Designation: E 203 – 08

Standard Test Method for

Water Using Volumetric Karl Fischer Titration1
This standard is issued under the fixed designation E 203; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the Department of Defense.

1. Scope* 2.2 ASTM Standards:2

1.1 This test method is intended as a general guide for the D 789 Test Methods for Determination of Solution Viscosi-
application of the volumetric Karl Fischer (KF) titration for ties of Polyamide (PA)
determining free water and water of hydration in most solid or D 803 Test Methods for Testing Tall Oil
liquid organic and inorganic compounds. This test method is D 890 Test Method for Water in Liquid Naval Stores
designed for use with automatic titration systems capable of D 1123 Test Methods for Water in Engine Coolant Concen-
determining the KF titration end point potentiometrically; trate by the Karl Fischer Reagent Method
however, a manual titration method for determining the end D 1152 Specification for Methanol (Methyl Alcohol)
point visually is included as Appendix X1. Samples that are D 1193 Specification for Reagent Water
gaseous at room temperature are not covered (see Appendix D 1348 Test Methods for Moisture in Cellulose
X4). This test method covers the use of both pyridine and D 1364 Test Method for Water in Volatile Solvents (Karl
pyridine-free KF reagents for determining water by the volu- Fischer Reagent Titration Method)
metric titration. Determination of water using KF coulometric D 1533 Test Method for Water in Insulating Liquids by
titration is not discussed. By proper choice of the sample size, Coulometric Karl Fischer Titration
KF reagent concentration and apparatus, this test method is D 1568 Test Methods for Sampling and Chemical Analysis
suitable for measurement of water over a wide concentration of Alkylbenzene Sulfonates
range, that is, parts per million to pure water. D 1631 Test Method for Water in Phenol and Related
1.2 The values stated in SI units are to be regarded as Materials by the Iodine Reagent Method
standard. D 2072 Test Method for Water in Fatty Nitrogen Com-
1.3 This standard does not purport to address all of the pounds3
safety concerns, if any, associated with its use. It is the D 2575 Methods of Testing Polymerized Fatty Acids3
responsibility of the user of this standard to establish appro- D 3277 Test Methods for Moisture Content of Oil-
priate safety and health practices and determine the applica- Impregnated Cellulosic Insulation
bility of regulatory limitations prior to use. Specific warnings D 3401 Test Methods for Water in Halogenated Organic
are given in 3.1 and 7.3.3. Solvents and Their Admixtures
1.4 Review the current Material Safety Data Sheets (MSDS) D 4017 Test Method for Water in Paints and Paint Materials
for detailed information concerning toxicity, first aid proce- by Karl Fischer Method
dures, and safety precautions for chemicals used in this test D 4377 Test Method for Water in Crude Oils by Potentio-
procedure. metric Karl Fischer Titration
D 4672 Test Methods for Polyurethane Raw Materials:
2. Referenced Documents Determination of Water Content of Polyols
2.1 A list of existing ASTM Karl Fischer methods, their D 4928 Test Methods for Water in Crude Oils by Coulom-
applications to various products, and the sponsoring commit- etric Karl Fischer Titration
tees is given in Appendix X3. D 5460 Test Method for Rubber Compounding Materials—

1 2
This test method is under the jurisdiction of ASTM Committee E15 on For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Industrial and Specialty Chemicals and is the direct responsibility of Subcommittee contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
E15.01 on General Standards. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved Oct. 1, 2008. Published November 2008. Originally the ASTM website.
3
approved in 1962 as E 203 – 62 T. Last previous edition approved in 2001 as Withdrawn. The last approved version of this historical standard is referenced
E 203 – 01. on www.astm.org.

*A Summary of Changes section appears at the end of this standard.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

1
 E 203 – 08
Water in Rubber Additives Anhydrides Sulfides
D 5530 Test Method for Total Moisture of Hazardous Waste Disulfides Thiocyanates
Esters Thioesters
Fuel by Karl Fischer Titrimetry Inorganic Compounds
D 6304 Test Method for Determination of Water in Petro- Acids (Note 5) Cupric oxide
leum Products, Lubricating Oils, and Additives by Coulo- Acid oxides (Note 6) Desiccants
Aluminum oxides Hydrazine sulfate
metric Karl Fischer Titration Anhydrides Salts of organic and inorganic acids (Note 6)
E 180 Practice for Determining the Precision of ASTM Barium dioxide
Methods for Analysis and Testing of Industrial and Spe- Calcium carbonate
cialty Chemicals NOTE 1—Some acids, such as formic, acetic, and adipic acid, are slowly
E 1064 Test Method for Water in Organic Liquids by esterified. For high accuracy with pyridine-based reagents, use 30 to 50 %
Coulometric Karl Fischer Titration pyridine in methanol as the solvent. When using pyridine-free reagents,
commercially available buffer solutions4 can be added to the sample prior
to titration. With formic acid, it may be necessary to use methanol-free
3. Summary of Test Method
solvents and titrants (1).5
3.1 The sample, containing a maximum of 100 mg of water, NOTE 2—Examples of stable aldehydes are formaldehyde, sugars,
is dissolved or dispersed in a suitable liquid and titrated with chloral, etc. Formaldehyde polymers contain water as methylol groups.
KF reagent, which consists of iodine, sulfur dioxide, organic This combined water is not titrated. Addition of an excess of NaOCH3 in
base, and a solvent (typically an alcohol, such as methanol, methanol permits release and titration of this combined water, after
approximate neutralization of excess base with acetic acid (see Note 9).
ethylene glycol, or 2-methoxyethanol). The titration end point NOTE 3—Weak amines are considered to be those with Kb value
is determined potentiometrically with a platinum electrode <2.4 3 10−5.
which senses a sharp change in cell resistance when the iodine NOTE 4—Examples of stable ketones are diisopropyl ketone, camphor,
is reduced by sulfur dioxide in the presence of water. benzophenone, benzil, dibenzolacetone, etc.
(Warning—KF reagent contains four toxic compounds, NOTE 5—Sulfuric acid up to a concentration of 92 % may be titrated
namely, iodine, sulfur dioxide, pyridine or other organic bases, directly; for higher concentrations see Note 13.
and methanol or glycol ether. The reagent should be dispensed NOTE 6—Compounds subject to oxidation-reduction reactions in an
iodine-iodide system interfere.
in a well-ventilated area. Care must be exercised to avoid
inhalation of the reagent or direct contact of the reagent with 5. Interferences
the skin.) 5.1 Condensation and oxidation-reduction reactions cause
3.2 The general equation to this reaction is as follows: interference in this titrimetric method. Also, a number of
H2O 1 I2 1 SO2 1 R8OH 1 3 RN . ~RNH!SO4R8 1 2~RNH!I (1) substances and classes of compounds interfere in the determi-
nation of water by this method. Complete descriptions may be
where:
found in the literature (2).
RN = an organic base such as pyridine, and
R8OH = alcohol. 5.2 Interferences of many classes of compounds can be
eliminated by chemical reactions to form inert compounds
4. Significance and Use prior to titration. The following are in this category:
Aldehydes and ketones, active (Note 7)
4.1 Titration techniques using KF reagent are one of the Amines, strong (Note 8)
most widely used for the determination of water. Ammonia (Note 9)
4.2 Although the volumetric KF titration can determine low Ferric salts (Note 10)
Hydrazine derivatives (Note 9)
levels of water, it is generally accepted that coulometric KF Hydroxylamine salts (Note 11)
titrations (see Test Method E 1064) are more accurate for Mercaptans (Note 12)
Sodium methylate (Note 9)
routine determination of very low levels of water. As a general Sulfuric acid (Note 13)
rule, if samples routinely contain water concentrations of 500 Thioacids (Note 12)
mg/kg or less, the coulometric technique should be considered. Thiourea (Note 12)
4.3 Applications can be subdivided into two sections: (1) NOTE 7—This interference may be reduced by use of pyridine rather
organic and inorganic compounds, in which water may be than methanol as solvent for the same or by the use of KF reagent and
determined directly, and (2) compounds, in which water cannot solvent prepared with ethylene glycol monomethyl ether in place of
be determined directly, but in which interferences may be methanol. For pyridine-free reagents, use ethylene glycol monomethyl-
eliminated by suitable chemical reactions or modifications of ether, ethylene glycol, benzyl alcohol or dimethylformamide in place of
the methanol solvent and use a methanol-free titrant (1). The cyanhydrin
the procedure. Further discussion of interferences is included reaction may be used to eliminate the interference (2).
in Section 5 and Appendix X2. NOTE 8—Strong amines are considered to be those with Kbvalue
4.4 Water can be determined directly in the presence of the >2.4 3 10−5. Use salicylic acid-methanol solution (Section 7). Glacial
following types of compounds: acetic acid is applicable in certain cases.
Organic Compounds NOTE 9—Addition of acetic acid eliminates the interference.
Acetals Ethers
Acids (Note 1) Halides
Acyl halides Hydrocarbons (saturated and unsaturated)
Alcohols Ketones, stable (Note 4) 4
Cresent Chemicals, 1324 Motor Parkway, Hauppauge, NY, 11788, Hydranalt
Aldehydes, stable (Note 2) Nitriles buffer has been found satisfactory.
Amides Orthoesters 5
The boldface numbers in parentheses refer to the list of references at the end of
Amines, weak (Note 3) Peroxides (hydro, dialkyl) this test method.

2
 E 203 – 08
N OTE 10—Ferric fluoride does not interfere. Reaction with Reagents with titers of 1.00, 2.00, and 5.00 mg H2O/mL can be
8-hydroxyquinoline is reported to eliminate this interference (3). commercially obtained.
NOTE 11—With pyridine-based reagent, add 1 mol/L SO2 in 1 + 1 7.3.2 Pyridine-Free Karl Fischer Solvent8—Anhydrous
pyridine-methanol or spent KF reagent. With pyridine-free reagents, the
two component reagent methods should be used and 1 mL of sulfuric acid
methanol is the most frequently used solvent, however, other
is added to the solvent prior to titration (Note 15). alcohols including glycols and glycol ethers are used. Some
NOTE 12—Olefin addition reaction eliminates interferences (2). Oxida- commercially available solvents also contain an organic base
tion with neutral iodine solution eliminates the interference of mercaptans and sulfur dioxide.
(4). 7.3.3 Karl Fischer Reagent Containing Pyridine—The KF
NOTE 13—Sulfuric acid, above 92 %. Add the sample (10 g) to a large reagent may be either prepared in the laboratory or purchased.
excess of pyridine (35 mL), swirl to dissolve precipitate, and titrate.
Two types of reagent are commonly used. Directions for
Addition of 8 mL of 1 + 1 pyridine-dioxane/1 g of sample also is
satisfactory, maintaining a homogeneous solution throughout the titration. preparing these and diluting if necessary, along with commer-
cial sources of supply, are as follows: (Warning—Follow
5.3 If there is a question of compounds listed in 5.2 causing standard precautions for handling toxic gases in preparing the
an interference, the recovery of spiked additions of water to the reagents (1) or (2) as described in 7.3.3.1 and 7.3.3.2. Carry out
sample matrix should be checked. all operations in a hood. Wear rubber gloves and a face shield
5.4 Many materials react stoichiometrically with KF re- when handling pyridine and sulfur dioxide and when mixing
agent. When their concentration is known, suitable corrections chemicals. Special precautions must be observed when dis-
can be applied. A list of such materials is given in Appendix pensing sulfur dioxide to prevent drawback of the solution into
X2. the gas cylinder, which might cause an explosion. This is best
accomplished by placing a trap in the line between the gas
6. Apparatus cylinder and absorption vessel.)
6.1 Karl Fischer Volumetric Titrator,6 consisting of a titra- 7.3.3.1 Karl Fischer Reagent (Ethylene Glycol Monomethyl
tion cell, dual platinum electrode, magnetic stirrer, dispensing Ether Solution, 1 mL = 6 mg H2O) (2)—For each litre of
buret and control unit. Many manufacturers of general purpose solution, dissolve 133 6 1 g iodine in 425 6 5 mL of pyridine
laboratory titrators offer optional accessories that allow their in a dry glass-stoppered bottle. Add 425 6 5 mL of ethylene
instrument to perform KF titrations. glycol monomethyl ether. Cool to below 4°C in an ice bath.
Bubble 102 to 105 g of gaseous sulfur dioxide (SO2) into the
7. Reagents cooled mixture. Determine the amount of SO2 added by the
7.1 Purity of Reagents—Use reagent grade chemicals in all change in weight of the SO2 cylinder or the increase in volume
tests. Unless otherwise indicated, all reagents shall conform to (about 70 mL) of the reagent mixture. Alternatively, add about
the specifications of the Committee on Analytical Reagents of 70 mL of freshly drawn liquid SO2 in small increments. Mix
the American Chemical Society7 where such specifications are well and set aside for at least 12 h before using. (Warning—
available. Other grades may be used, provided it is first see 7.3.3.)
ascertained that the reagent is of sufficiently high purity to 7.3.3.2 Karl Fischer Reagent (Methanol Solution, 1 mL = 6
permit its use without lessening the accuracy of the determi- mg H2O)—For each litre of solution, dissolve 133 6 1 g of
nation. iodine in 4256 5 mL of pyridine in a dry, glass-stoppered
7.2 Purity of Water—Unless otherwise indicated, references bottle. Add 425 6 5 mL of methanol. Cool the mixture in an
to water shall mean reagent water as defined by Type II and III ice bath to below 4°C. Bubble 102 to 105 g of gaseous sulfur
of Specification D 1193. dioxide (SO2) into the cooled mixture. Determine the amount
7.3 Karl Fischer Reagents—Traditionally, pyridine was the of SO2 added by the change in weight of the SO2 cylinder or
organic base used in KF reagents. Pyridine-free formulations, the increase in volume (about 70 mL) of the reagent mixture.
however, are available now and are preferred by most KF Alternatively, add about 70 mL of freshly drawn liquid SO2 in
instrument manufacturers for use with their equipment. These small increments. Mix well and set aside for at least 12 h
reagents are less toxic, less odorous, and more stable than those before using. (Warning—see 7.3.3.)
containing pyridine. The use of pyridine-free reagents is 7.3.3.3 Karl Fischer Reagent (Ethylene Glycol Monomethyl
recommended whenever possible. Solution, Stabilized, 1 mL = 6 mg H2O).9,10
7.3.1 Pyridine-Free Karl Fischer Titrant—Typically con- 7.3.3.4 Karl Fischer Reagent, Dilute—Prepare more dilute
sists of a mixture of an organic base, sulfur dioxide and iodine solutions of the KF reagent by diluting with the proper solvent
dissolved in a solvent such as methanol or 2-methoxyethanol. as follows:
Desired Strength, mg H2O/mL Litres of Diluent to Add/litre of 6 mg/
mL KF reagent
3 0.85
6
Automatic volumetric titrators specifically designed for KF determinations are 2 1.6
manufactured by many different companies. Models are available from EM Science,
Metrohm, Mettler, Photovolt, Mitsubishi, and others.
7
Reagent Chemicals, American Chemical Society Specifications , American
8
Chemical Society, Washington, DC. For suggestions on the testing of reagents not Pyridine-free KF reagents can be purchased from Cresent Chemical, JT Baker,
listed by the American Chemical Society, see Analar Standards for Laboratory EM Science, GFS Chemicals, and others.
9
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia Fisher Scientific Co., Catalog No. SK 3-500 has been found satisfactory for this
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, purpose.
10
MD. Mallinckrodt Catalog No. 5651 has been found satisfactory for this purpose.

3
 E 203 – 08
1 3.2 TABLE 1 Recommended Sample Amount
0.5 5.7 1 mg H2O/mL 2 mg H2O/mL 5 mg H2O/mL
Water Content
Titrant Titrant Titrant
These dilute solutions cannot be prepared by simple propor-
100 % ... ... 25 to 50 mg
tion, since water added with the diluent must be accounted for. 10 % 25 to 50 mg 25 to 100 mg 50 to 250 mg
The volumes to add, indicated above, are calculated assuming 1% 0.1 to 0.5 g 0.2 to 11 g 0.5 to 2.5 g
the diluent contains 0.05 % water. 0.1 % 1 to 5 g 2 to 10 g 5 to 20 g
100 ppm 5 to 10 g 10 to 20 g ...
7.4 Methanol, Standard (1 mL = 1 mg H2O)11—This solu- 25 ppm >20 g ... ...
tion can be stored conveniently in a bottle with rubber cap and
portions removed with a hypodermic syringe.
7.5 Sodium Tartrate Dihydrate—Grind certified material 9. End Point Detection
(water content 15.61 to 15.71 %) to a fine powder (preferably
overnight in a sealed ball mill) and store the ground material in 9.1 There are many commercial titration assemblies on the
a stoppered bottle. If doubt exists as to its water content, dry a market that are specifically designed for performing volumetric
2 to 3-g sample in an oven at 155 6 5°C to constant weight type KF titrations. All that is required of these units is pressing
(min 4 h). (See Note 16.) a “start titration” or “start” key on the instrument keyboard just
prior to or after the sample has been added to the titration cell.
7.6 Solvents:
End point detection is automatic and the amount of water in the
7.6.1 Acetic Acid, glacial. sample is calculated once the operator enters the sample weight
7.6.2 Ethylene Glycol Monomethyl Ether, maximum 0.1 % into the instrument’s memory. The method for color end point
water. (See Note 1.) detection is given in Appendix X1.
7.6.3 Methanol, max 0.15 % water,12 in accordance with
Specification D 1152. (See Note 1.) 10. Procedure for Soluble Materials, Either Liquid or
7.6.4 Pyridine, maximum 0.1 % water. (See Note 1.) Solid
7.7 Solvents, Mixed—In addition to the single solvents 10.1 Pipet 25 to 50 mL of the selected solvent into the
(7.6), the following mixed solvents are useful for dissolving titration cell. Titrate the water in the solvent with KF reagent
various samples: according to the instrument manufacturer’s instructions. The
7.7.1 Methanol—Chloroform (1 + 3)—Mix 1 volume of KF reagent that is used should be of appropriate titer as
methanol with 3 volumes of chloroform. Use for liquid determined by the amount of water anticipated in the sample
petroleum products. (see 10.2).
7.7.2 Methanol—Salicyclic Acid—Dissolve 150 g of salicy- 10.2 Weigh or pipet a sample containing an anticipated
clic acid in 1 L of methanol. Use for amines. water content that will give a fast and accurate titration. KF
7.7.3 Pyridine—Ethylene Glycol (1 + 4)—Mix 1 volume of instrument operation manuals typically list suggested sample
pyridine with 4 volumes of ethylene glycol. Use for com- sizes, however, Table 1 also can be used as a guideline for
pounds containing carbonyl groups. sample sizes of the three most common titrant titers. Keep in
7.7.4 Pyridine—Methanol (1 + 4)—Mix 1 volume of pyri- mind that very small sample amounts may be difficult to
dine with 4 volumes of methanol. Use for organic acids. accurately weigh and transfer, whereas, very large sample
amounts may result in incomplete miscibility with the chosen
7.8 Sulfur Dioxide, anhydrous grade. (See Note 1 and
solvent.
7.3.3.)
NOTE 14—The KF technique described here is sometimes referred to as
8. Drying of Solvents the “one component” method because all the reagents are in the titrant,
and the solvent is used basically as a medium to dissolve the sample.
8.1 If it is necessary to prepare dry solvents in the labora- There is also a “two component” KF volumetric titration in which the
tory, the following three methods can be used: titrant contains the usual reagents, but the solvent also contains sulfur
8.1.1 Azeotropic Distillation Using Benzene, to reduce the dioxide and a base. There are advantages to the two component system
moisture to 0.05 %. Add 1 volume of benzene to 19 volumes of since strongly basic or acid samples can overcome the buffering capacity
of the single component system and cause the pH of the reaction mixture
pyridine, ethylene glycol monomethyl ether, or mixtures
to shift from the optimum range. The two component system provides
thereof, and distill. Discard the first 5 % and use the dry initial sample buffering capacity in the solvent which may provide a faster
residual 95 %. reaction time. Rapid end point determination also can provide more
8.1.2 Molecular Sieves—Solvents other than methanol may accurate measurement of trace water concentrations. Two component
be dried to a moisture content of 0.05 % by passing upward reagents, however, are more susceptible to side reaction from noncom-
through a molecular sieve13 column, using 1 part molecular plexed sulfur dioxide than single component systems (5).
NOTE 15—The range of water indicated is for macro titrations. Con-
sieve per 10 parts of solvent. siderably smaller amounts of water can be determined precisely on a
micro scale. For example, less than 300 µg of water were titrated in 1-mL
samples of benzene by a micro amperometric technique (6).
11
Fisher Scientific Co., Catalog No. SW2 and Hartman-Leddon Co., Catalog No. 10.3 Calculation—Calculate the water content of the
1849 have been found satisfactory for this purpose.
12
sample as follows:
Other acceptable grades are Mallinckrodt Catalog No. 3017, max 0.02 %
water, or Fisher Scientific Co., Catalog No. A412, max 0.1 % water. ~A 2 B! 3 F 3 0.001 3 100
13
Linde Type 4A Molecular Sieve has been found satisfactory for this purpose.
water, weight % 5 W (2)

4
 E 203 – 08

where: E = milligrams of water per millilitre in the water-in-

A = millilitres of reagent required for titration of the methanol standard.
sample,
B = millilitres of reagent required to titrate solvent blank, 12. Procedure for Insoluble Solids
F = water equivalent, in milligrams of water per millilitre 12.1 In case the sample is insoluble in the solvent or solvent
of KF reagent, and mixture used, one of two modifications may be applied. The
W = grams of sample. entire sample-solvent slurry may be titrated, or after stirring
and standing, an aliquot of the clear supernatant liquid may be
11. Standardization of Karl Fischer Reagent withdrawn and titrated. The latter modification is particularly
11.1 Standardize the KF reagent daily or as necessary using useful for alkaline samples which are relatively insoluble in the
the amounts of water, sodium tartrate dihydrate, or water-in- solvent used (8).
methanol shown below: 12.2 Weigh the sample into a clean and dry titration cell,
Water add 25 to 50 mL of the selected solvent (Section 7) and stopper
Sodium Tartrate Water-in-Methanol,
Equivalent F, Water, mg
Dihydrate, g Standard, mL
the cell. Extract the water by stirring with a magnetic stirrer for
mg/mL 15 min or longer, or warming if indicated. Titrate the mixture
0.5 2.5–10 0.015–0.060 2.5–10
1 5–20 0.30–0.12 5–20 at room temperature with KF reagent as described in 11.2
2 10–40 0.06–0.24 10–40 (Note 17). Also titrate the same volume of solvent as a blank.
5 25–100 0.15–0.6 ...
NOTE 17—If desired, a known excess of KF reagent may be added to
11.2 Pipet 25 to 50 mL of methanol or appropriate solvent to the cell, allowed to stand, and then back-titrated with standard water-in-
a clean, dry titration cell and pretitrate according to the methanol reagent, as described in Test Methods D 1348.
instrument manufacturer’s instructions. 12.3 Calculation—Calculate the water content of the
11.3 Transfer the selected standard to the pretitrated solvent. sample as follows:
11.3.1 Weigh, to the nearest 0.0001 g, the indicated amount ~A 2 B! 3 F 3 0.001 3 100
of water from a suitable weighing pipet, hypodermic syringe, water, weight % 5 W (6)
or other device, or
11.3.2 Transfer the weighed sodium tartrate dihydrate by where:
means of a dry spatula, dipping the spatula into the alcohol to A = millilitres of reagent required to titrate the sample
ensure removal of any adhering tartrate (Note 16), or mixture,
B = millilitres of reagent required to titrate the solvent
11.3.3 Use a hypodermic syringe of suitable capacity to
blank,
transfer the standard water-in-methanol solution to the titration
F = water equivalent, in milligrams of water per millilitre
flask.
of KF reagent, and
NOTE 16—To facilitate transferral of the tartrate to vessels having W = grams of sample.
constricted openings or narrow necks, a spatula with the tip bent at a right 12.4 Alternatively, add 50 to 100 mL of the solvent to the
angle to the handle is satisfactory. If the tartrate is used for standardizing sample in a volumetric flask, stopper, and extract as before.
Karl Fischer reagent for use with samples containing more than 1 % water, Make up to the mark with solvent, mix, and allow to stand until
a bias may exist which has been described in Ref (7). clear. Transfer a suitable aliquot of the supernatant liquid to a
11.4 Titrate with KF reagent to the instrument manufactur- titration cell, and titrate with KF reagent as described in 11.2.
er’s instructions. Also titrate the same volume of the solvent, as a blank.
11.5 Calculation—Calculate the water equivalent, E, of the 12.5 Calculation—Calculate the water content of the
KF reagent, in milligrams per millilitre, as follows: sample as follows:
Water as Standard: ~A 2 B! 3 F 3 0.001 3 100 3 R
water, weight % 5 W (7)
G
F 5 1000 3 A (3)
where:
Water-in-Methanol as Standard: A = millilitres of reagent required to titrate the sample,
E
B = millilitres of reagent required to titrate the solvent
F5D3A (4) blank,
F = water equivalent, in milligrams of water per millilitre
Sodium Tartrate Dihydrate as Standard: of KF reagent,
C W = grams of sample, and
F 5 156.6 3 A (5) R = aliquot factor.

where: 13. Report

G = grams of water used, 13.1 Report the percentage of water to the nearest 0.001 %.
C = grams of sodium tartrate dihydrate used,
A = millilitres of reagent required for titration of the 14. Precision and Bias
standard, 14.1 Sensitivity, precision, and bias depend on several
D = millilitres of water-in-methanol standard required, and factors, for example, concentration of the KF reagent, titration

5
 E 203 – 08
technique, apparatus, quantity of water titrated, and nature of 14.4.1 Repeatability (Single Analyst)—The standard devia-
material being analyzed. tion for a single determination has been estimated to be
14.2 When using pyridine-based reagents, sensitivity is less 0.0034 % absolute at 40 df. The 95 % limit for the difference
than 0.02 mg of water when measurements are made using the between two such runs is 0.010 % absolute.
amperometric endpoint. 14.4.2 Laboratory Precision (Within-Laboratory, Between-
14.3 The following (see Note 18) is an example of the Days Variability)—The standard deviation of results (each the
precision attained at an interlaboratory study for determining average of duplicates), obtained by the same analyst on
water with pyridine-based reagents on two samples of acetone different days, has been estimated to be 0.0050 % absolute at
containing 0.1 % and 0.4 % water and two samples of methyl 20 df. The 95 % limit for the difference between two such
ethyl ketone containing 0.05 % and 0.17 % water. averages is 0.014 % absolute.
14.3.1 Repeatability (Single Analyst)—The 95 % for the 14.4.3 Reproducibility (Multilaboratory)—The standard de-
difference between two runs is 0.008 %. viation of results (each the average of duplicates), obtained by
14.3.2 Laboratory Precision (Within-Laboratory, Between- analysts in different laboratories has been estimated to be
Days, Variability)—The 95 % limit for the difference between 0.0277 % absolute at 8 df. The 95 % limit for the difference
two averages of duplicates by the same analyst obtained on between two such averages 0.078 % absolute.
different days is 0.015 %. NOTE 19—The above precision estimates are based on an interlabora-
14.3.3 Reproducibility (Multiple Laboratory)—The 95 % tory study of analyses performed in 1994 on a sample of n-butyl acetate
limit for the difference between two results (each the average containing approximately 0.096 % water and a sample of methyl amyl
of duplicates) obtained by analysts in different laboratories is ketone containing approximately 0.066 % water. One analyst in each of 12
0.027 % absolute. laboratories performed duplicate determinations on the n-butyl acetate
sample and repeated one day later, for a total of 48 determinations. The
NOTE 18—The interlaboratory study was carried out by ASTM Com- methyl amyl ketone sample was analyzed in a similar manner except 11
mittee D01 on Paint, Varnish, Lacquer, and Related Products, Subcom- laboratories participated for a total of 44 determinations.14 The analysts
mittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. were not restricted to any particular instrumentation, titrant, or solvent
Seven laboratories participated, with a single analyst performing duplicate system. Practice E 180 was used in developing these precision estimates.
determinations on each of two days, using two methods on the four
samples described above. Test Method D 1364 was the subject of the test 14.5 Bias—Because of the wide scope of this test method
program being compared with each laboratory’s own version of a KF and varying degrees of interferences, it is impractical to
method. As neither the means nor the variances of the two sets of data estimate the bias of this test method.
proved significantly different, all of the results were pooled to give
estimates of the repeatability based on 55 df and reproducibility based on 15. Keywords
47 df. Practice E 180 was used to develop the precision estimates. 15.1 free water; Karl Fischer reagent; pyridine-free; volu-
14.4 The following is an example of the precision attained metric; water; water of hydration
in an interlaboratory study for determining water with
pyridine-free reagents on one sample each of n-butyl acetate 14
Details of the interlaboratory study are available from ASTM Headquarters.
and methyl amyl ketone (see Note 19). Request RR:E15-1043.

APPENDIXES

(Nonmandatory Information)

X1. SUGGESTED APPARATUS FOR KARL FISCHER METHOD

X1.1 Scope—Described in this Appendix is a manual tube.15 Select the size buret and bottle needed. An overhead
procedure for the KF method using a visual means of detecting reservoir16 with micro buret may also be used.
the titration end point. X1.2.1.2 Tube, Drying, calcium chloride, one bulb, 200 mm
long.
X1.2 Titration Assembly:
X1.2.1.3 Bottle, Aspirator, with outlet for tubing connec-
X1.2.1 The storage and dispensing assembly shall consist of
tions, 500-mL capacity.
the following parts (see Fig. X1.1):
X1.2.1.1 Buret, automatic, with TFE-fluorocarbon resin
plug and automatic zero, reservoir bottle, and connecting
15
Kimble Glass Co., Catalog No. 17124F has been found satisfactory for this
purpose.
16
Kimble Glass Co., Catalog No. 17138F has been found satisfactory for this
purpose.

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X1.6 End Point Detection:
X1.6.1 Color End Point—The titration to a visual end point
is not as accurate or precise as the electrometric end point, and
cannot be used for highly colored samples. It may be adequate,
however, for routine determinations of water above 0.1 to
0.2 %, in a relatively colorless system. The end point is taken
during titration when the color changes from yellow to
orange-red and persists for at least 30 s. The sensitivity of this
titration is about 0.1 mg of water.

X1.7 Standardization of Karl Fischer Reagent:

X1.7.1 Standardize the KF reagent daily or as necessary
using the amounts of water, sodium tartrate dihydrate, or
water-in-methanol shown below:
Water Equivalent Sodium Tartrate Water-in-Methanol
Water, g
F, mg/mL Dihydrase, g Standard, mL
0.5 0.01 to 0.02 0.1 to 0.15 10 to 20
1 0.03 to 0.05 0.2 to 0.3 30 to 50
3 0.09 to 0.15 0.6 to 0.9 ...
6 0.18 to 0.30 1.1 to 1.9 ...

X1.7.2 Pipet 25 to 50 mL of solvent to a clean, dry titration

NOTE 1—Not to scale. flask containing a stirring bar. Close the neck of the flask with
FIG. X1.1 Karl Fischer Titration Apparatus Assembly a two-hole-rubber cap. Adjust the magnetic stirrer to give a
smooth stirring action. Titrate with KF reagent to the color end
X1.2.1.4 Stirrer, Magnetic, with stirring bar coated with point.
TFE-fluorocarbon resin. X1.7.3 Continue as described in 11.3-11.3.3.
X1.2.1.5 Flask, Titration, 250-mL capacity.17 X1.7.4 Titrate with KF reagent to the color end point.
X1.2.1.6 Rubber Cap, 38 mm in outside diameter.18 Punch X1.7.5 Calculations—Calculate the water equivalent, F, of
two holes, 3 to 4 mm in diameter, through the cap. the KF reagent as in 11.5.

X1.3 Assembly of Apparatus: X1.8 Procedure for Soluble Materials, Either Liquid or
X1.3.1 Assemble the apparatus as shown in Fig. X1.1. Fill Solid:
the drying tube and aspirator bottle with desiccant.19 Insert the X1.8.1 Pipet 25 to 50 mL of the selected solvent and
buret tip through one hole in the rubber cap. Use the other hole proceed as in X1.7.2.
for inserting a pipet or hypodermic syringe containing liquid X1.8.2 Continue as described in 10.2, except use color end
samples. Under humid conditions, keep the second hole point.
plugged except when introducing a sample, or pass a slow X1.8.3 Calculations—Calculate water content of sample as
stream of dry nitrogen into the flask. in 10.3.
X1.4 Reagents—Refer to Section 7. X1.9 Report—Report the percentage of water to nearest
X1.5 Drying of Solvents—Refer to Section 8. 0.01 %.

X1.10 Procedure for Insoluble Solids—Follow 12.1, 12.2,

17
A. H. Thomas Co., Catalog No. 9682-K-40 titration cell has been found 12.3, 12.4, and 12.5, using color end point procedure.
satisfactory for this purpose.
18
Davol Rubber Co., Catalog No. 270 or E. H. Sargent Co., Catalog No.
S-73185, 4 to 5 in., have been found satisfactory for this purpose. X1.11 Report—Report the percentage of water to nearest
19
Indicating-type Drierite has been found satisfactory for this purpose. 0.01 %.

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X2. INTERFERING COMPOUNDS THAT REACT STOICHIOMETRICALLY WITH KF REAGENT, THEREBY ENABLING
FREE WATER TO BE CALCULATED AFTER APPLYING CORRECTION

X2.1 Many interfering substances react stoichiometrically TABLE X2.1 Materials Reacting Stoichiometrically With KF
with constituents of the KF reagent. Consequently, when Reagent
independent analyses can be made for these compounds, Moles of
Apparent H2O
suitable corrections can be applied to the apparent water Class or Compound Do Not React
per Mole
results. Also in many cases moisture can be separated from the Compound
interfering substance by extraction with a water-miscible liquid Ascorbic acid 1
Hydrazine derivatives 1 hydrazine sulfate
in which the sample is insoluble or by distillation, preferably Mercaptans 0.5
using a carrier that forms a homogeneous azeotrope, for Silanols, R3SiOH 1
example, dioxane, ethanol-benzene. Materials in this class are R2Si(OH)2 2
Arsenate, RAsO4 3
given in Table X2.1. Arsenite, RAsO2 2
Boric acid, H3BO3 3
HBO2 2
X2.2 Some compounds react only partially with KF reagent Boric oxide, B2O3 3
when titrated under normal conditions. These include the Bicarbonates 1
following:20,21 Carbonates 1 calcium carbonate
19
Cupric salts 0.5
Methylolurea Dichromates Ferric salts 0.5 ferric fluoride
Peroxides, diacyl20 Iron oxide Metal hydroxides, MOH 1
Peracids20 Nickel oxide M(OH)2 2
Quinone Sodium peroxide Metal oxides, CaO, MgO, ZnO, 1 aluminum, cupric,
Arsenious oxide Sodium sulfide Ag2O, HgO, Cu2O, MnO2, barium oxides
Chromates PbOA, PbO2A
Pb3O4 3
Pyrosulfites 1 pyrosulfate
Sodium nitriteB 0.5
Sulfites 1 hyposulfite
Stannous salts 1
Tetraborate 7
Thiosulfate 0.5
A
The lead oxides react only partially when dispersed in methanol, probably
20
Interference of methylolurea can be eliminated by titration at − 40°C (2). because of insolubility. In acetic acid solution, however, these oxides react
21
Diacyl peroxides and peracids fairly rapidly oxidize the HL of spent KF quantitatively.
B
reagent. After a short time interval following addition of KF reagent, this reaction Reaction is fairly slow. Apparently free water can be determined in presence of
may be quantitative (2). NaNO2 by rapid titration with KF reagent.

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X3. OTHER ASTM KARL FISCHER REAGENT WATER METHODS

Designation Sponsoring Committee Title of Method

D 789 D20 Test Methods for Determination of Solution Viscosities of Polyamide (PA)
D 803 D01 Test Methods for Testing Tall Oil
D 890 D01 Test Method for Water in Liquid Naval Stores
D 1123 D15 Test Method for Water in Engine Coolant Concentrate by the Karl Fischer Reagent Method
D 1348 D01 Test Methods for Moisture in Cellulose
D 1364 D01 Test Method for Water in Volatile Solvents (Karl Fischer Reagent Titration Method)
D 1533 D27 Test Method for Water in Insulating Liquids (Karl Fischer)
D 1568 D12 Methods for Sampling and Chemical Analysis of Alkylbenzene Sulfonates
D 1631 D16 Test Method for Water in Phenol and Related Materials by the Iodine Reagent Method
D 2072 D01 Test Method for Water in Fatty Nitrogen Compounds
D 2575 D01 Methods of Testing Polymerized Fatty Acids
D 3277 D27 Test Methods for Moisture Content of Oil-Impregnated Cellulosic Insulation
D 3401 D26 Test Method for Water in Halogenated Organic Solvents and Their Admixtures
D 4017 D01 Test Method for Water and Paint Materials by Karl Fischer Method
D 4377 D02 Test Method for Water in Crude Oils by Potentiometric Karl Fischer Titration
D 4672 D20 Test Methods for Polyurethane Raw Materials: Determination of Water Content of Polyols
D 4928 D02 Test Methods for Water in Crude Oils by Coulometric Karl Fischer Titration
D 5460 D11 Test Method for Rubber Compounding Materials Water in Rubber Additives
D 5530 D34 Test Method for Total Moisture of Hazardous Waste Fuel by Karl Fischer Titrimetry
D 6304 D02 Test Method for Determination of Water in Petroleum Products, Lubricating Oils, and Additives by Coulometric Karl
Fischer Titration
E 1064 E15 Test Method for Water in Organic Liquids by Coulometric Karl Fischer Titration

X4. DETERMINATION OF WATER IN GASES

X4.1 Procedures for determining moisture in gases are X4.3 The manufacturers of gases have developed very
described in the literature (2, 9, 10, 11, 12). precise KF procedures for measuring moisture down to a few
milligrams per kilograms (11, 12). They should be consulted
X4.2 As mentioned in Section 1, this test method does not when need arises. Also, there are available commercial instru-
include procedures for samples that are gaseous at room
ments that operate on the dew point, infrared, conductance,
temperature. The safe handling and analysis of gases require a
electrolysis principle, etc., which are rapid and accurate for
thorough knowledge of their properties and also the use or
determining moisture in gas samples (2, 10).
special apparatus and techniques. The moisture content may
range from 1000 down to 2 to 3 mg/kg.

REFERENCES

(1) Riedel-deHaen, “Hydranal—Water Reagent According to Eugen (7) Beasley, T. H., Ziegler, H. W., Charles, R. L., and King, P., “Critical
Scholz for Karl Fischer Titration,” 3rd Ed., p. 30, available from Evaluation of the Karl Fischer Water Method,” Analytical Chemistry,
Cresent Chemical Co., Inc., 1324 Motor Parkway, Hauppauge, NY, ANCHA, Vol 44, 1972, p. 1833.
11788. (8) Gard, L. N., and Butler, R. C., “Determination of Moisture in Sodium
(2) Mitchell, J., Jr., and Smith, D. M., “Aquametry, a Treatise on Methods Bicarbonate—Karl Fischer Method,” Analytical Chemistry, ANCHA,
for the Determination of Water,” Part III, The Karl Fischer Reagent, Vol 26, 1954, p. 1367.
2nd Ed., J. Wiley and Sons, Inc., New York, NY, 1980. (9) Jones, A. G., “A Review of Some Developments in the Use of the Karl
(3) Laurene, A. H., “Determination of Water by Karl Fischer Titration in Fischer Reagent,” Analyst, Vol 76, 1951, p. 5.
the Presence of Ferric Salts,” Analytical Chemistry, ANCHA, Vol 24,
1952, p. 1496. (10) Mitchell, J., Jr., “Treatise on Analytical Chemistry,” Part II, Vol 1,
(4) Brickell, W. F., “Determination of Water Vapor in Natural Gas by Interscience Publishers, Inc., 1961, p. 69.
Direct Chemical Method,” Petroleum Engineer, PENGA, Vol 24, (11) Morton, J. D., and Fuchs, L. K., “Determination of Moisture in
1952, p. 58. Fluorocarbons,” presented at a meeting of the American Society of
(5) MacLeod, S. K., “Moisture Determination Using Karl Fischer Titra- Heating, Refrigeration, and Air-Conditioning Engineers, June 13–15,
tions,” Analytical Chemistry, Vol 63, 1991, p. 557A. 1960.
(6) Bastin, E. L., Siegel, H., and Bullock, A. B.,“ Microdetermination of (12) E. I. du Pont de Nemours & Co., Freon Technical Bulletin B-23,
Water by Titration With Fischer Reagent,” Analytical Chemistry, “Moisture Determination in 8Freon’ Fluorocarbons by Karl Fischer
ANCHA, Vol 31, 1959, p. 467. Titration,” June 1961.

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SUMMARY OF CHANGES

Subcommittee E15.01 has identified the location of selected changes to this standard since the last issue
(E 203-01) that may impact the use of this standard.

(1) Updated units of measure to comply with the International in Scope and Summary of Test Method.
System of Units (SI). (4) Deleted (Formerly called Repeatability) from the Precision
(2) Added numbered paragraph in Scope stating that the SI section.
units are to be considered standard.
(5) Added Summary of Changes section.
(3) Changed term “amperometrically” to “potentiometrically”

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