Titration on a whole new level

Michael Margreth
Senior Product Specialist Titration
Metrohm International Headquarters
www.metrohm.com
 FUNDAMENTALS OF
KARL FISCHER TITRATION
KF titration – Universal method for
water content determination

• in technical products (plastics, oil and gases)

• in cosmetic products
• in pharmaceutical products
• in food industry
• …
KF titration – Why?
• Selective
in contrast to drying, KF is a selective method
• Measuring range
ppm up to % range
• Accurate
small standard deviations can be achieved
• Fast
usually 1 – 3 minutes per determination
• Universal
almost any sample can be analyzed
KF titration – Stoichiometry

I.

CH3OH + SO2 + RN → [RNH]SO3CH3

II.

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

(RN = Base)
KF titration – Reagents

• Sulphur dioxide SO2

• Solvent Methanol
• Buffer Imidazol
• Iodine I2
 KF titration – pH dependency

log K 6

0
0 2 4 6 8 10 12 pH
Optimum → pH range between 5 and 7
Volumetry

Classical titration → Working medium and titrant

Volumetry – Reagents
One component Two component
reagents reagents

Titrant Solvent Titrant Solvent

I2, SO2, alcohol I2 and SO2,

base and alcohol base and
alcohol alcohol
Volumetry – Reagents

One component reagents:

• Advantage:
theoretically unlimited water capacity and flexibility
regarding solubility promoters

• Disadvantage:
The titer decreases 5% per year in the closed
bottle!
Volumetry – Reagents

Two component reagents:

• Advantage:
pH optimal in the solvent → fast reaction / titer is
very stable

• Disadvantage:
limited water capacity (SO2 is limited), reagent
needs to be exchanged after some determinations
Volumetry – Titer determination
• Determination of the water equivalent of the KF
titrant
• In KF titration, the titer has a unit

mg/mL

• The titer indicates how many mg of water can be

titrated with 1 mL of titrant
Volumetry – Titer determination

Requirements
• Water standard with certified water content
• Syringe with needle
• Balance

Calculation
sample size amount of water standard × water content of the standard
titer =
volume of dosed titrant at endpoint
Volumetry
Buret Molecular
Step by step: sieve
• Fill titration vessel Pt electrode
with solvent Septum plug
• Pretitration with
KF reagent
• Add the sample
• Titrate with KF reagent
Coulometry – Generator electrodes

Iodine is generated in titration cell (anodic oxidation)

Coulometry – Electronic buret
- +
• Current is the buret
• Iodine is produced from
an iodide containing solvent
by anodic oxidation
• Generating current is
switched off as soon as H+ H
slight excess of free iodine -
is present -
• Free iodine is indicated by I- I

a double platinum electrode

Coulometry – Generator electrodes

without diaphragm with diaphragm

Coulometry – How to fill a generator
electrode with diaphragm?
• Catholyte: 5 mL
Reduction: 2 H+ + 2 e- → H2
Change catholyte weekly!
• Anolyte: about 100 mL
Oxidation: 2 I- → I2 + 2 e-
• Reagents should have
the same level!
Coulometry – Comparison generator
electrodes
Generator electrode Generator electrode with
without diaphragm diaphragm
• Recommendable for most • Reagents with low
applications conductivity (addition of
chloroform, xylene, etc.
• Sample should have a good
> 10%
solubility in alcohol
• Ketone reagents
• Absolute water content
< 50 ppm
Generator I: 400 mA Generator I: auto
Coulometry – Reagents

Capacity of ~ 1000 mg of water (for 100 mL reagent)

• Reagents for cells without diaphragm

• Reagents for cells with diaphragm
• Anodic and cathodic reagents
• Combined reagents
• Special reagents for ketones

• Reagents suitable for both cells

Coulometry – An absolute method
• No titrant added (electronic buret)
• Iodine is generated electrolytically from iodide
• No titer determination is required

→ In coulometric KF titration water standards are

used to check the system (recovery).
 Molecular
Coulometry sieve

Pt electrode
Step by step:
Generator
• Fill titration cell with Septum electrode
reagent
• Conditioning
• Add the sample
• Titrate sample
Volumetry or coulometry?
Which method should you choose?

• Volumetric titration
range of application: 0.1 % - 100 %

• Coulometric titration
range of application: 0.001 % - 1 %
(10 µg – 200 mg absolute water content), mainly
liquids and gases
Endpoint indication
Bivoltametry Ipol = 50 µA (KFV)
10 µA (KFC)
Constant current applied to double Pt electrode

During titration Excess H2O

→ High voltage between Pt wires

At end of titration Small excess of free iodine

→ Voltage decreases sharply
Endpoint indication

250 mV
Drift

Permanent consumption of KF reagent

Aim: Constant and low drift

Optimal: Volumetry < 10 µL/min
Coulometry 2...10 µg/min

Influence on results → drift correction (mainly KFC)

Drift
• Start drift → acceptable drift value for start of
determination (cond. OK)
• Stop criteria drift
• Absolute drift
the entered value is the stop drift
• Relative drift
the stop drift is calculated from the measured drift
value (at titration start) and the entered value
 Drift Determination time, used for
drift correction (time x drift)
Drift
[µL/min]
[µg/min]

Abs. stop
drift (KFV)
Start Rel. stop drift (KFC)
drift

Time [s]
Cond ok Titration

Drift lower than Start of titration, End of titration,

start drift drift value for drift conditioning
correction follows
 SIDE REACTIONS IN
KARL FISCHER TITRATION
Direct titration

samples scheme procedure

1. Samples that Sample is added

are soluble directly to
in KF titration vessel,
reagent solved in
working
2. Samples that medium and
release their titrated
water in KF Ti Stand 803

compatible Smpl
Sample matrix
solubility
is added to the
promoters
vessel as well
Side reactions

• Acids
• Bases
• Aldehydes and ketones
• Carbonates, hydroxydes and oxides
• Silanole / Siloxane
• Strong reducing agents
• Strong oxidizing agents
Karl Fischer reaction
Ketone /
Aldehyde Aldehyde

Silanole CH3OH + SO2 + RN (RNH)SO3CH3

Acid / Base Oxidant

Acid

H2O + I2 + (RNH)SO3CH3 + 2 RN (RNH)SO4CH3 + 2 (RNH)I

Hydroxide,
Reducing agent Carbonate
 KF titration curve

Curve with side reaction!

Good titration curve!

Reaction of aldehydes and ketones
with methanol
• Steady side reaction
• Acetals or ketals respectively are formed
• Water is formed
R
R CH3OH R OMe
O + + H 2O
CH3OH
R
OMe

• No stable endpoint
• Too high results
→ Use of methanol free reagents
Reaction of aldehydes with SO2

• Slow side reaction

• Water is reaction partner
H
H R SO3HNR'
O + SO2 + H2O + NR'
R
OH
• No stable endpoint
• Too low water contents
• Test: add a defined amount of water
→ Fast titrations to suppress bisulfite addition
Further side reactions
• Acids and bases
• Carbonates, hydroxydes and oxides
• Silanoles and soloxanes
• Strong reducing/oxidizing agents

How to avoid side reactions?

• Choose special reagents
• Indirect titration (oven method)
• Decrease temperature in titration cell (freeze side reaction)
• Adjustment of the pH
Gas extraction

direct titration liquid extraction gas extraction

1. Samples 1. Samples that 1. Samples that

soluble in KF release water are not
reagent in organic soluble in KF
liquids reagent
2. Samples that
2. Samples that
release water
cause side
in KF
reactions
compatible
solubility
promoters
Gas extraction (oven method)

to coulometric or
volumetric cell

double hollow needle

vial placed in the oven

Gas extraction
Advantages

• No contamination of titration cell

• No contamination of electrodes
• No memory effects
• No side reactions
• Fast release of water 860 KF Thermoprep

• Minimal sample preparation

Gas extraction
• Step 1: (use empty vial)
- Heat up KF oven
- Start gas flow
- Titrate cell to dryness
• Step 2: (use empty vial)
- Determine blank value
• Step 3:
- Put sample vial into the oven
- Heat up sample and transfer released water with carrier
gas to KF cell
Gas extraction

Sample: Motor oil

• Oven, 160°C, N 2 curve with side reaction

Content: ~ 390 ppm

• Direct measurement
Content: ~ 960 ppm
long determination time
Gas extraction - automated

885 Compact Oven SC 874 Oven Sample Processor

Checking the functionality of a KF
system
Performance
→ Determination of water standard (liquid)
→ Minimum threefold determination

Evaluation
→ Recovery should be between 97 and 103 %
→ If not, check system!
Influence of sample matrix?

Performance
→ Run determinations with sample
→ Add water or water standard to the working medium
(minimum threefold determination)
Evaluation
- Recovery 97...103% → no influence of sample matrix
- Recovery < 97% → influence of sample matrix
- Recovery > 103% → influence of sample matrix
Checking the functionality of a KF
system with oven
Performance
→ Determination of oven standard
→ Minimum threefold determination

Evaluation
→ Recovery should be between 97 and 103 %
→ If not, check system!
Influence of sample matrix?

Performance
→ Run determinations with sample
→ Add water or water standard to the working medium
(minimum threefold determination)
Evaluation
- Recovery 97...103% → no influence of sample matrix
- Recovery < 97% → influence of sample matrix
- Recovery > 103% → influence of sample matrix
Metrohm instruments in the course
of time
 OMNIS
A WHOLE NEW LEVEL OF PERFORMANCE
 OMNI IS A
LATIN PREFIX
MEANING
"ALL" OR
"EVERY".
HARDWARE –
ALL NEW!
 OMNIS
TITRATOR All you need for starting with OMNIS!
Main unit – the brain - of the titration system

Stand alone titrator with built-in buret

One or two measuring modules can be controlled

→ analog and/or intelligent sensors

With or without magnetic stirrer available

17.09.2018
 MAGNETIC
STIRRER Necessary to stir?
Direct control via front panel
→ no annoying search for the manual control in
the software anymore
Fix connection to instrument
→ more stable
If preferred, a rod stirrer can be connected and
contolled via front panel

17.09.2018
 ROD STIRRER
Rod Stirrer preferred? No problem!
Connection via MDL connector to Titrator
Requires Magnetic Stirrer (direct control via On/Off
Button and control panel)
LED Status indication
Automatic detection of blockage
Adjustable length of propeller stirrer

17.09.2018
MODULAR ON
A WHOLE
NEW LEVEL
 MODULARITY ON A WHOLE NEW LEVEL

Controlled dosing of e.g. solvent / auxillary solution?

Expand an OMNIS Titrator with additional Titration and Dosing Modules
Parallel titration with OMNIS Titrator and Dosing Module possible
Increase speed

17.09.2018
 MODULARITY ON A WHOLE NEW LEVEL

Combine different applications

Add further applications, e.g. volumetric Karl Fischer Titration
New OMNIS Solvent Module for contact free reagent exchange
New Karl Fischer Titration cell

17.09.2018
 MODULARITY ON A WHOLE NEW LEVEL

Where are the limits?

Up to five parallel applications on one manual titration system
→Have your application ready for urgent samples!
Buy what you need now and expand later!

17.09.2018
 OMNIS
TITRATION Additional measuring interfaces and/or solutions
needed?
MODULE Expands the OMNIS Titrator with
one additional buret for titration/dosing
max. two measuring interfaces
one magnetic stirrer (optional)
Power supply and titration modes via OMNIS
Titrator
to be used as independent titrator

17.09.2018
 OMNIS
DOSING Additional solutions needed?
Expands the OMNIS Titrator with
MODULE
one additional buret for titration/dosing with a
Titrator
one additional buret for dosing with a Sample
Robot
one magnetic stirrer (optional)
to be used as additional titration stand

17.09.2018
 NEW BUILT-
IN BURET

HIGHEST BURET
RESOLUTION
Use of different cylinder sizes not
required anymore for smaller or
larger volumes

AVAILABLE AS 2, 5, 10,
20, 50 ML

17.09.2018
 BUT ALSO….

Only filled just before Dosing / Titration

Almost no bubbles

No need of wasting expensive chemicals for daily

prep

Less corrosion of glass cylinder

Increased lifetime

17.09.2018
 OMNIS
SOLVENT Reagent exchange in Karl Fischer Titration
Expands the OMNIS Titrator with
MODULE
contact free reagent exchange
Manual or software controlled
Siphon breaker technology to avoid siphon effect
Suitable for 0.5, 1.0 and 2.5 L bottles

17.09.2018
SAFER ON A
WHOLE NEW
LEVEL
SAFER

Safety on a whole new level

Contact-free reagent exchange in matter of
seconds
System ready? Green LEDs tell you so!
Full traceability of your reagents
OMNIS monitors itself
 LEDS CONFIRM SYSTEM STATUS

LED on…
• …Titrator
• …dTrode
• …Rod Stirrer / Magnetic Stirrer
• …Liquid Adapter
• …Buret
• …Sample Robot
• …Pump
Red: system error
Yellow: connecting
Green: ready to go
17.09.2018
 LIQUID ADAPTER WITH 3S ADAPTER TECHNOLOGY

Layoutbild

Safe & contact-free chemical handling

Secure information transfer via RFID – fully traceable reagent data
Smart connection of the reagents with one single click

17.09.2018
 CONTACT-FREE AND EASY REAGENT EXCHANGE

• Easy connection of a new bottle by a single click

• Bottle caps remain on the bottle and can be

closed for storage

17.09.2018
 LED
INDICATION
LIQUID ADAPTER WITH 3S
ADAPTER TECHNOLOGY
LED indication of proper connection
and validity of the reagents

17.09.2018
EXCHANGE SOLUTION WITHOUT ADDITIONAL
RINSING STEP

Disconnect old bottle

Reconnect new bottle

Perform "preparing" step via manual control in the

software

System ready for use

After preparation of a 20 mL buret, the carry-over

volume of the old solution is less than 1 µL in 10 mL
new solution
 dTRODE – THE NEW REFERENCE
FOR DIGITAL ELECTRODES

Intelligent electrodes with automatic recognition

Intelligent electrode and measuring amplifier in one

rugged sensor
LED status indication
Automatic transfer of sensor data to software
Signal converted in electrode head → undisturbed
transfer of digital signal to instrument

17.09.2018
 MEASURING MODULES

Analog and digital measuring modules

Analog Measuring Module for standard electrodes
Digital Measuring Module for new dTrodes
Simple installation/upgrade/exchange
Measuring range -2400…+2400 mV
Optical signal transfer to Titrator/Titration Module
→ Less signal noise

17.09.2018
 NEW
AUTOMATION
HARDWARE OMNIS Sample Robot

Most flexible titration automation system

New sample handling philosophy

→ Separated analysis from sample transport

Highest throughput ever

17.09.2018
 NEW
AUTOMATION
HARDWARE Work station modules

Pick&Place modules for titration

Pump modules for cleaning purposes

Upgrade whenever necessary

17.09.2018 74
 DEDICATED BEAKER FOR RINSING
OF TITRATION EQUIPEMENT

Slide moves beakers back and forth

No need to waste a sample beaker for rinsing
Rinsing can be done at the same time as the
exchange of sample beaker

Rinsing Position

Sample Position
 MODULARITY OPENS NEW FLEXIBILITY

Three sizes of sample robot S – M – L

Two, five or seven racks can be placed
Pick&Place modules with or without magnetic stirrer
Pump modules with two or four pumps

17.09.2018 76
 OMNIS SAMPLE ROBOT S

Up to two Pick&Place modules

Up to four pumps on a single Pump module
Max. 50 x 75 mL on two sample racks

17.09.2018 77
 WORK STATION ARRANGEMENT ON S

Adjusted according to your wishes

Dummy plate for not used slots

17.09.2018 78
 OMNIS SAMPLE ROBOT M

Six slots for working stations in total

Max. 125 x 75 mL on five sample racks

17.09.2018 79
 OMNIS SAMPLE ROBOT L

Six slots for working stations in total

Max. 175 x 75 mL on seven sample racks

17.09.2018 80
 WORK STATION ARRANGEMENT ON M AND L

Up to four Pick&Place modules

Up to eight pumps with two Pump modules
Easy addition of another application to the system

17.09.2018 81
 NUMBER OF SAMPLES ON THE SAMPLE ROBOT

Beaker size/ mL S with 2 racks M with 5 racks L with 7 racks

75 50 125 175
120 32 80 112
250 18 45 63

17.09.2018 82
 OMNIS SAMPLE ROBOT
YOU WILL
LIKE IT!

HIGH THROUGHPUT
EXTREMELY EFFICIENT
FLEXIBILTY ALLOWS UPGROWTH
PRICE ATTRACTIVE
FASTER ON A
WHOLE NEW
LEVEL
 UP TO 4 TITRATIONS AT THE SAME TIME WHEN
WORKING AUTOMATED

• Applications can all be the same…

→ Speed up

• …or they can be different

→ dedicated work stations per application
→ Speed up
→ only one sample robot necessary and not
4 different sample changers → footprint↓
→ analysis separated from sample transport

17.09.2018
DEDICATED WORKSTATIONS FOR DIFFERENT
METHODS Hardness Chloride
pH
Alkalinity
Example:
FASTER

Throughput on a whole new level

Automate up to 175 samples
Perform 4 titration at the same time
Exchange batches of samples on a running system
by changing single racks
 EASILY EXCHANGE YOUR SAMPLES WHEN SYSTEM IS
STILL RUNNING

• No need to stop the

system
• Samples can be stored on
the rack before analysis
• Exchange whole racks at
once
• Racks for dedicated
workstations

17.09.2018
 TIME SAVINGS BY ADDING ADDITIONAL WORK
STATIONS FOR SAME TYPE OF ANALYSIS

100

Reduction of up to
60% in time
compared to
60 samples determined
on just one single
Pick&Place module.
40

JUST 1 PARALLEL ON 2 PARALLEL ON 4

17.09.2018 89
 TIME SAVINGS COMPARED TO 814 SP

110
100

Same number of
samples takes 10%
longer in time than
60 on Sample Robot
with a single
Pick&Place module.
40

JUST 1 PARALLEL ON 2 PARALLEL ON 4 814 SINGLE

17.09.2018 90
 FIRMWARE MODULARITY ON A WHOLE NEW LEVEL

Firmware LQH MEAS MEAS CAL SET MET DET Parallel Parallel KF
package U/ T/ Ipol/U w/o Dosing Titration Titration
pH/ pol cond.
CONC
Opt. Opt.
Basic Opt. Opt.

Advanced Opt. Opt.

Professional Opt.

Standard firmware packages

Upgrade to higher package or with single options

17.09.2018
 SUMMARY
WHY
OMNIS?

MORE SAMPLES
Place more samples on a automated system
than ever before

MUCH FASTER
Many more samples in less time

MODULAR & FLEXIBLE

Just the right system for every request

MORE EFFICIENT
Runs several samples at the same time

17.09.2018
WHAT DO I
GET FOR MY
MONEY?
MORE!
 KEEN
ON

PERFORMING
ON A WHOLE NEW LEVEL

95
DO YOU HAVE
QUESTIONS?

96
AUTOMATED SYSTEMS IN KARL
FISCHER TITRATION
Topics
• Why use an automated system?
• Instruments for KF automation
• MATi 4
• MATi 10
• MATi 11
• Principle of oven method
• Instruments for oven method
• 885 Compact Oven Sample Changer
• 874 Oven Sample Processor
• 875 Gas Analyzer
Automation – Why?

• High sample number

• Sample preparation
• Lab security
• Better results / accuracy
• System runs day and night
Automation – benefits

• Less costs

• Better results

• Increased security

• Saves time
MATi 4
• Automated coulometric
KF titration
MATi 4

• Automated system for coulometric determination of

up to 160 samples
• Automatic transfer of the sample to titration cell
• Consists of 815 Robotic USB Sample Processor XL,
851 Titrando, Dosino and Dosing Unit, ...
• System is controlled by tiamo™
MATi 10
• Automated
volumetric
KF titration
MATi 10

• Fully automated system for volumetric KF titration

• Up to 24 samples
• Samples are placed in beakers on the rack
• Beakers closed with aluminium foil
• Reagent is added automatically
• Consists of 814 USB Sample Processor, 901
Titrando, 741 Stirrer, Dosino and Dosing Unit, ...
• System is controlled by tiamo™
MATi 11
• Automated
vol. KF titration
including
homogenization
MATi 11

• Fully automated system for volumetric KF titration

• Up to 53 samples
• Samples are placed in beakers on the rack
• Beakers closed with aluminium foil
• Reagent is added automatically
• Consists of 815 USB Sample Processor, 901
Titrando, Polytron, Dosino and Dosing Unit, ...
• System is controlled by tiamo™
Principle of the oven technique

gasflow to
coulometric cell hollow needle (outlet)

hollow needle (inlet)

oven

vial placed in
the oven
885 Compact Oven Sample Changer
885 Compact OSC
• Small footprint – 885 provides automation in a
very small place.
• Flexible – 885 can be used with all stand-alone KF
titrators with sample data silo.
• Easy to use – controlled by way of integral keypad.
No software/computer needed.
• Reusable sample vials – screw cap vials can easily
be opened, cleaned and reused. Only septum
needs to be replaced.
874 Oven Sample Processor
874 Oven Sample Processor
• USB device → Instrument is recognized
automatically when connected to a PC
• Use your own sample vials → Oven and rack can be
adjusted to different sample vials
• 4 MSB ports → Dosinos can be connected and e.g.
the reagent exchange be automated
• Find the optimal oven temperature with the
temperature gradient
• The heated transfer tubing ensures the complete
transfer to the titration cell
875 KF Gas Analyzer
Features of the 875 KF Gas Analyzer

• Complete system suitable for pressures of up to 40 bar

• Chemical and electronic parts are separated

• Built-in oven to avoid condensation and formation of ice at

the precision control valve

• Precise mass flow measurement

• Automated analysis

• Predefined tiamo™ methods

• Water determination in gases and liquefied gases

Safety

• Before delivery a pressure test is carried out (certificate

included)

• Method included to release pressure before sample container

is changed

• Cover to protect gas handling system

• Separation of the gas handling system from electronics and

power supply
Applications

• Methyl chloride • Butadiene

• Ethyl chloride • Dimethyl ether

• Vinyl chloride • Refrigerants

• Propane • Hydrogen

• Butane • Carbon dioxide

• Propene

→ Other samples need to be tested.

 KARL FISCHER TITRATION –
TROUBLESHOOTING, TIPS AND
TRICKS
Volumetric and coulometric
titration cell
Conditioning before titration
After addition of fresh solvent the drift is too high
Conditioning before titration
This indicates that the cell is not completely sealed
→ Humidity penetrates into the cell

You should check (and possibly exchange)

• All tube connections
• The septum
• O-rings / PTFE sleeves
• Molecular sieve
Conditioning before titration
How has the titration cell/equipment been cleaned?

• Water
• Solvent
• Cleaning agent
• In the dishwasher

→ Never use ketones to clean a titration cell!

Conditioning before titration
KF electrodes

Indicator electrodes
for coulometry for volumetry
KF electrodes

Generator electrodes
without diaphragm with diaphragm
KF electrodes - cleaning

How to clean an indicator electrode?

• Clean with a soft tissue

Be careful not to damage the Pt-pins!
• Polish with polishing set (6.2802.000)
or with tooth paste
• Rinse with water and methanol
KF electrodes - cleaning

How to clean a generator electrode?

• Fill electrode with HNO3 conc. and let acid flow

through the diaphragm
• Rinse with water (repeat 2 to 3 times)
• Rinse with methanol

→ Rinse means filling the cathode compartment with

water/solvent and allow the filling to drain out.
KF electrodes - maintenance
Make sure platinum pins are parallel
KF electrodes - maintenance
Make sure platinum pins are parallel
KF electrodes - storage
All KF electrodes are stored dry
→ No need of a storage solution

Alternatively the electrodes can

be stored in KF reagent, directly
in the titration cell
Titer determination
The sodium tartrate is not completely dissolved
• Use less sample
• Use a longer extraction time
• Pay attention to avoid sticking standard at the
glass walls and on the electrode

KF reagents have limited capacity to solve sodium

tartrate
• Change the solvent at frequent intervals
• Use liquid water standard
Titer determination
Sodium tartrate dihydrate as primary standard
Sample addition
Different possibilities to add sample to titration cell
Sample addition
Sample addition using a syringe
Sample determination
The drift is high (after titration)
Sample determination
The sample is not completely dissolved
→ Water is still released

• Longer extraction time

• Titration at elevated temperatures
• Sample preparation is required
• Addition of a solubility promoter
Dissolving sample
Titration at elevated temperatures

• 40°C/50°C
vegetable samples, salts, fatty samples, food

• 65°C (Boiling heat, reflux)

roasted coffee, leather
Dissolving sample
Use of a homogenizer
Vegetable samples, gelatine containing samples,
tablets

Advantage: good replacement of halogenated

solubility promoters
Dissolving sample
Mechanical treatment of the sample

Mortar
• Attention with hygroscopic and
moist samples
• If necessary use of a glove box

Lab mill
• Preferential with cooling system
Dissolving sample
Use of a solubilizer

Solvent Percentage Sample

Formamide Max. 50 % KFV Sugar samples,

Max. 20 % KFC salts
Chloroform Max. 70 % Oil, grease
Max. 30 %
Long-chained Max. 50 % Oil, grease
alcohols Max. 30 %
Xylene, toluene Max. 70 % Crude oils with
Max. 30 % tars
Sample determination
The sample reacts with the reagent
→ Side reaction

• Special reagents
• Titration at low temperatures
• Liquid Extraction
• Oven method
Liquid extraction
Samples that release water in organic liquids

• Solvent is added to sample

in an external vessel
• Only an aliquot of the
solvent is added
to the titration cell
• Blank value of solvent
needs to be determined
Gas extraction - principle

to titration cell

double hollow needle

vial placed in the oven

Oven method – optimal
temperature
How do you find the optimal oven temperature?
→ collect information from literature
• Melting point
• Boiling point
• Decomposition temperature
•…
If the information is not available, run a temperature
gradient.
Oven method – temperature
gradient

Water release curve of KF Oven Standard (50 to 250°C

with nitrogen as carrier gas)
Sample size - volumetry
How much sample should be used?

The sample size is depending on the water content

• Adapt sample size to buret size (10 to 90% of the

buret volume)
• Not too small → weighing error
• Not too large → dissolving of complete sample
Sample size - volumetry
If sample size cannot be changed, adapt water
equivalent of the titrant

• 5, 2 or 1 mg/mL
• Low consumption → lower titer
• High consumption → hihger titer
Sample size - coulometry
• Representative sample
• Balance error
• Solubility in reagent
• Best measuring range 500 – 2000 µg absolute
water
• Maximum of 10000 µg absolute water per injection
• Water contents lower than 100 µg → generator
electrode with diaphragm
Sample size - coulometry

H2O content of Sample H2O to be

sample weight determined
100000 ppm = 10 % 50 mg 5000 µg
10000 ppm = 1 % 10 … 100 mg 100 … 1000 µg
1000 ppm = 0.1 % 100 … 1000 mg 100 … 1000 µg
100 ppm = 0.01 % 1g 100 µg
10 ppm = 0.001 % 5g 50 µg
Sample determination
Wrong results caused
by overtitration
Sample determination
• Clean the Pt-electrode
• Check the antidiffusion tip
• Check settings for titration

Reagents on Reagents on
ethanol basis methanol basis
Polarisation 20 μA 50 μA
current Ipol
Endpoint 500 mV 250 mV
voltage EP
Sample determination
• Exchange working medium
• Increase stirring speed
• Is the Pt-electrode immeresed in the solvent
• Is the cable connected correctly to the electrode
and the titrator
• Are the correct reagents used for the analysis
Karl Fischer titration –
troubleshooting, tips and tricks

Summary
• Set up the KF titration cell carefully
• Clean the KF electrodes from time to time
• Titer determination is essential to obtain correct
results
• Make sure the sample dissolves completely
• Chose suitable sample size
Thank you very much for your
attention!
Questions