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E 203-08 Karlfisher
E 203-08 Karlfisher
E 203-08 Karlfisher
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This test method is under the jurisdiction of ASTM Committee E15 on For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Industrial and Specialty Chemicals and is the direct responsibility of Subcommittee contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
E15.01 on General Standards. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved Oct. 1, 2008. Published November 2008. Originally the ASTM website.
3
approved in 1962 as E 203 – 62 T. Last previous edition approved in 2001 as Withdrawn. The last approved version of this historical standard is referenced
E 203 – 01. on www.astm.org.
reaction time. Rapid end point determination also can provide more
8.1.2 Molecular Sieves—Solvents other than methanol may accurate measurement of trace water concentrations. Two component
be dried to a moisture content of 0.05 % by passing upward reagents, however, are more susceptible to side reaction from noncom-
through a molecular sieve13 column, using 1 part molecular plexed sulfur dioxide than single component systems (5).
NOTE 15—The range of water indicated is for macro titrations. Con-
sieve per 10 parts of solvent. siderably smaller amounts of water can be determined precisely on a
micro scale. For example, less than 300 µg of water were titrated in 1-mL
samples of benzene by a micro amperometric technique (6).
11
Fisher Scientific Co., Catalog No. SW2 and Hartman-Leddon Co., Catalog No. 10.3 Calculation—Calculate the water content of the
1849 have been found satisfactory for this purpose.
12
sample as follows:
Other acceptable grades are Mallinckrodt Catalog No. 3017, max 0.02 %
water, or Fisher Scientific Co., Catalog No. A412, max 0.1 % water. ~A 2 B! 3 F 3 0.001 3 100
13
Linde Type 4A Molecular Sieve has been found satisfactory for this purpose.
water, weight % 5 W (2)
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ethyl ketone containing 0.05 % and 0.17 % water. averages is 0.014 % absolute.
14.3.1 Repeatability (Single Analyst)—The 95 % for the 14.4.3 Reproducibility (Multilaboratory)—The standard de-
difference between two runs is 0.008 %. viation of results (each the average of duplicates), obtained by
14.3.2 Laboratory Precision (Within-Laboratory, Between- analysts in different laboratories has been estimated to be
Days, Variability)—The 95 % limit for the difference between 0.0277 % absolute at 8 df. The 95 % limit for the difference
two averages of duplicates by the same analyst obtained on between two such averages 0.078 % absolute.
different days is 0.015 %. NOTE 19—The above precision estimates are based on an interlabora-
14.3.3 Reproducibility (Multiple Laboratory)—The 95 % tory study of analyses performed in 1994 on a sample of n-butyl acetate
limit for the difference between two results (each the average containing approximately 0.096 % water and a sample of methyl amyl
of duplicates) obtained by analysts in different laboratories is ketone containing approximately 0.066 % water. One analyst in each of 12
0.027 % absolute. laboratories performed duplicate determinations on the n-butyl acetate
sample and repeated one day later, for a total of 48 determinations. The
NOTE 18—The interlaboratory study was carried out by ASTM Com- methyl amyl ketone sample was analyzed in a similar manner except 11
mittee D01 on Paint, Varnish, Lacquer, and Related Products, Subcom- laboratories participated for a total of 44 determinations.14 The analysts
mittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. were not restricted to any particular instrumentation, titrant, or solvent
Seven laboratories participated, with a single analyst performing duplicate system. Practice E 180 was used in developing these precision estimates.
determinations on each of two days, using two methods on the four
samples described above. Test Method D 1364 was the subject of the test 14.5 Bias—Because of the wide scope of this test method
program being compared with each laboratory’s own version of a KF and varying degrees of interferences, it is impractical to
method. As neither the means nor the variances of the two sets of data estimate the bias of this test method.
proved significantly different, all of the results were pooled to give
estimates of the repeatability based on 55 df and reproducibility based on 15. Keywords
47 df. Practice E 180 was used to develop the precision estimates. 15.1 free water; Karl Fischer reagent; pyridine-free; volu-
14.4 The following is an example of the precision attained metric; water; water of hydration
in an interlaboratory study for determining water with
pyridine-free reagents on one sample each of n-butyl acetate 14
Details of the interlaboratory study are available from ASTM Headquarters.
and methyl amyl ketone (see Note 19). Request RR:E15-1043.
APPENDIXES
(Nonmandatory Information)
X1.1 Scope—Described in this Appendix is a manual tube.15 Select the size buret and bottle needed. An overhead
procedure for the KF method using a visual means of detecting reservoir16 with micro buret may also be used.
the titration end point. X1.2.1.2 Tube, Drying, calcium chloride, one bulb, 200 mm
long.
X1.2 Titration Assembly:
X1.2.1.3 Bottle, Aspirator, with outlet for tubing connec-
X1.2.1 The storage and dispensing assembly shall consist of
tions, 500-mL capacity.
the following parts (see Fig. X1.1):
X1.2.1.1 Buret, automatic, with TFE-fluorocarbon resin
plug and automatic zero, reservoir bottle, and connecting
15
Kimble Glass Co., Catalog No. 17124F has been found satisfactory for this
purpose.
16
Kimble Glass Co., Catalog No. 17138F has been found satisfactory for this
purpose.
X1.3 Assembly of Apparatus: X1.8 Procedure for Soluble Materials, Either Liquid or
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X2. INTERFERING COMPOUNDS THAT REACT STOICHIOMETRICALLY WITH KF REAGENT, THEREBY ENABLING
FREE WATER TO BE CALCULATED AFTER APPLYING CORRECTION
X2.1 Many interfering substances react stoichiometrically TABLE X2.1 Materials Reacting Stoichiometrically With KF
with constituents of the KF reagent. Consequently, when Reagent
independent analyses can be made for these compounds, Moles of
Apparent H2O
suitable corrections can be applied to the apparent water Class or Compound Do Not React
per Mole
results. Also in many cases moisture can be separated from the Compound
interfering substance by extraction with a water-miscible liquid Ascorbic acid 1
Hydrazine derivatives 1 hydrazine sulfate
in which the sample is insoluble or by distillation, preferably Mercaptans 0.5
using a carrier that forms a homogeneous azeotrope, for Silanols, R3SiOH 1
example, dioxane, ethanol-benzene. Materials in this class are R2Si(OH)2 2
Arsenate, RAsO4 3
given in Table X2.1. Arsenite, RAsO2 2
Boric acid, H3BO3 3
HBO2 2
X2.2 Some compounds react only partially with KF reagent Boric oxide, B2O3 3
when titrated under normal conditions. These include the Bicarbonates 1
following:20,21 Carbonates 1 calcium carbonate
19
Cupric salts 0.5
Methylolurea Dichromates Ferric salts 0.5 ferric fluoride
Peroxides, diacyl20 Iron oxide Metal hydroxides, MOH 1
Peracids20 Nickel oxide M(OH)2 2
Quinone Sodium peroxide Metal oxides, CaO, MgO, ZnO, 1 aluminum, cupric,
Arsenious oxide Sodium sulfide Ag2O, HgO, Cu2O, MnO2, barium oxides
Chromates PbOA, PbO2A
Pb3O4 3
Pyrosulfites 1 pyrosulfate
Sodium nitriteB 0.5
Sulfites 1 hyposulfite
Stannous salts 1
Tetraborate 7
Thiosulfate 0.5
A
The lead oxides react only partially when dispersed in methanol, probably
20
Interference of methylolurea can be eliminated by titration at − 40°C (2). because of insolubility. In acetic acid solution, however, these oxides react
21
Diacyl peroxides and peracids fairly rapidly oxidize the HL of spent KF quantitatively.
B
reagent. After a short time interval following addition of KF reagent, this reaction Reaction is fairly slow. Apparently free water can be determined in presence of
may be quantitative (2). NaNO2 by rapid titration with KF reagent.
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X4.1 Procedures for determining moisture in gases are X4.3 The manufacturers of gases have developed very
described in the literature (2, 9, 10, 11, 12). precise KF procedures for measuring moisture down to a few
milligrams per kilograms (11, 12). They should be consulted
X4.2 As mentioned in Section 1, this test method does not when need arises. Also, there are available commercial instru-
include procedures for samples that are gaseous at room
ments that operate on the dew point, infrared, conductance,
temperature. The safe handling and analysis of gases require a
electrolysis principle, etc., which are rapid and accurate for
thorough knowledge of their properties and also the use or
determining moisture in gas samples (2, 10).
special apparatus and techniques. The moisture content may
range from 1000 down to 2 to 3 mg/kg.
REFERENCES
(1) Riedel-deHaen, “Hydranal—Water Reagent According to Eugen (7) Beasley, T. H., Ziegler, H. W., Charles, R. L., and King, P., “Critical
Scholz for Karl Fischer Titration,” 3rd Ed., p. 30, available from Evaluation of the Karl Fischer Water Method,” Analytical Chemistry,
Cresent Chemical Co., Inc., 1324 Motor Parkway, Hauppauge, NY, ANCHA, Vol 44, 1972, p. 1833.
11788. (8) Gard, L. N., and Butler, R. C., “Determination of Moisture in Sodium
(2) Mitchell, J., Jr., and Smith, D. M., “Aquametry, a Treatise on Methods Bicarbonate—Karl Fischer Method,” Analytical Chemistry, ANCHA,
for the Determination of Water,” Part III, The Karl Fischer Reagent, Vol 26, 1954, p. 1367.
2nd Ed., J. Wiley and Sons, Inc., New York, NY, 1980. (9) Jones, A. G., “A Review of Some Developments in the Use of the Karl
(3) Laurene, A. H., “Determination of Water by Karl Fischer Titration in Fischer Reagent,” Analyst, Vol 76, 1951, p. 5.
the Presence of Ferric Salts,” Analytical Chemistry, ANCHA, Vol 24,
1952, p. 1496. (10) Mitchell, J., Jr., “Treatise on Analytical Chemistry,” Part II, Vol 1,
(4) Brickell, W. F., “Determination of Water Vapor in Natural Gas by Interscience Publishers, Inc., 1961, p. 69.
Direct Chemical Method,” Petroleum Engineer, PENGA, Vol 24, (11) Morton, J. D., and Fuchs, L. K., “Determination of Moisture in
1952, p. 58. Fluorocarbons,” presented at a meeting of the American Society of
(5) MacLeod, S. K., “Moisture Determination Using Karl Fischer Titra- Heating, Refrigeration, and Air-Conditioning Engineers, June 13–15,
tions,” Analytical Chemistry, Vol 63, 1991, p. 557A. 1960.
(6) Bastin, E. L., Siegel, H., and Bullock, A. B.,“ Microdetermination of (12) E. I. du Pont de Nemours & Co., Freon Technical Bulletin B-23,
Water by Titration With Fischer Reagent,” Analytical Chemistry, “Moisture Determination in 8Freon’ Fluorocarbons by Karl Fischer
ANCHA, Vol 31, 1959, p. 467. Titration,” June 1961.
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Subcommittee E15.01 has identified the location of selected changes to this standard since the last issue
(E 203-01) that may impact the use of this standard.
(1) Updated units of measure to comply with the International in Scope and Summary of Test Method.
System of Units (SI). (4) Deleted (Formerly called Repeatability) from the Precision
(2) Added numbered paragraph in Scope stating that the SI section.
units are to be considered standard.
(5) Added Summary of Changes section.
(3) Changed term “amperometrically” to “potentiometrically”
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