Designation: D 2194 – 02

Standard Test Method for

Concentration of Formaldehyde Solutions1
This standard is issued under the fixed designation D 2194; 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 * 5. Apparatus
1.1 This test method covers the determination of the form- 5.1 Buret, calibrated, 100-mL, with a 50 or 75-mL reservoir
aldehyde content of commercially available formaldehyde on top of a lower portion calibrated in 0.1-mL divisions. A
solutions ranging in concentration from 36 to 55 weight %. TFE-fluorocarbon resin stopcock is suitable for this purpose.
1.2 For purposes of determining conformance of an ob- 5.2 Erlenmeyer Flask, 500-mL capacity.
served value or a calculated value using this test method to 5.3 Vials, specimen, short, style, 1 to 11⁄2-dram (4 to 6-mL)
relevant specifications, test result(s) shall be rounded off “to capacity.
the nearest unit” in the last right-hand digit used in expressing
the specification limit, in accordance with the rounding-off 6. Reagents
method of Practice E 29. 6.1 Purity of Reagents—Reagent grade chemicals shall be
1.3 For hazard information and guidance, see the supplier’s used in all tests. Unless otherwise indicated, it is intended that
Material Safety Data Sheet. all reagents shall conform to the specifications of the Commit-
1.4 This standard does not purport to address all of the tee on Analytical Reagents of the American Chemical Society,
safety concerns, if any, associated with its use. It is the where such specifications are available.4 Other grades may be
responsibility of the user of this standard to establish appro- used, provided it is first ascertained that the reagent is of
priate safety and health practices and determine the applica- sufficiently high purity to permit its use without lessening the
bility of regulatory limitations prior to use. accuracy of the determination.
6.2 Purity of Water—Unless otherwise indicated, references
2. Referenced Documents to water shall be understood to mean reagent water conforming
2.1 ASTM Standards: to Type IV of Specification D 1193.
D 1193 Specification for Reagent Water2 6.3 Sodium Sulfite Solution (125 g/L)—Dissolve 125 g of
E 29 Practice for Using Significant Digits in Test Data to anhydrous sodium sulfite (Na2SO3) in water and dilute to 1 L.
Determine Conformance with Specifications3
NOTE 1—Sodium sulfite gradually oxidizes to sodium sulfate on
exposure to air and therefore should be kept in a tightly closed container.
3. Summary of Test Method
For best results freshly prepared reagent should be used.
3.1 The specimen is reacted with an excess of sodium sulfite
6.4 Sulfuric Acid (0.5 N)—Prepare and standardize 0.5 N
solution and the resulting sodium hydroxide is titrated with
sulfuric acid (H2SO4) against 0.5 N sodium hydroxide (NaOH)
sulfuric acid using thymolphthalein indicator.
solution which has been standardized against potassium acid
3.2 The sample should be essentially neutral; 0.1 % acidity
phthalate to a thymolphthalein end point.
(as formic acid) is equivalent to 0.065 % formaldehyde.
6.5 Thymolphthalein Indicator (0.1 % Alcohol Solution)—
4. Significance and Use Dissolve 1.0 g of thymolphthalein in 100 mL of methanol,
ethanol, or isopropanol and dilute to 1 L with additional
4.1 This test method provides a measurement of formalde-
alcohol.
hyde content (assay) of formaldehyde solutions. The results of
these measurements can be used for specification acceptance. 7. Procedure
7.1 Add 100 mL of Na2SO3 solution to a sufficient number
of 500-mL Erlenmeyer flasks to make all blank and specimen
1
This test method is under the jurisdiction of ASTM Committee D01 on Paint
and Related Coatings, Materials, and Applications and is the direct responsibility of 4
Reagent Chemicals, American Chemical Society Specifications, American
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved July 10, 2002. Published September 2002. Originally listed by the American Chemical Society, see Analar Standards for Laboratory
published D 2194 – 63 T. Last previous edition D 2194 – 99. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
Annual Book of ASTM Standards, Vol 11.01. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
3
Annual Book of ASTM Standards, Vol 14.02. MD.

*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.

1
 D 2194
determinations in duplicate. 10. Precision and Bias
7.2 Weigh a 2-g specimen to the nearest 0.1 mg in the
10.1 The following criteria should be used for judging the
weighing vials and transfer the vials to the Erlenmeyer flasks,
acceptability of results at the 95 % confidence level.
being careful to avoid getting any of the sample on the sides of
the flasks. 10.1.1 Repeatability—The difference between two results,
7.3 Add 3 to 5 drops of the thymolphthalein indicator each the mean of duplicate determinations, obtained by the
solution to each of the flasks containing specimens as well as same analyst on different days is normally about 0.05 %
the blanks and titrate to a colorless end point. absolute. Two such results should be considered suspect if they
differ by more than 0.12 % absolute.
8. Calculation 10.1.2 Reproducibility—The average difference between
8.1 Calculate the weight percent of formaldehyde, W, as two results (each the mean of duplicate determinations) ob-
follows: tained by analysts in different laboratories is normally about
W 5 @~V 2 B! 3 N 3 F#/S 3 100 (1) 0.08 % absolute. Two such results should be considered
suspect if they differ by more than 0.23 % absolute.
where:
V = H2SO4 required for titration of the specimen, mL, NOTE 2—The above precision estimates are based on two interlabora-
B = H2SO4 required for titration of the blank, average, mL, tory studies involving five and nine laboratories, respectively, using two
N = normality of the H2SO4, different samples in each case with a single analyst performing duplicate
F = 0.03003 (the milliequivalent weight of formaldehyde), results on each of two days. The formaldehyde levels studied were as
and follows: 36.85 %, 36.98 %, 37.15 %, and 37.23 %.
S = sample used, g. 10.2 Bias—Bias has not been determined for this test
method because primary standards do not exist.
9. Report
9.1 Report the percent formaldehyde to the nearest 0.01 %. 11. Keywords
Duplicate runs that agree within 0.12 % are acceptable for
averaging (95 % confidence level). 11.1 concentration; formaldehyde

SUMMARY OF CHANGES

Committee D01.35 has identified the location of selected changes to this standard since the last issue
(D 2194 - 99) that may impact the use of this standard.

(1) Added reference to Practice E 29 in Scope section. (2) Added Practice E 29 to list of Referenced Documents.

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