Designation: D 2375 – 85 (Reapproved 1999)

AMERICAN SOCIETY FOR TESTING AND MATERIALS

100 Barr Harbor Dr., West Conshohocken, PA 19428
Reprinted from the Annual Book of ASTM Standards. Copyright ASTM

Standard Test Method for

Manganese in Paint Driers by EDTA Method1
This standard is issued under the fixed designation D 2375; 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.

1. Scope 5. Apparatus
1.1 This test method covers a titrimetric determination of 5.1 Centrifuge, capable of developing 1000 to 2000 g.
manganese in liquid paint driers that can be dissolved in a
toluene-alcohol mixture and utilizes the disodium salt of 6. Reagents
ethylenediaminetetraacetic acid dihydrate (EDTA). 6.1 Purity of Reagents—Reagent grade chemicals shall be
1.2 This test method is not applicable to drier blends. used in all tests. Unless otherwise indicated, it is intended that
1.3 All cations that can be titrated with EDTA in alkaline all reagents shall conform to the specifications of the Commit-
media interfere and must not be present in the sample. tee on Analytical Reagents of the American Chemical Society,
1.4 This standard does not purport to address all of the where such specifications are available.5 Other grades may be
safety concerns, if any, associated with its use. It is the used, provided it is first ascertained that the reagent is of
responsibility of the user of this standard to establish appro- sufficiently high purity to permit its use without lessening the
priate safety and health practices and determine the applica- accuracy of the determination.
bility of regulatory limitations prior to use. 6.2 Purity of Water—Unless otherwise indicated, references
to water shall be understood to mean reagent water conforming
2. Referenced Documents to Type II of Specification D 1193.
2.1 ASTM Standards: 6.3 Ammonium Chloride (NH4Cl).
D 600 Specification for Liquid Paint Driers2 6.4 Ammonium Hydroxide (sp gr 0.90)—Concentrated am-
D 1193 Specification for Reagent Water3 monium hydroxide (NH4OH).
E 180 Practice for Determining the Precision of ASTM 6.5 l-Ascorbic Acid.
Methods for Analysis and Testing of Industrial Chemicals4 6.6 Buffer Solution—Add 350 mL of concentrated NH4-OH
E 300 Practice for Sampling Industrial Chemicals4 (sp gr 0.90) to 54 g of NH4Cl and dilute to 1 L with water.
6.7 Eriochrome Black-T Indicator—Triturate 0.2 g of Erio-
3. Summary of Test Method chrome Black-T and 100 g of NaCl, and store the mixture in a
3.1 The liquid drier is dissolved in toluene and ethyl alcohol tightly stoppered bottle. This mixture remains stable for several
and treated with an excess of standard EDTA solution. The years.
excess is titrated with standard zinc chloride solution using 6.8 Ethyl Alcohol (95 %), pure or denatured.
Eriochrome Black-T as the indicator. 6.9 EDTA, Standard Solution (0.05 M)—Dissolve 18.62 g
of EDTA in water and dilute to 1 L. Store in a polyethylene or
4. Significance and Use borosilicate glass bottle.
4.1 The amount of manganese drier used in oxidizing-type 6.10 Hydrochloric Acid (sp gr 1.19)—Concentrated (hydro-
coatings significantly affects their drying properties. This test chloric acid (HCl).
method may be used to confirm the stated manganese content 6.11 Sodium Chloride (NaCl).
of pure liquid manganese drier soluble in toluene-alcohol and 6.12 Toluene.
manufactured for use by the coatings industry. 6.13 Zinc, Granular.
6.14 Zinc Chloride, Standard Solution (0.05 M)—Weigh
3.2690 g of zinc to the nearest 0.5 mg and dissolve in 50 mL
of dilute HCl (14 mL of concentrated HCl (sp gr 1.19) to 36 mL
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint
and Related Coatings, Materials, and Applications and is the direct responsibility of
5
Subcommittee D01.21 on Chemical Analysis of Paints and Paint Materials. Reagent Chemicals, American Chemical Society Specifications, American
Current edition approved Nov. 29, 1985. Published January 1986. Originally Chemical Society, Washington, DC. For suggestions on the testing of reagents not
published as D 2375 – 65 T. Last previous edition D 2375 – 79. listed by the American Chemical Society, see Analar Standards for Laboratory
2
Annual Book of ASTM Standards, Vol 06.04. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
3
Annual Book of ASTM Standards, Vols 06.01 and 11.01. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
4
Annual Book of ASTM Standards, Vol 15.05. MD.

1
 D 2375
of water). Warm if necessary. Dilute the zinc chloride (ZnCl2) the total weight. Weigh by difference two or three 1-g speci-
solution to 1 L in a volumetric flask. mens (10 drops weigh about 0.2 g) to the nearest 0.5 mg into
M1 5 3.2690/65.37 (1) 400-mL assay beakers or wide-mouthed flasks (Note 2). Add
10 mL of toluene to each specimen and swirl to mix. Add 100
where: mL of 95 % ethyl alcohol and swirl again until the specimen is
M1 5 molarity of ZnCl2 solution, and dissolved and well dispersed. From a buret measure 40.0 mL of
65.37 5 zinc to produce a 1 M solution, g. EDTA solution into each beaker. Add 0.3 g of ascorbic acid, 15
mL of buffer solution, and 0.2 g of the indicator mixture. Mix
7. Sampling
thoroughly by swirling. Titrate with the standard ZnCl2 solu-
7.1 Take a small sample of liquid drier from bulk using the tion to the first permanent tinge of red. Maintain vigorous
procedures in Practice E 300 appropriate for the size of the swirling during the titration to ensure thorough mixing of the
container: section on Bottle Sampling for tanks and tank cars, two phases which may appear.
or section on Tube Sampling for drums and cans.
NOTE 2—If a magnetic stirrer is available, it is convenient to titrate in
NOTE 1—Liquid driers are normally homogeneous so that only simple an ordinary beaker. Stirring magnetically ensures thorough mixing during
physical tests, such as specific gravity or solids content, on top and bottom the titration.
samples from tanks, are required to confirm that separation has not NOTE 3—If the end point is overstepped, add 1.0 mL of the EDTA
occurred. Agitate drums in accordance with section on Tube Sampling in solution to the mixture and titrate again with standard ZnCl2 solution. Use
Practice E 300. total volume of each solution for the calculation.
7.2 Examine the sample of drier for sediment or suspended
matter which, if present, is evidence of noncompliance with 10. Calculation
Specification D 600. 10.1 Calculate the percent manganese present, A, as fol-
7.3 If the sample is homogeneous keep it in a stoppered lows:
vessel to prevent solvent evaporation prior to analysis.
A 5 @~~V2 3 M2! 2 ~V3 3 M1!! 3 5.494#/S (3)
8. Standardization
where:
8.1 EDTA, Standard Solution (0.05 M)—Measure 40.00 V2 5 EDTA solution, mL,
mL of the EDTA solution into a 250-mL flask that contains 10 V3 5 ZnCl2 solution required for specimen, mL,
mL of toluene and 100 mL of alcohol. Add 15 mL of buffer S 5 specimen used, g, and
solution and 0.2 g of indicator mixture, and mix thoroughly. 5.494 5 millimolar weight of manganese 3 100.
Titrate with the standard zinc chloride solution to the first
permanent appearance of a red color. 11. Precision and Bias (see Practice E 180)
8.1.1 Calculate the molarity of the EDTA solution, M2, as 11.1 Precision:
follows: 11.1.1 Repeatability—Two results, each the mean of dupli-
M2 5 V1M1/40.0 (2) cate determinations, obtained by the same operator on different
days should be considered suspect if they differ by more than
where: 0.05 % manganese.
V1 5 ZnCl2 solution, mL,
40.0 5 EDTA solution titrated, mL. 11.1.2 Reproducibility—Two results, each the mean of du-
plicate determinations, obtained by operators in different labo-
9. Procedure ratories should be considered suspect if they differ by more
9.1 Check the clarity of the drier. If not clear, centrifuge a than 0.15 % manganese.
portion of the sample until it is clear. Keep the centrifuge tube 11.2 Bias—Bias has not been determined for this test
stoppered so that solvent will not evaporate. method.
9.2 From a buret place a few grams of the drier in a 50-mL
Erlenmeyer flask that is fitted with a cork through which a 12. Keywords
dropping tube and rubber bulb (or eye dropper) pass and obtain 12.1 EDTA method; manganese; drier analysis

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