Designation: D 1844 – 86 (Reapproved 2003)

Standard Test Methods for

Chemical Analysis of Basic Lead Silicochromate1
This standard is issued under the fixed designation D 1844; 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 D 280 Test Methods for Hygroscopic Moisture (and Other

1.1 These test methods cover the chemical analysis of the Matter Volatile Under the Test Conditions) in Pigments
pigment commercially known as basic lead silicochromate and D 281 Test Method for Oil Absorption of Pigments by
are applicable to pigment supplied by the manufacturer and to Spatula Rub-Out
pigment, but not mixed pigments, separated from liquid D 387 Test Method for Color and Strength of Color Pig-
coatings. The presence of basic lead silicochromate species ments with a Mechanical Muller
shall be confirmed by X-ray diffraction analysis (see Specifi- D 1193 Specification for Reagent Water
cation D 1648). D 1648 Specification for Basic Lead Silicochromate Pig-
1.2 For liquid coatings the pigment must first be separated ment
from the vehicle before conducting the analysis. D 2371 Test Method for Pigment Content of Solvent-
1.3 The analytical procedures appear in the following order: Reducible Paints
Sections
3. Significance and Use
Lead oxide 6 to 14 3.1 These test methods may be used to confirm the stated
Chromium trioxide 15 to 23
Silica 24 to 27
lead oxide, chromium trioxide and silica content of basic lead
Moisture and other volatile matter 28 silicochromate and is useful for quality control.
Coarse particles 29
Oil absorption 30 4. Purity of Reagents
Mass color and tinting strength 31
4.1 Reagent grade chemicals shall be used in all tests.
1.4 The values stated in SI units are to be regarded as the Unless otherwise indicated, it is intended that all reagents shall
standard. The values given in parentheses are for information conform to the specifications of the Committee on Analytical
only. Reagents of the American Chemical Society, where such
1.5 This standard does not purport to address the safety specifications are available.3 Other grades may be used, pro-
concerns, if any, associated with its use. It is the responsibility vided it is first ascertained that the reagent is of sufficiently
of the user of this standard to establish appropriate safety and high purity to permit its use without lessening the accuracy of
health practices and determine the applicability of regulatory the determination.
limitations prior to use. 4.2 Unless otherwise indicated, references to water shall be
understood to mean reagent water conforming to Type II of
2. Referenced Documents
Specification D 1193.
2.1 ASTM Standards: 2
D 185 Test Methods for Coarse Particles in Pigments, 5. Preparation of Sample
Pastes, and Paints 5.1 Thoroughly mix liquid coatings and separate in accor-
dance with Test Method D 2371 sufficient pigment to enable
1
the required analyses to be carried out.
These test methods are under the jurisdiction of ASTM Committee D01 on
Paint and Related Coatings, Materials, and Applications and are the direct
responsibility of Subcommittee D01.31 on Pigment Specifications.
3
Current edition approved Dec. 1, 2003. Published December 2003. Originally Reagent Chemicals, American Chemical Society Specifications, American
approved in 1961. Last previous edition approved in 1986 as D 1844 – 86 (1999). Chemical Society, Washington, DC. For suggestions on the testing of reagents not
2
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 [email protected]. 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.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

1
 D 1844 – 86 (2003)
5.2 Thoroughly mix pigment supplied as such and grind h. Filter, using paper pulp, and wash once with cold isopropyl
separated pigment to a fine powder in a mortar and pestle alcohol (50 %) containing 10 mL of H2SO4(sp gr 1.84)/100
before taking portions for analysis. mL.
8.4 Transfer the precipitate to the original beaker with 150
TOTAL LEAD AS LEAD OXIDE-GRAVIMETRIC mL of water, add 50 mL of the ammonium acetate solution, and
METHOD boil the solution until the lead sulfate dissolves. Filter while hot
through the original paper and wash well (6 to 8 washes) with
6. Apparatus hot water. To the filtrate add 5 mL of glacial acetic acid, heat
6.1 Glass Filtering Crucible (medium-porosity fritted the solution to boiling, and add 20 mL of saturated K2Cr2O7
disk), dried to constant weight before use. solution. Boil the solution until the precipitate turns orange,
6.2 Platinum Dish. and allow to stand on a warm plate for at least 2 h. Filter
through a glass filtering crucible (medium-porosity fritted
7. Reagents disk), wash three times with hot water, and finally once with
alcohol. Dry in an oven at 105°C for 2 h, cool, and weigh.
7.1 Acetic Acid (Glacial).
7.2 Ammonium Hydroxide (sp gr 0.90)—Concentrated am- 9. Calculation
monium hydroxide (NH4OH).
9.1 Calculate the percent of total lead as lead oxide (PbO) as
7.3 Ammonium Acetate, Acid Solution—To 300 mL of water
follows:
add an equal volume of NH4OH. Neutralize with glacial acetic
acid and add 20 mL in excess. PbO, % 5 ~P 3 69.06!/S
7.4 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro- where:
chloric acid (HCl). P = lead chromate (PbCrO4) precipitate, g,
7.5 Hydrofluoric Acid (47 %)—Concentrated hydrofluoric S = sample used, g, and
acid (HF).
molecular weight ~PbO!
7.6 Hydrogen Sulfide (H2S)—Handle and use H2S in hood.
molecular weight ~PbCrO4 5
7.7 Isopropyl Alcohol (50 and 98 %). 223.21
7.8 Nitric Acid (sp gr 1.42)—Concentrated nitric acid 323.21 5 0.6906 3 100 ~for percent! 5 69.06
(HNO3) (see 7.4.1).
7.9 Potassium Dichromate Solution (saturated)—Prepare a 69.06 represents the gravimetric factor to convert grams of
saturated solution of potassium dichromate (K2Cr2O7) in water. PbCrO 4 to grams of PbO.
7.10 Sulfuric Acid (1 + 1)—Carefully mix 1 volume of This gravimetric factor has led to high results due to the
concentrated sulfuric acid (H2SO4, sp gr 1.84) with 1 volume presence of mixed lead chromates and an empirical factor can
of water (see 7.4.1). be used to compensate:
Empirical factor 5 69.06 3 0.9944 5 68.67
8. Procedure
ALTERNATIVE METHOD FOR TOTAL LEAD AS
8.1 Weigh accurately (to 0.1 mg) 1 g of the sample into a LEAD OXIDE—TITRIMETRIC METHOD
platinum dish. Add 5 mL of HNO3 and 10 mL of HF.
Cautiously evaporate to dryness on a steam bath. Repeat the 10. Apparatus
addition of HNO3 and HF and again cautiously evaporate to 10.1 Platinum Dish.
dryness. Wash the sides of the dish with a little water and 10.2 Filter Paper, ashless, medium texture, or paper pulp.
evaporate to dryness. Wet the residue with 5 mL of HNO3,
warm gently, and transfer the residue to a 400-mL beaker using 11. Reagents
a policeman. Neutralize with NH4OH, and then make the 11.1 Ammonium Hydroxide (sp gr 0.90)—Concentrated am-
solution just acid with HCl, adding 5 mL in excess. Dilute to monium hydroxide (NH4OH).
200 mL and heat to just below the boiling point until solution 11.2 Glacial Acetic Acid (min 99.7 %)—Concentrated gla-
is complete. cial acetic acid (CH3COOH).
8.2 Pass H2S through the solution for about 20 min. Filter, 11.3 Acid Ammonium Acetate Buffer—Mix 400 mL of
using paper pulp. Wash the precipitate five to six times with distilled water and 400 mL of ammonium hydroxide (sp gr
water just acid with HCl and saturated with H2S. Transfer the 0.90). Add 375 mL of reagent grade glacial acetic acid slowly
paper and precipitate to the original beaker, add 25 mL of while stirring.
HNO3, boil until the residue is white, then add 10 mL of H2SO4 11.4 Cupric Sulfate Solution (0.1M)—Dissolve 25 g of
(1 + 1). Destroy the organic material by evaporating the CuSO4·5H2O in distilled water and dilute to 1 L.
solution to dense white fumes, making further additions of 11.5 Disodium Ethylenediaminetetracetate Dihydrate (0.05
HNO3 until there is no charring. M) (EDTA solution)4—Dissolve 18.6 g of the salt in distilled
8.3 Cool the solution, add 10 mL of water, and evaporate to water and dilute to 1 L. Standardize the solution as follows:
fumes. Repeat the addition of water and the evaporation. Cool
the solution, add 40 mL of water, and bring the solution to
boiling. Cool the solution and add 50 mL of isopropyl alcohol 4
The standardized solution may also be purchased from Corco Chemical Corp.
(98 %), stir, and allow the solution to stand cold for at least 4 Catalog No.—Special.

2
 D 1844 – 86 (2003)
Transfer 25 mL of lead standard (11.14) to a 400-mL beaker. 13. Calculation
Add concentrated ammonium hydroxide (11.1) dropwise until 13.1 Calculate the percent lead oxide as follows:
a permanent precipitate just forms. Add 25 mL of acid
V 3 L 3 100
ammonium acetate (11.3), dilute to 200 mL, heat to boiling, PbO, % 5 S
add 4 drops of copper EDTA (11.7) and 12 drops of PAN
(11.13) and titrate with the EDTA to a clear yellow. where:
1 mL Na2 EDTA 5 0.2790/V g PbO V = EDTA required for titration, mL,
L = lead equivalent of EDTA solution, and
where: S = specimen weight, g.
V = EDTA required for titration, mL
g = lead oxide, g, and 14. Precision and Bias
0.05 M 3 0.22321 = 0.01116 g PbO in 1 mL of lead standard 14.1 On the basis of an interlaboratory study of the method
(10.14) (25 mL) (0.05 M) (0.22321) = 0.2790 g PbO in 25 mL in which operators in three laboratories analyzed two paints
of lead standard (10.14). containing basic lead silicochromate with iron oxide the
11.6 Murexide Indicator Tablets—Ammonium salt of pur- following criteria should be used for judging the acceptability
puric acid. of the results at the 95 % confidence level:
11.7 Copper-EDTA Solution—Mix equivalent amounts of 14.1.1 Repeatability—Two results, each the mean of dupli-
cupric sulfate solution (11.4) and EDTA solution (11.5) and cate determinations obtained by the same operator should be
store in a dropping bottle. The cupric sulfate EDTA equiva- considered suspect if they differ by more than the following:
lence may be determined as follows: Pipet 10 mL of cupric Percent Absolute PbO
sulfate into a beaker, add concentrated ammonium hydroxide 28 % 0.20
dropwise until the precipitate which forms just redissolves. 45 % 0.30

Dilute to 200 mL with water, add two Murexide indicator 14.1.2 Reproducibility—A realistic range could not be es-
tablets, and titrate immediately with EDTA to a color change tablished for results between laboratories because of the
from yellow to purple. limited number of participating laboratories.
11.8 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro- 14.1.3 Bias—A bias statement could not be established
chloric acid (HCl) (see 7.4.1). because of the limited number of participating laboratories.
11.9 Hydrofluoric Acid (47 %)—Concentrated hydrofluoric
acid (HF). CHROMIUM TRIOXIDE
11.10 Hydrogen Sulfide (H2S)—Cylinder. Handle and use in
a hood. 15. Interference
11.11 Hydrogen Sulfide Wash Solution— Add 10 mL of HCl 15.1 Soluble Fe+3 will cause high results. See Section 20
(sp gr 1.19) to 1 L of water and saturate with H2S. .
11.12 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
(HNO3). 16. Reagents
11.13 Pan Indicator (1-(2-pyridylazo)-2-naphthol)— 16.1 Potassium Dichromate, Standard Solution (0.1 N)—
Dissolve 0.1 g in 100 mL of ethanol. Weigh 4.904 g of dried potassium dichromate (K2Cr2O7),
11.14 Primary Standard (0.05 M lead nitrate)—Dissolve dissolve it in water, and dilute to 1 L with water in a volumetric
16.5615 g of reagent grade lead nitrate in distilled water and flask.
dilute to 1 L. 16.2 Potassium Iodide Solution (150 g/L)—Dissolve 150 g
1 mL 5 0.01116 g PbO of potassium iodide (KI) in water and dilute to 1 L.
16.3 Hydrochloric Acid Mixture—Saturate water with NaCl
11.15 Sulfuric Acid (1 + 1)—Carefully mix 1 volume of (about 350 g/L). To each litre of this solution add 150 mL of
concentrated sulfuric acid (H2SO4, sp gr 1.84) with 1 volume water and 100 mL of concentrated HCl (sp gr 1.19).
of water. 16.4 Sodium Thiosulfate Solution (0.1 N)—Dissolve 24.8 g
of reagent grade Na2S2O3·5H2O in recently boiled water and
12. Procedure dilute to 1 L with additional recently boiled water. To stan-
12.1 Dissolve 1 g of pigment in accordance with 8.1 and dardize, pipet 25 mL of the standard potassium dichromate
8.2. solution (exactly 0.1000 N) into a 250-mL Erlenmeyer flask.
12.2 Cool, so that the addition of 25 mL of water does not Add 100 mL of water, 15 mL of potassium iodide solution, and
cause excessive splattering of the sulfuric acid; the solution at 15 mL of concentrated hydrochloric acid (sp gr 1.19). Titrate
this point should be water white. Add ammonium hydroxide the liberated iodine with sodium thiosulfate solution until the
(sp gr 0.90) until the pH of the solution is 5 to 5.5 (as indicated reddish-brown color becomes quite faint. Add 5 mL of starch
by pH paper). Add 50 mL of acid ammonium acetate (11.3), solution and continue the titration dropwise until the blue color
boil 5 min, dilute to 200 mL with water, heat to boiling, add 4 changes to a pale green. Calculate the normality of the sodium
drops of copper-EDTA (11.7) and 12 drops of PAN thiosulfate solution as follows:
(11.1311.13) and titrate while hot with standard EDTA to a 2.5000
N 5
clear yellow. M

3
 D 1844 – 86 (2003)

where: 20. Reagents

N = normality, and 20.1 Ammonium Hydroxide (sp gr 0.90)—Concentrated am-
M = sodium thiosulfate solution, mL, monium hydroxide (NH4OH).
16.5 Starch Indicator Solution—Make a homogeneous 20.2 Disodium Ethylenediaminetetracetate Dihydrate
paste of 10 g of soluble starch in cold water. Add to this 1 L of (0.05 M) (EDTA)— Dissolve 18.6 g of the reagent grade salt in
boiling water, stir rapidly, and cool. Salicylic acid (1.25 g/L) distilled water and dilute to 1 L. See 11.5 for standardization.
may be added to preserve the indicator. If long storage is 20.3 Hydrochloric Acid Mixture—See 16.3.
required, the solution should be kept in a refrigerator at 4 to 20.4 Hydrofluoric Acid (47 %)—Concentrated hydrofluoric
10°C (40 to 50°F). Prepare fresh indicator when the end point acid (HF).
of the titration from blue to colorless or blue to light green fails 20.5 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
to be sharp. (HNO3).
20.6 Perchloric Acid (sp gr 1.67)—Concentrated perchloric
17. Procedure acid (HClO4).
17.1 Weigh to 0.1 mg about 1 g of sample into a 500-mL 20.7 Potassium Dichromate, Standard Solution (0.1 N)—
Erlenmeyer flask. Add 100 mL of NaCl-HCl solution and See 16.1.
dissolve the sample without heat, keeping the solution cold. 20.8 Potassium Iodide Solution (150 g/Litre)—See 16.2.
(Silica will not dissolve, but it does not interfere with the 20.9 Sodium Thiosulfate Solution (0.1 N)—See 16.4.
analysis.) Add 10 mL of KI solution and titrate with 0.1 N 20.10 Starch Indicator Solution—See 16.5.
sodium thiosulfate solution until the reddish-brown color is 21. Procedure
almost gone. Add 5 mL of starch solution and titrate slowly,
dropwise, until the blue color changes to a light green. 21.1 Transfer 0.5 g of pigment to a 500-mL high-silica
Erlenmeyer flask.5 Add 10 mL of nitric acid (sp gr 1.42), and
18. Calculation 10 mL of perchloric acid (sp gr 1.67) and cover with a watch
glass. Evaporate to fumes (flask will fill with white vapor) of
18.1 Calculate the percent of chromium trioxide (CrO 3) as perchloric acid, cool, add 15 mL of water, and evaporate to
follows: fumes. Continue fuming for 15–20 min (the specimen should
CrO3, % 5 [~V1N 3 0.03334!/S 2# 3 100 be red-orange color). Cool immediately by placing the flask in
a cold water bath.
where: 21.2 Wash down the cover glass and sides of the flask with
V 1 = sodium thiosulfate solution required for titration of water. Add 50 mL of HCl mixture and 50 mL of 0.05 M EDTA
the specimen, mL solution. Adjust to pH 8 (determined with pH paper) with
N = normality of the sodium thiosulfate solution, ammonium hydroxide (sp gr 0.90) and add 50 mL of HCl
S 1 = sample used, g, and mixture (16.3). Cool the flask to 20 to 25°C, add 10 mL of
16 potassium iodide solution, 10 mL of starch solution, and titrate
CrO3 → Cr13 immediately with standard sodium thiosulfate solution to a
milliequivalent weight sharp change in the starch indicator. (The final solution color
may be lavender or green depending on the composition of the
molecular weight ~CrO3
5 sample).
1000 3 3 ~valence!
21.3 Add 2 to 3 mL of HF, (20.4) stir for 1⁄2 min and if the
99.99 indicator changes color titrate to the endpoint.
5 1000 3 3
5 0.03334 (1) 22. Calculation
22.1 Calculate the percent chromium trioxide (CrO 3) as
ALTERNATIVE METHOD FOR CHROMIUM follows:
TRIOXIDE CrO3, % 5 [~V2N1 3 0.03334!/S 3# 3 100

19. Scope where:

V 2 = sodium thiosulfate solution required for titration of
19.1 This test method determines total chromium as chro- the specimen, g,
mium trioxide. Iron oxide interference is masked by the use of N1 = normality of the sodium thiosulfate solution, and
EDTA. This procedure is not applicable when chromium oxide S3 = sample used, g.
green (Cr2O3) is present. This test method is limited to basic
lead silicochromate pigments with or without iron oxide. 23. Precision and Bias
19.2 The perchloric acid is employed as an oxidizing agent 23.1 On the basis of an interlaboratory study of this test
to ensure complete oxidation of any reduced chromium. When method in which operators in three laboratories analyzed two
perchloric acid is used, concentrated nitric acid must also be paints containing basic lead silicochromate with iron oxide the
used. The use of a perchloric acid hood is optional since the
specimen is covered with a watch glass and is being oxidized,
not wet ashed. 5
Vycor has been found suitable for this purpose.

4
 D 1844 – 86 (2003)
following criteria should be used for judging the acceptability contents. To the crucible add 2 drops of H2SO4 (1 + 4) and 15
of the results at the 95 % confidence level. mL of HF. Evaporate cautiously on a hot plate and ignite at
23.1.1 Repeatability—Two results, each the mean of dupli- 1000°C for approximately 5 min. Cool in a desiccator and
cate determinations, obtained by the same operator should be weigh to constant weight.
considered suspect if they differ by more than the following:
Percent Absolute
27. Calculation
CrO3 27.1 Calculate the percent of silica (SiO2) as follows:
3 % CrO3 0.15
5 % CrO3 0.40 SiO 2, % 5 [~W1 2 W2!/S 4# 3 100
23.1.2 Reproducibility—A realistic range could not be es- where:
tablished for results between laboratories because of the W 1 = weight of crucible and contents before HF treat-
limited number of participating laboratories. ment, g,
23.1.3 Bias—A bias statement could not be established W2 = weight of crucible and contents after HF treatment,
because of the limited number of participating laboratories. g, and
S4 = weight of sample used, g.
SILICA
MOISTURE AND OTHER VOLATILE MATTER
24. Apparatus
24.1 Platinum Crucible. 28. Procedure
25. Reagents 28.1 Determine moisture and other volatile matter in accor-
dance with Method A of Test Methods D 280.
25.1 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
chloric acid (HCl). COARSE PARTICLES
25.2 Hydrofluoric Acid (47 %)—Concentrated hydrofluoric
acid (HF). 29. Procedure
25.3 Nitric Acid (sp gr 1.42)—Concentrated nitric acid 29.1 Determine the percent coarse particles in the pigment
(HNO3). as received in accordance with Test Methods D 185.
25.4 Nitric Acid (1 + 19)—Mix 1 volume of concentrated
HNO3(sp gr 1.42) with 19 volumes of water. OIL ABSORPTION
25.5 Perchloric Acid (sp gr 1.67)—Concentrated perchloric
acid (HClO4). 30. Procedure
25.6 Sulfuric Acid (1 + 4)—Carefully mix 1 volume of 30.1 Determine the oil absorption of the pigment in accor-
concentrated sulfuric acid (H2SO4, sp gr 1.84)4 with 4 volumes dance with Test Method D 281.
of water.
MASS COLOR AND TINTING STRENGTH
26. Procedure
26.1 Weigh 0.5 g of pigment and transfer to a 400-mL 31. Procedure
beaker. Add 10 mL each of HCl (sp gr 1.19) and HNO3(sp gr 31.1 Determine the mass color and tinting strength in
1.42). Warm slightly, if necessary, to dissolve the chromate. accordance with Test Method D 387.
Add 50 mL of HClO 4 and fume for 15 to 20 min. Wash the
sides of the beaker down with 30 to 40 mL of water, evaporate, 32. Precision and Bias
and fume for 10 min. Cool and dilute to 200 mL with water. 32.1 Precision and bias have not been determined.
Filter through a double acid-washed quantitative paper and
wash eight times with hot water, once with HNO3 (1 + 19) and 33. Keywords
finally again with hot water. 33.1 basic lead silicochromate; chromium in basic lead
26.2 Dry and ignite the paper and precipitate in a platinum silicochromate; lead in basic lead silicochromate; lead oxide;
crucible. Cool in a desiccator and weigh the crucible and pigment; silica in basic lead silicochromate

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