Intro_KF_Titration

See discussions, stats, and author profiles for this publication at: https://www.researchgate.
net/publication/320833693
Water Determination by Karl Fischer Titration
Presentation · November 2017
CITATIONS READS
2 11,022
2 authors, including:
Cosimo A. De Caro
METTLER TOLEDO
83 PUBLICATIONS 460 CITATIONS
SEE PROFILE
All content following this page was uploaded by Cosimo A. De Caro on 03 November 2017.
The user has requested enhancement of the downloaded file.

Water Determination by
Karl Fischer Titration
Cosimo A. De Caro
Albert Aichert
Mettler-Toledo GmbH, Analytical
Switzerland
Agenda
 Why water determination

 Methods for water determination
 History of Karl Fischer Titration

 Karl Fischer Titration
Karl Fischer Titration: An Introduction 1

Why Water Determination?
Sugar stored in silos
Too much surface moisture
Sugar removal with

pickaxes or
a hammer drill.
will NOT
trickle down

Flour
Too little moisture (less than 10% water).
dust explosion

Butter
Maximum water content is 16.5 % by law.
Optimization of the water content in the butter production, for

maximum profit.

Drugs: Lyophilized serum
Too much water. Decomposition of active agent.
The serum is not active anymore, when you need it!

CD Disc
Production needs plastic granulate with water < 5 ppm
Too much water Bad music quality

Brake fluid
On steep mountain roads brakes get too hot !
Too much water Brakes do not work anymore.

Absorbable Suture Material
Complete absorption after 17 – 21 days.

Material: polyglycolic acid Water content max. 400 ppm.
Too much water Absorption too early

Gun powder
Water content is important
Water content too low: Barrel burst
Water content too high

Kerosene in aircraft jet engine
Water content must be very low
High water content: Kerosene freezing, blockage of tubing

Water in transformer oil
Almost no water in transformer oil to avoid short-circuit
A too high water content will lead to a short circuit

Agenda



Methods for Water Determination
Drying oven
Dry sample in a drying oven at higher temperature until the mass is

constant.
Advantages: Large number of samples.

Large sample size possible.
Disadvantages: Long measurement time (some hours)

Large amount of manual effort.
Other volatile substances evaporate.

Moisture analyzer
Dry sample by IR or halogen heater on a balance until the mass is

constant.
HR73 Halogen
Moisture Analyzer
Advantages: Simple operation.

Short measurement time (5 – 15 minutes)
Disadvantages: Single sample at a time.

Other volatile substances evaporate.
Decomposition of the sample.
 Fast (1 ... 2 minutes)

 Selective for water
 Accurate and precise
 Wide measuring range (ppm - 100%)
 No decomposition

Agenda


History of Karl Fischer Titration
Karl Fischer
Karl Fischer: Petroleum Chemist 1901 - 1958
His job:
Start up oil refineries all over the world.
His problem:
Water determination in oil.

Karl Fischer
Karl Fischer on the way to the next job overseas
Bunsen reaction:
2 H2O + SO2 + I2  H2SO4 +2 HI

Karl Fischer back in the Lab
Bunsen reaction:
2 H2O + SO2 + I2  H2SO4 +2 HI
Methanol as solvent
Pyridine as base
happened to be around in the Lab
3 years hard work, backstrokes and success
1935 First publication by Karl Fischer

Karl Fischer Petroleum Chemist 1901 - 1958
 1935 Scientific publication by Karl Fischer

 1950 First Karl Fischer Titrator commercially available.
 1970 First coulometric KF Titrator commercially available.
 1980 Pyridine free Karl Fischer reagents.
 1984 DL18 first microprocessor controlled KF Titrator
with automatic drift compensation, from METTLER TOLEDO
 1990 DL37 first KF coulometer from METTLER TOLEDO
 1998 Introduction of the volumetric KF Titrators DL31 / DL38
 2001 Introduction of the coulometric KF Titrators DL32 / DL39
 2008 The new Compact KF V20/V30 Volumetric
and C20/C30 Coulometric Instruments
 Today One of the most used titration methods.
Over 1 million KF titrations every day!

Agenda



Karl Fischer Reaction
Two step reaction
1. SO2 + RN + CH3OH  (RNH)SO3CH3

Methylsulfite
2. (RNH)SO3CH3 + H2O + I2 + 2 RN  (RNH)SO4CH3 + 2 (RNH)I

Methylsulfate
Iodine (I2) reacts with water 1:1
The solvent (methanol, CH3OH) is involved in the reaction.

50 % of the solvent must be methanol.
A suitable base (RN) keeps the pH value between 5 – 7

In the past: Pyridine now: Imidazole

Volumetric & Coulometric Karl Fischer Titration
Volumetric Karl Fischer:

Iodine is added by burette during titration.
Water as a relevant component: 100 ppm - 100 %
- +
Coulometric Karl Fischer:

Iodine is generated electrochemically during titration.
Water in trace amounts: 1 ppm - 5 %

Summary
 The Karl Fischer titration is a quantitative analytical technique for the

determination of water in different samples.
 It is based on a chemical reaction between 5 components:

iodine, sulfur dioxide, an alcohol (methanol), a base (imidazole) and water.
 Depending on the water content, two kinds of Karl Fischer methods are
used:
- The volumetric technique (100 ppm-100%)
- The coulometric technique (1 ppm-5%)
 Nowadays, the water content is determined by means of fully automated

Karl Fischer titrators.

View publication stats

Intro_KF_Titration

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Intro_KF_Titration

Uploaded by

Copyright:

Available Formats

See discussions, stats, and author profiles for this publication at: https://www.researchgate.

Water Determination by Karl Fischer Titration

Presentation · November 2017

The user has requested enhancement of the downloaded file.

 Why water determination

 History of Karl Fischer Titration

Karl Fischer Titration: An Introduction 1

Sugar removal with

Karl Fischer Titration: An Introduction 2

Karl Fischer Titration: An Introduction 3

Maximum water content is 16.5 % by law.

Optimization of the water content in the butter production, for

Karl Fischer Titration: An Introduction 4

Too much water. Decomposition of active agent.

The serum is not active anymore, when you need it!

Karl Fischer Titration: An Introduction 5

Production needs plastic granulate with water < 5 ppm

Too much water Bad music quality

Karl Fischer Titration: An Introduction 6

On steep mountain roads brakes get too hot !

Too much water Brakes do not work anymore.

Karl Fischer Titration: An Introduction 7

Complete absorption after 17 – 21 days.

Too much water Absorption too early

Karl Fischer Titration: An Introduction 8

Water content is important

Water content too low: Barrel burst

Water content too high

Karl Fischer Titration: An Introduction 9

Water content must be very low

High water content: Kerosene freezing, blockage of tubing

Karl Fischer Titration: An Introduction 10

Almost no water in transformer oil to avoid short-circuit

A too high water content will lead to a short circuit

Karl Fischer Titration: An Introduction 11

 Why water determination

 History of Karl Fischer Titration

Karl Fischer Titration: An Introduction 12

Dry sample in a drying oven at higher temperature until the mass is

Advantages: Large number of samples.

Disadvantages: Long measurement time (some hours)

Karl Fischer Titration: An Introduction 13

Dry sample by IR or halogen heater on a balance until the mass is

Advantages: Simple operation.

Disadvantages: Single sample at a time.

 Fast (1 ... 2 minutes)

Karl Fischer Titration: An Introduction 15

 Why water determination

 Karl Fischer Titration

Karl Fischer Titration: An Introduction 16

Karl Fischer: Petroleum Chemist 1901 - 1958

Karl Fischer Titration: An Introduction 17

Karl Fischer on the way to the next job overseas

Karl Fischer Titration: An Introduction 18

3 years hard work, backstrokes and success

1935 First publication by Karl Fischer

Karl Fischer Titration: An Introduction 19

 1935 Scientific publication by Karl Fischer

Over 1 million KF titrations every day!

 Why water determination

 History of Karl Fischer Titration

Karl Fischer Titration: An Introduction 21

Two step reaction

1. SO2 + RN + CH3OH  (RNH)SO3CH3