The Karl Fischer method can be used with a wide range of substances. However, the method depends on a kind of iodometry based on the reaction between the Karl Fischer reagent and water. The results will therefore show a positive error if the sample includes substances that react with iodine, and a negative error if the sample includes substances that produce iodine by oxidizing iodide compounds. The following tables list substances that can be titrated directly with Karl Fischer reagents, substances that cannot be titrated directly but can be titrated by means of adjustments based on appropriate chemical reactions or processes, and substances that react with Karl Fischer reagents and are therefore unsuitable for direct titration. Even if a substance cannot be titrated directly, its moisture content can be measured by indirect means, such as the water vaporization method.

Compounds that can be titrated directly

Organic compounds
Hydrocarbons(saturated, unsaturated compounds)
Alcohols, Polyhydric alcohols, Phenols, Ethers
Inert ketones(diisopropyl ketone, et al)
Inert aldehydes(formaldehyde, chloral, et al)
Organic acids, Hydroxylic acids, amino acids
Acid anhydrides
Esters, Lactones, Inorganic acid esters
Amines( Proteins, Amides, Anilides
Nitriles, Cyanhydrins, Cyanic acid derivatives
Nitro compounds, Oximes, Hydroxamic acids
Thiocyanate, Thioethers, Thioesters
Halogenated hydrocarbons, Halogenated acyls
Sugars, Organic salts and their hydrates
Inorganic compounds
Inorganic salts and their hydrates
Inorganic acids
Chelate compounds
Fertilizers
Calcium carbonate
Polytungsten salts

Compounds that react with Karl Fischer reagents and cannot be titrated directly

Organic compounds
Ascorbic acid, Diacyl peroxides
Peracids, Quinone
Inorganic compounds
Sodium sulfide, Sodium peroxide
Chromates, Dichromates
Ferric oxide, Nickel oxide, Arsenic trioxide
Arsenates, Arsenites, Borates, Boron oxide
Hydrogencarbonates, Carbonates
Metal hydroxides, Metal oxides
Sulfites, Pyrosulfites
Sodium nitrite, Thiosulfates
Cupric salts, Stannous salts

Compounds that can be titrated directly after special processing or under certain conditions

The examination will be necessary for the following compounds though it was said that these could be titrated directly by the following treatments in former references.

Compound Treatment
Ammonia Add acetic acid.
Ferric salts Add 8-hydroxyquinoline.
Hydrazine derivatives Add acetic acid.
Hydroxylamine salts Add sulfur dioxide: pyridine solution (1:1).
Thiol(mercaptan) Prevent interference by adding olefins(octene, etc.).
Sulfuric acid If the sulfuric acid is 92%pure or higher, add a large surplus of pyridine and titrate it as a salt.
Thioacid Prevent interference by adding olefins(octene, etc.).
Thiourea Prevent interference by adding olefins(octene, etc.).

Examples of how AQUAMICRON™ can be used with compounds that cause interference

Compound Interference reaction Treatment
Volumetric titration Coulometric titration
Ketones React with methanol to produce ketal and water Titrant SS-Z + Solvent KTX AKX + CXU
Titrant SS + Solvent CP
Aldehydes React with methanol to produce acetal and water React with sulfur dioxide and water Titrant SS-Z + Solvent KTX AKX + CXU
(suitable only for a certain aromatic aldehydes)
Titrant SS + Solvent CP
Lower carboxylic acids React with methanol to produce ester and water Titrant SS-Z + Solvent KTX AKX + CXU
Titrant SS + Solvent CP
Amines above pKa 9
(above pKa 9)
Consume iodine gradually and the end-point becomes unstable Titrant SS-Z + Solvent GEX
salicylic acid 10g
AXI or AX + CXU / salicylic acid 10g
Titrant SS + Solvent MS
salicylic acid 10g