Natural Science Laws Experience "Live" - Learn Easily: The Method at A Glance

Titration
experiments
Karl Fischer
KF Guide 4
School
An Overview
Natural science laws experience “live” –

Karl Fischer
The Method atlearn easily
a Glance
Editorial / Content
Editorial
Dear Reader
As many samples are analyzed according to Karl Fischer as many

methods have emerged since the first Karl Fischer application to petro-
chemicals. Currently KF titration is applicable to practically any type of
sample or compound no matter of which origin.
This guide recommends the methods specifically suitable for each
sample type and summarizes the various KF titration methods currently
in use. The guide is compiled in table form for a fast and easy overview.
Take the fast lane to practically tested and proven water content determi-
nation methods according to Karl Fischer.
We wish you successful Karl Fischer titrations.
2
Content 3

1. Samples 4
1.1 Solid samples 4
1.1.1 Organic Chemicals 4
1.1.2 Inorganic Chemicals 5
1.1.3 Technical products – organic 6
1.1.4 Technical products – inorganic 7
1.1.5 Technical products – natural 7
1.1.6 Food 8
1.2 Liquid samples 9
1.2.1 Organic and inorganic chemicals 9
1.2.2 Foods and technical products 10
2. Titration Methods 11
2.1 Volumetric methods 11
2.2 Coulometric methods 13
3. Sample Preparation and Input 15
3.1 Solids: Characteristics 15
3.2 Solids: Sample input 15
3.3 Liquids: Characteristics 16
3.4 Liquids: Sample input 17
4. Accessories for Sample Input 18
5. More Information 19
5.1 Literature 19
5.2 More guides 19
5.3 Application brochures 19
3
1. Samples
Samples
1.1 Solid 1.1.1 Organic chemicals

samples
Substance Examples Method
Acetals R1-CH-(OR2)2 V2, C20
Method Chlorobenzaldehyde, nitrobenzaldehyde V11
C0
Mono-/poly- > C12 Stearyl alcohol, diphenylmethanol V2,V3,
alcohols V4, C20
Amines Weakly basic pKa >8: V2
Imidazole, indole, carbazole C20
Strongly basic: aminopyridine V16, C0
Reaction with methanol: V10, C0
naphthylamine, anisidine, toluidine
Oxidizable with iodine: aminophenol V0, C0
Carbamates RO-CONH2 V2, V3, V4
Carboxylic R-CONR´, e.g.: benzamide, stearamide V2, V3, V4
acid amides C20
Mono-/poly- Weakly acidic: benzoic acid V2, V3, V4
carboxylic C20
acids Strongly acidic: malonic acid, oxalic acid V15, C20
Oxidizable with iodine: ascorbic acid V0, C0
Ethers Linear and cyclic V2,V4,
V5, C20
Esters Carboxylic acid ester V2,V3,
R-COOR´ V4
Carbonic anhydride ROCOOR´ C20
Halogenated R-Cl, R-Br, R-I V2,V4,V5
hydrocarbons C20,C22
Isocyanates R-NCO V2,V4,V8
C20
Ketones Benzophenone V10, C24
Hydrocarbons > C12 V4,V5
Biphenyl, anthracene,pyrene, naphthalene C20,C22
> C20, such as tar, bitumen etc V3,V7
Nitro- di-Nitrobenzene, nitrotoluene, nitrochloro- V2,V3
compounds benzene C20
4
Peroxides Dialkylperoxide V2,V3,V4
R-OO-R Alkylperoxide C20
R-OOH
Diacyl peroxide V0, C0
Phenols Low pKa value: V2
phenol, cresol, salicylic acid C20
High pKa value: 2-chlorophenol, o-cresol V15
Side reaction: naphthol, aminophenol V0, C0
Sulfur Aromatic/aliphatic sulfonic acids V2,V4,V5
compounds sulfides R-S-R´, disulfides R-SS-R´, C20
thiocyanates, R-SCN
Mercaptans V0, C0
1.1.2 Inorganic chemicals

Arsenic Na2HAsO3 , NaAsO2 V30, C30
compounds
Bicarbonates KHCO3, NaHCO3, Na2CO3 V34, C32
carbonates
Boron B2O3, HBO3, H3BO3 V31, C32
compounds
Hydroxides, NaOH, KOH, MgO, CaO V21, V32
oxides C21, C34
Halogenides NaCl, KJ, CaCl2 , MgCl2 V2, V32
C20, C34
Cu(I) salts: CuCl2 V31, C33
Nitrates NaNO3, NH4NO3 V2, V31
C20, C32
Nitrites NaNO2 V31, C32
5
Samples

Phosphates NaH2PO4, Na2HPO4 V2, V31
C20, C32
tert. Phosphate, e.g.: Na3PO4 V15, V31
C32
Silicon Silicon oxide, Silicon dioxide V2, V32
compounds C20, C34
Silanols, R3Si(OH) V10
Sulfates Na2SO4, ZnSO4 V2, V32
C21, C34
Thiosulfates Na2S2O3, NaSO3, Na2S2O5 V2, V31
C20, C32
Tin(II)salts SnCl2 V31, C32
1.1.3 Technical products – organic

Agro- Insecticides, fungicides, herbicides V2
chemicals
Dyes Soluble: wool dyes, indicator dyes, etc. V2
Insoluble: pigments, dispersion dyes V2, V8
Cosmetics Creams, lotion V4, V5
Lipstick V5
Soaps V2
Toothpaste V20
Adhesives All-purpose glue, glue stick V2
Rubber cement V5
Plastics Polyethylene, PVC, polypropylene, poly- V30, V31
Polymers amides, polystyrene, polyurethane, etc. C31, C32
Petro- Waxes, paraffins: shoepolish, ski wax V12, C0
chemicals Tar, bitumen V7
lubricating grease, multipurpose grease V5, V30
6
Pharma- Antibiotics, disinfectants V2
ceuticals Salves, creams V4, V5
Suppositories V12
Tablets V2
Lyophilized preparations V40,C40
Textile Surfactants powder V2
auxiliaries optical brightener
1.1.4 Technical products – inorganic

Building Mortar, plaster, cement V32 (C34)
materials
Fertilizers Adherent moisture V6
Total water V30
Minerals Zeolites V32
Detergents Laundry detergent with brightener V30, V21
(hydroxides, perborates)
without brightener V2
1.1.5 Technical products – natural

Cellulose Paper, wood V30, C30
products
Cellulose powder V2
Fibrous Wool, silk V20
materials
7
Samples
1.1.6 Food

Fats Butter, margerine, mayonnaise V4, V5
Shortening, hardened fat V5
Grains and Biscuits, Zwieback, noodles, wheat, rye, V13, (V30)
starchy foods corn, potato chips
Potato flakes V22, V23
Dough, noodles, Zwieback V30, (V25)
Protein Cheese, meat spread, broth V23
products
Yogurt, ice cream V2
Dried albumen V13
Powdered milk V2, V23
Spices Pepper, curry, mixed spice V23
Mustard V24, (V5)
Adherent moisture: plain salt, sea salt V6, C23
Total water: plain salt, sea salt V32, C34
Sugar and Sugar: total water cont., jellied fruits, V13
sugar products gummi bears, candy, caramel, pudding
powder, almond paste
Instant ice tea, jam V8
Honey, jelly V2
Sugar: adherent moisture V6
Chocolate V5
Vegetable Cacao, coffee beans, tea, instant coffee, V22, V23
products tobacco, dried vegetables and fruits
Hazelnuts,almonds instant coffee V13
8
1.2 Liquid 1.2.1 Organic and inorganic chemicals
samples
Acetals Acetal, ethylal, methylal V1, C1
Aldehyde Acetaldehyde, benzaldehyde V11, C0
Alcohols Propanol, hexanol, benzyl alcohol V1, C1
Amines Weakly basic: V1, C1
N-methyl aniline, heterocyclic amines
pyridine, chinoline
Strongly basic: V16, C0
alihatic amines, N-butylamine,
hexylamine
Reaction with methanol: V10, C0
aniline, toluidine, diamine
Easily oxidized with iodine: V0, C0
hydrazine, hydroxylamine
Carboxylic C1 to C2 (formic acid, acetic acid) V15, C0
acids
> C2 (e.g. propionic acid, acrylic acid) V1, C1
Ethers Dimethylether, dioxane, anisole V1, C1
Esters Methyl benzoate, ethyl acetate V1, C1
Halogenated Methyl chloride, t-butyl chloride, V1, C1
hydrocarbons chlorobenzene, chlorotoluene
Ketones Acetone, acetophenone, methylethylketone V10, C10
Hydrocarbons C1 to C7 V1, C1
saturated and hexane, pentane, isobutane, cyclohexene,
unsaturated cyclohexane,
benzene, toluene, xylene
C7 to C14 (e.g. gasoline, petroleum, V4, C1
dodecane)
> C14, such as heavy oil, crude oil, V5, C30
paraffin
Mineral acids H2SO4, HNO3, HCl V15, C0
9
Samples / KF – Titration methods

Nitro- Nitrobenzene, nitrotoluene, nitrochloro- V1, C1
compounds benzene
Nitriles Acetonitrile V1, C1
Peroxides H2O2 V15
Acid amides Dimethyl-formamide V1, C1
Sulfur- Sulfides, disulfides, sulfonic acids V1, C1
compounds
Mercaptans V0, C0
1.2.2 Foods and technical products

Aqueous Foods: V1
solutions spiced sauce: soy sauce
beverages: beer, wine, liquor
Pharmaceuticals: extrakts, tinctures V1
Cosmetics: perfume, shampoo V1
Tensides and detergents V1
Aqueous Milk products: milk, cream, condensed milk V4
emulsions
Tensides and detergents V1
Agrochemicals (sprays): herbicides, V1
fungicides
Acrylic enamels V29
Emulsions in Agrochemicals (sprays): insecticides V4, C1
solvents
Synthetic enamels V7
Vegetable oils Foods: salad oil, sunflower oil V4, C1
Pharmaceuticals and cosmetics: V4
ethereal oils, massage oil C1
Technical oils Hydraulic oil, brake fluid, transformer oil, V5, C1
silicon oil
Motor oils V30, C30
10
2. Titration Methods
2.1 Volumetric The methods have been developed using 2-component reagents.
methods The methods can be also performed using the one-component reagent.
In this case methanol is used as a solvent.
Nr. Volumetric method

V1 Direct titration
Titrant: two component reagent 5 or 2 mg H2O/mL
Solvent: 40 mL KF solvent
Stir time: 10 s
V2 Direct titration
Stir time: 60 - 120 s
V3 Direct titration with added 2-propanol
Solvent: 40 mL KF solvent / propanol 1:1
V4 Direct titration with added 1-decanol
Solvent: 40 mL KF solvent / 1-decanol 1:1
V5 Direct titration with added chloroform
Solvent: KF solvent / chloroform 1:1 to 1:2
V6 Direct titration with added chloroform
Solvent: 40 mL KF solvent / chloroform 1:5
Delay time: 7 seconds.
V7 Direct titration with added toluene
Solvent: 40 mL KF solvent / toluene 1:1
V8 Direct titration with added formamide
Titrant: two component reagent 5 mg H2O/mL
Solvent: 40 mL KF solvent / formamide 1:1
Stir time: 5 - 10 minutes
11
KF – Titration methods

V10 Direct titration methanol free
Titrant: two comp. reagent 5 mg H2O/mL for ketone und aldehyde
Solvent: 40 mL KF solvent for ketone und aldehyde
Stir time: 30 – 60 s
V11 Direct titration methanol free
Titrant: two comp. reagent 5 mg H2O/mL for ketone und aldehyde
Solvent: 40 mL KF solvent for ketone und aldehyde
Start immediately (autostart)
V12 Direct titration with heat (at 50°C)
V13 Direct titration with added formamide and heat, 50°C
V15 Direct titration with neutralization
Solvent: 30 mL KF solvent and 20 mL buffer or 7g imidazole
V16 Direct titration with neutralization
Solvent: 30 mL KF solvent and 5 g benzoic acid
Stir time: 1-2 minutes
V20 External extraction with methanol at room temperature
V21 External extraction with methanol at room temperature in sonicator
Remove aliquots of extraction solution over membrane filter with syringe.
V22 External extraction with methanol at 50 °C
V23 External extraction with formamide
V24 External extraction with 1-decanol/formamide 1:1
12
V25 External extraction with 1-decanol/formamide/methanol 8:2:1
V29 External extraction with formamide
V30 With drying oven at 110 - 150°C
Stir time: 10 - 20 min
V31 With drying oven at 160 - 220°C
Titrant: two component reagent 5 or 2mg H2O/mL
V32 With drying oven at 300°C
V40 Special method for lyophilized preparations
Dissolve sample in septum flask with 10-20 mL titrated solvent and
inject entire solution into titration cell and titrate.
V0 Side reaction: KF titration not possible
2.2 Coulometric Nr. Coulometric method

methods C1 Direct titration
Anolyte: 100 mL anode reagent
Catholyte: 5 mL cathode reagent
C5 Direct titration with added chloroform
Anolyte: 70 mL anode reagent and 30 mL chloroform
C10 Direct titration methanol free
Anolyte: 100 mL anode reagent for ketones
Catholyte: 5 mL cathode reagent for ketones
C20 External extraction with methanol or external dissolution in methanol
13
KF – Titration methods / Sample handling
Nr. Coulometric method

C21 External extraction with Methanol in sonicator
Remove aliquots of extraction solution over membrane filter with syringe.
C22 External extraction with 1-decanol or external dissolution in 1-decanol
C23 External extraction with chloroform or external dissolution in chloroform
C24 External extraction or external dissolution in chloroform (methanol free)
Anolyte: 100 mL anode reagent for ketones
Catholyte: 5 mL cathode reagent for ketones
C30 With drying oven at 110-130°C
Titration time: 10-20 minutes
C34 With drying oven at 300°C
C40 Special method for lyophilized preparations
Dissolve sample in septum flask with 10-20 mL titrated anolyte and
inject entire solution into titration cell and titrate.
C0 Coulometric determination not possible
14
3. Sample Preparation and Input
3.1 Solids: Property Examples Method

Characteristics Very hard Minerals, rocks S1
e.g.: CaCO3 , SiO2
Hard, brittle Salts, cristalline products S1, S2
Hard natural products Wheat, noodles, pepper, S1, S3
almonds, coffee, Zwieback S10, S11
Property Examples Method
Fibrous natural products Dried vegetables and fruits, S4, S10
tobacco, tea, meat S11
Tenacious products Jellied fruits, gummi bears, S4, S10
paper, wool, silk S11
Soft products Cheese, almond paste, broth S10, S11
Hard, greasy Hardened fat, chocolate S6, S8
S10
Soft, greasy Butter, margarine S7, S10
Soft, brittle Phenols, napthalene, S2, S3
potato flakes
Soft, resinous Tar, bitumen S2, S5
S10
Waxes Paraffins, shoepolish S8
Creams, pastes Salves, creams gel, honey, jelly, S9
ice cream, yogurt
Pulverized soluble Salts, active ingredients S12
Na-tartrate
3.2 Solids: Nr. How to do Hints

Sample input
S1 finely ground sample Grind in sealed, cooled analysis mill.
with weighing boat
S2 finely ground sample Pulverize with mortar.
with weighing boat
S3 finely ground sample Pulverize with mixer.
with weighing boat
S4 with spatula Press through small holes e.g. meat
grinder.
15
Sample handling
Nr. How to do Hints

S5 with spatula or weighing Cut in small pieces with scissors or
boat knife.
S6 with spatula or weighing Use grate to reduce size.
boat
S7 with spatula Homogenize sample well. After s ample
Do not use syringe, the removal keep sample sealed.
moisture will be
pressed out
S8 with pre-heated syringe Melt sample.
(with needle Ø 0.8 mm ) (Pre-heat syringe with hair dryer or in
drying oven.)
S9 Fill in backend of syringe Homogenize sample well. After sample
removal keep sample sealed. Use sy-
ringe with needle Ø 1.5 mm or without
needle; for very thick pastes drill hole in
bottom of syringe.
S10 syringe with needle Ø In external extraction solvent (metha-
0.8 mm nol, 1-decanol, formamide). Dissolve
sample or extract water. Stir, shake
or sonicate. At room temp. or up to
approx. 60° C. Let solids settle and re-
move aliquot of remaining solution with
syringe. Inject into titration cell.
S11 syringe without needle Break and disperse with high-speed
(Fill very thick samples mixer (up to 24000 cpm) in external
in back of syringe) extraction solvent (methanol,
1-decanol, formamide).
S12 weighing boat No further preparation necessary.
(Select stir time so that sample
dissolves completely.)
3.3 Liquids: Property Examples Method

Characteristics
Liquid Propanol, acetone, L1
gasoline, acetic acid
Turbid Silicon oil, crude oil, L2
glycerine
Low boiling point 5 - 15°C Acetaldehyde L3
Hygroscopic Methanol, H2SO4, L4
glycerine
16
Low moisture content (< 1000 ppm) Hexane, toluene, petroleum, L4
acetone, salad oil
Non-hygroscopic, Perfume, after-shave L1
average moisture content
High moisture content (> 50%) Beverages, detergents, L5
milk, aqueous emulsions
Inhomogeneous Acrylic enamels, synthetic L6
enamels, cream
3.4 Liquids: Property Examples Method

Sample input
L1 Injection with syringe Fluid liquid sample
(with needle Ø 0.8 mm) Inject sample into titration cell
through septum or needle hole of
three-hole adapter with 1 mL or
10 mL syringe.
L2 Injection with syringe Turbid liquid sample
(without or with Inject sample into titration cell
needle Ø 1.5 mm) through septum or needle hole of
10 mL syringe.
L3 Injection with syringe after Boiling point 5 - 15 °C
cooling sample –C ool sample to approx. 0°C in
(with needle Ø 0.8 mm) ice bath.
– Inject sample into titration cell
10 mL syringe.
L4 Injection with syringe Hygroscopic sample or low
moisture content (< 1000 ppm)
–K eep sample in a septum flask.
through septum or needle hole
of three-hole adapter with 10 mL
syringe (with needle Ø 0.8 mm).
–R inse syringe with sample 2-3
times (pull up and discard) and
condition for 5 minutes.
– T he pressure loss during sample
removal must be compensated
with dried air.
17
Accessories for sample input / More Information

L5 Injection with syringe Samples with high moisture
content (> 50%)
–R inse syringe with sample
2-3 times.
– F or each titration use 1 mL
syringe (with needle Ø 0.8 mm)
to remove fresh sample from
sample flask and inject this into
titration cell through septum or
needle hole of three-hole adapter.
L6 Injection with syringe after Inhomogeneous emulsions
sample homogenization –H omogenize thoroughly by
(with needle Ø 0.8 mm) shaking or stirring prior to
sample removal.
–R emove sample immediately.
10 mL syringe.
4. Accessories for Sample Input

Tool Remarks Order number
Syringe 1 mL ME-71492
10 mL ME-71482
Injection needle 1.2 mm ME-71483
0.8 mm ME-71484
Weighing boat, glass ME-23951
Visco-Spoon™ ME-51107668
Septum NS24 ME-23950
Three-hole adapter ME-23982
18
5. More Information
5.1 Literature HYDRANAL®- Manual, „Eugen Scholz Reagents for Karl FischerTitration“,
Sigma -Aldrich Laborchemikalien GmbH, D- 30918 Seelze / Germany,
2006.
SCHOLZ. E., „Karl Fischer Titration“, Springer Verlag Berlin, 1984.
WIELAND, G., „Wasserbestimmung durch Karl-Fischer-Titration –
Theorie und Praxis“, GIT Verlag G mbH, Darmstadt / Germany, 1985.
5.2 More guides METTLER TOLEDO has prepared a set of guides for the Karl Fischer titra-
tion. They explain basics, methods and techniques and provide tips and
hints for the daily practice.
1 Introduction to Karl Fischer Titration

2 Sample Preparation for Karl Fischer Titration
3 Taking Samples for Karl Fischer Titration
4 The Method at a Glance
5.3 Application Many more details regarding the Karl Fischer titration are published in
brochure the application brochures.
– Good Titration Practice™ in Karl Fischer Titration (ME 517252145).
– METTLER TOLEDO Methods for Water Content Determination,
Application Brochure Nr 38 (ME 51725075A).
19
Good Measuring Practices
For Balances, Titrators and Pipettes
METTLER TOLEDO’s risk-based guidelines for titration, weighing and

pipetting empowers you to take the right decision when and where it
really matters. The five steps of Good Measuring Practices cover the
entire lifecycle of your instruments and provide you with practical guid-
ance to implement a sound quality management system.
1. Evaluation
5
Routine 1 Analyze your process flows
Operation Evaluation and its associated criteria to
consistently assure the high-
Good est quality of your application
Measuring and your data.
4
Calibration / Practices 2
Qualiﬁcation Selection 2. Selection
Choose the ideal combination
3 of instrument and measuring
Installation / technology to best match your
Training
process needs.
3. Installation & Training

Enjoy every confidence in your new device and master it with full profes-
sional skills right from day one.
4. Calibration & Qualification

Trust the manufacturer-trained METTLER TOLEDO Service Team when it
comes to calibrating and qualifying your instruments.
5. Routine Operation
Benefit from tangible recommendations for optimal performance
verification, calibration and maintenance.
www.mt.com/gtp
www.mt.com/karl-fischer
For more information
Mettler-Toledo AG, Analytical

CH-8603 Schwerzenbach, Switzerland
Tel. +41-44-806 77 11
Fax +41-44-806 73 50
Subject to technical changes

© 10/2012 Mettler-Toledo AG
Printed in Switzerland 30056834
Global MarCom Switzerland

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Titration

Natural science laws experience “live” –

As many samples are analyzed according to Karl Fischer as many

1.1 Solid 1.1.1 Organic chemicals

1.1.2 Inorganic chemicals

Substance Examples Method

Substance Examples Method

1.1.3 Technical products – organic

1.1.4 Technical products – inorganic

Substance Examples Method

1.1.5 Technical products – natural

Substance Examples Method

Substance Examples Method

Substance Examples Method

1.2.2 Foods and technical products

Substance Examples Method

Nr. Volumetric method

Nr. Volumetric method

2.2 Coulometric Nr. Coulometric method

Nr. Coulometric method

3.1 Solids: Property Examples Method

3.2 Solids: Nr. How to do Hints

Nr. How to do Hints

3.3 Liquids: Property Examples Method

3.4 Liquids: Property Examples Method

Property Examples Method

4. Accessories for Sample Input

1 Introduction to Karl Fischer Titration

METTLER TOLEDO’s risk-based guidelines for ­titration, weighing and

3. Installation & Training

4. Calibration & Qualification

Mettler-Toledo AG, Analytical

Subject to technical changes

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METTLER TOLEDO’s risk-based guidelines for titration, weighing and