Designation: D 3401 – 97 (Reapproved 2001)

Standard Test Methods for

Water in Halogenated Organic Solvents and Their
Admixtures1
This standard is issued under the fixed designation D 3401; 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 3. Summary of Test Methods

1.1 These test methods describe the use of the Karl Fischer 3.1 In the Karl Fischer reaction, water will react with iodine
(KF) titration for determination of water in halogenated or- in the presence of sulfur dioxide, alcohol, and an organic base
ganic solvents and mixtures thereof. Water concentrations from according to the following equation:
2 to 1000 ppm can be determined in these solvents. Two test H2O 1 I2 1 SO 2 1 CH3 OH 1 3RN → ~RNH!SO4CH 3 1 2~RNH!I
methods are covered as follows: (1)
1.1.1 Test Method A, Water Determination Using a Coulo-
metric KF Titrator—The coulometric test method is known for where RN = organic base.
its high degree of sensitivity (typically < 10 µg H2O) and 3.2 When the volumetric titration test method is used for
should be the test method of choice if water concentrations are this determination, the halogenated sample is added to a KF
typically below 50 ppm or if only small amounts of sample are solvent that usually consists of sulfur dioxide and an amine
available for water determinations. This test method requires dissolved in anhydrous methanol. This solution is titrated with
the use of equipment specifically designed for coulometric an anhydrous solvent containing iodine. The iodine titrant is
titrations. first standardized by titrating a known amount of water.
1.1.2 Test Method B, Water Determination Using a Volumet- 3.3 In the coulometric titration test method, the sample is
ric KF Titrator—The volumetric test method is a more injected into an electrolytic cell where the iodine required for
traditional approach to KF water determinations. Although the reaction with water is produced by anodic oxidation of
titrators are specifically designed for KF volumetric determi- iodide. With this technique, no standardization of reagents is
nations, many automatic titrators on the market can be adapted required.
to perform KF titrations. 3.4 In both test methods, the end point is determined
1.2 Either of these test methods can be used to determine amperometrically with a platinum electrode that senses a sharp
typical water concentrations (15 to 500 ppm) found in haloge- change in cell resistance when the iodine has reacted with all
nated solvents. of the water in the sample.
1.3 These test methods recommend the use of commercially
available Karl Fischer titrators and reagents. 4. Significance and Use
1.4 This standard does not purport to address all of the 4.1 High water concentrations can have a detrimental effect
safety concerns, if any, associated with its use. It is the on many uses of halogenated solvents.
responsibility of the user of this standard to establish appro- 4.1.1 Water can cause corrosion and spotting when solvents
priate safety and health practices and determine the applica- are used for metal cleaning.
bility of regulatory limitations prior to use. For specific 4.1.2 Water can reduce the shelf life of aerosol formula-
precautionary statements, see Sections 11 and 15. tions.
2. Referenced Documents 4.1.3 Water can inhibit desired reactions when solvents are
used in formulations.
2.1 ASTM Standards:
E 203 Test Method for Water Using Karl Fischer Titration2 5. Interferences
5.1 Certain compounds or classes of compounds interfere
1
These test methods are under the jurisdiction of ASTM Committee D26 on
with the accurate determination of water by the Karl Fischer
Halogenated Organic Solvents and Fire Extinguishing Agents and are the direct test method. They include aldehydes, ketones, free halogens,
responsibility of Subcommittee D26.04 on Test Methods. ferric salts, and strong oxidizing and reducing agents.
Current edition approved Dec. 10, 1997. Published May 1998. Originally 5.2 Free halogens can oxidize the iodate in the KF reagents
published as D 3401 – 75. Last previous edition D 3401 – 96.
2
Annual Book of ASTM Standards, Vol 15.05.
to form iodine; this causes erroneously low water values.

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

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 D 3401
5.3 A more detailed discussion of KF interferences can be 8.4 Transfer solvent to the bottles as quickly as possible.
found in Test Method E 203 and other sources.3,4 Adjust the liquid level to come within 1 in. of the top of the
bottle. Immediately place the cap on the bottle and tighten.
6. Apparatus 8.5 When removing a portion of sample from the bottle for
6.1 Coulometric Titrator, 5 (for Test Method A only) con- KF analysis, use pipets or syringes that have been thoroughly
sisting of a single or dual bath electrolytic cell, dual platinum dried. Replace the cap on the bottle immediately.
electrode, magnetic stirrer, and control unit. 8.6 If more than one portion of sample is to be taken from
6.2 Volumetric Titrator, 5 (for Test Method B only) consist- the bottle or if the sample is to be retained for further water
ing of a titration cell, dual platinum electrode, magnetic stirrer, analysis, it is a good practice to blanket the top of the bottle
dispensing buret, and control unit. with dry nitrogen when removing the sample. If septum cap
6.3 Syringes, 2, 5, 10, or 20-mL sizes. closures are being used, dry nitrogen can be introduced with a
6.4 Syringe, 5-µL size. syringe at the same time a portion of the sample is being
6.5 Silicon Rubber Blocks or Silicon Rubber Septa. removed with a second syringe.
6.6 Drying Oven, air circulating.
6.7 Desiccator. TEST METHOD A—WATER DETERMINATION
6.8 Analytical Balance, capable of weighing to 60.01 g. USING A COULOMETRIC KF TITRATOR
7. Reagents 9. Summary of Test Method
7.1 Anode Reagent, for dual bath titration (for Test Method
9.1 The dual bath coulometric titration cell consists of a
A only), use reagent recommended by manufacturer of titrator.
sealed vessel containing both an anode and cathode compart-
7.2 Cathode Reagent, for dual bath titration (for Test
ment. The anodic compartment usually contains a solution
Method A only), use reagent recommended by manufacturer of
consisting of sulfur dioxide, iodide, and an amine in a
titrator.
methanol/chloroform solvent. The cathodic compartment con-
7.3 Single Bath Reagent, (for Test Method A only), use
tains similar reagents optimized for cathodic reduction.
reagent recommended by manufacturer of titrator.
9.2 When a sample containing water is injected into the
7.4 Karl Fischer Volumetric Titrant, 4 (for Test Method B
anode compartment, the electrolytic cell generates its own
only) typically consists of a mixture of an organic amine, sulfur
supply of iodine from the iodide present. The iodine reacts
dioxide, and iodine dissolved in a non-hydroscopic solvent(s).
stoichiometrically with the water and the completion of the
Reagents with titers of 1.00, 2.00, and 5.00 mg of H2O/mL can
reaction is detected with a platinum sensing electrode. The
be commercially obtained.
coulombs of electricity required to generate the necessary
7.5 Karl Fischer Solvent, 4 (for Test Method B only)
amount of iodine is then translated by the microprocessor in the
typically consists of a mixture of an organic amine and sulfur
control unit into the amount of water that was present in the
dioxide dissolved in anhydrous methanol.
sample.
NOTE 1—Pyridine was the organic amine that was traditionally used in 9.3 The single bath coulometric titration cell consists of a
Karl Fisher reagents, however, pyridine-free formulations are now avail- sealed vessel filled with single bath reagent and dual platinum
able and preferred by most KF instrument manufacturers for use with their electrodes. When a sample containing water is injected into the
equipment. Pyridine-free reagents are said to be less toxic, less odorous,
and more stable than pyridine types.
vessel, the electrolytic cell generates its own supply of iodine
from the iodide present in the single bath reagent. The iodine
8. Sampling reacts stoichiometrically with the water and the completion of
8.1 Since halogenated solvents normally contain low con- the reaction is detected by a platinum sensing electrode. The
centrations of water, care must be taken to eliminate the coulombs of electricity required to generate the necessary
introduction of water from sampling equipment and atmo- amounts of iodine is then translated by the microprocessor in
spheric moisture. the control unit into the amount of water that was present in the
8.2 Without taking the proper sampling precautions, more sample.
error is typically introduced into the determination of water
through sampling techniques than in the titration process itself. 10. Verification of Instrument Accuracy
8.3 Dry sample bottles and closures in an oven at 110°C for 10.1 Coulometric titrators do not have a titrant that needs to
several hours. Place caps on the bottles immediately after be standardized since the iodine is being generated on demand
removing from the oven. by the titration cell. However, occasional checks of the
instrument accuracy are recommended. This can be done by
titrating a known amount of water and comparing this amount
3
Mitchell, J., Jr. and Smith, D. M., Aquametry—A Treatise on Methods for the with the amount of water reported by the titrator.
Determination of Water, Part III—The Karl Fischer Reagent, 2nd ed., J. Wiley and
Sons, Inc., New York, NY, 1977. 10.2 Use a 5-µL syringe to inject exactly 3.0 µL of water
4
Hydranal—Eugen Scholz Reagents for Karl Fischer Titration, 4th ed., by into the titration cell. Once the titration is complete, the titrator
Riedel-deHaen Aktiengesellschaft (US Distributor—Cresent Chemical Co., Inc.).
5
should report a value of 3000 µg (3.0 mg) H2O. The deviation
Automatic coulometric and volumetric titrators are manufactured by many
different companies. Models that have been found satisfactory for this purpose are
from this value should not be larger than 10 %. If the value is
available from Fisher Scientific, EM Science, Metrohm, Mettler, Photovolt, Mit- larger than 10 %, consult the instrument manual or manufac-
subishi, and others. turer to determine the cause.

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 D 3401
10.3 Alternatively, standard solutions containing known 12.6 Cover the syringe needle with a silicone rubber block
amounts of water dissolved in either methanol or a non- or piece of silicone rubber septa to further prevent evaporation
hydroscopic solvent are available from reagent suppliers for or spillage during the weighing process.
accuracy verification. A known volume of this solution is 12.7 Transfer the filled syringe to an analytical balance and
titrated and the reported amount of water is compared with the weigh the syringe and contents to the nearest 0.01 g.
theoretical amount stated by the supplier. 12.8 Remove the silicone block and insert the needle into
the titration cell septum. Inject the sample slowly, taking care
11. Precautions not to touch the needle to the surface of the anode solution.
11.1 Amounts of coulomatic reagents usually recommended While the syringe is still inside the cell, draw any remaining
for addition to the reaction cell typically have the capacity to sample that may remain in the syringe needle back into the
react with approximately 100 to 200 mg of water. These barrel and remove the needle from the cell.
reagents must be replaced when they are depleted. 12.9 Place the silicone block back onto the tip of the needle
11.2 Coulomatic reagents are hydroscopic and must be and reweigh the empty syringe. The weight difference between
stored in tightly capped containers to reduce the absorption of the first and second weighings will be the amount of sample
atmospheric moisture. injected into the titration cell.
11.3 Since the titrator automatically generates iodine to 12.10 The make and model of the titrator being used will
keep the reaction vessel in a dehydrated state, it is important to determine the actual steps performed to carry out the titration
keep the cell sealed to prevent introduction of excess atmo- process. In most cases, all that is required is pressing a start
spheric moisture that will decrease reagent life. titration or run key on the instrument keyboard either just prior
11.4 The total amount of solution in the anode compartment to or just after the sample injection.
can affect the KF reaction. Typically, the total volume of 12.11 Once the titration is complete, the amount of water
sample liquids that are added to the reaction cell should not (µg or mg) that was found in the solvent will appear on the
exceed 50 % of the original reagent in the compartment. If the instrument’s digital display. Most instruments will also calcu-
reagents become too dilute, the stoichiometry and rate of the late concentrations (ppm or %) if the sample weight is keyed
Karl Fischer reaction can be adversely affected. This fact into the instrument’s control panel.
should be considered when using large sample sizes.
11.5 Follow the recommended maintenance procedures of 13. Calculation
the instrument manufacturer. 13.1 Calculate the water content of the solvent as follows:
ppm H2O 5 µg H2O found/grams of solvent injected (2)
12. Procedure
12.1 Set up the coulometric titrator according to the manu-
facturer’s instructions, and add the proper amount of coulomat TEST METHOD B—WATER DETERMINATION
reagents to the anode and cathode compartments of the titration USING A VOLUMETRIC KF TITRATOR
cell.
12.2 The cell solutions must be anhydrous prior to introduc- 14. Summary of Test Method
tion of the sample. This is accomplished by either pretitrating 14.1 The volumetric titration cell consists of a sealed glass
the cell contents or by adding a small amount of an iodine/ vessel containing a dual platinum electrode. To the cell, a
methanol solution until a faint brownish coloration appears. suitable solvent (usually methanol based) is added. The sample
Following the procedure recommended by the instrument is injected into the cell, the mixture is stirred thoroughly and
manufacturer is suggested. titrated with a Karl Fischer reagent. This reagent typically
12.3 The amount of halogenated solvent that is injected into contains an organic amine, sulfur dioxide, and iodine dissolved
the cell depends on the quantity of water in the solvent. Table in a non-hydroscopic solvent such as xylene. The iodine reacts
1 lists recommended sample sizes for anticipated water con- stoichiometrically with the water, and the completion of the
centrations. reaction is detected with the platinum electrode.
12.4 Thoroughly clean and dry the sampling syringe. One
method is to dry it in an oven and desiccate before use. 15. Precautions
12.5 Fill the syringe to the desired level with sample and 15.1 It is important to keep the cell sealed to prevent
draw back the plunger so that no sample remains in the needle. introduction of excess atmospheric moisture that will decrease
reagent life.
TABLE 1 Recommended Sample Amount for Coulometric
15.2 The total amount of solution in the titration cell can
Titration affect the KF reaction. Typically, the total volume of sample
Water Content, ppm Sample Weight, g
liquids that are added to the cell should not exceed 100 % of
the original solvent in the cell. If the reagents become too
1000 0.5
500 0.5 dilute the stoichiometry and rate of the Karl Fischer reaction
100 1.0 can be adversely affected.
50 2.0 15.3 All solvents and reagents should be protected from
10 5.0
1 10 atmospheric moisture. Drying tubes containing molecular
sieves should be used on all storage containers.

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 D 3401
15.4 Good stirring action in the titration cell is needed to 17.8 Cover the syringe needle with a silicone rubber block
mix the solution very rapidly during the titration in order for or piece of silicone rubber septa to further prevent evaporation
the electrode to determine the correct end point. or spillage during the weighing process.
15.5 Follow the recommended maintenance procedures of 17.9 Transfer the filled syringe to an analytical balance and
the instrument manufacturer. weigh the syringe and contents to the nearest 0.01 g.
17.10 Remove the silicone block and insert the needle into
16. Standardization of Titrant the titration cell septum. Inject the sample slowly, taking care
16.1 Since the exact water equivalence of a titrant must be not to touch the needle to the surface of the anode solution.
known for accurate moisture determinations, its titer should be While the syringe is still inside the cell, draw any sample that
checked on a regular basis. remains in the syringe needle back into the barrel and remove
16.2 Non-methanol-based titrants are more stable than their the needle from the cell.
methanol-based counterparts and are therefore recommended 17.11 Place the silicone block back onto the tip of the needle
for the determination of low moisture contents typically and reweigh the empty syringe. The weight difference between
encountered in halogenated solvents. the first and second weighings will be the amount of sample
16.3 To determine the titer, use a 5-µL syringe to inject injected into the titration cell.
exactly 3.0 µL of water into the titration cell containing solvent 17.12 The make and model of the titrator being used will
that has been pre-titrated to remove residual moisture. When determine the actual steps performed to carry out the titration
the titration is complete, perform the following calculation: process. In most cases, all that is required is pressing a start
3.0 mg H2O/mL of titrant consumed titration or run key on the instrument keyboard either just prior
to or just after the sample injection.
5 mg/mL H2O equivalent of titrant (3) 17.13 Once the titration is complete, the amount of water
16.4 Alternatively, standard solutions of either methanol or (µg or mg) that was found in the solvent will appear on the
non-hydroscopic solvents that have known amounts of water instruments digital display. Most instruments will also calcu-
added to them are available from reagent suppliers for titer late concentrations (ppm or %) if the sample weight is keyed
standardization. into the instrument’s control panel.

17. Procedure 18. Calculation

17.1 Set up the volumetric titrator according to the manu- 18.1 Calculate the water content of the solvent as follows:
facturer’s instructions. ppm H2O 5 µg H2O found/grams of solvent injected (4)
17.2 Fill the cleaned and dry titration cell with an appropri-
ate amount of solvent. The minimum amount required will be
6
enough to cover the electrode ends and the titrant buret tip. 19. Precision and Bias
17.3 Select a stirring speed that is sufficient to create a 19.1 Precision of Test Method A, Coulometric:
well-defined vortex with the solvent. 19.1.1 At levels of water below 200 ppm the coulometric
17.4 Pre-titrate the solvent so that all the moisture has been test method can be expected to have a precision (one standard
removed prior to introduction of the sample. deviation) of less than 2 ppm. For levels near 1000 ppm water,
17.5 The amount of halogenated solvent injected into the the precision is about 15 ppm.
cell depends on the quantity of water in the solvent. Table 2 19.2 Precision of Test Method B, Volumetric:
lists recommended sample sizes for anticipated water concen- 19.2.1 At levels of water below 200 ppm the volumetric test
trations and various titrant concentrations. method can be expected to have a precision (one standard
NOTE 2—In most cases, a titrant with a capacity of 1 or 2 mg H2O/mL deviation) of 3 ppm or less. For levels near 1000 ppm water,
will be most appropriate for determining water content in halogenated the precision is about 10 ppm.
solvents. 19.3 Bias—The bias of these test methods cannot be deter-
17.6 Thoroughly clean and dry the sampling syringe. One mined due to the lack of stable standards of water in the
method is to dry in an oven and desiccate before use. solvents. The solvents readily pick up moisture making it
17.7 Fill the syringe to the desired level with sample and nearly impossible to maintain a consistent standard.
draw back the plunger so that no sample remains in the needle.
20. Keywords
TABLE 2 Recommended Sample Amount for Volumetric Titration 20.1 coulometric Karl Fischer titration; halogenated organic
Water Content, 5 mg H2O/mL 2 mg H2O/mL 1 mg H2O/mL
solvents; Karl Fischer test method—water content; moisture
ppm Titrant, g Titrant, g Titrant, g content; solvents; volumetric Karl Fischer titration; water
1000 2.5 to 10 1 to 10 0.5 to 5 content
500 5 to 20 2 to 20 1 to 10
100 20 10 to 20 5 to 20
50 ... 20 10 to 20
6
10 ... 20 or more 20 or more Research reports are available from ASTM Headquarters. Request RR:D26-
1004 and RR:D26-1009.

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 D 3401
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