ASTM D3969-01(2006)

Designation: D3969 − 01 (Reapproved 2006)
Standard Test Method for
Zirconium in Paint Driers by EDTA Method
This standard is issued under the fixed designation D3969; 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.
1. Scope cialty Chemicals (Withdrawn 2009)
E300Practice for Sampling Industrial Chemicals
1.1 This test method covers the titrimetric determination of
zirconiuminzirconiumdriersusedinthecoatingsindustryand
3. Summary of Test Method
utilizes the disodium salt of ethylenediaminetetraacetic acid
3.1 The zirconium drier is digested with concentrated sul-
dihydrate (EDTA).
furic acid and 30% hydrogen peroxide to destroy all organic
1.2 This test method is limited to the determination of the
matter.The diluted solution is boiled with an excess of EDTA,
zirconium content of a liquid zirconium drier that does not
the pH adjusted, and the excess titrated with bismuth nitrate
contain other drier elements. The test method is not applicable
using xylenol orange as the indicator.
to drier blends and does not differentiate hafnium from
zirconium.
4. Significance and Use
1.3 AllcationsthatcanbetitratedwithEDTAinacidmedia
4.1 The amount of zirconium drier used in oxidizing-type
interfere and must not be present in the sample.
coatings significantly affects their drying properties. This test
method may be used to confirm the stated content of a pure
1.4 This test method has been tested for concentrations of 6
liquid zirconium drier manufactured for use by the coatings
and 12% zirconium, but there is no reason to believe that it is
industry.
not suitable for higher or lower zirconium concentrations,
provided specimen size is adjusted proportionately.
5. Apparatus
1.5 The values stated in SI units are to be regarded as
5.1 Centrifuge, capable of developing 1000 to 2000 g.
standard. No other units of measurement are included in this
standard.
6. Reagents
1.6 This standard does not purport to address all of the
6.1 Purity of Reagents—Reagent grade chemicals shall be
safety concerns, if any, associated with its use. It is the
used in all tests. Unless otherwise indicated, it is intended that
responsibility of the user of this standard to establish appro-
all reagents shall conform to the specifications of the Commit-
priate safety and health practices and determine the applica-
tee onAnalytical Reagents of theAmerican Chemical Society,
bility of regulatory limitations prior to use.
where such specifications are available. Other grades may be
used, provided it is first ascertained that the reagent is of
2. Referenced Documents
sufficiently high purity to permit its use without lessening the
2.1 ASTM Standards:
accuracy of the determination.
D600Specification for Liquid Paint Driers
6.2 Purity of Water—Unless otherwise indicated, references
D1193Specification for Reagent Water
towatershallbeunderstoodtomeanreagentwaterconforming
E180Practice for Determining the Precision of ASTM
to Type II of Specification D1193.
Methods for Analysis and Testing of Industrial and Spe-
6.3 Ammonium Hydroxide (sp gr 0.90)—Concentrated, am-
monium hydroxide (NH OH).
This test method is under the jurisdiction of ASTM Committee D01 on Paint
and Related Coatings, Materials, andApplications and is the direct responsibility of
Subcommittee D01.21 on Chemical Analysis of Paints and Paint Materials. The last approved version of this historical standard is referenced on
Current edition approved June 1, 2006. Published June 2006. Originally www.astm.org.
approved in 1980. Last previous edition approved in 2001 as D3969–01. DOI: Reagent Chemicals, American Chemical Society Specifications, American
10.1520/D3969-01R06. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
For referenced ASTM standards, visit the ASTM website, www.astm.org, or listed by the American Chemical Society, see Analar Standards for Laboratory
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Standards volume information, refer to the standard’s Document Summary page on and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
the ASTM website. MD.
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D3969 − 01 (Reapproved 2006)
6.4 Bismuth Nitrate, Standard Solution (0.05 M)—Dissolve 8. Standardization
24.25 g of bismuth nitrate (Bi(NO )·5H O) in 20 to 30 mL of
3 2
8.1 Zinc Chloride, Standard Solution (0.100 M)—Calculate
concentrated nitric acid (use a magnetic stirrer if possible).
the molarity, M , of the zinc chloride (ZnCl ) solution as
1 2
After solution is complete, dilute to 1 L with water.
follows:
NOTE 1—Add the water very slowly to the acid solution, while cooling
S
M 5 (1)
the flask in an ice bath to prevent splattering.
65.37
6.5 EDTA, Standard Solution (0.05 M)—Dissolve 18.61 g
of EDTAin 300 to 500 mLof water and dilute to 1 L. Store in
where:
a polyethylene or borosilicate glass bottle.
S = zinc used, g, and
65.37 = zinc to producea1M solution, g/L.
6.6 Eriochrome Black-T Indicator—Triturate 0.100 g of
powdered Eriochrome Black-T with 100 g of sodium chloride
8.2 EDTA, Standard Solution (0.05 M)—Pipet 20 or 25-mL
(NaCl),andstorethemixtureinatightlystopperedbottle.This
portions (use calibrated pipets) of the standard ZnCl solution
mixture remains stable for several years.
into a 250-mL Erlenmeyer flask. Add concentrated NH OH
dropwise until the precipitate which forms redissolves. Add 3
6.7 Formic Acid (sp gr 1.22, 90%) HCOOH.
mL more of NH OH.Add 0.20 to 0.25 g Eriochrome Black-T
6.8 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
indicator mixture and titrate with EDTA until the solution
chloric acid (HCl).
changes from red to clear blue.
8.2.1 Calculate the molarity of the EDTA solution, M,as
6.9 Hydrogen Peroxide (30%). 2
follows:
6.10 Isopropyl Alcohol (99.5%).
M 5 V M /V (2)
2 1 1 2
6.11 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
where:
(HNO ).
V = volume of ZnCl solution, mL, and
1 2
6.12 Phenolphthalein Indicator (1.0%) —Dissolve 1.0 g of
V = volume of EDTA solution, mL.
phenolphthalein indicator in 100 mL of methanol, ethanol, or
8.3 Bismuth Nitrate, Standard Solution (0.05 M)—Pipet 24
isopropanol.
mL of 0.05 M EDTA into a 250-mL Erlenmeyer flask, add 75
6.13 Sodium Sulfite (Na SO ).
mL of distilled water, neutralize with concentrated NH OH to
2 3
a pink end point with phenolphthalein, and then add 15 mLof
6.14 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
...