Basics of Karl Fischer Titration

Andrea Felgner
Market Segment Manager HYDRANAL

sigma-aldrich.com

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Karl Fischer Titration - History

1935

Karl Fischer published a reagent for water determination

consisting of iodine, SO2, pyridine and methanol

1955

Peters and Jungnickel stabilized the reagent by replacing

methanol with 2-methoxyethanol

1958

Oehme developed the coulometric KF titration

1979

Eugen Scholz and Helga Hoffmann, Riedel-de Han,

replaced pyridine by imidazole and invented HYDRANAL
reagents

1980

First pyridine-free HYDRANAL reagents are launched

1998

Sigma-Aldrich Laborchemikalien introduced the first

ethanol-based KF reagents, the HYDRANAL E-types

2008

HYDRANAL reagents brand change

from Riedel-de Han to Fluka
3

HYDRANAL Production and Quality Control

Production site in Seelze, Germany

Locations in 40 countries, selling to

160 countries
38 production sites in 10 countries
High global stock levels support 24hour product delivery
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HYDRANAL Technical Service

Accreditation according to ISO/IEC 17025

ISO/IEC 17025:2005 General requirements for the competence of

testing and calibration laboratories
Accreditation as a testing laboratory according to ISO/IEC 17025 for
Water Standards and Karl Fischer Reagents since December 2009
Audited by the German Accreditation Council (DAR)
Accreditation details and logo of the accreditation body on CoA and label
for each produced lot
Accreditation includes all HYDRANAL products
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Why Karl Fischer titration?

Selective
Determination of the water content
- Drying techniques cannot differentiate between water and moisture
- Chemically combined water (water of crystallization) may not be
detected completely through drying
Loss on drying
Accurate
Very small standard deviations are achievable
Large measuring range
ppm - %
Fast
1-3 minutes average / per determination

Reagents for KF titration

need

Iodine
Sulfur dioxide
ideally suited buffer substance
(strong influence on reagent reactivity)

suitable solvent
(influence on stability)
7

Influence on pH-value
and therefore on the KF reaction

log K

4
Side reaction
3

pH of HYDRANAL reagents

2
1

Slow reaction

0
No reaction
-1
2

10

pH

Ideal range of pH

Karl Fischer Titration

Quantitative determination of water

Karl Fischer reaction mechanism

(1)

CH3OH + SO2 + RN [RN]SO3CH3

(2)

H2O + I2 + [RN]SO3CH3 + 2 RN [RN]SO4CH3 + 2 [RNH]I

(RN = base)

KF reagent reacts quantitatively and selectively with water

KF reagent (volumetric) consists of iodine, sulfur dioxide, a base and an
alcohol as solvent

Forms of KF Titration

Water content ranges are flexible!

Techniques and Reagents

Consider sample properties when

choosing the method!

Volumetric titration
for high amounts of
water (0.1-100%)

Coulometric titration
for low amounts of
water (0.001-1%)

I2 is part of the
reagents

I2 is generated

One component
reagents

Contains all reactants

in one solution
(plus alcohol as
working medium)

Two component
reagents

Titrant

Solvent

Contains I2
in alcohol

Contains SO2
and base in
alcohol

Cell with
diaphragm

Cell without
diaphragm

Catholyte
and
Anolyte

Only
Anolyte

10

Basic forms of KF titration

Volumetric titration with one-component reagent
Water measured in mg
Water content approx. 0.02% (200 ppm) to 100% H2O
Volumetric titration with two-component reagent
Water measured in mg
Water content approx. 0.02% (200 ppm) to 100% H2O
Coulometric determination of water content
Water measured in g
Water content < 10 ppm to 5%
Cell with diaphragm / cell without diaphragm
water content ranges are flexible
 consider sample properties for choosing the method


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Volumetric KF techniques
One-Component Reagent
Titrating agent
HYDRANAL-Composite
(contains iodine, SO2, base, DEGEE)

Titrating
agent

Working medium
HYDRANAL-Methanol dry
HYDRANAL-Methanol Rapid
HYDRANAL-CompoSolver E
(contain only alcohol)
pH approx. 5

Working
medium

Advantages
Unlimited water capacity
Highly flexible (solvent/working medium)
12

Volumetric KF techniques
Two-Component Reagent
Titrating agent
HYDRANAL-Titrant (E)
(contains iodine, alcohol)

Titrating
agent

Working medium
HYDRANAL-Solvent (E)
(contain SO2, base, alcohol)
pH approx. 6

Working
medium

Advantages
High titration speed
High buffer capacity
High titer stability
13

HYDRANAL-Composite
One-component reagent

Improved Quality
No crystal formation
Better stability
Same performance
Formulation proprietary

I2
SO2
Imidazole

*DEGEE = Diethylene glycol monoethyl ether

2-Methylimidazole
DEGEE

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Rapidity of volumetric titration

2-component
1-component

Pyridine-containing reagents

Volume [mL]
B

Graph

Reagents

HYDRANAL-Titrant 5 +
HYDRANAL-Solvent

HYDRANAL-Composite 5 +
HYDRANAL-Methanol dry

Titration with reagents

containing pyridine

0
2

Time [min]
15

HYDRANAL-Methanol Rapid

Methanol Rapid
Methanol dry

Sample: 20 mg water, titrated

with HYDRANAL-Composite 5

 HYDRANAL-Methanol dry is not buffered (only methanol)

 HYDRANAL-Methanol Rapid contains accelerators (SO2, imidazole)
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Reagents for volumetric KF titration

One-component reagents

Two-component reagents

Titrating agents
34805 HYDRANAL-Composite 5*

34801 HYDRANAL-Titrant 5

34806 HYDRANAL-Composite 2*

34811 HYDRANAL-Titrant 2

34827 HYDRANAL-Composite 1*

34732 HYDRANAL-Titrant 5 E*
34723 HYDRANAL-Titrant 2 E*

Working media
34741 HYDRANAL-Methanol dry

34800 HYDRANAL-Solvent

37817 HYDRANAL-Methanol Rapid

34730 HYDRANAL-Solvent E*

34734 HYDRANAL-CompoSolver E*

*ethanol/DEGEE-based

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Coulometric KF technique

Advantages
Easy to use
For small amounts of water
High accuracy

Source of iodine
coulometric titration
iodine electrochemically generated
from the oxidation of iodide (iodide contained in the reagents)
(volumetric titration
iodine contained in the reagents)

Calculation based on the amount of produced (consumed)

current over time (acc. to Faradays law)

Catholyte

Anolyte

Reagent solutions
catholyte (Coulomat C*) and anolyte (Coulomat A*)

Double Pt
electrode

Cell with diaphragm

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Coulometric cell WITH DIAPHRAGM

2 reagent solutions needed:
anolyte + catholyte (e.g. HYDRANAL-Coulomat AG and Coulomat CG)

Cathodic compartment filled

with catholyte solution

Anodic compartment filled with

anolyte solution
Iodine formation at the anode
2I-
I2 + 2e- (oxidation)

Titration begins
Hydrogen formation at the cathode
2H+ + 2e-
H2

Ideal for small amounts of water (low ppm) and

for reagents with high amount of added solubilizing agent

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Coulometric cell WITHOUT DIAPHRAGM

only one reagent solution needed:
e.g. HYDRANAL-Coulomat AD, Coulomat E

Cathode (reduction)
H2 formation:
2H+ + 2e-
H2

Anode (oxidation)
I2 formation:
2I-
I2 + 2e(brown color)

Only one reagent necessary, no cleaning of diaphragm

Double platinum
indicator electrode

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Reagents for coulometric KF titration

for cells with diaphragm

Anolyte solutions with high amounts of added solubilizing agents

34807 HYDRANAL-Coulomat A
(contains chloroform)
34868 HYDRANAL-Coulomat Oil
(contains chloroform and xylene)
34843 HYDRANAL-Coulomat AG-H
(contains pentanol)
To be used with catholyte solution:
34840 HYDRANAL-Coulomat CG
(10 ampules 5 mL)

Reagents with high amounts of solubilizing agents cause too high results in
cells without diaphragm (Recovery rates 103-105 %)

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Reagents for coulometric KF titration

for cells without diaphragm
*ethanol-based

Reagents w/o solubilizing agents / w/o halogenated hydrocarbons

34726 HYDRANAL-Coulomat E*
(to be used as anolyte and catholyte, cells with and w/o diaphragm)
34810 HYDRANAL-Coulomat AD
(standard reagent for cells w/o diaphragm)
34836 HYDRANAL-Coulomat AG
(standard reagent for cells with and w/o diaphragm)
34739 HYDRANAL-Coulomat AG-Oven
(for cells with and w/o diaphragm)
Determination of ketones in the coulometric cell:
34820 HYDRANAL Coulomat AK (for cells with and w/o diaphragm)
34821 HYDRANAL Coulomat CG-K
Standard catholyte:
34840 HYDRANAL-Coulomat CG (10 ampules 5 mL)
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Classification according to GHS

(Globally Harmonized System)

Methanol-containing reagents

Imidazole-containing reagents

Plus:
H360D (May damage the unborn child)
23

New classification
for imidazole-containing HYDRANAL reagents
Link to ECHA (new classification of imidazole)

New and more stringent evaluation of chemicals by the European

Chemicals Agency (ECHA)
imidazole classified as a dangerous
component


New guidelines defining how to safely handle HYDRANAL products

According to the new European Regulation on Classification, Labeling and

Packaging of chemical substances and mixtures (CLP):

reagents containing imidazole of 0.3% w/w or more must show

the following Pictograms and Hazard statements:
GHS08 (Health Hazard)
H360D (May damage the unborn child)
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New classification
for imidazole-containing HYDRANAL reagents

Newly measured values for imidazole concern oral intake of the substance,
whereas values for dermal and inhalation remain unchanged


Karl Fischer reagents are handled in closed systems

direct contact with the chemicals is typically prevented and can only occur

accidentally


Hydranal reagents contain imidazole only in dissolved and diluted form

Imidazole in its free form is only contained to a low degree

(example 34805 Composite 5 approx. 0.05 mol/L (0.3 %)

risk of exposure to inhalation of powder dust is negligible

use of personal protection is advised, especially gloves (avoid skin contact)

25

HYDRANAL E-type reagents

Advantages of eliminating Methanol

Less dangerous for user and environment

Improve solubility of long-chained hydrocarbons especially in

HYDRANAL-CompoSolver E

Ketones like acetone can be titrated in HYDRANAL-CompoSolver E (not

possible in methanol-based working media)

HYDRANAL-Coulomat E is a one-component reagent for coulometry,

can be used as anolyte and catholyte

Corresponding to regulations of ISO 14001 (environmental management)

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HYDRANAL E-type reagents

based on ethanol / DEGEE

One-Component reagents

Two-Component Reagents

34805 HYDRANAL-Composite 5

34730 HYDRANAL-Solvent E

34816 HYDRANAL-Composite 5 K

34732 HYDRANAL-Titrant 5 E

34806 HYDRANAL-Composite 2

34723 HYDRANAL-Titrant 2 E

34827 HYDRANAL-Composite 1
34734 HYDRANAL-CompoSolver E
Coulometric Reagent
34726 HYDRANAL-Coulomat E

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Questions ?

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