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    ASTM E203 - 16

    Standard Test Method for Water Using Volumetric Karl Fischer Titration

    Active Standard ASTM E203 | Developed by Subcommittee: D16.04

    Book of Standards Volume: 06.04

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    Significance and Use

    4.1 Titration techniques using KF reagent are one of the most widely used for the determination of water.

    4.2 Although the volumetric KF titration can determine low levels of water, it is generally accepted that coulometric KF titrations (see Test Method E1064) are more accurate for routine determination of very low levels of water. As a general rule, if samples routinely contain water concentrations of 500 mg/kg or less, the coulometric technique should be considered.

    4.3 Applications can be subdivided into two sections: (1) organic and inorganic compounds, in which water may be determined directly, and (2) compounds, in which water cannot be determined directly, but in which interferences may be eliminated by suitable chemical reactions or modifications of the procedure. Further discussion of interferences is included in Section 5 and Appendix X2.

    4.4 Water can be determined directly in the presence of the following types of compounds:

    Organic Compounds



    Acids (Note 1)


    Acyl halides

    Hydrocarbons (saturated and unsaturated)


    Ketones, stable (Note 4)

    Aldehydes, stable (Note 2)




    Amines, weak (Note 3)

    Peroxides (hydro, dialkyl)







    Inorganic Compounds

    Acids (Note 5)

    Cupric oxide

    Acid oxides (Note 6)


    Aluminum oxides

    Hydrazine sulfate


    Salts of organic and inorganic acids (Note 6)

    Barium dioxide


    Calcium carbonate


    Note 1: Some acids, such as formic, acetic, and adipic acid, are slowly esterified. For high accuracy with pyridine-based reagents, use 30 to 50 % pyridine in methanol as the solvent. When using pyridine-free reagents, commercially available buffer solutions can be added to the sample prior to titration. With formic acid, it may be necessary to use methanol-free solvents and titrants (1).4

    Note 2: Examples of stable aldehydes are formaldehyde, sugars, chloral, etc. Formaldehyde polymers contain water as methylol groups. This combined water is not titrated. Addition of an excess of NaOCH3 in methanol permits release and titration of this combined water, after approximate neutralization of excess base with acetic acid (see Note 9).

    Note 3: Weak amines are considered to be those with Kb value <2.4 × 10−5.

    Note 4: Examples of stable ketones are diisopropyl ketone, camphor, benzophenone, benzil, dibenzolacetone, etc.

    Note 5: Sulfuric acid up to a concentration of 92 % may be titrated directly; for higher concentrations see Note 13.

    Note 6: Compounds subject to oxidation-reduction reactions in an iodine-iodide system interfere.

    1. Scope

    1.1 This test method is intended as a general guide for the application of the volumetric Karl Fischer (KF) titration for determining free water and water of hydration in most solid or liquid organic and inorganic compounds. This test method is designed for use with automatic titration systems capable of determining the KF titration end point potentiometrically; however, a manual titration method for determining the end point visually is included as Appendix X1. Samples that are gaseous at room temperature are not covered (see Appendix X4). This test method covers the use of both pyridine and pyridine-free KF reagents for determining water by the volumetric titration. Determination of water using KF coulometric titration is not discussed. By proper choice of the sample size, KF reagent concentration and apparatus, this test method is suitable for measurement of water over a wide concentration range, that is, parts per million to pure water.

    1.2 The values stated in SI units are to be regarded as standard.

    1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Specific warnings are given in 3.1 and 7.3.3.

    1.4 Review the current Safety Data Sheets (SDS) for detailed information concerning toxicity, first aid procedures, and safety precautions for chemicals used in this test procedure.

    2. Referenced Documents (purchase separately) The documents listed below are referenced within the subject standard but are not provided as part of the standard.

    ASTM Standards

    D789 Test Methods for Determination of Solution Viscosities of Polyamide (PA)

    D803 Test Methods for Testing Tall Oil

    D890 Test Method for Water in Liquid Pine Chemicals

    D1123 Test Methods for Water in Engine Coolant Concentrate by the Karl Fischer Reagent Method

    D1152 Specification for Methanol (Methyl Alcohol)

    D1193 Specification for Reagent Water

    D1348 Test Methods for Moisture in Cellulose

    D1364 Test Method for Water in Volatile Solvents (Karl Fischer Reagent Titration Method)

    D1533 Test Method for Water in Insulating Liquids by Coulometric Karl Fischer Titration

    D1568 Test Methods for Sampling and Chemical Analysis of Alkylbenzene Sulfonates

    D1631 Test Method for Water in Phenol and Related Materials by the Iodine Reagent Method

    D2072 Test Method for Water in Fatty Nitrogen Compounds

    D2575 Methods of Testing Polymerized Fatty Acids

    D3277 Test Methods for Moisture Content of Oil-Impregnated Cellulosic Insulation

    D3401 Test Methods for Water in Halogenated Organic Solvents and Their Admixtures

    D4017 Test Method for Water in Paints and Paint Materials by Karl Fischer Method

    D4377 Test Method for Water in Crude Oils by Potentiometric Karl Fischer Titration

    D4672 Test Method for Polyurethane Raw Materials: Determination of Water Content of Polyols

    D4928 Test Method for Water in Crude Oils by Coulometric Karl Fischer Titration

    D5460 Test Method for Rubber Compounding MaterialsWater in Rubber Additives

    D5530 Test Method for Total Moisture of Hazardous Waste Fuel by Karl Fischer Titrimetry

    D6304 Test Method for Determination of Water in Petroleum Products, Lubricating Oils, and Additives by Coulometric Karl Fischer Titration

    E180 Practice for Determining the Precision of ASTM Methods for Analysis and Testing of Industrial and Specialty Chemicals

    E1064 Test Method for Water in Organic Liquids by Coulometric Karl Fischer Titration

    ICS Code

    ICS Number Code 71.040.40 (Chemical analysis)

    UNSPSC Code

    UNSPSC Code

    Referencing This Standard
    Link Here
    Link to Active (This link will always route to the current Active version of the standard.)

    DOI: 10.1520/E0203-16

    Citation Format

    ASTM E203-16, Standard Test Method for Water Using Volumetric Karl Fischer Titration, ASTM International, West Conshohocken, PA, 2016, www.astm.org

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