This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

Designation: D1533 − 20

Standard Test Method for

Water in Insulating Liquids by Coulometric Karl Fischer
Titration1
This standard is issued under the fixed designation D1533; 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.

1. Scope 3. Summary of Test Method

1.1 This test method covers the measurement of water 3.1 This test method is based on the reduction of iodine
present in insulating liquids by coulometric Karl Fischer containing reagent according to the traditional Karl Fischer
titration. This test method is used commonly for test specimens reaction. The proposed reaction mechanism is as follows:3
below 100 % relative saturation of water in oil. The coulomet- SO2 1CH3 OH1RN 5 @ RNH# SO3 CH3 (1)
ric test method is known for its high degree of sensitivity
(typically 10 µg H2O). This test method requires the use of H 2 O1I 2 1 @ RNH# SO3 CH3 12RN 5 @ RNH# SO4 CH3 12 @ RNH# I
equipment specifically designed for coulometric titration. ~ RN 5 Base!
1.2 This test method recommends the use of commercially The endpoint is determined amperometrically with a plati-
available coulometric Karl Fischer titrators and reagents. num electrode that senses a sharp change in cell resistance
1.3 The values stated in SI units are to be regarded as when the iodine has reacted with all of the water in the test
standard. No other units of measurement are included in this specimen.
standard. 3.2 The coulometric Karl Fischer test method requires the
use of an automatic titrator with commercially available
1.4 This standard does not purport to address all of the
reagents. Karl Fischer instruments regenerate iodine coulo-
safety concerns, if any, associated with its use. It is the
metrically from the iodide in the Karl Fischer reagent. The test
responsibility of the user of this standard to establish appro-
specimen is injected into a titration cell where the iodine
priate safety, health, and environmental practices and deter-
consumed by the reaction with water is electrolytically regen-
mine the applicability of regulatory limitations prior to use.
erated by anodic oxidation of iodide. The completion of the
For specific precautionary statements see 8.1 and A2.1. reaction is detected with a platinum sensing electrode. The
1.5 This international standard was developed in accor- coulombs of electricity required to generate the necessary
dance with internationally recognized principles on standard- amount of iodine then is converted into the amount of water
ization established in the Decision on Principles for the present in the test specimen by use of the Faraday equation.
Development of International Standards, Guides and Recom-
3.3 Titration Cell—The coulometric titration cell consists of
mendations issued by the World Trade Organization Technical
either a sealed vessel containing both an anode and cathode
Barriers to Trade (TBT) Committee. which are separated by a diaphragm or a sealed vessel
containing an anode and cathode which are not separated by a
2. Referenced Documents diaphragm. In both cells the anode compartment contains a
2.1 ASTM Standards:2 solution consisting of sulfur dioxide, iodide, and an amine in a
D923 Practices for Sampling Electrical Insulating Liquids solvent containing methanol/chloroform or methanol/longer
chain alcohol. In the cell with a diaphragm the cathode
compartment contains similar reagents optimized for cathodic
1
reduction.
This test method is under the jurisdiction of ASTM Committee D27 on
Electrical Insulating Liquids and Gasesand is the direct responsibility of Subcom-
mittee D27.06 on Chemical Test.
4. Significance and Use
Current edition approved Nov. 1, 2020. Published November 2020. Originally 4.1 Electrical characteristics of an insulating liquid may be
approved in 1958. Last previous edition approved in 2012 as D1533 – 12. DOI:
10.1520/D1533-20.
affected deleteriously by excessive water content. A high water
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
3
Standards volume information, refer to the standard’s Document Summary page on Scholz, E., “Karl-Fischer Titration,” Springer-Verlag, Berlin, Heidelberg, New
the ASTM website. York, Tokyo, 1984, 140 pp.

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

1
 D1533 − 20
content may make a dielectric liquid unsuitable for some 6.1.1 Detector Electrodes—This electrode pair ampero-
electrical applications due to deterioration of properties such as metrically determines the end point of titration by measuring a
the dielectric breakdown voltage. sharp change in cell resistance.
4.2 This test is suitable for use in acceptance specifications, 6.1.2 Generator Electrodes—This electrode pair performs
in control of processing, and in evaluating the condition of the cathodic reduction of iodide, which allows the Karl Fischer
dielectric liquids in service. reaction to take place. It may consist of two platinum meshes
or wires separated by a diaphragm within a glass assembly or
5. Interferences two platinum meshes or wires not separated by a diaphragm.
5.1 Compounds such as aldehydes, ketones, free halogens, 6.2 Titration Flask—The titration flask will be of suitable
most acids, and oxidizing or reducing agents may interfere capacity and will be protected against atmospheric moisture. A
with coulometric Karl Fischer titrators. If a drifting end point bottom drain cock is desirable but not necessary for removing
is noted, an alternative solvent system or another titration reagents.
method is warranted. If this drifting end point cannot be 6.3 Stirrers—Means for agitation during titration will con-
corrected, the water values should be regarded as suspect. A sist of a magnetic stirrer with a glass or TFE-fluorocarbon-
detailed discussion of interfering substances can be found in covered stirring bar about 2 to 5 cm long or appropriate to the
the treatise on aquametry.4 titration vessel. The bar should be cleaned thoroughly, rinsed
5.2 Studies have shown that the water content of an insu- with methanol, dried in an oven for 1 h at 100°C, and stored in
lating liquid sample may be influenced significantly by the a desiccator until used. In a sealed system, recleaning and
sample container.5 A sample may either gain or lose water on redrying are not necessary for routine use.
storage in a glass container depending upon the initial water 6.4 Transfer Syringes—Syringes shall be used of a suitable
content of the sample, the manner in which the container is size to accommodate instrument manufacturers’ recommenda-
cleaned and dried, and the length of storage time before tion of sample size. Syringes may be glass or plastic. Glass
analysis. In addition, sample bottles should not be dried at syringes shall be cleaned and dried for 1 h at 100°C prior to
temperature in excess of 110°C and should be rinsed with the use. Plastic syringes shall be disposed of following each
liquid being tested prior to taking the test specimen. Plastic sample use.
containers should not be used. Glass syringes or metal cans that 6.5 Needles—Needles that are to be fitted to the transfer
can be filled to the very top and capped are the most suitable syringes shall be long enough to inject samples directly below
containers for this test. the surface of the Karl Fischer reagent. They should be of a
5.3 Erroneous low readings may be obtained if previous large enough gauge to allow for easy transfer of the sample.
spent oil test specimens are not removed from the solvent 6.6 Septums, used to seal sample port, allowing the intro-
system on a routine basis. Excess oil may not mix thoroughly duction of test specimens with a minimum amount of contami-
with the solvent system thus preventing the total water content nation from atmospheric moisture.
of that test specimen from being measured properly. Stirring
should be at such a rate that an oil layer will not form on top 6.7 Sealing Grease—If the apparatus does not have a gasket
of the reagent. If such an oil layer does form while at the seal, use a sealing grease to seal the titration chamber against
instruments maximum stirrer speed, stop testing and remove atmospheric moisture.
the oil layer. If accurate results can not be obtained, the 6.8 Drying Oven, vacuum or air circulating.
solution should be discarded. 6.9 Desiccator, standard laboratory type with color change
5.4 Upon setting up of the titration vessel and solvent indicator.
system, the walls of the titration vessel should be wetted by 6.10 Analytical Balance, capable of weighing to 6 0.001 g.
swirling the solvent system solution around in the vessel.
5.5 Some solvent systems may not perform well with 7. Reagents
natural esters. Alternate solvent systems should be explored to 7.1 Purity of Reagents—Unless otherwise indicated, all
provide the best analysis. reagents shall conform to the specifications of the Committee
on Analytical Reagents of the American Chemical Society,
6. Apparatus where such specifications are available.6
6.1 Coulometric Titrator, consisting of a detector electrode, 7.2 Coulometric Karl Fischer Reagent, can be obtained
generator electrode, titration vessel, magnetic stirrer, and commercially. Refer to Annex A1 for information on alterna-
control unit. tive solvent systems.

4 6
Mitchell, J., Jr. and Smith, D. M., “Aquametry—A Treatise on Methods for the Reagent Chemicals, American Chemical Society Specifications, American
Determination of Water, Part III—the Karl Fischer Reagent,” 2nd ed., J. Wiley and Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Sons, Inc., New York, NY 1977. listed by the American Chemical Society, see Analar Standards for Laboratory
5
Gedemer, T., “Determination of Water in Oil by Karl Fischer Method, Part II, Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Changes in Moisture Content During Storage,” American Laboratory, 7 (10), pp. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
43-50, 1975. MD.

2
 D1533 − 20
7.2.1 Anode Reagent, frequently referred to as vessel solu- Follow the instructions provided in Annex A2 for detailed
tion. instructions on cleaning.
7.2.2 Cathode Reagent, frequently referred to as generator 10.2 Fill reagent reservoirs with appropriate reagents ac-
solution. cording to the manufacturer’s instructions.
7.3 Verification Solutions—Verification solutions are avail- 10.3 Turn the instrument on and allow to stabilize.
able commercially.7 Verification solutions may be formulated
in-house from long chain alcohols. 11. Verification of System Operation
7.3.1 The moisture content of water-saturated octanol is:
11.1 The accuracy of titration of the instrument and reagents
Water-saturated 1-Octanol 39.2 ± 0.85 mg/mL of solution8
shall be verified prior to beginning of testing by use of a
7.3.2 The water-saturated alcohol can be prepared by adding suitable verification solution (see 7.3) containing a known
deionized water to the alcohol (ACS reagent grade) at 25°C quantity of water. It is desirable to verify the system operation
such that the final mixture consists of a two-phase system in using a solution that approximates the same range of water
which the lower water phase is at least 2 cm high. Initially, this expected to be in the samples. Verification solutions shall be
solution should be mixed thoroughly and allowed to stand at run with new reagents prior to testing. If verification solution
room temperature for at least three days to achieve complete results lie outside parameters established by the manufacturer
equilibration. for acceptable water content of the solution, reagents shall be
NOTE 1—For the best accuracy the solution should not be mixed or changed and reverified.
shaken after standing. Remove the sample aliquot from the top phase and
inject it immediately into the titration cell. The degree of saturation of the 12. Procedure
water-saturated 1-Octanol varies <1 % between 10 and 30°C. 12.1 After verifying the system is operating properly, allow
7.3.3 The response of the instrument shall be verified with 1 the instrument to restabilize prior to use.
to 2 µL of water; this can give a response value of 1000 to 2000
12.2 Follow the manufacturer’s instructions for suggested
µg within the specified precision of the instrument.
specimen size for an expected range of water content.
8. Safety Precautions 12.3 Using an appropriate syringe and needle (see 6.4 and
8.1 Pyridine was the organic amine that was traditionally 6.5) sample the insulating fluid to be tested. Prior to sampling,
used in Karl Fischer reagents; however, pyridine-free formu- rinse the syringe and needle with the liquid to be tested one
lations are now available commercially. Pyridine-free reagents time.
titrate faster and are less toxic, less odorous, and more stable 12.4 Determine the sample mass by difference to three
than pyridine types. The reagents may contain potentially significant figures by weighing the test specimen before and
hazardous chemicals, such as iodine, pyridine, sulfur dioxide, after injection. Alternately, inject a known volume of a sample
methanol, chloroform, chlorinated hydrocarbons, or other or- whose density is known at the test temperature to determine
ganic materials. Wear chemical resistant gloves when mixing sample size.
the reagents and removing solution from the titration chamber. 12.5 Reagent solutions can be used until verification solu-
Care must be exercised to avoid unnecessary inhalation of tions no longer test accurately. See Section 11 for instructions
reagent vapors or direct contact of the reagents with the skin or on the use of verification solutions.
eyes. Following accidental spillage, flush the affected area with
copious amounts of water. 13. Calculation
NOTE 2—Carefully read and follow manufacturers’ instructions and 13.1 Most commercially available coulometric Karl Fischer
Safety Data Sheet when using commercially available reagent systems. instruments automatically calculate the water content in ppm or
percent. If not, calculate the amount of water in the sample as
9. Sampling
follows:
9.1 The preferred method for sampling insulating liquids is
Water Content, mg/kg ~ ppm! 5 A/B (2)
Practices D923. If the sample is cloudy or contains free water,
it may be difficult to obtain a representative test specimen. where:
A = mass of water, (µg) (instrument readout), and
10. Preparation of Apparatus B = mass of test specimen, g.
10.1 Thoroughly clean and dry the titration vessel and then
reassemble according to the manufacturer’s recommendations. 14. Report
14.1 Report the following information:
14.1.1 Water content of the test specimen in mg/kg (ppm)
7
The sole source of supply of verification solutions, RM 8506 and RM 8507, rounded to the nearest integer.
known to the committee at this time is the National Institute of Standards and
Technology (NIST), Gaithersburg, MD 20899. If you are aware of alternative 14.1.2 Sample identification.
suppliers, please provide this information to ASTM International Headquarters. 14.1.3 Sample temperature when collected, if available.
Your comments will receive careful consideration at a meeting of the responsible
technical committee,1 which you may attend. 15. Precision and Bias
8
SRM 2890 Water Saturated 1-Octanol Certificate of Analysis, NIST,
Gaithersburg, MD, 25 August 1998. 15.1 Precision:

3
 D1533 − 20
15.1.1 The following criteria may be used for judging NOTE 3—The MDL is defined here as the minimum concentration of a
precision of test results on new and used oils at the 95 % substance that can be measured and reported with 95 % confidence using
a 7–mL oil sample. The value of 8 ppm has been determined from the
probability level. The precision statements for this test method reproducibility of the results in interlaboratory test of two new and one
were based on 9 samples and 37 laboratories.9 used oil sample containing about 11 mg/kg (ppm) water.
15.1.1.1 Repeatability—The difference between results ob- NOTE 4—A value of the MDL for an individual laboratory may be
tained by the same operator with the same apparatus under calculated from the results of n replications of complete analysis of a
constant operating conditions on identical test material, in the sample using the following equation:10
long run, would exceed 7 ppm, only 1 case in 20, in the 0 to 50 MDL0.95 5 t ~ n21, 0.95! 3 S (3)
mg/kg (ppm) range.
15.1.1.2 Reproducibility—The difference between two where:
single and independent results obtained by different operators t(n–1, 0.95) = student’s t value for n – 1 df and a confidence
working in different laboratories on identical test material, in level of 95 %, and
the long run, would exceed 14 ppm, only 1 case in 20, in the S = standard deviation of n replicate analyses.
0 to 50 mg/kg (ppm) range. The MDL for an individual laboratory may differ from the
15.2 Bias—The bias of the procedure in this test method for MDL of 8 mg/kg (ppm) calculated for this collaborative study.
measuring water content of electrical insulating fluids has not
been determined from the collaborative interlaboratory round- 16. Keywords
robin study, since there is no suitable standard for which the 16.1 coulometric Karl Fischer titration; free water; Karl
exact water content is known. Fisher method; Karl Fischer reagent; solvent verification solu-
15.3 The typical method detection limit (MDL) at the 95 % tions; water content
confidence level has been found to be 8 ppm water for the
mineral oil samples.
10
Glaser, J. A., Foerst, D. L., McKee, G. D., Quave, S. A., and Budde, W. L.,
9
Supporting data have been filed at ASTM International Headquarters and may “Trace Analysis for Wastewaters,” Environmental Science and Technology, Vol 15,
be obtained by requesting Research Report RR:D27-1012. pp. 1426-1435 (1981).

ANNEXES

(Mandatory Information)

A1. ALTERNATIVE SOLVENT SYSTEMS

A1.1 Some high viscosity oils, as well as silicones, may A1.5 If an alternative solvent system is used, instrument or
give erroneous water values when titrated in accordance with titrant calibration checks must be made before and after the
this test method. Many of these problems, however, may be addition of the test specimen. If significant calibration discrep-
overcome by the use of alternative solvent systems. ancies are noted, the results should be regarded as suspect.
A1.2 If a problem with erroneous answers is known to exist, A1.6 To determine the accuracy of a method when using an
or is suspected, check the instrument calibration before and alternative solvent system, test specimens of known water
after the introduction of a suspected test specimen. If calibra- content should be analyzed. If such samples are not available,
tion discrepancies are noted, the solvent system or the appli- commercial standards7 or water-saturated octanol8 should be
cability of the method is suspect and changing of the solvent used to assess the response of the instrument.
system from a methanol-chloroform system to a more appro-
priate solvent system probably is indicated. A1.7 Because of the wide variety of insulating liquids and
solvent systems possible, no precision and bias statement is
A1.3 For certain high viscosity oils, the addition of a low
possible for these modifications.
molecular weight hydrocarbon solvent, such as heptane or
toluene, to the titration vessel has been found to be suitable.
A1.4 For dimethylsilicones, a 1:1 mix of Karl Fischer
reagent and formamide for the titration solvent has been found
to be suitable.

4
 D1533 − 20

A2. CLEANING OF THE TITRATION VESSEL AND ELECTRODES

A2.1 The system must be kept clean to obtain reliable A2.5 Most deposits can be removed with the use of 75 %
results. (Warning—Procedures listed herein involve the use of nitric acid. Some deposits may require the use of hot, concen-
nitric acid, either hot, concentrated acid or 75 % aqueous trate nitric acid. An aqueous 75 % nitric acid solution should be
solutions. Nitric acid and its vapors can cause severe burns. tried first, and only if that does not remove the deposits, should
Handle concentrated nitric acid with extreme care. This pro- concentrated nitric acid be used.
cedure must be used by persons knowledgeable in the safe
handling and disposal of this material.) A2.6 After cleaning the deposits from the frit or generator,
or both, (with nitric acid, as described in A2.3 – A2.5) make
A2.2 Cleaning is best done with an appropriate solvent for sure that all the nitric acid is rinsed from the equipment with
the samples analyzed. Since the commercial generators are water to be followed by methanol.
made of glass, platinum and TFE-fluorocarbon, they will
withstand most solvents and strong acids. If a solvent is known A2.7 Dry the entire assembly in an oven for at least 30 min
that adequately will clean the frit, it may be used. Otherwise, at 65°C before assembling and refilling the unit.
the following method may be used.
A2.8 The entire system will require occasional cleaning
A2.3 If the frit is clogged, it generally can be cleaned by the while the generator will require periodic cleaning. Inspect the
use of methanol followed by a water rinse, and then nitric acid. sensing electrode for any cracks in the glass or vapor in the
The use of a water aspirator or vacuum pump to pull the fluid glass tube. If there are vent holes in the cover or generator
through the frit helps to ensure that the pores in the frit will be tubes, these should be kept open and inspected occasionally.
cleaned. Consult the manufacturer’s manuals for general cleaning
A2.4 First disassemble the generator and rinse in water. Fill procedures.
a small beaker with enough nitric acid to cover the frit as the
generator is slowly lowered into it. Attach the aspirator to the
generator, and pull enough acid through the frit to at least cover
the cathode. The acid initially will be dark brown. Discard this
acid and pull additional acid through the frit until the acid is
colorless.

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or [email protected] (e-mail); or through the ASTM website
(www.astm.org). Permission rights to photocopy the standard may also be secured from the Copyright Clearance Center, 222
Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http://www.copyright.com/