MT-PH/Villariña

04.13.2018

Karl Fischer Titration

Precise and Efficient Water Content Determination
Agenda 2

1 KF Titration: Measurement Principle

2 Volumetric vs. Coulometric

3 Drift

4 Coulometric Electrolyte: To replace or not?

5 Volumetric KF: Titrant Concentration Determination

6 KF Titration: Is it the right solvent?

7 Sampling Preparation

8 Sample Addition

9 Sampling Analysis: Summary

10 Repeatability

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Measurement Principle
 Definition and Chemical Reaction
 Types
KF Titration: Definition 4

Specific standard method for the determination of water content

 Gives accurate and precise results within minutes
 Based on the redox reaction:

 Buffer - for neutralization of acids formed during analysis

 pH range: 5.5 – 8.0
- More Methyl sulfite (intermediate product) ions formed -> faster reaction
- Max reaction rate
- Beyond pH 8.5: side reactions take place
 Solvent: mainly methanol
- Can be exchanged or mixed with other solvents to increase solubility
- Methanol content: minimum 20 % to maintain 1:1 ratio of Iodine reaction to water
o Still depends on the type of sample to analyze

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KF Titration: Type 5

2 types: Volumetric KF titration and Coulometric KF Titration

 Volumetric KF Titration
- Designed for a wide range of water content
applications: determinations from 100 ppm to 100%
water
- Titration vessel: optimized to retain a low drift value
- Offers the possibility to determine the water content
of liquid, solid and gaseous samples

 Coulometric KF Titration
- Samples with a low water content from 1 ppm to
5%
- Titration vessel: made completely from glass which
ensures a uniquely low drift and hence makes the
most accurate and precise results possible
- Most convenient without diaphragm
o Complicated and expensive catholyte and anolyte
reagents removed
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Volumetric vs. Coulometric
 Differences
 Volumetric KF: Titrant Type
 Coulometric KF: With or Without
Diaphragm
Coulometric vs. Volumetric 7

KF Titration Type Volumetric Coulometric

Solution containing Iodine is Generated by electrochemical

Addition of Iodine added – motorized piston oxidation in the cell – generator
burette electrode

Water content range 100 ppm to 100 % 1 ppm to 5 %

• 1-Component
• With diaphragm: Catholyte and
• 2-Component
Type of Titrant Anolyte
• Pyridine-containing
• Without diaphragm: Fritless
• Special

• Methanol
Type of Solvent • Methanol mixture None
• Methanol-free (special)

Titrant Standardization Yes No

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 Volumetric KF: Titrant Type 8

Pyridine-
Type One-Component Two-Component Special
Containing

• Methanol-free 1-
• Iodine Same as 1-
• Iodine Comp
Composition • Sulfur dioxide Comp or 2-
• Methanol • Ethanol-based
• Imidazole Comp titrants
2-Comp

• 1-Comp: 2-
chloroethanol &
• Methanol • Sulfur dioxide Same as 1-
trichloromethane
Solvent • Methanol mixture • Imidazole Comp or 2-
• Diethanolamine
• Methanol-free • Methanol Comp titrants
& EtOH

• Both
Improved
• Up to 2 years components:
stability due to
• Decrease in very stable in
separation of
Life Span concentration: 0.5 storage
titrant
mg/mL per year, • Stable titer in
composition
sealed bottle tightly sealed
and/or solvent
bottle

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Volumetric KF: Titrant Type 9

Pyridine-
Type One-Component Two-Component Special
Containing

• 5 mg/mL: water
content of 1000
ppm to 100 % • 5 mg/mL: water
• 2 mg/mL: water content of 1000
Available
content < 1000 ppm to 100 % - -
Concentrations
ppm • 2 mg/mL: water
• 1 mg/mL: water content < 1000 ppm
content < 200
ppm

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 Coulometric KF: With or Without Diaphragm? 10

Diaphragm – porous ceramic frit separating cathode (inner) from anode (outer)
 With Diaphragm:
- Classical coulometric cell with 2 parts: Anode compartment and Cathode Compartment
o Separated by "diaphragm"
- Anode: contains anolyte (KF electrolyte) required to oxidize Iodide to Iodine
o Applied current – generator electrode
o Releases electrons
- Cathode: contains catholyte that enables completion of whole reaction
o Reducing Hydronium ions to Hydrogen (uses released electrons from Anode)
o Contains Ammonium salt for Hydrogen production
- Required for:
o Samples with very low water content (< 50 μg water/sample)
o Very accurate determinations
o Easily reducible samples like Nitro compounds and unsaturated HC's

 Without Diaphragm:
- Cathode too small to be reached by generated Iodine
- Generated H (g) forms bubbles around cathode (protection)
- Relatively higher stirrer speed: more rapid distribution of generated Iodine molecules
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Coulometric KF: With or Without Diaphragm? 11

Fritless: Advantages and Limitations

 Advantages:
- No contamination/blockage of diaphragm
- Easier cleaning
- Lower drift
- Ideal for compounds such as:
o HCs (chlorinated HC)
o OH (phenols)
o RCOOR (ether)
o RCOR (ketone)
o Etheric oils and essences
o Petroleum oils

 Limitations:
- Not suitable for easily reduced samples
o Nitro compounds, unsaturated FA
o Formation of nascent H

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Drift 12

Indicates the quantity of water that enters the titration stand over a defined
period
 Drift Determination
- titration of the dry solvent for a defined time
 During standby titration: titrator continuously titrates the water that diffuses into the cell,
and its value is displayed on the screen
 Drift value is subsequently used in the calculation of the result in order to compensate for
the moisture that entered the titration cell
 For accurate results: Drift value – as low as possible and stable before start of a titration

Source for Drift Explanation

Online Last measured value of standby
Determination The drift is determined and stored as raw result DRIFT
Fix value A fixed value is defined into method
Request The value can be entered immediately after starting sample
titration

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Coulometric Electrolyte: To replace or not? 13

With diaphragm (in practice) : common to replace both the anolyte and
catholyte at the same time

 Situations:
 If the capacity (monitored by the coulometers) of the electrolyte is exceeded
- Anolyte solutions (100 mL): after 1000 mg water,
- Catholyte solutions (5 mL): after 200 mg water
 If after adding samples, the level of the solvent or the anolyte exceeds the 150 mL mark
 If the conductivity of the anolyte drops to a very low value, e.g. below 10 μS
 If an emulsion forms in the anode compartment
 If the drift is too high
 After being used for two weeks

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 Volumetric KF: Titrant Concentration Determination 14

Essential for accurate, repeatable results

 Change in titrant concentration occurs:
- titrant is not chemically stable, e.g. the one-component titrant
- titrant may absorb moisture from the atmosphere reducing its concentration (the
anhydrous methanol in the titrant is very hygroscopic)
- significant change in temperature may occur

 How often?
- Depends on: choice of titrant, tightness of titrant bottle, and desired level of accuracy
- Sufficient: weekly, based on chemical stability of titrant
- Determination also tests tightness of titration stand, proper functioning of burette, end-
point indication

We recommend to determine the titrant concentration daily!

o Variable T and/or no AC

 Determine concentration under the same conditions as for sample analysis

- Same: titration stand, volume of solvent, T
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Volumetric KF: Titrant Concentration Determination 15

May use different standards (solid or liquid)

 Disodium tartrate dehydrate
- Primary standard for KF titration
- Stable and non-hygroscopic
- 15.66 % water content, under normal conditions
- Slowly dissolves in MeOH (variable solubility with different MeOH solvent mixtures)

 Water Standard
- Consists of a mixture of organic solvents containing a specific amount of water
- Water content confirmed by test certificate included in every package
- Supplied in glass ampoules, protected against ingress of moisture
- Can be stored unopened up to 5 years
- Should be immediately used after opening (one-time use only!)

 Pure Water
- Requires practice and precise working: very small sample amount needed to analyze
- Not as recommended as the first two standards

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 KF Titration: Is it the right solvent? 16

Solvent – used to completely dissolve sample to release water completely

 Can be pure or a mixture of solvents,
depending on type of sample
 Largest composition: always an alcohol
(most preferably MeOH)
- Ensures correct stoichiometric ratio of
Iodine to water
 Should contain as few water as possible
- Water content > 100 ppm: titration too
long, titrant wasted
 Addition of buffering agents (if necessary)
must be done before titration
 Correct ratio of solvent mixture and/or
temperature matters
 Should be replaced timely

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Sample Preparation
 Sample Amount
 Characteristics and Procedure
 How to Release Water?
 Sample Preparation 18

KF Samples – with different properties, comes different sample preparations

 Sample amount – dependent on expected water content and required accuracy and precision
- Coulometric: optimum amount of water is in the range from 0.5 to 2 mg water per sample

- Volumetric: optimum amount of water is approximately 10 mg per sample

 Sample preparation: dependent on sample type (composition and property): Solid, Liquid, Gas
- Solids: finely crushed/ground
- Liquid: solubility in solvent matters (as well as with Solid and Gas)
- Gas: sample vessel must be purged thoroughly
 Samples must be taken with extreme caution to exclude atmospheric moisture: most common
source of error

NOTE: Bigger sample size, lesser inaccuracy in results! 

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Sample Preparation 19

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Sample Preparation: How to Release Water 20

 Internal Extraction
- For insoluble solids that release water quickly when crushed
- Can speed up the extraction of water from the sample by
o heating the solution with a thermostating titration beaker
o grinding the sample additionally with a built-in homogenizer
Note: Homogenizer eliminates the need to use auxiliary reagents such as formamide
with samples like hazelnuts, potato chips, sugar, etc.
 External Extraction
- For insoluble solids that release water only slowly when crushed as well as for
samples with an extremely inhomogeneous water distribution
- Water is extracted from the sample by means of a defined quantity of solvent of known
water content
- Extraction improved by:
o Shaking the solution (mechanical shaker, shaking bath)
o Placing the solution in an ultrasonic bath for a certain time
o Reducing the sample further with a built-in homogenizer
- Most commonly used solvents: MeOH, Decanol/Octanol, Formamide, Chloroform

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Sample Preparation: How to Release Water 21

 External Dissolution
- Defined as the complete dissolution of a sample in a defined amount of solvent of
known water content
- For soluble solids
o With an extremely inhomogeneous water distribution, or
o With a very low water content, or
o With a high water content
- May use pure solvents for dissolution; addition of MeOH not necessary
- Most commonly used solvents: Methanol, Formamide, Chloroform, Toluene
- Corresponds to external extraction except that the sample dissolves completely in the
external solvent

 Lyophilized substance in septum bottles

- For extremely low water content of freeze-dried substances (e.g. biological tissue,
serum, foodstuffs)
- Use of anolyte aliquot; blank value correction is too large
- If sample is completely dissolved: use the method type “External extraction” and the
calculation for the "External dissolution"
- If a suspension is formed: use the method type “External Extraction” and the calculation
for the "External extraction"
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Sample Preparation: How to Release Water 22

 Water in Gases
- Gas must be directed to the titration vessel for a defined period of time
- With constant flow rate for volume determination and water content calculation
- Water content in ppm is calculated by entering the volume and the density
- Direct addition to vessel or use of sample vessel (differential weighing required)
- Sample vessel and tubings must be purged thoroughly beforehand

 Drying Oven
- for solids and liquids that cause side reactions with KF reagent, or that release water
very slowly
- Principle: sample heated in an oven; water evaporates; gas transferred to titration cell
using an inert gas (purge gas); water content is determined

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InMotion KF Oven Autosampler 23

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Sample Addition
 Liquid Samples
 Solid Samples
Sample Addition: Liquid Samples 25

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Sample Addition: Solid Samples 26

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Sample Addition: Solid Samples 27

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 Sampling Analysis: Different Methods
Type of Sample Coulometric
• Not possible: Direct
Measurement
Solids • Possible: External Extraction,
External Dissolution, Drying
Oven
Liquids Direct Measurement*
Direct Measurement
• With constant flow rate to
determine correct sample
Gases
volume and correct calculation
Use of Sample Vessels
• Differential weighing required
28
Volumetric
Direct Measurement*
Direct Measurement*
Direct Measurement
• With constant flow rate to
determine correct sample
volume and correct calculation
Use of Sample Vessels
• Differential weighing required
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Repeatability 29

Closeness of the agreement between the results of successive

measurements of the same sample

 Can be expressed quantitatively as the relative standard deviation, srel, given as %

- Repeatability of a sample series becomes worse with decreasing water content

 With decreasing sample size the relative standard deviation srel becomes worse
- Use the optimum sample size in order to achieve precise results
 Good repeatability: achieved the sample size is increased particularly for low water content
values.
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Question? Comments? 30

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