Astm D1364
Astm D1364
Astm D1364
This standard has been approved for use by agencies of the Department of Defense.
1
D 1364 – 02
5. Significance and Use electrodes and capable of indicating a current flow of 10 to 20
5.1 Volatile solvents are used in a variety of chemical µA by means of a galvanometer or radiotuning eye circuit.5
processes which may be affected by water. Therefore, this test 6.4 Buret Assembly for Karl Fischer reagent, consisting of a
method provides a test procedure for assessing compliance 25 or 50-mL buret connected by means of glass (not rubber)
with a specification. connectors to a source of reagent; several types of automatic
dispensing burets6 may be used. Since the reagent loses
6. Apparatus strength when exposed to moist air, all vents must be protected
6.1 Titration Vessel—For color end point titrations, use a against atmospheric moisture by adequate drying tubes con-
100 or 250-mL volumetric flask, which need not be calibrated; taining indicating calcium sulfate drying agent. All stopcocks
a 250-mL flask fitted with interchangeable electrodes (Fig. 1)4 and joints should be lubricated with a lubricant not particularly
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 on Analytical Reagents of the American Chemical Society,
where such specifications are available.7 Other grades may be
used, provided it is first ascertained that the reagent is of
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 H2O per
mL)8—For each liter of solution, dissolve 133 6 1 g of I2 in
4256 2 mL of anhydrous (less than 0.1 % H2O) pyridine in a
dry glass-stoppered bottle. Add 425 6 2 mL of anhydrous (less
than 0.1 % H2O) 2-methoxyethanol. Cool to below 4°C in an
ice bath and add gaseous SO2, dried by bubbling through
concentrated H2SO4(sp gr 1.84); determine the amount of SO2
added by measuring the change in weight of the SO2 cylinder
(102 6 1 g) or the increase in volume (70 6 1 mL) of the
reagent mixture. Alternatively, add 70 mL of freshly drawn
NOTE 1—All dimensions in millimetres. liquid SO2 in small increments.
FIG. 1 Titration Flask Assembly 7.1.2 Solvent Mixture—Mix 1 volume of anhydrous (less
than 0.1 % H2O) pyridine with 4 volumes of anhydrous (less
than 0.1 % H2O) ethylene glycol.
may also be used for the instrumental end point and is
particularly suitable for titrations at ice temperatures. For NOTE 3—Pyridine, ethylene glycol, and 2-methoxyethanol, each con-
permanently mounted assemblies, the vessel should have a taining less than 0.1 % water, are available and should be used.
capacity about equal to that of a 300-mL tall-form beaker; and
be provided with a tight-fitting closure to protect the sample 5
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
Headquarters. Your comments will receive careful consideration at a meeting of the
mixture. It is desirable to have a means for cooling the titration responsible technical committee,1 which you may attend.
vessel to ice temperature. 6
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 glass Apparatus 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,1 which you may attend. These
will cover them. specifically designed burets present the minimum contact of reagent with stopcock
6.3 Instrument Depolarization Indicator, having an internal lubricant.
7
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.
4 8
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 free adaptations are available and may be used if precision can be established. If you
aware of alternative suppliers, please provide this information to ASTM Interna- are aware of alternative suppliers, please provide this information to ASTM
tional Headquarters. Your comments will receive careful consideration at a meeting International Headquarters. Your comments will receive careful consideration at a
of the responsible technical committee,1 which you may attend. meeting of the responsible technical committee,1 which you may attend.
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D 1364 – 02
NOTE 4—If adequately dry reagents cannot be procured, they can each TABLE 1 Recommended Specimen Sizes
be dried by distillation through a multiple-plate column, discarding the Water Manner Specimen
first 5 % of material distilling overhead and using the 95 % remaining. Specimen Size
Content, % Taken
Drying may also be accomplished by the addition of 1 volume of toluene 2.5 to 10 weight containing 0.15 to weighing pipet
or cyclohexane to 19 volumes of the pyridine-glycol, or of the pyridine 0.18 g of H2O
ethylene glycol monomethyl ether mixture, followed by distillation; the 0.5 to 2.5 10 mL calibrated volumetric pipet
first 5 % distilled is discarded and the residual 95 % is used. Below 0.5 25 mL same as for 0.5 to 2.5
8. Sampling
8.1 Hygroscopic Solvents, including for example, ketones, required, cool the reaction mixture in ice water during the addition of Karl
acetates, alcohols, and glycol ethers, absorb ambient moisture. Fischer reagent.
It is essential to avoid changes in the water content of these (b) Organic Acids—Cool the reaction mixture in ice water prior to the
materials during sampling operations. Errors from this source addition of Karl Fischer reagent.
are particularly significant in the analysis of materials having NOTE 6—When using the volumetric flask type titration vessel in humid
low water content. When analyzing materials that absorb climates, place a piece of thin sheet rubber over the mouth of the vessel;
provide a small hole for introducing the buret tip. In less humid climates
ambient water readily, limit as much as possible contact with it is sufficient to lower the tip of the buret deeply into the long neck of the
air in transferring the specimen into the titration vessel. Avoid titration flask.
intermediate sample containers, if possible. NOTE 7—In titrating with the volumetric flask type titration vessel,
avoid wetting the stopper and upper end of the flask with either the reagent
9. Standardization of Reagent or the sample solvent. Each time the titration is interrupted, touch the buret
9.1 Standardize the Karl Fischer reagent each day used by tip to the neck of the flask to remove droplets which, if not removed,
either the color or instrument end point (Section 3) method would absorb moisture from the atmosphere. When the flask is removed
using the same procedure as used for titrating the sample. from under the buret tip, wipe the tip with a clean dry cloth in a downward
motion.
9.1.1 Add to each flask 25 mL of ethylene glycol-pyridene
mixture, and titrate this as described in Section 10. Add to the 11. Calculation
solvent thus titrated, in place of the sample, 0.15 to 0.18 g of
11.1 Calculate the water content of the specimen as follows:
water from a weighing bottle or weighing pipet, weighed to the
nearest 0.1 mg. Complete titration with Karl Fischer reagent as Water, %, by weight 5 ~V 3 W!/~10 3 S! (3)
described in Section 10. where:
9.1.2 Calculate the equivalency factor, W, of the reagent in V = volume of Karl Fischer reagent required for titrating
terms of water content per millilitre by means of the following by the specimen, mL,
equation: W = equivalency factor for Karl Fischer reagent, water per
W 5 A/V (2) millilitre of reagent, mg, and
S = specimen weight used, g.
where:
W = equivalency factor, mg of water per mL, NOTE 8—If specimen was added volumetrically by means of a cali-
A = weight of water used in the standardization, mg, and brated volumetric pipet, then S = volume of specimen 3 density of
V = volume of Karl Fischer reagent required, mL. specimen, g.
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D 1364 – 02
13.1.2 Reproducibility—Two results, each the mean of du- 13.2.1 Repeatability—Two results, each the mean of dupli-
plicate determinations, obtained by operator in different labo- cate determinations, obtained by the same analyst should be
ratories should be considered suspect if they differ by more considered suspect if they differ by more than 0.030 = x̄ %
than 0.027 % absolute. absolute, where x̄ is the average of two determininations.
13.2 Precision for Water 0.010 to 0.100 % by Weight9—In 13.2.2 Reproducibility—Two results, each the mean of du-
another interlaboratory study, one operator in each of seven plicate determinations, obtained by analysts in different labo-
different laboratories, on two different days, made duplicate
ratories should be considered suspect if they differ by more
determinations on five randomly coded samples of hexyl
than 0.060 = x̄ % absolute, where x̄ is the average of two
acetate containing 0.015, 0.034, 0.052, 0.071, and 0.098 %
water. One of the seven laboratories used three different determinations.
equipment or procedural variations, or both, thereby making 13.3 Bias—Bias cannot be determined for this test method
this, in effect, a nine interlaboratory study. The statistically because there is no available material having an accepted
designed study covered a variety of equipment, analytical reference value. Refer to 8.1 and Note 5, Note 6, and Note 7 for
methods, and reagents using the Karl Fischer chemistry. factors that might influence test bias.
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14. Keywords
Supporting data is available from ASTM International Headquarters. Request
RR: D01–1049. 14.1 Karl Fisher method; solvents; water content
SUMMARY OF CHANGES
Committee D01.35 has identified the location of selected changes to this standard since the last issue
(D 1364 - 95 (1999)) that may impact the use of this standard.
(1) Added reference to Practice E 29 in Section 1.3 of the (2) Added Practice E 29 to Referenced Documents section.
Scope.
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