Merck KGaA

Darmstadt, Germany

Live Session
19th August 2020

Karl Fischer Titration

Agenda 4

1 Introduction

2 Karl Fischer Titration

3 Difference between Volumetric and Coulometric titration

4 What is Drift?

5 Reasons for unstable drift

6 How to achieve good drift /overcome unstable drift

7 Optimum Sample size for Karl Fischer Titration

8 FAQ

9 Q&A

For internal use - Confidential

Nice to meet you all! 5

Hello !
Name: Tan Poh Wei
Educational Qualification : Master of Science in Analytical Chemistry
Working proudly with MT- MY : From 2016, Jan
Designation : Senior Application Specialist
Major focus areas : Titration, Density/Refracto, MP/DP, UV/VIS and LabX Software
Agenda 6

1 Introduction

2 Karl Fischer Titration

3 Difference between Volumetric and Coulometric titration

4 What is Drift?

5 Reasons for unstable drift

6 How to achieve good drift /overcome unstable drift

7 Optimum Sample size for Karl Fischer Titration

8 FAQ

9 Q&A

For internal use - Confidential

Karl Fischer 7

 Karl Fischer is an analytical technique used to measure the moisture (water) content in
solid, liquid or gases.
 Karl Fischer reagent consists of
• Iodine, (I2 reacts with water 1:1)
• Sulfur dioxide,
• a base and
• a solvent, such as methanol

 The solvent (methanol) is involved in the reaction.

50 % of the solvent must be methanol
 A suitable base (RN) keeps the pH value between Mettler Toledo solution for water
5.5 – 8 content determination from 1 ppm to
In the past: Pyridine 100 %.
Today: Imidazole

Chemical reaction:

H2O + I2 + SO2 + 3 RN + ROH → (RNH)SO4R + 2(RNH)I

Agenda 8

1 Introduction

2 Karl Fischer Titration

3 Difference between Volumetric and Coulometric titration

4 What is Drift?

5 Reasons for unstable drift

6 How to achieve good drift /overcome unstable drift

7 Optimum Sample size for Karl Fischer Titration

8 FAQ

9 Q&A

For internal use - Confidential

Difference between Volumetric and Coulometric titration 1/2 9

Volumetric Method

Double pin
Iodine It is added by burette platinum
(as titrant) during electrode -
titration. Measurement

Calculation Titrant consumption

Suitable
solvent (most
Burette – Titrant of the time it is
(KF Reagent) Methanol) and
Sample of
interest
Technique Sample having water
is suitable content from
100 ppm to 100 %

Direct Solid, liquid and

titration: gaseous samples
Difference between Volumetric and Coulometric titration 2/2 10

Double pin
platinum
electrode -
Measurement

Generator cell
1. With Diaphragm
2. Without
Diaphragm
Coulometric Method
Iodine It is electrochemically generated by the generator cell during titration.

Calculation generated current.

Technique is suitable For the Samples with low water content from 1 ppm up to 5 %

Direct titration Liquid and gaseous samples

 Coulometric titration – Generator Cell 11

With or without diaphragm

– +
Catholyte

Anolyte

– +

Anolyte
Agenda 12

1 Introduction

2 Karl Fischer Titration

3 Difference between Volumetric and Coulometric titration

4 What is Drift?

5 Reasons for unstable drift

6 How to achieve good drift /overcome unstable drift

7 Optimum Sample size for Karl Fischer Titration

8 FAQ

9 Q&A

For internal use - Confidential

What is Drift? 13

The drift is amount of water (atmospheric humidity) enter into the titration
stand per minute

• High drift Pretitration mode

• Low and steady/stable drift

“ready” (Standby) mode

For internal use - Confidential

What is Drift? 14

Since it is a closed system, where are the water (air humidity)

entry points ?

 The titration stand is never 100% tight

 Automatic drift compensation in the result calculation

For internal use - Confidential

Automatic drift compensation 15

Sample result = total amount of water determined – (drift * titration time)

Example:

Drift: 5 ug/min
Titration time: 2 min

Sample result
= water determined – (5ug/min x 2min)
= water determined – 10ug

Ideal conditions for standby:

Display of instrument screen
represents stable / steady drift and E ≤ 100 mV
ready for std/spl analysis. Drift ≤ 25 µg/min
For internal use - Confidential
Agenda 16

1 Introduction

2 Karl Fischer Titration

3 Difference between Volumetric and Coulometric titration

4 What is Drift?

5 Reasons for unstable drift

6 How to achieve good drift /overcome unstable drift

7 Optimum Sample size for Karl Fischer Titration

8 FAQ

9 Q&A

For internal use - Confidential

Reasons for unstable drift… 17

Root cause of unstable drift at two different

conditions

Pre titration After Titration

Titration stand is not 1. Incomplete

protected from dissolution of sample/
atmospheric humidity extraction of water
from sample
2. Side reaction of
sample with KF
reagent

For internal use - Confidential

Agenda 18

1 Introduction

2 Karl Fischer Titration

3 Difference between Volumetric and Coulometric titration

4 What is Drift?

5 Reasons for unstable drift

6 How to achieve good drift /overcome unstable drift

7 Optimum Sample size for Karl Fischer Titration

8 FAQ

9 Q&A

For internal use - Confidential

How to achieve good drift… 1/2 19

Pre titration condition

Root Good practice/ Troubleshooting

cause
Volumetric KF titration Coulometric KF titration

Moisture - Replace molecular sieves and - Replace anolyte

entering in silica gel in drying tube
titration - Level of anolyte should be higher than
vessel / - Check whether titration stand is that of the catholyte (3-5mm)
completely tight.
Moisture - Clean titration cell and generator
present in - Grease the tapered joints electrode and dry at 50 – 80 °C. Let it
cathode cool down overnight before reuse.
compartme - Condition Titration stand –
nt and Gently shake titration vessel - Check whether titration stand is
diaphragm completely tight.

Oven:
- Replace silica gel and molecular sieve in
the gas drying unit
Don't Do not install titrator close to air flow. E.g. Air-conditioner,
Fume wood
For internal use - Confidential
How to achieve good drift… 2/2 20

After sample titration

Root cause Good practice/ Troubleshooting

Volumetric KF titration Coulometric KF titration

Incomplete Use longer mixing time or different Use longer mixing time or suitable
dissolution solvents which dissolves the solvents to dissolve the samples
of sample/ sample or extracts the water quicker.
extraction Heating oven technique: water is not
of water - Heating oven technique: water is completely vaporized
from not completely vaporized
sample - Increase oven temperature - Higher oven temperature
- Increase vaporization time, e.g. - Increase vaporization time, e.g.
increase t(max) increase t(max)
Side Use suitable reagent for example - Use a different method
reaction of For ketone sample, K-reagents are
sample with used.
KF reagent
Use different method, e.g. external
extraction, drying oven, etc.

For internal use - Confidential

Agenda 21

1 Introduction

2 Karl Fischer Titration

3 Difference between Volumetric and Coulometric titration

4 What is Drift?

5 Reasons for unstable drift

6 How to achieve good drift /overcome unstable drift

7 Optimum Sample size for Karl Fischer Titration

8 FAQ

9 Q&A

For internal use - Confidential

How to decide correct sample size? 1/4 22

Manual way of calculating using below scale

Determine graphically the amount of sample for a water content in the range from 1 ppm to
100%
How to calculate optimum
sample size?
1. Start from the optimum point
10 mg for volumetric KF,
Expected water content

1 mg for coulometric KF

Coulometric
detection range 2. Connected by a straight line to
the expected water content.
Volumetric
detection range
3. The intersection point of this
line with the "Amount of
sample"
Sample size
For internal use - Confidential
How to decide correct sample size? 2/4 23

Calculate optimum sample size 100% 1g

required for 1000 ppm water content Coulo
for Volumetric KF titration?
10% 10g
Given :
Expected water content of sample = 1000
ppm 1% 0.01g 100g

Calculation Steps: 0.1g

1000ppm 1g 1mg
1. Volumetric optimum point on scale = 10 mg
10g

100ppm 100g 10mg

2. Connect a line from 10 mg of volumetric
detection point to expected water content i.e.
1000 ppm
10ppm 100mg

3. Intercept point on sample size scale will

Volu
provide suitable sample size required for
analysis. In this case it is approx. 5 g. 1ppm 1000mg
Content Sample size Water amount
How to decide correct sample size? 3/4 24

Calculate optimum sample size 100% 1g

required for 100 ppm water content for Coulo

Coulometric KF titration?
10% 10g
Given :
Expected water content of sample = 100 ppm
1% 0.01g 100g

Calculation Steps: 0.1g

1000ppm 1g 1mg
1. Coulometric optimum point on scale = 1 mg
10g

100ppm 100g 10mg

2. Connect a line from 10 mg of volumetric
detection point to expected water content i.e.
100 ppm
10ppm 100mg

3. Intercept point on sample size scale will

Volu
provide suitable sample size required for
analysis. In this case it is approx. 12 g. 1ppm 1000mg
Content Sample size Water amount
How to decide correct sample size? 4/4 25

MT offers built-in
sample size
calculator for routine
samples

Flowchart to explain 'how to

use inbuilt sample size
calculation'?
Enter
Click on option
expected
'More' which is Click on option
water
Method Start located at on the 'Sample size
content and
ribbon of display calculation'
required
screen
unit

Click on
Calculate
For internal use - Confidential
Built in calculator in detail…
Calculation steps which is incorporated in algorithm during calculating sample size by
instrument:

1. Titrant Consumption (30 – 70 %)

To get accurate and precise measurement result, MT recommends to choose sample
size which will consume titrant with volume 30 – 70 % of burette size
If we take 5 mL as burette size, then volume of titrant consumption should be in the
range of 1.5 mL to 3.5 mL.

Example:
Titrant concentration = 5 mg/mL
Burette size = 5 mL
Upper limit = 3.5 mL x 5 mg/mL = 17.5 mg (required water content)
Lower Limit = 1.5 mL x 5 mg/mL = 7.5 mg (required water content)

Likewise we can make for 10 mL burette volume what will be the limits to use it for
further calculation of sample size.

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Built in calculator in detail… with example!

Volumetric Karl Fischer Titrator

Calculate the optimum sample size for volumetric Karl Fischer titration when
 Burette volume= 5 mL,
 Titrant concentration = 5 mg/mL,
 Expected water content = 2 % (20 mg/g)
20 mg in 1 g

Lower limit Upper limit

(7.5 mg of water) (17.5 mg of water)

20 mg water = 1 g sample 20 mg water = 1 g sample

7.5 mg = 'X' 17.5 mg = 'X'

After cross multiplication, After cross multiplication,

'X' = 0.375 g 'X' = 0.875 g

27
 Built in calculator for Coulometric KF titrator

Coulometric Karl Fischer Titrator

Calculate the optimum sample size for Coulometric Karl Fischer titration:
Expected water content = 750 ppm (0.750 mg/g)
0.750 mg in 1 g

Lower limit Upper limit

(0.5 mg of water) (2mg of water)

0.75 mg water = 1 g sample 0.75 mg water = 1 g sample

0.5 mg = 'X' 2 mg = 'X'

After cross multiplication, After cross multiplication,

'X' = 0.67 g 'X' = 2.67 g

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Agenda 29

1 Introduction

2 Karl Fischer Titration

3 Difference between Volumetric and Coulometric titration

4 What is Drift?

5 Reasons for unstable drift

6 How to achieve good drift /overcome unstable drift

7 Optimum Sample size for Karl Fischer Titration

8 FAQ

9 Q&A

For internal use - Confidential

Frequently asked questions 30

1. pH Shift of the titration solution - Avoid values less

than 5.5 and greater than 8
Solution:
Adjust acidic and basic samples by adding buffering
agents
 For acidic sample: imidazole,
 For basic sample: salicylic acid)

2. Our Karl Fischer says 'OVER TITRATION' and the reagent is turning really dark. Why?
Solution:
"Over Titration" means that the reagent "anolyte" has released more then enough iodine to
consume the amount of moisture that exists inside the vessel.
Over titration is common sign of coated sensor pins. Use paper tower to clean the double
pins.

Sensor double pins

Frequently asked questions 31

3. Should I use KF grease?

Solution:
"Some vessels are designed differently and have ground glass fitting instead of screw on
caps . As we are working with ground glass fittings, then it is require to use KF grease to seal
the fittings.

Ground glass fittings

4. How can I make sure my instrument is giving me good results?

Solution:
Check periodically with water standards & Sodium Tartrate Dihydrate (Vol. KF). It can help
one verify that the instrument is performing properly.
Agenda 32

1 Introduction

2 Karl Fischer Titration

3 Difference between Volumetric and Coulometric titration

4 What is Drift?

5 Reasons for unstable drift

6 How to achieve good drift /overcome unstable drift

7 Optimum Sample size for Karl Fischer Titration

8 FAQ

9 Q&A

For internal use - Confidential

Thank You

In case you have any further questions, please email to support.my@mt.com

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