ASTM D3401-97(2017)

Standard Test Methods for Water in Halogenated Organic Solvents and Their Admixtures

SIGNIFICANCE AND USE
4.1 High water concentrations can have a detrimental effect on many uses of halogenated solvents.  
4.1.1 Water can cause corrosion and spotting when solvents are used for metal cleaning.  
4.1.2 Water can reduce the shelf life of aerosol formulations.  
4.1.3 Water can inhibit desired reactions when solvents are used in formulations.
SCOPE
1.1 These test methods describe the use of the Karl Fischer (KF) titration for determination of water in halogenated organic solvents and mixtures thereof. Water concentrations from 2 to 1000 ppm can be determined in these solvents. Two test methods are covered as follows:  
1.1.1 Test Method A, Water Determination Using a Coulometric KF Titrator—The coulometric test method is known for its high degree of sensitivity (typically 2O) and should be the test method of choice if water concentrations are typically below 50 ppm or if only small amounts of sample are available for water determinations. This test method requires the use of equipment specifically designed for coulometric titrations.  
1.1.2 Test Method B, Water Determination Using a Volumetric KF Titrator—The volumetric test method is a more traditional approach to KF water determinations. Although titrators are specifically designed for KF volumetric determinations, many automatic titrators on the market can be adapted to perform KF titrations.  
1.2 Either of these test methods can be used to determine typical water concentrations (15 to 500 ppm) found in halogenated solvents.  
1.3 These test methods recommend the use of commercially available Karl Fischer titrators and reagents.  
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use. For specific precautionary statements, see Sections 11 and 15.  
1.5 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.

General Information

• Status: Historical
• Publication Date: 31-Oct-2017
• ICS: 71.080.20 - Halogenated hydrocarbons
• Technical Committee: D26 - Halogenated Organic Solvents and Fire Extinguishing Agents
• Drafting Committee: D26.04 - Test Methods

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D3401 − 97 (Reapproved 2017)
Standard Test Methods for
Water in Halogenated Organic Solvents and Their
1
Admixtures
This standard is issued under the fixed designation D3401; 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 Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
1.1 These test methods describe the use of the Karl Fischer
Barriers to Trade (TBT) Committee.
(KF) titration for determination of water in halogenated or-
ganicsolventsandmixturesthereof.Waterconcentrationsfrom
2. Referenced Documents
2 to 1000 ppm can be determined in these solvents. Two test
2
2.1 ASTM Standard:
methods are covered as follows:
E203 Test Method for Water Using Volumetric Karl Fischer
1.1.1 Test Method A, Water Determination Using a Coulo-
Titration
metric KF Titrator—The coulometric test method is known for
its high degree of sensitivity (typically < 10 µg H O) and
2
3. Summary of Test Method
should be the test method of choice if water concentrations are
typically below 50 ppm or if only small amounts of sample are 3.1 In the Karl Fischer reaction, water will react with iodine
available for water determinations. This test method requires in the presence of sulfur dioxide, alcohol, and an organic base
the use of equipment specifically designed for coulometric according to the following equation:
titrations.
H O1I 1SO 1CH OH13RN→ RNH SO CH 12 RNH I (1)
~ ! ~ !
2 2 2 3 4 3
1.1.2 TestMethodB,WaterDeterminationUsingaVolumet-
where RN = organic base.
ric KF Titrator—The volumetric test method is a more tradi-
tional approach to KF water determinations.Although titrators
3.2 When the volumetric titration test method is used for
are specifically designed for KF volumetric determinations,
this determination, the halogenated sample is added to a KF
many automatic titrators on the market can be adapted to
solvent that usually consists of sulfur dioxide and an amine
perform KF titrations.
dissolved in anhydrous methanol. This solution is titrated with
1.2 Either of these test methods can be used to determine an anhydrous solvent containing iodine. The iodine titrant is
first standardized by titrating a known amount of water.
typical water concentrations (15 to 500 ppm) found in haloge-
nated solvents.
3.3 In the coulometric titration test method, the sample is
injected into an electrolytic cell where the iodine required for
1.3 These test methods recommend the use of commercially
the reaction with water is produced by anodic oxidation of
available Karl Fischer titrators and reagents.
iodide. With this technique, no standardization of reagents is
1.4 This standard does not purport to address all of the
required.
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 3.4 In both test methods, the end point is determined
priate safety, health, and environmental practices and deter- amperometrically with a platinum electrode that senses a sharp
mine the applicability of regulatory limitations prior to use. change in cell resistance when the iodine has reacted with all
For specific precautionary statements, see Sections 11 and 15. of the water in the sample.
1.5 This international standard was developed in accor-
4. Significance and Use
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
4.1 High water concentrations can have a detrimental effect
on many uses of halogenated solvents.
1
These test methods are under the jurisdiction of ASTM Committee D26 on
Halogenated Organic Solvents and Fire Extinguishing Agents and are the direct
2
responsibility of Subcommittee D26.04 on Test Methods. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Nov. 1, 2017. Published December 2017. Originally contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
approved in 1975. Last previous edition approved in 2012 as D3401 – 97(2012). Standards volume information, refer to the standard’s Document Summary page on
DOI: 10.1520/D3401-97R17. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1

---------------------- Page: 1 ----------------------
D3401 − 97 (2017)
NOTE 1—Pyridine was the organic amine that was traditionally used in
4.1.1 Water can cause corrosion and spotting when solvents
Karl F
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D3401 − 97 (Reapproved 2012) D3401 − 97 (Reapproved 2017)
Standard Test Methods for
Water in Halogenated Organic Solvents and Their
1
Admixtures
This standard is issued under the fixed designation D3401; 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
1.1 These test methods describe the use of the Karl Fischer (KF) titration for determination of water in halogenated organic
solvents and mixtures thereof. Water concentrations from 2 to 1000 ppm can be determined in these solvents. Two test methods
are covered as follows:
1.1.1 Test Method A, Water Determination Using a Coulometric KF Titrator—The coulometric test method is known for its high
degree of sensitivity (typically < 10 μg H O) and should be the test method of choice if water concentrations are typically below
2
50 ppm or if only small amounts of sample are available for water determinations. This test method requires the use of equipment
specifically designed for coulometric titrations.
1.1.2 Test Method B, Water Determination Using a Volumetric KF Titrator—The volumetric test method is a more traditional
approach to KF water determinations. Although titrators are specifically designed for KF volumetric determinations, many
automatic titrators on the market can be adapted to perform KF titrations.
1.2 Either of these test methods can be used to determine typical water concentrations (15 to 500 ppm) found in halogenated
solvents.
1.3 These test methods recommend the use of commercially available Karl Fischer titrators and reagents.
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use. For specific precautionary statements, see Sections 11 and 15.
1.5 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.
2. Referenced Documents
2
2.1 ASTM Standards:Standard:
E203 Test Method for Water Using Volumetric Karl Fischer Titration
3. Summary of Test Methods Method
3.1 In the Karl Fischer reaction, water will react with iodine in the presence of sulfur dioxide, alcohol, and an organic base
according to the following equation:
H O1I 1SO 1CH OH13RN→ RNH SO CH 12 RNH I (1)
~ ! ~ !
2 2 2 3 4 3
where RN = organic base.
3.2 When the volumetric titration test method is used for this determination, the halogenated sample is added to a KF solvent
that usually consists of sulfur dioxide and an amine dissolved in anhydrous methanol. This solution is titrated with an anhydrous
solvent containing iodine. The iodine titrant is first standardized by titrating a known amount of water.
1
These test methods are under the jurisdiction of ASTM Committee D26 on Halogenated Organic Solvents and Fire Extinguishing Agents and are the direct responsibility
of Subcommittee D26.04 on Test Methods.
Current edition approved March 1, 2012Nov. 1, 2017. Published June 2012December 2017. Originally approved in 1975. Last previous edition approved in 20062012 as
D3401 – 97(2006).(2012). DOI: 10.1520/D3401-97R12. 10.1520/D3401-97R17.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1

---------------------- Page: 1 ----------------------
D3401 − 97 (2017)
3.3 In the coulometric titration test method, the sample is injected into an electrolytic cell where the iodine required for the
reaction with water is produced by anodic oxidation of iodide. With this technique, no standardization of reagents is required.
3.4 In both test methods, the end point is determined amperometrically with
...