Designation: D49 − 83 (Reapproved 2014)

Standard Test Methods of

Chemical Analysis of Red Lead1
This standard is issued under the fixed designation D49; 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 (´) indicates an editorial change since the last revision or reapproval.

1. Scope thoroughly mixed and a representative portion taken and

1.1 These test methods cover procedures for the chemical powdered if lumpy or not finely ground. The sample in all
analysis of red lead having the approximate formula Pb3O4 cases shall be thoroughly mixed before taking portions for
(probably PbO2·2PbO). analysis. All samples shall be preserved in stoppered bottles or
containers.
1.2 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this 4. Purity of Reagents
standard. 4.1 Reagent grade chemicals shall be used in all tests.
1.3 This standard does not purport to address all of the Unless otherwise indicated, it is intended that all reagents shall
safety concerns, if any, associated with its use. It is the conform to the specifications of the Committee on Analytical
responsibility of the user of this standard to establish appro- Reagents of the American Chemical Society where such
priate safety and health practices and determine the applica- specifications are available.4 Other grades may be used pro-
bility of regulatory limitations prior to use. vided it is first ascertained that the reagent is of sufficiently
2. Referenced Documents high purity to permit its use without lessening the accuracy of
the determination.
2.1 ASTM Standards:2
D50 Test Methods for Chemical Analysis of Yellow, Orange, 4.2 Unless otherwise indicated, references to water shall be
Red, and Brown Pigments Containing Iron and Manga- understood to mean reagent water conforming to Type II of
nese Specification D1193.
D215 Practice for the Chemical Analysis of White Linseed 5. Moisture
Oil Paints (Withdrawn 2005)3
D280 Test Methods for Hygroscopic Moisture (and Other 5.1 Determine moisture content with a 2-g specimen in
Matter Volatile Under the Test Conditions) in Pigments accordance with Method A of Test Methods D280. The
D1193 Specification for Reagent Water specimen is dried for 2 h at 105°C. The loss in weight is
D1208 Test Methods for Common Properties of Certain considered as moisture.
Pigments
6. Organic Color
D1301 Test Methods for Chemical Analysis of White Lead
Pigments 6.1 Boil 2 g of the sample with 25 mL of 95 % ethyl alcohol,
D1959 Test Method for Iodine Value of Drying Oils and let settle, decant the supernatant liquid; boil the residue with 25
Fatty Acids (Withdrawn 2006)3 mL of distilled water and decant as before; boil the residue
with 25 mL of diluted NH4OH (1 + 4) and again decant. Boil
3. Treatment of Sample another 2-g portion of the sample with 25 mL of chloroform,
3.1 If the pigment is lumpy or not finely ground, grind it to let settle, and decant the supernatant liquid. If any one of the
a fine powder and mix thoroughly. Large samples may be above solutions is colored, organic coloring matter is indicated.
If the solutions remain colorless, organic colors are probably
1
These test methods are under the jurisdiction of ASTM Committee D01 on absent.
Paint and Related Coatings, Materials, and Applications and are the direct
responsibility of Subcommittee D01.31 on Pigment Specifications. NOTE 1—If it is desired to test for organic colors resistant to the above
Current edition approved Dec. 1, 2014. Published December 2014. Originally reagents, the test procedures described in the following books may be
approved in 1917. Last previous edition approved in 2008 as D49 – 83 (2008ε1).
DOI: 10.1520/D0049-83R0814.
2 4
For referenced ASTM standards, visit the ASTM website, www.astm.org, or Reagent Chemicals, American Chemical Society Specifications, American
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Standards volume information, refer to the standard’s Document Summary page on listed by the American Chemical Society, see Analar Standards for Laboratory
the ASTM website. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
3
The last approved version of this historical standard is referenced on and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
www.astm.org. MD.

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

1
 D49 − 83 (2014)
used, taking into account the nature of the pigment involved (1,2,3).5 8.1 Solutions Required: (a) Red Lead Solution—Dissolve in
1-L beaker 600 g of crystallized sodium acetate and 48 g of KI
7. Total Lead and Insoluble Matter
in about 500 mL of acetic acid (1 + 3) (made by mixing 150
7.1 Treat 1 g of the sample with 15 mL of HNO3 (1 + 1) and mL of glacial acetic acid with 450 mL of water). Warm the
sufficient H2O2 to dissolve all PbO2 on warming. If any beaker and contents on a steam bath, stirring occasionally, until
insoluble matter is present, add 25 mL of water, boil, filter, and a clear solution is obtained. Cool this solution to room
wash with hot water. The insoluble matter contains free SiO2 temperature, dilute to exactly 1000 mL with the acetic acid
and should be examined for BaSO4 and silicates, if appre- (1 + 3) and mix thoroughly. If preferred, the red lead solution
ciable. may be prepared separately for each titration, as follows:
7.2 To the original solution or filtrate from the insoluble Dissolve 30 g of the crystallized sodium acetate and 2.4 g of KI
matter add 20 mL of H2SO4 (sp gr 1.84) and evaporate to SO3 in 25 mL of the acetic acid (1 + 3), warming gently and stirring
fumes. Cool, add 150 mL of water, and 150 mL of 95 % ethyl until a clear solution is obtained. Cool this solution to room
alcohol, let stand cold for 2 h, filter, on a Gooch crucible, wash temperature, dilute to 50 mL with the acetic acid solution
with 95 % alcohol, dry at 105 to 110°C, and weigh as PbSO4. (1 + 3), and mix thoroughly.
Calculate to PbO.
8.2 Sodium Thiosulfate Solution (0.1N)—Dissolve 24.83 g
7.3 Red lead is rarely adulterated, but should the specimen of sodium thiosulfate (Na2S2O3·5H2O), freshly pulverized and
contain soluble barium compounds, the PbSO4 obtained in 8.2 dried between filter paper, and dilute with water to 1 litre at the
will contain BaSO4. In this case, precipitate the lead as sulfide temperature at which the titrations are to be made. The solution
from a slightly acid (HCl) solution, dissolve the PbS in hot is best made with well-boiled water free from CO2, or let stand
diluted HNO3, and determine the lead as sulfate or chromate. 8 to 14 days before standardizing, as described in Section 5 of
7.4 If the specimen contains significant amounts of calcium Test Method D1959.
or magnesium, boil the HNO3 − H2O2 solution (7.1) until all 8.3 Starch Solution—Stir 2 to 3 g of potato starch with 100
the lead is converted into nitrate and then determine the lead as mL of salicylic acid solution (1 %), and boil the mixture until
PbCrO4. the starch is practically dissolved, then dilute to 1 L (Note 3),
7.5 If soluble barium, calcium, or magnesium are to be or prepare as described in 7.8.2 of Test Method D1959.
determined, precipitate the lead as sulfide from a slightly acid
solution (HCl), dissolve the PbS in hot diluted HNO3, and NOTE 3—Lead Peroxide—If the pigment contains an appreciable
amount of nitrite (nitrate has no effect on the method), leach out
determine the lead as sulfate. Boil the filtrate from the PbS to water-soluble matter as below, dry the residue and determine PbO2 as
expel H2S, add a little bromine water to oxidize iron (if above, calculating to basis of original specimen.
present), boil to expel bromine, and precipitate the barium with
a few millilitres of H2SO4 (1 + 3). Filter and weigh as BaSO4. 9. Procedure
Calculate to BaO or BaCO3. To the filtrate from the BaSO4 add
NH4OH in slight excess, filter off any precipitate of 9.1 Weigh 1 g of the finely ground sample, transfer to a
Fe(OH)3 + Al(OH)3, wash with hot water. Manganese, if 200-mL Erlenmeyer flask, add 20 mL of water; then add as
present, can be precipitated by adding bromine and NH4OH quickly as possible 40 mL of the “red lead solution” at room
and warming. Filter, wash with hot water, ignite, and weigh as temperature. If the sample is red lead that has been extracted
Mn3O4. Unite all the filtrates, make slightly acid with acetic from a paint or paste, in place of the water use 10 mL of a
acid, heat to boiling and pass H2S into the hot solution until mixture of 7 parts by volume of chloroform and 3 parts by
saturated (20 to 30 min); add 5 g of NH4Cl and let stand 5 h, volume of glacial acetic acid, and then add without delay the
filter off any ZnS, wash with H2S water, dissolve the ZnS in hot red lead solution. Add 30 mL of water containing 5 or 6 g of
diluted HCl and determine the zinc by titration with sodium acetate and titrate at once with 0.1 N Na2S2O3 solution,
K4Fe(CN)6. Or, boil off the H2S, filter out any separated sulfur adding the latter rather slowly and keeping the liquid con-
and determine the zinc as Zn2P2O7. Calcium may be deter- stantly in motion by whirling the flask. When the solution has
mined in the filtrate from the ZnS by expelling H2S and then become light yellow, rub-up any undissolved particles with the
adding NH4OH and ammonium oxalate. Titrate the calcium rod until free iodine no longer forms, wash off rod, add the
oxide precipitate using the procedure described in 13.3 of Test Na2S2O3 solution until pale yellow, add starch solution, and
Methods D50. In the filtrate from calcium determine magne- titrate until colorless. Add the 0.1 N iodine solution until blue
sium by precipitating with sodium phosphate solution, finally color is just restored and subtract the amount used for the
weighing as Mg2P2O7. volume of Na2S2O3 that had been added.

8. Lead Peroxide (PbO2) and True Red Lead (Pb3O4) 10. Calculation
NOTE 2—Method of Diehl (4) modified by Topf (5)—not applicable
when substances are present, other than oxides of lead, that liberate iodine 10.1 Calculate the lead peroxide and true red lead contents
under conditions given, or substances such as metallic lead which reduce as follows:
PbO2 to PbO without the liberation of iodine.
PbO2 = I × 0.942
Pb3O4 = PbO2 × 2.866 = I × 2.7
5
The boldface numbers in parentheses refer to a list of references at the end of
these test methods. where: I = iodine value of the Na2S2O3 solution,

2
 D49 − 83 (2014)
PbO 2 239.19 water, filter, and wash with hot water. Redissolve in HCl,
0.942 5 5 , and (1)
I2 253.81 reprecipitate as above, and wash thoroughly with hot water.
Acidify the united filtrates with HCl, adding a slight excess;
Pb 3 O 4 685.57 boil and add a slight excess of BaCl2 solution (10 %). Let stand
2.86616 5 5
PbO 2 239.19 on a steam bath for 1 h. Filter and wash with hot water. Ignite
11. Zinc and weigh as BaSO4. Calculate to SO3 (includes SO3 formed
from SO2).
11.1 If the volume is appreciable, evaporate off the alcohol
from the filtrate from total lead, make alkaline with NH4OH, 15.2 Or, dissolve 0.5 g of the sample in 25 mL of water, 10
then acid with HCl (sp gr 1.19), add 3 mL more of HCl, dilute mL of NH4OH (sp gr 0.90) and HCl in slight excess; dilute to
to about 250 mL with water, heat nearly to boiling and titrate about 150 mL with water and add a piece of aluminum foil
with standard K4Fe(CN)6 solution in accordance with 16.1.11 which should about cover the bottom of the beaker (being held
of Practice D215. Report as ZnO (includes cadmium). Iron, on the bottom by means of a stirring rod). Heat gently till all
copper, or other interfering substances should first be removed lead is precipitated, decant through a filter, pressing the lead
as described in 25.2.3 of Practice D215. sponge with a flattened rod, and washing with hot water. Add
to the filtrate a little bromine water, boil until bromine is
12. Matter Soluble in Water expelled, add 15 mL of BaCl2 solution (10 %), let stand on a
12.1 Determine the amount of water soluble material pres- steam bath for 1 h, filter, wash with hot water, ignite, and weigh
ent in accordance with the procedure in Section 5 of Test as BaSO4 (any SrSO4 present is not decomposed in this
Methods D1208 or determine in accordance with Test Methods method).6
D1301. 16. Iron Oxide
13. Total Silica 16.1 Determine iron oxide in accordance with Section 12 of
13.1 Digest 5 g of the sample in a covered casserole with 5 Test Methods D50, or in a large beaker, treat 20 g of the sample
mL of HCl and 15 mL of HNO3 (1 + 1). Evaporate to dryness with 20 mL of water, 20 mL of HNO3 (sp gr 1.42), and 3 mL
to dehydrate. Cool, treat with hot water and HNO3, boil, filter, of formaldehyde solution. Warm until all PbO2 is dissolved,
wash with hot acid ammonium acetate solution, then dilute dilute with water, warm, filter off insoluble matter, and wash
HCl and finally hot water. Ignite and weigh as SiO2. The with hot water. Ignite filter and insoluble matter, and evaporate
residue may be treated with H2SO4 and HF in cases of doubt as with H2SO4 and HF. To filtrate from insoluble matter add 14
to purity. mL of H2SO4 (1 + 1), filter off PbSO4, and wash. Dissolve the
residue from HF and H2SO4 in H2SO4 and add to the filtrate
14. Carbon Dioxide from PbSO4. Dilute to 500 mL and determine iron colorimetri-
cally in an aliquot, using the same amounts of HNO3, H2SO4,
14.1 Determine carbon dioxide by the evolution method,
and formaldehyde in the comparison solution Ref (7). Calcu-
using diluted HCl and stannous chloride.
late to Fe2O3.
15. Soluble Sulfates
17. Keywords
15.1 Sulfates Other Than Barium Sulfate—Treat 0.5 g of the
sample with 5 mL of water, 3 g of NH4Cl, and 5 mL of HCl 17.1 chemicals analysis; lead dioxide; red lead; tetra lead
saturated with bromine. Digest (covered) on steam bath about oxide
15 min. Add 25 mL of water, neutralize with dry Na2CO3, and
add about 2 g more. Boil 10 to 15 min, let settle, dilute with hot 6
The solubility of BaSO4 is increased by the presence of aluminum chloride (6).

REFERENCES

(1) Zerr, and Mayer, Tests for Coal Tar Colors in Aniline Lakes. (5) Zeitschrift für Analytische Chemie, ZANCA, Vol 26, p. 296.
(2) Schultz, and Julius, A Systematic Survey of the Organic Coloring (6) Skoog, D. A. and West, D. M., Fundamentals of Analytical Chemistry,
Matters. Holt, Rinehart and Winston, Inc., New York, 1969, p. 192.
(3) Mulliken, Identification of Pure Organic Compounds; Commercial (7) Lunge-Berl, “Chemische-technisch Untersuchungs-Methoden,” Vol 2,
Dyestuffs, Vol III. p. 95, 6th Ed.
(4) Dinglers, Dinglers Polytechnisches Journal, DPJOA, Vol 246, p. 196.

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 D49 − 83 (2014)
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