Application

Water in Morpholine
Karl Fischer application

Product group
Amines

General Information concerning the product group

Amines
Weakly alkaline amines pose no problems in the water determination after Karl Fischer and can be titrated
according to standard methods.
For strongly alkaline amines the buffer capacity of the Karl Fischer solution is not sufficient. A shift of pH into
the alkaline range leads to a side reaction of the iodine. This can be recognised by the dragging end points, or
a continuous consumption of iodine solution, respectively. If turn-off criteria are reached nevertheless, the result
is too high. This side reaction, caused by the disproportionation of iodine molecules above pH 8, can be avoided
through additional buffering of the working medium with a weak acid. Aquastar buffer solution for strong bases,
benzoic or salicylic acid are the most suitable because, unlike acetic acid, they do not show any tendency for
esterification in the Karl Fischer solution. The acids are added to the solvent prior to titration and can even be
employed in excess.
Some amines react with the Karl Fischer solution. Measures to suppress or overcome this side reaction are,
for example, titration in methanol-free working media, utilisation of small sample sizes, as well as titration to a
fast end point.

Special Information concerning the sample and the methods

This substance possesses medium alkaline properties. Through the addition of benzoic acid the amount of sample
that can be determined in the KF solvent increases.

Titration one component system

Reagents
Titrant: Aquastar - CombiTitrant 5 188005
One component reagent for volumetric Karl Fischer titration, 1 mL = approx. 5 mg water
or Aquastar - CombiTitrant 2 188002
one component reagent for volumetric Karl Fischer titration, 1 mL = 2 mg water
Solvent: Aquastar - CombiMethanol 188009 30 mL
Solvent for volumetric Karl Fischer titration with one component reagents, max. 0.01 % water
and benzoic acid 100136 5g
as buffer substance
Titration parameters
Default titration settings, e.g.:
I(pol) = 20 - 50 µA, U(EP) = 100 - 250 mV
Stop criterion: drift < 20 µL/min
Sample size
1 mL

Merck KGaA, 64271 Darmstadt, Germany, Tel. 2011-12-13 Page 1 of 3

+49(0)6151 72-2440
EMD Millipore Corporation, 290 Concord Road,
Billerica, MA 01821, USA, +1-978-715-4321
Application

Procedure
The titration medium is first placed into the cell and titrated dry by means of the titrant. Then the sample is added
with a syringe (exact sample weight determination by weighing of syringe before and after injection) and the
titration is started.

Titration two component system

Reagents
Titrant: Aquastar - Titrant 5 188010
Titrant for volumetric titration with two component reagents, 1 mL = approx. 5 mg water
or Aquastar - Titrant 2 188011
Titrant for volumetric titration with two component reagents, 1 mL = approx. 2 mg water
Solvent: Aquastar - Solvent 188015 30 mL
Solvent for volumetric titration with two component reagents
and benzoic acid 100136 5g
as buffer substance
Titration parameters
Default titration settings, e.g.:
I(pol) = 20 - 50 µA, U(EP) = 100 - 250 mV
Stop criterion: drift < 20 µL/min
Sample size
1 mL
Procedure
The titration medium is first placed into the cell and titrated dry by means of the titrant. Then the sample is added
with a syringe (exact sample weight determination by weighing of syringe before and after injection) and the
titration is started.

Coulometry with diaphragm

Reagents
Catholyte: Aquastar - CombiCoulomat frit 109255 5 mL
Coulometric Karl Fischer reagent for cells with diaphragm
Anolyte: Aquastar - CombiCoulomat frit 109255 100 mL
Coulometric Karl Fischer reagent for cells with diaphragm
and benzoic acid 100136 20 g
as buffer substance
Titration parameters
Default coulometer settings for cell with diaphragm:
For end point indication, e.g.:
I(pol) = 5 - 10 µA, U(EP) = 50 - 100 mV
Stop criterion for fast titration: drift < 15 µg/min
Sample size
0.3 - 0.5 mL
Procedure
The Karl-Fischer reagent is placed into the cathode and anode compartment of the titration cell with diaphragm.
The coulometer is started and the solvent is titrated dry. After preliminary titration and stabilisation of drift the
sample is injected into the titration cell with a syringe (exact sample weight determination by weighing of syringe
before and after injection) and the water determination is started. Titration is carried out to fast end point.

Merck KGaA, 64271 Darmstadt, Germany, Tel. 2011-12-13 Page 2 of 3

+49(0)6151 72-2440
EMD Millipore Corporation, 290 Concord Road,
Billerica, MA 01821, USA, +1-978-715-4321
Application

Coulometry without diaphragm

Reagents
Working Aquastar - CombiCoulomat fritless 109257 100 mL
medium:
Coulometric Karl Fischer reagent for cells with or without diaphragm
and benzoic acid 100136 20 g

Titration parameters
Default coulometer settings for cell without diaphragm:
For end point indication, e.g.:
I(pol) = 5 - 10 µA, U(EP) = 50 - 100 mV
Stop criterion for fast titration: drift < 15 µg/min
Sample size
0.3 - 0.5 - 1 mL
Procedure
The Karl-Fischer reagent is placed into the titration cell without diaphragm. The coulometer is started and the
solvent is titrated dry. After preliminary titration and stabilisation of drift the sample is injected into the titration cell
with a syringe (exact sample weight determination by weighing of syringe before and after injection) and the water
determination is started. Titration is carried out to fast end point.

Ordering Information
Product Catalog No.

Benzoic acid for analysis EMSURE® Reag. Ph Eur 100136

CombiCoulomat frit Karl Fischer reagent for the coulometric water determination for cells 109255
with diaphragm Aquastar™
CombiCoulomat fritless Karl Fischer reagent for coulometric water determination for cells 109257
with and without diaphragm Aquastar™
CombiTitrant 2 one component reagent for volumetric Karl Fischer titration 1 ml ca. 2 mg 188002
H2O Aquastar™
CombiTitrant 5 one-component reagent for volumetric Karl Fischer titration 1 ml ≙ ca. 5 188005
mg H2O Aquastar™
CombiMethanol Solvent for volumetric Karl Fischer titration with one component reagents 188009
max. 0.01% H2O Aquastar™
Titrant 5 titrant for volumetric Karl Fischer titration with two component reagents 1 ml ≙ 188010
ca. 5 mg H2O Aquastar™
Titrant 2 titrant for volumetric Karl Fischer titration with two component reagents 1 ml ≙ 188011
ca. 2 mg H2O Aquastar™
Solvent solvent for volumetric Karl Fischer titration with two component reagents 188015
Aquastar™

Merck KGaA, 64271 Darmstadt, Germany, Tel. 2011-12-13 Page 3 of 3

+49(0)6151 72-2440
EMD Millipore Corporation, 290 Concord Road,
Billerica, MA 01821, USA, +1-978-715-4321