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

Designation: D1123 − 99 (Reapproved 2015)

Standard Test Methods for

Water in Engine Coolant Concentrate by the Karl Fischer
Reagent Method1
This standard is issued under the fixed designation D1123; 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 U.S. Department of Defense.

1. Scope 3.1.1 color end point—that point during the titration when
1.1 These test methods cover the determination of the water the color change from yellow to orange-red is sharp and easily
present in new or unused glycol-based coolant concentrates repeated. The orange-red color must persist for at least 30 s in
using a manual (Test Method A) or an automatic (Test Method order to indicate an end point.
B) coulometric titrator procedure. 3.1.1.1 Discussion—View the color by transmitted daylight
or by transmitted light from an artificial daylight lamp, such as
1.2 Many carbonyl compounds react slowly with the Fis- one that complies with the specification given in Test Method
cher reagent, causing a fading end point and leading to high D156.
results. A modified Fischer reagent procedure is included that
3.1.2 instrument end point—for the purpose of these tests,
minimizes these undesirable and interfering reactions.
that point in the titration when two small platinum electrodes,
1.3 The values stated in SI units are to be regarded as upon which a potential of 20 to 50 mV has been impressed, are
standard. No other units of measurement are included in this depolarized by the addition of 0.05 mL of Fischer reagent (6
standard. mg of water/mL), causing a change of current flow of 10 to 20
1.4 This standard does not purport to address all of the µA that persists for at least 30 s.
safety problems, if any, associated with its use. It is the 3.1.2.1 Discussion—This end point is sometimes incorrectly
responsibility of the user of this standard to establish appro- called the “dead stop,” which is the reverse of the above.
priate safety and health practices and determine the applica-
4. Summary of Test Method
bility of regulatory limitations prior to use. For specific hazards
statements see Sections 8 and 16. 4.1 These test methods are based essentially on the reduc-
tion of iodine by sulfur dioxide in the presence of water. This
2. Referenced Documents reaction can be used quantitatively only when pyridine and an
2.1 ASTM Standards:2 alcohol are present to react as follows:
D156 Test Method for Saybolt Color of Petroleum Products I 2 1SO2 1H 2 O→SO3 12HI (1)
(Saybolt Chromometer Method)
D1176 Practice for Sampling and Preparing Aqueous Solu- 4.2 In order to determine water, Karl Fischer reagent is
tions of Engine Coolants or Antirusts for Testing Purposes added to a solution of the sample in anhydrous high-purity
D1193 Specification for Reagent Water methanol until all water present has been consumed. This is
E203 Test Method for Water Using Volumetric Karl Fischer evidenced by the persistence of the orange-red end point color,
Titration or alternatively by an indication on a galvanometer or similar
current-indicating device that records the depolarization of a
3. Terminology pair of noble metal electrodes. The reagent is standardized by
3.1 Definitions of Terms Specific to This Standard: the titration of water.
NOTE 1—It is believed that these methods give all the information
1 required for determining the water in coolant formulations. Should
These test methods are under the jurisdiction of ASTM Committee D15 on
additional information on water determinations be needed, reference
Engine Coolants and Related Fluids and are the direct responsibility of Subcom-
mittee D15.04 on Chemical Properties.
should be made to Test Method E203.
Current edition approved May 1, 2015. Published June 2015. Originally
5. Significance and Use
approved in 1950. Last previous edition approved in 2009 as D1123 – 99(2009).
DOI: 10.1520/D1123-99R15.
2
5.1 The total apparent water in engine coolant concentrate
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
as determined by Karl Fischer titrations consists of the follow-
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on ing: (1) water present in the original glycol base; (2) water
the ASTM website. added (for example, inhibitor solutions); (3) water of hydration

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

1
 D1123 − 99 (2015)
of inhibitors (for example, Na2B4O7·5H2O); (4) water formed electrodes and capable of indicating a current flow of 10 to 20
in the chemical reaction between borate and ethylene glycol, µA by means of a galvanometer or radio tuning eye circuit.4
producing boratediol condensate and water; and (5) quantita- 6.4 Buret Assembly for Fischer reagent, consisting of a 25 or
tive interference by the reaction of the reagent with inhibitors 50-mL buret connected by means of glass (not rubber) con-
such as tetraborate or sodium hydroxide. nectors to a source of reagent; several types of automatic
TEST METHOD A—MANUAL TITRATION dispensing burets5 may be used. Since the reagent loses
strength when exposed to moist air, all vents must be protected
6. Apparatus against atmospheric moisture by adequate drying tubes con-
taining anhydrous calcium sulfate.6 All stopcocks and joints
6.1 Titration Vessel—For color end point titrations, use a should be lubricated with a lubricant not particularly reactive7
100 or 250-mL volumetric flask, which need not be calibrated. with the reagent.
For instrument end point, a 250-mL flask fitted with inter-
changeable electrodes (Fig. 1)3 may be used. This is particu- 6.5 Weighing Bottle, of the Lunge or Grethen type, or
larly good for titrations of coolant concentrate that is deeply equivalent.
colored from dye or any other cause. For permanently mounted 6.6 Some laboratory equipment suppliers offer a Karl Fis-
assemblies, the vessel should have a capacity about equal to cher apparatus. The noted model or its equivalent has been
that of a 300-mL tall-form beaker and should be provided with found to be suitable.8
a tight-fitting closure to protect the sample and reagent from
atmospheric moisture, a stirrer, and a means of adding sample 7. Reagents
and reagents and removing spent reaction mixture. It is 7.1 Purity of Reagents—Reagent grade chemicals shall be
desirable to have a means for cooling the titration vessel to ice used in all tests. Unless otherwise indicated, it is intended that
temperature. all reagents shall conform to the specifications of the Commit-
6.2 Instrument Electrodes, platinum with a surface equiva- tee on Analytical Reagents of the American Chemical Society,
lent to two No. 26 wires, 4.76-mm long. The wires should be where such specifications are available.9 Other grades may be
3 to 8 mm apart and so inserted in the vessel that the liquid will used, provided it is first ascertained that the reagent is of
cover them. sufficiently high purity to permit its use without lessening the
6.3 Instrument Depolarization Indicator, having an internal accuracy of the determination.
resistance of less than 5000 Ω and consisting of a means of 7.2 Unless otherwise indicated, references to water shall be
impressing and showing a voltage of 20 to 50 mV across the understood to mean reagent water, Type IV, conforming to
Specification D1193.
7.3 Karl Fischer Reagent, equivalent to 5 mg of water/
mL.10
3
Flasks made by Rankin Glass Blowing Co., 3920 Franklin Canyon Rd., 7.4 Methanol (Warning—See 8.1.)—Anhydrous, high pu-
Martinez, CA have been found satisfactory for this purpose.
rity.

8. Hazards
8.1 Methanol—Poison; flammable; may be fatal or cause
blindness if swallowed; cannot be made non-poisonous; harm-
ful if inhaled.

4
A type similar to the Precision Scientific Co. “Aquatrator” or Fisher Scientific
Co. “Fisher Titrimeter,” is suitable for the measurement of the instrument end point.
5
A type similar to Catalog No. J-821 of Scientific Glass Apparatus Co.,
Bloomfield, NJ, or Catalog No. 750 of Eck and Krebs, New York, NY, has been
specifically designed for this purpose and presents the minimum contact of reagent
with stopcock lubricant.
6
Indicating Drierite has been found satisfactory for this purpose.
7
Suitable lubricants include Apiezon N. (James G. Biddle and Co., Philadelphia,
PA); High Vacuum Silicone Grease (Dow Corning Co., Midland, MI); Sisco 300
(Swedish Iron and Steel Co., New York, NY).
8
Metrohm Herisau, Karl Fischer Titrator Type E-452 available from Brinkmann
Instruments, Inc., Cantaigue Road, Westbury, NY 11590.
9
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD.
NOTE 1—All dimensions in millimetres. 10
Reagents, as the pyridine-free hydranal reagent, available from Fisher
FIG. 1 Titration Flask Assembly Scientific, Pittsburgh, PA 15219.

2
 D1123 − 99 (2015)
9. Sampling it is sufficient to lower the tip of the buret deeply into the long neck of the
titration flask.
9.1 A representative sample of the contents of the original NOTE 3—In titrating with the volumetric flask-type titration vessel,
container shall be obtained as directed in Practice D1176; even avoid wetting the stopper and upper end of the flask with either the reagent
if two phases are present, the water-insoluble phase should not or the sample solvent. Each time the titration is interrupted, touch the buret
be separated. tip to the neck of the flask to remove droplets which, if not removed,
would absorb moisture from the atmosphere. When the flask is removed
from under the buret tip, wipe the tip with a clean dry cloth in a downward
10. Standardization of Reagent motion.
10.1 Standardize the Fischer reagent at least once, prior to
use, each day the procedure is used, by either the color or 12. Calculation
instrument end point (see Section 3) method, using the proce- 12.1 Calculate the total water content (free plus apparent) of
dure as used for titrating the sample (Section 11). the sample as follows:
10.1.1 Add to each 250 mL flask 25 mL of anhydrous, high Water, weight % 5 VF/10M (3)
purity methanol. Stir rapidly. Titrate with Karl Fischer reagent
according to 11.2. Add to the solution 0.15 to 0.18 g of water where:
(to 60.1 mg) by use of an accurately sized syringe. Titrate V = mL of Karl Fischer reagent required by the sample,
again and record the volume of titrant used. Repeat standard- F = equivalency factor for Karl Fischer reagent, mg of
ization two more times. water per mL of reagent, and
10.1.2 Calculate the equivalency factor of the reagent in M = sample used, g.
terms of water content per millilitre as follows:
13. Precision and Bias
Equivalency factor, F , mg of water/mL 5 A/B (2)
13.1 Precision—The following data should be used for
where: judging the acceptability of results (95 % probability):
A = mg of water used in the standardization, and 13.1.1 Repeatability—Duplicate results by the same opera-
B = Karl Fischer reagent required, mL. tor should be considered suspect if they differ by more than the
following amount:
11. Procedure
Repeatability 0.5 mL of titrant
11.1 Introduce 30 to 50 mL of the anhydrous high-purity 13.1.2 Reproducibility—The result submitted by one labo-
methanol into a 250 mL Erlenmeyer flask, making sure, if an ratory should not be considered suspect unless it differs from
instrument end point apparatus is used, that the electrodes are that of another laboratory by more than the following amount:
covered by this amount of methanol. If the color end point is to
Water Content, % Reproducibility, % of mean
be determined, make up a second flask as well.
0.1 to 1.0 15
11.2 Adjust the stirrer, if any, to provide adequate mixing 1.0 to 10 5
without splashing. Titrate the mixture to the instrument end
point (3.1.2), or the color end point (3.1.1), with Karl Fischer 13.2 Bias—Since there is no accepted reference material
reagent. If the color end point is to be observed, titrate one flask suitable for determining the bias for the procedure in this test
to match the first. Set aside the first flask as a comparison method, bias has not been determined.
standard for titrating the sample. TEST METHOD B—COULOMETRIC TITRATION
11.3 To the titration mixture thus prepared, add an amount
of sample as indicated in Table 1. Exercise care when the 14. Apparatus
sample is transferred so that water is not absorbed from the air, 14.1 Coulometric Titrator11,12—A complete control unit
particularly under conditions of high humidity. Again, titrate with titration chamber and clamp, platinum sensing electrodes,
the mixture with Karl Fischer reagent to the same instrument or generator, magnetic stirrer, and meeting requirements 14.2 and
color end point previously employed. Record the amount of 18.1.
reagent used to titrate the water in the sample.
14.2 The instrument used for determining water in liquids is
NOTE 2—When using the volumetric flask-type titration vessel in humid designed and calibrated to deliver a known number of milli-
climate, place a piece of thin paraffin wax over the mouth of the vessel. amperes of current which generates sufficient iodine to neu-
Provide a small hole for introducing the buret tip. In less humid climates tralize a known number of micrograms of water per minute.
14.3 In order to determine the water content of engine
TABLE 1 Recommended Sample Sizes coolants, this method requires a two-part titration solution that
is brought to zero dryness by iodine produced by the generator
Sample
Water Content,
Size, Sample Method
weight %
g
11
2.5 to 10 0.3 Introduce samples by using weigh bottles or This procedure is patented by the Photovolt Corp. under U. S. Patent 3,726,778
disposable, accurate syringes. Obtain sample and has been included in the standard under Paragraph 11.2 of the Regulations
weight by difference. Governing ASTM Technical Committees. Procedure A is a non-patented alternative
0.5 to 2.5 3 method.
12
Below 0.5 20 A detailed drawing is available from ASTM Headquarters. Request Adjunct
No. 12-415330-00.

3
 D1123 − 99 (2015)
when the instrument is powered up. The sample is added and the needle through the sample port septum and lower it until
the water content is read directly in micrograms. the tip of the needle is below the surface of the titration
14.4 Glass Syringe, 50-mL, for removing excess solution solution.
from the titration chamber. 17.6 Slowly inject the neutralizing reagent into the titration
14.5 Syringe, 25-µL, fitted with a 11.5-cm hypodermic solution until it changes color from brown to red. This
needle for introduction of samples into the titration chamber. indicates the end point is near. Continue the addition very
slowly. The total volume required will range between 5 and 15
14.6 Syringe, 1-µL, fitted with a 11.5-cm hypodermic needle mL depending on the residual moisture in the system.
for standardization of instrument.
17.7 All liquid samples to be tested should be at room
14.7 Fluorocarbon Sealing Grease,13 to seal the titration temperature for analyses.
chamber against atmospheric moisture.
14.8 Septums, to seal sample port but allow introduction of 18. Verification of System by Direct Titration of Water
samples by a needle with a minimum of moisture contamina- 18.1 To determine if the titration system is functioning
tion. Septum caps should be replaced as required to prevent air properly, fill a 1-µL syringe with distilled water to the 1-µL
leakage as indicated by instrument drift. mark. Weigh the filled syringe. Insert the needle through the
sample port septum and lower it until the tip of the needle is
15. Reagents14 below the surface of the titrating solution. Depress the START
15.1 Generator Solution—(Warning—see 16.1)—Provides key and immediately inject the water into the titration solution.
iodine in the reaction mixture. Remove the syringe and reweigh. The titration is complete
when the result is displayed with the symbol “mcg.” The
15.2 Titration Solutions, supplied in two parts, Part A and
weight of the water injected in micrograms should approximate
Part B. The two parts are mixed prior to adding to the titration
the instrument reading.
chamber.
15.3 Neutralizing Solution—Methanol—(Warning—see 19. Sample Sizes
16.2)—Anhydrous, high purity methanol containing approxi- 19.1 The sample size is governed by the expected range of
mately 20 mg H2O/mL. moisture content:
Expected Moisture Content Range of Sample Size
16. Hazards 1000 ppm (0.1 %) 0.1 to 3 g
1% 10 to 300 mg
16.1 Generator Solution—Refer to the manufacturer’s ma- 10 % 1 to 30 mg
terial safety data sheet for precautions and hazards. 100 % 0.1 to 3 mg

16.2 Methanol—Poison; flammable; may be fatal or cause

20. Procedure
blindness if swallowed; cannot be made non-poisonous; harm-
ful if inhaled. 20.1 Using an appropriate dry syringe and needle (see 19.1),
draw the sample liquid to be tested into the syringe and
17. Preparation of Apparatus discharge the contents into a waste container. Withdraw the
sample into the syringe until above the desired calibration
17.1 Clean, thoroughly dry, and assemble the titration
mark. Remove the needle from the sample container and force
chamber using sealing grease. Connect the titration chamber to
the extra liquid from the syringe to exactly the calibration
the titrator.
mark. Wipe the tip of the needle with a clean tissue or towel.
17.2 Pour Part B of the titration solution into Part A, close,
NOTE 4—For most determinations, the volumetric addition of the
thoroughly mix by shaking, and allow to cool to room sample is adequate. However, better accuracy may be obtained by
temperature. weighing the syringe before and after the addition of the sample.
17.3 Remove the septum from the sample port and pour the 20.2 The instrument should be left on stand-by when not in
mixture of Parts A and B, made in 17.2, through a dry funnel use. If the instrument is turned off, it is necessary to allow the
into the titration chamber. Immediately replace the septum cap. titration solution to stabilize or to replace the solution.
17.4 Add approximately 6 mL of the generator solution into
the generator cartridge. The surface of the generator solution 21. Calculation
should be below the level of the surface of the titrating solution 21.1 Calculate the amount of water present in the sample as
to prevent backflow contamination of the titrating solution. follows:
17.5 Attach the 11.5-cm hypodermic needle to a 20-mL µg water ~ readout number!
Water content ~ ppm! 5 (4)
syringe. Withdraw about 15 mL of neutralizing solution. Insert mass of sample, g

(The instrument can perform this computation automatically.

Consult the operating instructions.)
13
A suitable sealing grease can be obtained from Halocarbon Products, 8
Burlews Court, Hackensack, NJ 07601. 22. Precision and Bias
14
Reagents are available from the apparatus manufacturer and laboratory supply
houses. 22.1 Precision:

4
 D1123 − 99 (2015)
22.1.1 Repeatability—Duplicate results by the same opera- 22.2 Bias—Since there is no accepted reference material for
tor should not differ by more than 3 ppm, 95 % of the time. the procedure in this test method, bias has not been determined.
22.1.2 Reproducibility—The results submitted by one labo-
ratory should not differ from that of another laboratory by more 23. Keywords
than 10 ppm, 95 % of the time. 23.1 engine coolants; Karl Fischer; water content

ANNEX

(Mandatory Information)

A1. NOTES ON INTERFERENCES

A1.1 Some inhibitors react directly with the Karl Fischer react; when it is formed, one molecule of water is also formed
reagent by means of condensation or oxidation reactions during and this, of course, does react. The borate that is not combined
the titration and indicate more water than is actually present.15 chemically with glycol reacts directly with the Karl Fischer
Knowledge of the specific intereference factors is useful for reagent with the same stoichiometry as the above. Therefore, 1
calculating the true free water content of a sample. Without mol of sodium tetraborate appears in the titration as 7 mol of
complete compositional data, it is impossible for the analyst to water by either mechanism. In the case of 1 g of sodium
determine the true free water content. However, in many cases tetraborate decahydrate, 0.33 g of water are indicated by the
the total apparent water (free water plus apparent water) is titration; for 1 g of the pentahydrate, the result is 0.43 g of
determined and is satisfactorily used for qualification or water indicated; and for 1 g of anhydrous sodium tetraborate
production quality control purposes. the Karl Fischer titration indicates 0.63 g water.
A1.2 Many ethylene glycol-type engine coolant concen- A1.3 Monovalent metal hydroxide such as sodium hydrox-
trates contain sodium tetraborate. In the titration, some of the ide reacts with the Karl Fischer reagent to give 1 mol of
Karl Fischer reagent reacts with this borate either directly or apparent water per mol of hydroxide.
with the water formed by the borate-ethylene glycol conden-
sation reaction. The borate-ethylene glycol molecule does not A1.4 Other inhibitors such as nitrites react stoichiometri-
cally with constituents of the Karl Fischer reagent. For
15
example, 1 mol of sodium nitrite gives 0.5 mol of apparent
Jordan, C. B., “Use of Karl Fischer Reagent for the Determination of Water in
Condensates of Sodium Tetraborate and Diols,” Analytical Chemistry, Vol 36, water. In this case, however, the reaction is slow and the
February 1964, p. 424. interference can be ignored when the titration is rapid.

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