 1603
Titrant 1 mg H2O/mL — — — — 1602
Solvent 34800 9241 60625 8855 1610
Solvent for fats and oils 34812 9230 — — —
Two-component reagent
for ketones and aldehydes
Titrant 5 mg H2O/mL — 9233 — 8844 1604
Solvent — 9221 — 8840 1609
One-component reagent
Titrant 5 mg H2O/mL 34805 9258 60623 — 1600
Titrant 2 mg H2O/mL 34806 — — — 1601
Titrant 1 mg H2O/mL 34827 — — — 1606
Anhydrous methanol 34940 6012 65546 8047 814/1240
for ketones and aldehydes
Titrant 5 mg H2O/mL 34816 — — — 1600
Solvent 34817 — — — 1608
Reagents for coulometric
KF titration
Anolyte 34807 9255 — — 1612
Katholyte 34808 9255 — — 1613
Reagents for coulometric
KF titration (for ketones)
Anolyte 34820 — — — 1619
Katholyte 34821 — — — —
Titre standards
disodium tartrate dihydrate • 2 H2O 34803 6664 71994 0317 805
Standard 5 mg H2O/mL 34813 9259 — — 1617
Standard 1 mg H2O/mL 34828 — — — 1618
Methanol 5 mg H2O/mL 34802 — — — —
Standards for
pH-adjustment
Buffer 5 mmole acid/mL 34803 — — — 1615
Benzoic acid 18102 136 12349 1270 673
Salicylic acid 27301 635 84210 0251 799
Imidazole 63561 4716 56750 1747 —
Auxiliary solvents
Chloroform 32286 2445 25690 9257 816/1234
Methanol 32213 6009 65546 8047 814/1240
1-Dodecanol 62411 803463 30610 — —
1-Propanol 33538 997 82090 8397 —
Toluene 32249 8325 89681 8078 1052/1245
Formamide 62608 9684 47670 7042 1093
Bottle adaptore METTLER unnecessary ME-23774 ME-23817 unnecessary unavailable

Index of Suppliers
Riedel-de Haën AG Headquarters:

Wunstorfer Strasse 40
Postfach
D-3016 Seelze
Tel. (0 51 37) 7 07 0
Telefax (0 51 37) 9 19 79
E. MERCK Headquarters:
Postfach 4119
D-6100 Darmstadt 1
Frankfurter Strasse 250
Tel. (06151) 72 0
Telefax (06151) 72 33 68
Fluka AG Headquarters:
Fluka Chemie AG
Postfach 172
CH-9470 Buchs
Industriestrasse 25
Tel. 085 6 95 11
Telefax 085 6 54 49
J. T. Baker Headquarters:
J. T. Baker Inc.
222 Red School Lane
Phillipsburg
N.J. 08865
Tel. 908-8592151
Telefax 908-859 2865
Ericsen/GFS Headquarters:
GFS Chemicals
P.O. Box 245
Powell
OH 43065
Tel. (US) 800-858-9682
Tel. (outside US) 614-881-5501
Telefax 614-881-5989

13. Hazards and waste disposal tips
Contains: sulfur dioxide, iodine, base (imidazole) and solvent (methanol,
2-methoxyethanol or diethyleneglycolmonomethylether).
Safety precautions: flammable to extremely flammable. Irritant when inhaled. Health hazard when
inhaled, swallowed or allowed to contact skin. Keep container tightly closed. Keep away from open
flames or sparks. Do not let reagent contact skin or eyes.
Disposal: as an organic solvent.
Two-component reagent:
This titrant contains: iodine and solvent (methanol, 2-methoxyethanol, xylene or trichloroethylene).
The KF-solvent contains: sulfur dioxide, base (imidazole) and solvent (methanol,
2-methoxyethanol or diethyleneglycolmonomethylether).
Safety precautions: flammable to extremely flammable. Irritant when inhaled. Health hazard when
inhaled, swallowed or allowed to contact skin. Keep container tightly closed. Keep away from open
flames or sparks. Do not let reagent contact skin or eyes.
Reagents for coulometry:

This reagent contains iodide, sulfur dioxide, base (imidazole), and solvent (methanol, chloroform,
tetrachloromethane, 2-methoxyethanol).
Safety: Highly flammable. Skin irritant. Poisonous when inhaled or swallowed. Keep container tightly
closed and far removed from open flames or sparks. Do not let reagent contact skin or eyes.
Safety data for the KF-components and auxiliary solvents:

sulfur dioxide: MAK-value: 200 ppm
iodine: MAK-value: 0.1 ppm, oxidant
diethyleneglycol-
monomethylether: Flashpoint: 87 °C
2-methoxyethanol: Flashpoint: 46 °C, MAK value: 5 ppm
Flammable. Potential teratogen.
Health hazard when inhaled, swallowed or allowed to contact skin.
Irritant when inhaled.
methanol: Flashpoint: 11 °C, MAK value: 200 ppm
Highly flammable. Poisonous when inhaled or swallowed.
o-xylene: Flashpoint: 28 °C, MAK value: 100 ppm
Flammable. Health hazard upon inhalation.
chloroform: Flashpoint: does not burn, MAK value: 200 ppm
Health hazard when inhaled. Irreversible damage possible.
1-decanol: Flashpoint: 95 °C, Irritant for skin and eyes.
formamide: Flashpoint: does not burn, MAK value: 20 ppm
Irritant for skin and eyes. Potential teratogen.
toluene: Flashpoint: 6 °C, MAK value: 20 ppm
Extremely flammable. Health hazard upon inhalation.

14. Sample Index
Acetaldehyde 16,18 Glue stick 28 PVC 28

Acetic acid 16 Grease 22 Reactive dye 36
Acetone 16,18 Herbicide 36 Rubber cement 28
Acetonitrile 16 Hydraulic oil 24 Salicylic acid 10,12
Acetophenone 10,12 Impregnation agent 39 Shoe polish 22
Acrylic paint 36 Indicator dye 36 Silicon oil 22,24
Adhesives 27–30 Insecticide 36 Silk 41
Agrochemicals 35–37 Insulation paper 41 Skiwax 22
Aluminum oxide 6 iso-Amyl alcohol 16 Sodium carbonate 6
Aluminum powder 6,8 Isobutylmethylketone 16,18 Sodium chloride 6
Aniline 10,12 Isopropyl alcohol 18 Soft soap 39
Antibiotics 32 Kerosene 24 Soot 24
Aspirin 32 Knifing filler 43 Sulfuric acid 6
Benzaldehyde 10,12 Laundry detergent 39 Suppository 32
Benzamide 12 Liquid detergent 39 Surfactants 38–39
Benzyl alcohol 10,12 Lithium chloride 6 Synthetic enamel 36
Brake fluid 24 Lyophilized Plasma 34 Tonic 32
Calcium chloride 6 Magnesium oxide 6 Toluene 16,18
Calcium oxide 6 Massage oil 34 Transformer oil 24
Cellulose 41 Medicines 31–33 Turbine oil 24
Cement 43 Methyl benzoate 10,12 Urea 10
Chamomile extract 32 Methylene chloride 16 Valerian essence 32
4-Chlorotoluene 10,12 Mineral oil 21–25 Waxes 21–25
Cleaner liquid 39 Minerals 43 Wood 41
Cough drops 32 Motor oil 22 Wool 41
Crude oil 22,24,26 n-Butylamine 10,12 Wool dye 36
Cyanoacryl glue 28 n-Hexane 18,20 Zeolite 43
Cyclohexene 16,18 Naphtaline 12
Detergents 38–39 2-Nitrophenol 10
Diesel oil 22 Non-ionic surfactant 39
Diethylether 16,18 Ointment 32
Dimethylformamide 16,18 Optical brightener 36
Dish detergent 39 Oxalic acid 10
Disinfectant 32 Paint 36
Dispersion dye 36 Paper 41
Dyes 35–37 Paraffin 24
Epoxy resin 28 Petroleum 22,24
Ethylene glycol 16,18 Petroleum Products 21–25
Ethyl acetate 18 Phenol 12,14
Ethylen chloride 18 Phosphoric acid 6
Eucalyptus oil 34 Plaster of paris 43
Fabric softener 39 Plastics 27–30
Fats 21–25 Polyamide 28
Fungicide 35,37 Polyethylene 28,30
Gasoline 22,24 Polypropylene 28
Gel for sprains 32 Polystyrene 28

Notes

Notes

Notes

This application bulletin represents selected, possible application examples. These have been tested with all
possible care in our lab with the analytical instrument mentioned in the bulletin. The experiments were
conducted and the resulting data evaluated based on our current state of knowledge.
However, the application bulletin does not absolve you from personally testing its suitability for your intended
methods, instruments and purposes. As the use and transfer of an application example are beyond our control,
we cannot accept responsibility therefore.
When chemicals and solvents are used, the general safety rules and the directions of the producer must
be observed.

Mettler-Toledo GmbH
Analytical
CH-8603 Schwerzenbach, Schweiz
Telefon (01) 806 77 11, Fax (01) 806 73 50
Internet: http://www.mt.com
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METTLER TOLEDO TItrators

Karl Fischer Applications

2. Inorganic raw materials 5

3. Organic raw materials 9

6. Plastics and adhesives 27

8. Dyes and agrochemicals 35

9. Detergents and surfactants 38

10. Silk, wool, cellulose, paper and wood 40

11. Building materials and minerals 42

12. Index of reagents and suppliers 44

13. KF reagent hazards and waste disposal tips 46

14. Sample Index 47

References Fischer, K., Angew. Chem. 48, 394 (1935)

METTLER, Karl Fischer Applications 3

4 METTLER, Karl Fischer Applications

General comments Salts

Acids and bases

The following inorganic compounds react with Karl Fischer reagents in a

METTLER, Karl Fischer Applications 5

B) Coulometric determination using DL37

6 METTLER, Karl Fischer Applications

Comments concerning applications using DL37

METTLER, Karl Fischer Applications 7

Sample: 3 g Aluminum powder

8 METTLER, Karl Fischer Applications

General comments Hydrocarbons, halogenated hydrocarbons, alcohols, esters and ether

Aldehydes and ketones

References Scholz, E., Wasserbestimmung in Carbonsäuren,

METTLER, Karl Fischer Applications 9

10 METTLER, Karl Fischer Applications

4-Chlorotoluene, The direct titration is unproblematic. A titrant with a low concentration

METTLER, Karl Fischer Applications 11

12 METTLER, Karl Fischer Applications

Naphtaline A small weigh-in is needed, as napthaline is poorly soluble in methanol.

4-Chlorotoluene, The coulometric determination is straightforward.

Phenol Phenol is first dissolved externally in methanol.

n-Butylamine This is titrated coulometrically by adding benzoic acid. The determined

METTLER, Karl Fischer Applications 13

Sample: 0.3 g Phenol

14 METTLER, Karl Fischer Applications

General comments Hydrocarbons, halogenated hydrocarbons, alcohols, esters and ether

Aldehydes and ketones

References Scholz, E., Titration of Aldehydes and Ketones

METTLER, Karl Fischer Applications 15

16 METTLER, Karl Fischer Applications

Cyclohexene A diluted titrant with a concentration of 1 mg H2O/mL is used to determine

Dimethylformamide The Karl Fischer titration of DMF is straightforward. This is expected to be

Acetonitrile The water content determination of acetonitrile is unproblematic.

METTLER, Karl Fischer Applications 17

18 METTLER, Karl Fischer Applications

Cyclohexene, isopropa- The coulometric titration of these samples is straightforward.

Dimethylformamide This compound is easily analyzed by KF coulometry. This is to be expected

These examples show that the METTLER DL37 KF Coulometer provides

METTLER, Karl Fischer Applications 19

Sample: 2 g n-hexane dried over molecular sieve 3Å

Comments: Results und Statistics:

20 METTLER, Karl Fischer Applications

General Comments Mineral oils

Parafins and waxes

Tar and coal