Designation: E 1064 – 08

Standard Test Method for

Water in Organic Liquids by Coulometric Karl Fischer
Titration1
This standard is issued under the fixed designation E 1064; 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 (e) 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* dioxide in the presence of water to form sulfur trioxide and

1.1 This test method covers the determination of water from hydriodic acid. The reaction becomes quantitative only when
0 to 2.0 % mass in most liquid organic chemicals, with Karl pyridine or other organic base and methanol or other alcohol
Fischer reagent, using an automated coulometric titration are present. Unlike the volumetric Karl Fischer reagents that
procedure. Use of this test method is not applicable for include iodine, the coulometric technique electrolytically gen-
liquefied gas products such as Liquid Petroleum Gas (LPG), erates iodine, with 10.71 C of generating current corresponding
Butane, Propane, Liquid Natural Gas (LNG), etc. to 1 mg of water in accordance with Faraday’s law.
1.2 The values stated in SI units are to be regarded as 4. Significance and Use
standard. No other units of measurement are included in this
standard. 4.1 The coulometric technique is especially suited for de-
1.3 Review the current material safety data sheets (MSDS) termining low concentrations of water in organic liquids that
for detailed information concerning toxicity, first-aid proce- would yield small titers by the Karl Fischer volumetric
dures, handling, and safety precautions. procedure. The precision and accuracy of the coulometric
1.4 This standard does not purport to address all of the technique decreases for concentrations of water much greater
safety problems, if any, associated with its use. It is the than 2.0 % because of the difficulty in measuring the small size
responsibility of the user of this standard to establish appro- of sample required. The test method assumes 100 % efficiency
priate safety and health practices and determine the applica- of coulombs in iodine production. Provision is made for
bility of regulatory limitations prior to use. Specific precau- verifying this efficiency. (See Table 1 and Note 6.)
tionary statements are given in Section 8. 5. Interferences
2. Referenced Documents 5.1 Interfering substances are the same as are encountered
2.1 ASTM Standards: 2 in the volumetric Karl Fischer titration. A detailed discussion
D 1193 Specification for Reagent Water of interfering substances can be found in the treatise on
E 180 Practice for Determining the Precision of ASTM “Aquametry.”3
Methods for Analysis and Testing of Industrial and Spe- 5.2 Test Method E 203 discusses organic compounds in
cialty Chemicals which water may be determined directly and compounds in
E 203 Test Method for Water Using Volumetric Karl Fischer which water cannot be determined directly, but in which
Titration interferences may be eliminated by suitable chemical reactions.

3. Summary of Test Method 6. Apparatus

3.1 This test method is based on the Karl Fischer reaction 6.1 Automatic Titrator,4 consisting of a control unit, titration
for determining water—the reduction of iodine by sulfur vessel, dual platinum sensing electrode, generator assembly,
and magnetic stirrer. The instrument is designed to coulometri-
1
cally generate iodine that reacts stoichiometrically with the
This test method is under the jurisdiction of ASTM Committee E15 on
Industrial and Specialty Chemicals and is the direct responsibility of Subcommittee
E15.01 on General Standards.
3
Current edition approved April 1, 2008. Published May 2008. Originally J. Mitchell, Jr. and D. M. Smith, “Aquametry”—A Treatise on Methods for the
approved in 1985. Last previous edition approved in 2005 as E 1064 – 05. Determination of Water, Part III—The Karl Fischer Reagent, 2nd Ed., J. Wiley and
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or Sons, Inc., New York, NY 1990.
4
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Basic references to the automatic coulometric titrator: M. T. Kelley, R. W.
Standards volume information, refer to the standard’s Document Summary page on Stelzner, W. R. Laing, and D. J. Fisher, Analytical Chemistry 31, No. 2, 220 (1959)
the ASTM website. and A. W. Meyer, Jr. and C. M. Boyd, Analytical Chemistry 31, No. 2, 215 (1959).

*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.

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 E 1064 – 08
TABLE 1 Sample Size Estimation pyridine was the organic base used in KF reagents. Pyridine-
Expected Water Content Sample Size, mL free formulations are available and are preferred by most KF
0 to 500 mg/kg 5 instrument manufacturers for use with their equipment. The
500 to 1000 mg/kg 2 pyridine-free reagents are less toxic, less odorous, and more
1000 to 2000 mg/kg 1
0.2 to 0.5 % mass 0.5
stable than those containing pyridine. The use of pyridine-free
0.5 to 2.0 % mass 0.1 reagents is recommended whenever possible. Coulometric
titrations normally require two reagent solutions. An anolyte or
solvent titration solution and a catholyte or generator titrant
water present in the sample solution. The coulombs of elec- solution. However, now reagents can be purchased in one or
tricity required to generate the reagent are converted to two component reagent systems. A one component reagent
micrograms of water, which is obtained as a direct digital system contains all the components required for a Karl Fischer
readout. titration in a single solution. A two component system incor-
6.2 Syringe, 50-mL, fitted with an 115-mm hypodermic porates separate solutions for the solvent and titrant.
needle for removing excess solution from the titration chamber. NOTE 2—Two good references on pyridine-free reagents are the Hy-
dranalt Manual-Eugen Schotz Reagents for Karl Fischer Titration, from
NOTE 1—Rinse all glass syringes and needles with anhydrous acetone
Riedel-deHaen (www.rdhlab.de) or Sigma Aldrich (www.sigma-
after cleaning, then dry in an oven at 100°C for at least 1 h and store in
aldrich.com) and Moisture Measurement by Karl Fischer Titrimetry, 2nd
a desiccator. Plastic syringes shall be disposed of following use.
ed., by GFS Chemicals, Inc., January 2004.
6.3 Syringe, 20-mL, fitted with an 115-mm hypodermic
needle for introduction of neutralizing solution into the titration 7.3.1 Generator Titrant Solution (catholyte), containing io-
chamber (see Note 1). dine, sulfur dioxide, pyridine or other organic base and
6.4 Syringes, 1- and 5-mL, fitted with 115-mm hypodermic methanol or other alcohol to provide iodine in the reaction
needles for introduction of samples into titration chamber (see mixture.
Note 1). 7.3.2 Solvent Titration Solution (anolyte), prepared as per
6.5 Syringe, 5 μL, fitted with 115-mm hypodermic needle instrument specifications.
for standardization of instrument (see Note 1). 7.3.3 Neutralizing Solution, methanol containing approxi-
6.6 Fluorocarbon Sealing Grease or TFE-Fluorocarbon, to mately 20 mg H2O/mL.
seal the titration chamber against atmospheric moisture.
6.7 Septa, to seal sample port but allow introduction of 8. Safety Precautions
samples by a needle with a minimum of moisture contamina- 8.1 The reagents contain one or more of the following:
tion. Replace serum caps and septa as required to prevent air iodine, pyridine or other organic base, sulfur dioxide, and
leakage as indicated by instrument drift. methanol or other alcohol. Wear chemical resistant gloves
6.8 Serum Bottles. when mixing the reagents and removing solution from the
6.9 Oven, temperature 100 6 5°C. titration chamber. Care must be exercised to avoid inhalation of
6.10 Dessicator, standard laboratory type with color change reagent vapors, or direct contact of the reagent with the skin.
indicator.
6.11 Analytical Balance, capable of weighing to 60.0001 g. 9. Sampling
7. Reagents 9.1 Because of the low concentration of water to be mea-
sured, maximum care must be exercised at all times to avoid
7.1 Purity of Reagents—Unless otherwise indicated, it is contaminating the sample with moisture from the sample
intended that all reagents shall conform to the specifications of container, the atmosphere, or transfer equipment.
the Committee on Analytical Reagents of the American Chemi-
9.1.1 Dry the sample bottles and caps overnight in an oven
cal Society, where such specifications are available.5 Other
at 100°C before using. Allow to cool in a desiccator before
grades may be used, provided it is first ascertained that the
filling and sealing.
reagent is of sufficiently high purity to permit its use without
9.1.2 Fill the sample bottle as rapidly as possible to within
lessening the accuracy of the determination.
25 mm of the top and immediately seal.
7.2 Purity of Water—Unless otherwise indicated, reference
to water shall be understood to mean Type II or Type III 9.2 Remove the test specimens for analysis from the sample
reagent water, conforming to Specification D 1193. bottle with a dry hypodermic syringe. Inject dry nitrogen into
7.3 Karl Fischer Reagents—Commercial coulometric KF the sample bottle with the syringe to displace the sample that
reagents and reagent systems of various types are available for is removed.
use with autotitrators for water determination. Traditionally,
10. Preparation of Apparatus
10.1 Clean, dry, and assemble the titration chamber as
5
Reagent Chemicals, American Chemical Society Specifications , American directed in the manufacturer’s instructions. Use fluorocarbon
Chemical Society, Washington, DC. For suggestions on the testing of reagents not grease or TFE-fluorocarbon to seal the upper and lower
listed by the American Chemical Society, see Analar Standards for Laboratory
sections of the chamber from atmospheric moisture. Connect
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, the leads from the sensing and generator electrodes to the
MD. titrator.

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 E 1064 – 08
10.2 Prepare the titration solution (7.3.2) as directed by the 12. Procedure
instrument manufacturer and fill the instrument reservoir as 12.1 Assemble a dry syringe and needle and attach a small
directed by the manufacturer. piece of rubber septum to the needle tip. Withdraw 1 to 2 mL
10.3 Add the generator solution (7.3.1) to the generator of the sample into the syringe and discard the contents into a
assembly and replace the cover cap. The surface of the waste container. Using the following table as a guide, withdraw
generator solution must be below the level of the titration the proper amount of test sample into the syringe and seal with
solution to prevent backflow contamination of the titration the rubber septum. Obtain a tare weight to 60.1 mg. See Table
solution. The generator solution may have to be removed 1, Note 5 and Note 6.
periodically to maintain the lower level.
10.4 Agitate the titration solution by gently swirling the NOTE 5—If multiple analyses are performed on the same test sample or
if an appreciable volume of test sample is withdrawn, a slight pressure
titration chamber to remove any residual moisture from the
should be maintained on the sample bottle by means of a hypodermic
walls. Allow the solution to stir for at least 20 min to dry and needle attached to a dry nitrogen source.
stabilize the inner atmosphere. NOTE 6—Alternatively, if syringes of suitable accuracy are available, a
measured volume of sample can be injected and the mass calculated from
NOTE 3—Mitsubishi automatic moisture analyzers do not require the
the volume and density.
steps in 10.4.
10.5 Attach an 11.5-cm hypodermic needle to a 20-mL 12.2 With the analyzer stabilized, carefully insert the needle
syringe and withdraw about 15 mL of neutralizing solution of the sample syringe through the septum and below the level
(7.3.3). Insert the needle through the sample port septum and of solution in the titration chamber. Inject the sample slowly
lower it until the tip is just below the surface of the titration into the titration solution and begin titration. Withdraw the
solution. syringe needle, seal and again weigh to the nearest 60.1 mg to
10.6 Slowly inject the neutralizing solution into the titration determine the exact sample mass. Allow the titration to proceed
solution until the color changes from brown to light red. This until the end-point is indicated. Record the micrograms of
indicates that the end point is near. Continue the addition very water determined.
slowly until the ON light comes on, indicating an excess of NOTE 7—After numerous analyses, the level of solvent accumulated in
water is present, then carefully withdraw the syringe and the titration chamber may have to be reduced. This can be accomplished
needle. The total volume of neutralizing solution required will with a 50-mL syringe or by partially draining the solution if the titration
range from 5 to 15 mL. Allow the system to stabilize for 1 h. chamber is provided with a stopcock. Discard the solution and replace
with fresh titration solution if a stable reading cannot be obtained.
NOTE 8—Replace the generator solution when it becomes yellow and a
11. Verification of Calibration stable reading cannot be obtained.
11.1 Different autotitrators may vary in calibration proce-
dures. Consult the operating manual for the autotitrator in use. 13. Calculation
Stable, prepackaged Quality Control (QC) water standards are 13.1 Calculate the water content of the sample to the nearest
commercially available with 10 mg/kg. 100 mg/kg and 1 % 0.001 % mass as follows:
(m/m) water content for this purpose. It is desirable to verify μg water found
calibration with a standard solution that approximates the same water content, % mass 5 g sample 3 10 000 (1)
range of water expected to be in the samples.
11.2 It is recommended that a control chart measuring a QC 14. Report
standard sample be established and maintained according to 14.1 Report the percentage of water to the nearest 0.001 %
generally accepted guidelines.6 Measure the control sample mass.
each time a test sample(s) is tested. If the measured value
exceeds 65 % of the known amount, take appropriate action 15. Precision and Bias
before proceeding with the sample test.
15.1 In 2007, ASTM International Committee E15 on In-
NOTE 4—This may require replacing or regenerating the reagent dustrial and Specialty Chemicals conducted and completed
solutions. Interlaboratory Study No. 52 to determine Precision data for
six test methods used in the analysis of glycols. The precision
of this test method is based on the interlaboratory study of
E 1064, Standard Test Method for the Determination of Water
6
ASTM Manual on Presentation of Data and Control Chart Analysis, 7th in Organic Liquids by Coulometric Karl Fischer Titration,
Edition, ASTM Manual Series MNL 7A, (revision of Special Technical Publication conducted in 2007. Each of seventeen laboratories were asked
(STP) 15D).

TABLE 2 E 1064 Water in Organic Liquids by Coulometric Karl Fischer Titration

Repeatability Intermediate Reproducibility
Test Result % Average over all Repeatability Intermediate Reproducibility
Sample Standard Standard Standard
mass Laboratories Limit Unit Limit
Deviation Deviation Deviation
Water MEG 0.0086 0.0009 0.0014 0.0025 0.0026 0.0038 0.0071
Water DEG 0.0649 0.0012 0.0014 0.0049 0.0032 0.0039 0.0137
Water TEG 0.0498 0.0019 0.0129 0.0157 0.0054 0.0361 0.0439

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 E 1064 – 08
to test three different materials. Fourteen laboratories tested diate precision. The statistical analysis was conducted using
MEG, 13 laboratories tested DEG and 13 laboratories tested the SAS statistical analysis software, Version 8.0.
TEG. Every “test result” represents an individual determina- 15.1.3.1 The E 180 analysis considers the two test results
tion. Two test results were conducted on each of two days for from each day as being run under repeatability, intermediate,
a total of four test results per assay. Note that in the combined and reproducibilty precision for each assay. The repeatability
study, 8 laboratories used a single analyst, 7 laboratories used precision would be estimated from the two sets of duplicate test
two analysts (on different days) and 2 laboratories did not results within each day, and the intermediate precision would
record this information. In the event that there were missing be estimated from the agreement between the two days, all
values for one or more laboratories, this information was noted pooled over laboratories. Caveat: Since two days is a short time
in the results.7 period, the intermediate precision would probably be underes-
15.1.1 Repeatability—Two test results obtained within one timated by the E 180 analysis.
laboratory shall be judged not equivalent if they differ by more 15.1.4 Any judgment in accordance with these two state-
than the “r” value for that material; “r” is the interval ments would have an approximate 95 % probability of being
representing the critical difference between two test results for correct.
the same material, obtained by the same operator using the 15.2 Bias—At the time of the study, there was no accepted
same equipment on the same day in the same laboratory. reference material suitable for determining the bias for this test
15.1.2 Reproducibility—Two test results shall be judged not method, therefore no statement on bias is being made.
equivalent if they differ by more than the “R” value for that 15.3 The precision statement was determined through sta-
material; “R” is the interval representing the difference be- tistical examination of qualified results, from seventeen labo-
tween two test results for the same material, obtained by ratories, on three materials. These three materials were de-
different operators using different equipment in different labo- scribed as the following:
ratories. Fluid 1: Monoethylene Glycol
15.1.3 Intermediate Precision—The day-to-day standard Fluid 2: Diethylene Glycol
deviation within a laboratory for results produced by the same Fluid 3: Triethylene Glycol
operator, determined through statistical analysis following 15.3.1 To judge the equivalency of two test results, it is
ASTM E 180, Standard Practice for Determining the Precision recommended to choose the material closest in characteristics
of ASTM Methods for Analysis and Testing of Industrial and to the test material.
Specialty Chemicals. E 180 was used to conform to this
particular study design which required an estimate of interme- 16. Keywords
16.1 coulometric; Karl Fischer; organic liquids; pyridine;
7
The details of this study are given in ASTM Research Report No. E15-1062. pyridine-free; water

SUMMARY OF CHANGES

Committee E15 has identified the location of selected changes to this standard since the last issue (E 1064-05)
that my impact the use of this standard.

(1) A new Precision and Bias section was added. (2) Table 2 was added.

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