ASTM D1364-02(2007)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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: D1364 − 02 (Reapproved 2007)
StandardTest Method for
Water in Volatile Solvents (Karl Fischer Reagent Titration
Method)
This standard is issued under the fixed designation D1364; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber 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 Department of Defense.
1. Scope* 3. Terminology
1.1 This test method covers the determination of water in
3.1 Definitions of Terms Specific to This Standard:
volatile solvents and chemical intermediates used in paint,
3.1.1 instrumental end point, n—that point in the titration
varnish, lacquer, and related products.
whentwosmallplatinumelectrodes,uponwhichapotentialof
20 to 50 mV has been impressed, are depolarized by the
1.2 This test method is not applicable in the presence of
addition of 0.05 mLof Karl Fischer reagent (6 mg of H O per
mercaptans, peroxides, or appreciable quantities of aldehydes
mL), causing a change of current flow of 10 to 20 µA that
or amines.
persists for at least 30 s.
1.3 For purposes of determining conformance of an ob-
served or a calculated value using this test method to relevant
NOTE1—Thisendpointissometimesincorrectlycalledthe“deadstop”
specifications, test result(s) shall be rounded off “to the nearest which is the reverse of the above.
unit” in the last right-hand digit used in expressing the
3.1.2 color end point, n—During the titration, the solution
specificationlimit,inaccordancewiththerounding-offmethod
first turns yellow, then later deepens towards the end of the
of Practice E29.
titration; the end point is indicated by the change from yellow
1.4 The values stated in SI units are to be regarded as to orange-red which is quite sharp and easily repeated. The
orange-red color must persist for at least 30 s in order to
standard. No other units of measurement are included in this
standard. indicate an end point.
1.5 This standard does not purport to address all of the
NOTE 2—View the color by transmitted daylight or by transmitted light
safety concerns, if any, associated with its use. It is the
from an artificial daylight lamp, such as the one that complies with the
responsibility of the user of this standard to establish appro- specifications given in Test Method D1500.
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. 4. Summary of Test Method
1.6 For hazard information and guidance, see the supplier’s
4.1 This test method is based essentially upon the reduction
Material Safety Data sheet.
of iodine by sulfur dioxide in the presence of water. This
reaction can be used quantitatively only when pyridine and an
2. Referenced Documents
alcohol are present to react with the sulfur trioxide and
2.1 ASTM Standards:
hydriodic acid produced according to the following reactions:
D1500Test Method forASTM Color of Petroleum Products
H O1I 1SO 13C H N→2C H N·HI1C H N·SO (1)
2 2 2 5 5 5 5 5 5 3
(ASTM Color Scale)
E29Practice for Using Significant Digits in Test Data to
C H N·SO 1ROH→C H N·HSO R
5 5 3 5 5 4
Determine Conformance with Specifications
4.2 To determine water, Karl Fischer reagent (a solution of
iodine, pyridine, and sulfur dioxide, in the molar ratio of
This test method is under the jurisdiction of ASTM Committee D01 on Paint
1+10+3) dissolved in anhydrous 2-methoxyethanol is added
and Related Coatings, Materials, andApplications and is the direct responsibility of
to a solution of the sample in anhydrous pyridine-ethylene
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates.
glycol (1+4) until all water present has been consumed. This
Current edition approved June 1, 2007. Published June 2007. Originally
is evidenced by the persistence of the orange-red end-point
approved in 1955. Last previous edition approved in 2002 as D1364–02. DOI:
10.1520/D1364-02R07.
color; or alternatively by an indication on a galvanometer or
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
similarcurrent-indicatingdevicewhichrecordsthedepolariza-
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
tion of a pair of noble-metal electrodes. The reagent is
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. standardized by titration of water.
*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
D1364 − 02 (Reapproved 2007)
electrodes and capable of indicating a current flow of 10 to 20
µA by means of a galvanometer or radiotuning eye circuit.
6.4 Buret Assembly for Karl Fischer reagent, consisting of a
25 or 50-mL buret connected by means of glass (not rubber)
connectors to a source of reagent; several types of automatic
dispensing burets may be used. Since the reagent loses
strengthwhenexposedtomoistair,allventsmustbeprotected
against atmospheric moisture by adequate drying tubes con-
taining indicating calcium sulfate drying agent. All stopcocks
andjointsshouldbelubricatedwithalubricantnotparticularly
reactive with the reagent.
6.5 Weighing Bottle, of the Lunge or Grethen Type, or
equivalent.
7. Reagents
7.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
all reagents shall conform to the specifications of the Commit-
tee onAnalytical Reagents of theAmerican Chemical Society,
where such specifications are available. Other grades may be
NOTE 1—All dimensions in millimetres.
used, provided it is first ascertained that the reagent is of
FIG. 1 Titration Flask Assembly
sufficiently high purity to permit its use without decreasing the
accuracy of the determination.
7.1.1 Karl Fischer Reagent (equivalent to 6 mg of H O per
5. Significance and Use
mL) —For each liter of solution, dissolve 133 61gofI in
4256 2 mL of anhydrous (less than 0.1% H O) pyridine in a
5.1 Volatile solvents are used in a variety of chemical
dryglass-stopperedbottle.Add425 62mLofanhydrous(less
processes which may be affected by water. Therefore, this test
than 0.1% H O) 2-methoxyethanol. Cool to below 4°C in an
method provides a test procedure for assessing compliance
ice bath and add gaseous SO , dried by bubbling through
with a specification. 2
concentratedH SO (spgr1.84);determinetheamountofSO
2 4 2
added by measuring the change in weight of the SO cylinder
6. Apparatus 2
(102 6 1 g) or the increase in volume (70 6 1 mL) of the
6.1 Titration Vessel—For color end point titrations, use a
reagent mixture. Alternatively, add 70 mL of freshly drawn
100 or 250-mLvolumetric flask, which need not be calibrated;
liquid SO in small increments.
3 2
a 250-mLflask fitted with interchangeable electrodes (Fig. 1)
7.1.2 Solvent Mixture—Mix 1 volume of anhydrous (less
may also be used for the instrumental end point and is
than 0.1% H O) pyridine with 4 volumes of anhydrous (less
particularly suitable for titrations at ice temperatures. For
than 0.1% H O) ethylene glycol.
permanently mounted assemblies, the vessel should have a
capacity about equal to that of a 300-mLtall-form beaker; and
be provided with a tight-fitting closure to protect the sample
The sole source of supply of instrument depolarization indicator known to the
and reagent from atmospheric moisture, a stirrer, and a means
committee at this time is Fisher Scientific Co. (need address). If you are aware of
of adding sample and reagents and removing spent reaction
alternative suppliers, please provide this information to ASTM International
mixture.Itisdesirabletohaveameansforcoolingthetitration
Headquarters.Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend.
vessel to ice temperature.
The sole source of supply of automatic dispensing burets, No. J-821, known to
6.2 Instrument Electrodes—Platinum with a surface equiva-
the committee at this time is Scientifice glassApparatus Co., Bloomfield NJ. If you
are aware of alternative suppliers, please provide this information to ASTM
lent to two No. 26 wires 5 mm long. The wires should be 3 to
International Headquarters. Your comments will receive careful consideration at a
8 mm apart and so inserted in the vessel that 25 mL of liquid
meeting of the responsible technical committee, which you may attend. These
will cover them.
specifically designed burets present the minimum contact of reagent with stopcock
lubricant.
6.3 Instrument Depolarization Indicator, having an internal
Reagent Chemicals, American Chemical Society Specifications, American
resistance of less than 5000 V and consisting of a means of
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
impressing and showing a voltage of 20 to 50 mV across the
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.
3 7
The sole source of supply of flasks known to the committee at this time is the Karl Fischer Reagent is available from various laboratory suppliers. Pyridine-
Rankin Glass Blowing Co., 3920 Franklin Canyon Road, Martinez, CA. If you are freeadaptationsareavailableandmaybeusedifprecisioncanbeestablished.Ifyo
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