20C Applying Standard Oxidizing Agents  529

20C-5  Determining Water with the Karl Fischer

Reagent
In industry and commerce, one of the most widely used analytical methods is the Karl
Fischer titration procedure for the determination of water in various types of solids
and organic liquids. This important titrimetric method is based on an oxidation/
reduction reaction that is relatively specific for water.6

Describing the Reaction Stoichiometry

The Karl Fischer reaction is based on the oxidation of sulfur dioxide by iodine. In a
solvent that is neither acidic nor basic—an aprotic solvent—the reaction can be sum-
marized by

I2 1 SO2 1 2H2O S 2HI 1 H2SO4

In this reaction, two moles of water are consumed for each mole of iodine. The stoi-
chiometry, however, can vary from 2:1 to 1:1 depending on the presence of acids and
bases in the solution.

Classical Chemistry. In order to stabilize the stoichiometry and shift the

equilibrium further to the right, Fischer added pyridine (C5H5N) and used anhydrous
methanol as the solvent. A large excess of pyridine was used to complex the I2 and
SO2. The classic reaction has been shown to occur in two steps. In the first step, I2
and SO2 react in the presence of pyridine and water to form pyridinium sulfite and
pyridinium iodide.

C5H5N · I2 1 C5H5N · SO2 1 C5H5N 1 H2O S

              2C5H5N · HI 1 C5H5N · SO3 (20-2)

C5H5N · 1
SO32 1 CH3OH S C5H5N(H)SO4CH3 (20-3)

where I2, SO2, and SO3 are shown as complexed by the pyridine. This second step is
important because the pyridinium sulfite can also consume water:

C5H5N1 · SO32 1 H2O S C5H5NH1SO4H2 (20-4)

This last reaction is undesirable because it is not as specific for water. It can be
prevented completely by having a large excess of methanol present. Note that
the stoichiometry is 1 mole of I2 per mole of H2O present.
For volumetric analysis, the classical Karl Fischer reagent consists of I 2, SO2,
pyridine, and anhydrous methanol or another suitable solvent. The reagent decom-
poses on standing and must be standardized often. Stabilized Karl Fischer reagents
are available commercially from several suppliers. For ketones and aldehydes, spe-
cially formulated reagents are available from commercial sources. For coulometric
methods (see Chapter 22), the Karl Fischer reagent contains KI instead of I2 since, as
we will see, the I2 is generated electrochemically.

6
For a review of the composition and uses of the Karl Fischer reagent see S. K. MacLeod, Anal.
Chem., 1991, 63, 557A, DOI: 10.1021/ac00010a720; J. D. Mitchell, Jr. and D.M. Smith, Aquametry,
2nd ed., Vol. 3. New York: Wiley, 1977.

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530  chapter 20 Applications of Oxidation/Reduction Titrations

Pyridine-Free Chemistry. In recent years, pyridine, and its objectionable

odor, have been replaced in the Karl Fischer reagent by other amines, particularly
imidazole, shown in the margin. These pyridine-free reagents are available
commercially for both volumetric and coulometric Karl Fischer procedures. More
detailed studies of the reaction have been reported.7 The reaction is now thought
to occur as follows:

N 1. Solvolysis 2ROH 1 SO2 8 RSO32 1 ROH21

2. Buffering B 1 RSO32 1 ROH21 8 BH1SO3R2 1 ROH
N N 3. Redox B · I2 1 BH1SO3R2 1 B 1H2O 8 BH1SO4R2 1 2BH1I2
H
pyridine imidazole Note that the stoichiometry is again one mole of I2 consumed for each mole of H2O
present in the sample.

Interfering Reactions. There are several reactions that can occur that cause
interferences in the Karl Fischer titration. These undesired reactions can cause results
to be too high, too low, or just imprecise. Oxidation of iodide in the coulomet-
ric reagent by oxidizing agents such as Cu(II), Fe(III), nitrite, Br2, Cl2, or quinones
produces I2, which can react with H2O and cause low results since not as much
generated I2 is needed. The carbonyl groups on aldehydes and ketones can react with
SO2 and H2O to form bisulfite complexes. Since this reaction consumes water, the
titration results are again too low. Substitution of a weaker base like pyridine for
imidazole can lessen the problem.
The iodine generated coulometrically or present in the reagent can be reduced by
oxidizable species such as ascorbic acid, ammonia, thiols, Tl1, Sn21, In1, hydroxyl
amines, and thiosulfite. This reduction results in consumption of I2 and water deter-
minations that are too high. Phenolic derivatives and bicarbonates also cause reduc-
tion of I2.
Some interfering compounds react to produce water, which causes the water re-
sults to be too high. Carboxylic acids can react with alcohols to produce an ester and
water. To minimize this problem, the alcohol can be eliminated in the reagent, or an
alcohol that reacts at a slower rate than methanol can be used. The pH of the reagent
can be increased because the formation of esters is usually acid catalyzed. Ketones
and aldehydes can react with alcoholic solvents to form ketals and acetals with the
production of water according to

R2C�O 1 2CH3OH S R2C(OCH3)2 1 H2O

Aromatic ketones are less reactive than aliphatic ketones. Aldehydes are much more
reactive than ketones. Some commercial reagent preparations have been formulated
to minimize this problem by using alcohols that react slowly and a higher pH.
Silanols and cyclic siloxanes also can react with alcohols to produce ethers and
water. Some metal oxides, hydroxides, and carbonates can react with HI to produce
water. All of these reactions increase the amount of I2 consumed and produce results
that are too high.

7
E. Scholz, Karl Fischer Titration, (Berlin: Springer-Verlag, 1984).

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 20C Applying Standard Oxidizing Agents  531

Detecting the End Point

An end point in a Karl Fischer titration can be observed visually based on the brown
color of the excess reagent. More commonly, however, end points are obtained by
electroanalytical measurements. Several instrument manufacturers offer automatic or
semiautomatic instruments for performing Karl Fischer titrations. All of these instru-
ments are based on electrometric end point detection.

Reagent Properties
Karl Fischer reagent decomposes on standing. Because decomposition is particu-
larly rapid immediately after preparation, it is common practice to prepare the
reagent a day or two before it is to be used. Its strength must be established at
least daily against a standard solution of water in methanol. A proprietary com-
mercial Karl Fischer reagent reported to require only occasional restandardization
is now available.
It is obvious that great care must be exercised to keep atmospheric moisture
from contaminating the Karl Fischer reagent and the sample. All glassware must be
­carefully dried before use, and the standard solution must be stored out of contact
with air. It is also necessary to minimize contact between the atmosphere and the
solution during the titration.

Applications
Karl Fischer reagent has been applied to the determination of water in numerous
types of samples. There are several variations of the basic technique depending on
the solubility of the material, the state in which the water is retained, and the physi-
cal state of the sample. If the sample can be dissolved completely in methanol, a
direct and rapid titration is usually feasible. This method has been applied to the
determination of water in many organic acids, alcohols, esters, ethers, anhydrides,
and halides. The hydrated salts of most organic acids, as well as the hydrates of a
number of inorganic salts that are soluble in methanol, can also be determined by
direct titration.
Direct titration of samples that are only partially dissolved in the reagent usually
leads to incomplete recovery of the water. Satisfactory results with this type of sample
are often obtained, however, by the addition of excess reagent and back-titration with
a standard solution of water in methanol after a suitable reaction time. An effec-
tive alternative is to extract the water from the sample by refluxing with anhydrous
methanol or other organic solvents. The resulting solution is then titrated directly
with the Karl Fischer solution.

WEB Use a search engine to locate one of the many MSDS websites. Find and read the
WORKS MSDS for potassium dichromate and explore its chemical, toxicological, and carcino-
genic properties. Locate a second MSDS website and again explore the properties of
potassium dichromate. What differences did you find in the two documents? Which
site provided the most detailed information, particularly regarding health effects? Did
either site tend to emphasize certain properties over others? What do you conclude
from this exercise?

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deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.