Designation: E 37 – 95

Standard Test Methods for

Chemical Analysis of Pig Lead1
This standard is issued under the fixed designation E 37; 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 3. Significance and Use

1.1 These test methods cover the chemical analysis of pig 3.1 These test methods for the chemical analysis of metals
lead having chemical compositions within the following limits: and alloys are primarily intended to test such materials for
Element Concentration Range, % compliance with compositional specifications. It is assumed
Lead 99.5 to 99.99 that all who use these methods will be trained analysts capable
Silver 0.001 to 0.03 of performing common laboratory procedures skillfully and
Bismuth 0.002 to 0.2
Copper 0.001 to 0.1 safely. It is expected that work will be performed in a properly
Arsenic 0.0005 to 0.02 equipped laboratory.
Antimony 0.001 to 0.02
Tin 0.001 to 0.02 4. Apparatus, Reagents, and Photometric Practice
Zinc 0.001 to 0.005
Iron 0.0005 to 0.005 4.1 Apparatus and reagents required for each determination
1.2 The test methods appear in the following order: are listed in separate sections of each test method. The
apparatus, standard solutions, and certain other reagents used
Sections
Antimony by the Rhodamine-B Photometric Method 19-28 in more than one procedure are referred to by number and shall
Copper, Bismuth, Silver, and Zinc by the Atomic Absorption conform to the requirements prescribed in Practices E 50,
Method 8-18 except that photometers shall conform to the requirements
1.3 This standard does not purport to address all of the prescribed in Practice E 60.
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to consult and 5. Sampling
establish appropriate safety and health practices and deter- 5.1 For procedures for sampling the material, refer to
mine the applicability of regulatory limitations prior to use. Specification B 29.
For precautions to be observed in the use of certain reagents,
6. Rounding Calculated Values
refer to Practices E 50. Specific hazard statements are given in
the individual test methods. 6.1 Calculated values shall be rounded to the desired num-
ber of places as directed in 3.4 to 3.6 of Practice E 29.
2. Referenced Documents
7. Interlaboratory Studies
2.1 ASTM Standards:
B 29 Specification for Pig Lead2 7.1 These test methods have been evaluated in accordance
E 29 Practice for Using Significant Digits in Test Data to with Practice E 173, unless otherwise noted in the precision
Determine Conformance With Specifications3 section.
E 50 Practices for Apparatus, Reagents, and Safety Precau-
COPPER, BISMUTH, SILVER, AND ZINC BY THE
tions for Chemical Analysis of Metals4
ATOMIC ABSORPTION METHOD
E 60 Practice for Photometric and Spectrophotometric
Methods for Chemical Analysis of Metals4 8. Scope
E 173 Practice for Conducting Interlaboratory Studies of
8.1 This test method covers the determination of bismuth in
Methods for Chemical Analysis of Metals4
concentrations from 0.002 to 0.2 %, copper from 0.001 to
0.1 %, silver from 0.001 to 0.03 %, and zinc from 0.001 to
1
0.005 %.
These test methods are under the jurisdiction of ASTM Committee E-1 on
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct
responsibility of Subcommittee E01.05 on Zinc, Tin, Lead, Cadmium, Beryllium
9. Summary of Test Method
and Other Metals. 9.1 The sample is dissolved in a nitric-perchloric acid
Current edition approved Nov. 10, 1995. Published January 1996. Originally
published as E 37 – 42 T. Last previous edition E 37 – 76 (1990)e1.
mixture, the solution is fumed, and hydrochloric acid is added
2
Annual Book of ASTM Standards, Vol 02.04. to precipitate lead chloride. The hydrochloric-perchloric acid
3
Annual Book of ASTM Standards, Vol 14.02. solution is aspirated into the air-acetylene flame of an atomic
4
Annual Book of ASTM Standards, Vol 03.05.

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

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 E 37
absorption spectrophotometer. The absorption of the resonance 12.1.2 Curve Linearity—Calculate the difference between
line energy from the spectrum of each element is measured and the scale readings obtained with water and the lowest of the
compared with that of calibration solutions of the same five equally spaced calibration solutions. If necessary, convert
element. The lines used were Cu 3247, Bi 2230, Ag 3280, and this difference and the difference calculated in 12.1.1 to
Zn 2138 Å. absorbance. Divide the difference for the highest interval by
that for the lowest interval. If this ratio is not 0.70 or greater,
10. Concentration Range proceed as directed in 10.1.4.
10.1 The concentration range for each element must be 12.1.3 Minimum Stability—If the variability of the readings
determined experimentally because the optimum range will of the highest calibration solution and of water is not less than
depend upon the individual instrument. Determine the appro- 1.8 % and 1.4 %, respectively, as calculated below, proceed as
priate concentration range of each element as follows: directed in 10.1.5.

Œ
10.1.1 Prepare a dilute standard solution as directed in
100 (~C – C̄!2
Section 14. Refer to 14.1 for suggested initial concentrations. VC 5 (1)
C̄ n–1
10.1.2 Prepare the instrument for use as directed in 16.1.
Measure the instrument response while aspirating water, the
calibration solution with the lowest concentration, and the two Vo 5
100
C̄
Œ
(~O – Ō!2
n–1
with the highest concentrations. Determine the minimum
response and the curve linearity as directed in 12.1.1 and where:
12.1.2, respectively. VC 5 percent variability of the highest calibration
10.1.3 If the instrument meets or surpasses the minimum readings,
response and curve linearity criteria, the initial concentration C̄ 5 average absorbance value for the highest
range may be considered suitable for use. In this case proceed calibration solution,
as directed in 10.1.5. ( (C − X̄)2 5 sum of the squares of the n differences
10.1.4 If the minimum response is not achieved, prepare between the absorbance readings of the high-
another dilute standard solution to provide a higher concentra- est calibration solution and their average,
tion range, and repeat 10.1.2 and 10.1.3. If the calibration curve VO 5 percent variability of the readings on water
does not meet the linearity criterion, prepare another dilute relative to C̄,
standard solution to provide a lower concentration range, and Ō 5 average absorbance value of water,
repeat 10.1.2 and 10.1.3. If a concentration range cannot be ( (O − 5 sum of the squares of the n difference be-
found for which both criteria can be met, do not use this Ō)2 tween the absorbance readings of water and
method until the performance of the apparatus has been their average, and
n 5 number of determinations, three or more.
improved.
10.1.5 Perform the stability test as directed in 12.1.3. If 13. Reagents
either of the minimum stability requirements is not met, do not 13.1 Bismuth, Standard Solution (1 mL 5 1.00 mg Bi)—
use this method until the repeatability of the readings has been Transfer 1.00 g of bismuth (purity: 99.9 % min) to a 400-mL
suitably improved. beaker and dissolve in 50 mL of HNO3 (1 + 1), heating gently
if necessary. When dissolution is complete, cool, transfer to a
11. Interferences
1-L volumetric flask, add 100 mL of HNO3 (1 + 1), dilute to
11.1 Elements ordinarily present do not interfere if their volume, and mix. Store in a polyethylene bottle.
concentrations are under the maximum limits shown in 1.1. 13.2 Copper, Standard Solution (1 mL 5 1.00 mg Cu)—
Proceed as directed in 13.1, but substitute 1.00 g of copper
12. Apparatus (purity: 99.9 % min) for the bismuth.
12.1 Atomic Absorption Spectrophotometer—Use hollow- 13.3 Silver, Standard Solution (1 mL 5 1.00 mg Ag)—
cathode lamps, operated in accordance with manufacturers’ Proceed as directed in 13.1 but substitute 1.00 g of silver
recommendations as sources for the following lines: Cu 3247, (purity: 99.9 % min) for the bismuth.
Bi 2230, Ag 3280, and Zn 2138 Å. Aspirate the solutions into 13.4 Zinc, Standard Solution (1 mL 5 0.100 mg Zn)—
an air-acetylene flame of a premix burner. Determine that the Proceed as directed in 13.1 but substitute 0.100 g of zinc
atomic absorption spectrophotometer is satisfactory for use in (purity: 99.9 % min) for the bismuth.
this method by proceeding as directed in 12.1.1-12.1.3.
14. Calibration
NOTE 1—Optimum settings for the operating parameters of the atomic 14.1 Dilute Standard Solution—Using pipets, transfer to
absorption spectrophotometer vary from instrument to instrument.
500-mL volumetric flasks the following volumes of each
12.1.1 Minimum Response—Calculate the difference be- standard solution: bismuth, 20 mL; copper, 10 mL; silver, 5
tween the readings of the two highest of five equally spaced mL; and zinc, 10 mL. Dilute to volume and mix. Adjust the
(14.2) calibration solutions. This difference must be at least 40 concentration of a dilute standard solution if the proper range
scale units. is not obtained when the 5, 10, 15, 20, and 25-mL portions are
NOTE 2—The scale unit is defined as the smallest numerical interval diluted to 100 mL and tested.
that is estimated in taking each reading on the instrument. If the scale is 14.2 Calibration Solutions—Prepare five calibration solu-
non-linear, the largest unit defined in this manner is used. tions for each element to be determined. Using pipets, transfer

2
 E 37
5, 10, 15, 20, and 25-mL portions of the appropriate dilute 16.2.3 Proceed as directed in 16.2.2 at least twice more.
standard solution to 100-mL volumetric flasks. Add sufficient
volumes of HCl and HClO4 to each flask to yield final acid 17. Calculations
concentrations equal to that of the corresponding test solution, 17.1 Calculate the variability of the readings for water and
dilute to volume, and mix. Do not use solutions that have stood the highest calibration solution as directed in 12.1.3 to deter-
more than 24 h. mine whether they are less than 1.4 % and 1.8 %, respectively.
If they are not, disregard the data, readjust the instrument, and
15. Procedure proceed again as directed in 16.2.
15.1 Test Solution: 17.2 If necessary, convert the average of the readings for
15.1.1 Transfer a 10.0-g sample, weighed to the nearest 10 each calibration solution to absorbance. Calculate the net
mg, to a 300-mL Erlenmeyer flask (Note 3). Add 3 mL of absorbance of the test solution by subtracting the absorbance of
HNO3 and 15 mL of HClO4, and heat until dissolution is the reagent blank solution.
complete. Evaporate to strong fumes of perchloric acid and 17.3 Prepare a calibration curve by plotting the absorbance
cool. values for the calibration solutions against milligrams of the
elements per millilitre.
NOTE 3—Due to the limited solubility of silver chloride, the silver
concentration in the sample solution should be less than 1 mg/100 mL. If
17.4 Convert the net absorbance value of the test solution to
the expected silver concentration is higher than 0.01 %, choose a sample milligrams of the element per millilitre by means of the
weight that limits the silver concentration to less than 1 mg/100 mL. appropriate calibration curve.
15.1.2 Add 50 mL of water and, while swirling, heat to 17.5 Calculate the percentage of the element as follows
boiling. Add 25 mL of HCl. If less than a 10-g sample is used, (Note 5):
add 20 mL HCl plus 0.5 mL for each gram of sample used. Element, % 5 @~A 3 B 3 0.977!/C# 3 100 (2)
Heat again to boiling and cool to room temperature.
where:
15.1.3 Transfer the solution and precipitate to a 100-mL
A 5 milligrams of element per millilitre,
volumetric flask, dilute to volume with water, and mix thor- B 5 final volume of test solution in millilitres, and
oughly. Allow the precipitated lead chloride to settle. Use the C 5 milligrams of sample represented in final volume of
supernatant solution, or dilute an appropriate aliquot of the test solution.
supernatant solution to provide a concentration of the element
being measured which lies within the concentration range NOTE 5—The factor 0.977 is used to compensate for the volume error
determined in Section 10. in the 100 mL of final test solution caused by the 13.1 g of lead chloride
precipitate. If less than 10 g of sample is used, calculate and apply an
15.2 Reagent Blank Solution—Prepare a reagent blank by appropriate factor.
adding 3 mL of HNO3 and 15 mL of HClO4 to a 300-mL
Erlenmeyer flask and proceed as directed in 15.1. 18. Precision and Bias
16. Photometry 18.1 Seven laboratories cooperated in testing this method,
with one laboratory reporting a second pair of values; the data
16.1 Instrument Adjustment—Optimize the response of the are summarized in Table 1.
instrument as directed in 16.1.1-16.1.4. 18.2 The accuracy of this method could not be evaluated
16.1.1 Set the instrument parameters approximately at the because adequate certified standard reference materials were
values obtained in 12.1, and light the burner. unavailable at the time of testing. The user is cautioned to
16.1.2 Adjust the instrument to the approximate wavelength verify by the use of certified reference materials, if available,
for the element to be determined, permit the instrument to that the accuracy of this method is adequate for the contem-
reach thermal equilibrium, and complete the wavelength ad- plated use.
justment to obtain maximum absorption while aspirating the
highest calibration solution. ANTIMONY BY THE RHODAMINE-B
16.1.3 Optimize fuel, air, and burner adjustments while PHOTOMETRIC METHOD
aspirating the highest calibration solution.
19. Scope
16.1.4 Aspirate water long enough to establish that the
absorbance reading is stable and then set the initial reading 19.1 This test method covers the determination of antimony
(approximately zero absorbance or 100 % transmittance). in pig lead in concentrations from 0.0008 to 0.005 %.
16.2 Photometry:
TABLE 1 Statistical Information
16.2.1 Aspirate the test solution and note, but do not record
the reading. Repeatability (R1, Reproducibility (R2,
Test Specimen Element Found, %
E173) E173)
NOTE 4—Avoid transferring particles of precipitated lead chloride that Bi B-2 0.0024 0.0010 0.0010
may clog the aspirator during the measurements of the test solution. A-2 0.223 0.016 0.021
Cu B-2 0.0014 0.0002 0.0002
16.2.2 Aspirate water until the initial reading is again A-2 0.112 0.010 0.012
obtained. Aspirate the calibration solutions and test solution in Ag B-2 0.0010 0.0002 0.0002
order of increasing instrument response, starting with the A-2 0.0308 0.0052 0.0052
Zn C-1 0.0001 0.0004 0.0004
reagent blank. When a stable response is obtained for each D-1 0.0021 0.0003 0.0009
solution, record the reading.

3
 E 37
20. Summary of Test Method 25.4 Color Development:
20.1 After nitric acid dissolution of the sample, lead is 25.4.1 Add 10 mL of HCl and swirl to dissolve the residue.
separated as the sulfate. Antimony is oxidized with sulfatoceric Transfer to a 125-mL separatory funnel. Rinse the beaker with
acid and extracted into isopropyl ether; rhodamine-B is added 7 mL of HCl and add the rinsings to the separatory funnel.
and photometric measurement is made at approximately 550 Using a pipet, add 1 mL of sulfatoceric acid solution and mix.
nm. Using a pipet, add 20 mL of the washed isopropyl ether. Shake
for approximately 30 s, releasing the pressure periodically.
21. Concentration Range 25.4.2 To the original beaker, add 6 mL of water, swirl, and
21.1 The recommended concentration range is from 0.002 transfer to the separatory funnel. Repeat one more time. Shake
to 0.020 mg of antimony per 20 mL of solution, using a 1-cm for approximately 30 s and allow to cool to room temperature.
cell. 25.4.3 Shake for another 30 s. Allow the phases to separate
and discard the lower (aqueous) phase. Add 20 mL of
NOTE 6—This method has been written for cells having a 1-cm light
rhodamine-B solution and shake for approximately 30 s. Allow
path. Cells having other dimensions may be used, provided suitable
adjustments can be made in the amounts of sample and reagents used. the phases to separate and discard the lower phase.
25.4.4 Draw off the ether phase into a dry, stoppered test
22. Stability of Color tube and allow to settle for approximately 30 s before trans-
22.1 Because of the volatility of ether, it is advisable to ferring to the absorption cell.
make readings promptly. 25.5 Photometry:
25.5.1 Multiple-Cell Photometer—Measure the cell correc-
23. Interferences tion using absorption cells with a 1-cm light path and a light
23.1 Elements ordinarily present do not interfere if their band centered at approximately 550 nm. Using the test cell,
concentrations are under the maximum limits shown in 1.1. take the photometric readings of the calibration and reagent
blank solutions.
24. Reagents 25.5.2 Single-Cell Photometer—Transfer a suitable portion
24.1 Antimony, Standard Solution A (1 mL 5 0.1 mg Sb)— of the reference solution to an absorption cell with a 1-cm light
Dissolve 0.100 g of antimony (purity: 99.8 % min) in 1 mL of path and adjust the photometer to the initial setting, using a
HNO3 and 20 mL of H2SO4. Heat until dissolution is complete light band centered at approximately 550 nm. While maintain-
and then fume for 5 min. Cool, dilute carefully to about 200 ing this adjustment, take photometric readings of the calibra-
mL, and transfer to a 1-L volumetric flask. Cool, dilute to tion and reagent blank solutions.
volume, and mix. 25.6 Calibration Curve—Plot the net photometric readings
24.2 Antimony, Standard Solution B (1 mL 5 0.005 mg of the calibration solutions against milligrams of antimony per
Sb)—Using a pipet, transfer 10 mL of Solution A (1 mL 5 0.1 20 mL of solution.
mg Sb) to a 200-mL volumetric flask. Add 5 mL of H2SO4.
Cool, dilute to volume, and mix. 26. Procedure
24.3 Isopropyl Ether, Washed—Transfer 500 mL of isopro- 26.1 Test Solution:
pyl ether to a 1-L separatory funnel. Add 200 mL of HCl and 26.1.1 Transfer a 1.00-g sample, weighed to the nearest 1
shake for 1 min. (Take care to avoid pressure build-up.) Add mg, to a 250-mL beaker. Add 10 mL of HNO3 (1 + 2) and heat
200 mL of water and shake for 30 s. Allow the phases to gently until dissolution is complete. Add 5 mL of H2SO4
separate and discard the aqueous phase. Wash the organic (1 + 1), dilute to 30 mL, mix thoroughly, and cool to room
phase with 200 mL of water, and shake for 30 s. Allow the temperature. Filter through an 11-cm coarse paper into a
phases to separate and discard the aqueous phase. Repeat one 250-mL beaker. Wash the precipitate with three 5-mL portions
more time. Do not use the reagent if it has stood more than 24 of cold water. Discard the precipitate.
h. 26.1.2 For antimony concentrations from 0.0008 to
24.4 Rhodamine-B Solution (0.1 g/L in 0.5 M HCl)— 0.002 %, use the entire filtrate for color development. For
Dissolve 50 mg of rhodamine-B in water. Add 22 mL of HCl antimony concentrations from 0.002 to 0.005 %, transfer the
and dilute to 500 mL. filtrate to a 100-mL volumetric flask, dilute to volume, and mix
24.5 Sulfatoceric Acid Solution (2.0 g/L)—Dissolve 200 mg (Note 7). Using a pipet, transfer 40 mL to a 250-mL beaker.
of sulfatoceric acid (H4Ce(SO4)4) in water. Add 3 mL of
H2SO4 (1 + 1) and dilute to 100 mL. NOTE 7—If concentrations greater than 0.005% are encountered, a
correspondingly larger volumetric flask or a smaller aliquot portion should
25. Preparation of Calibration Curve be used.
25.1 Calibration Solutions—Using pipets, transfer 1, 2, 3, 26.1.3 Evaporate the filtrate or the aliquot to dryness, but do
4, and 5 mL of Solution B (1 mL 5 0.005 mg Sb) to 250-mL not bake. Remove from the heat and cool to room temperature.
beakers. Add 1 mL of H2SO4 and evaporate to dryness, but do Proceed as directed in 34.4.
not bake. Proceed as directed in 33.4. 26.2 Reagent Blank—Carry a reagent blank through the
25.2 Reference Solution—Isopropyl ether, washed. entire procedure using the same amount of all reagents with the
25.3 Reagent Blank—Transfer 1 mL of H2SO4 to a 250-mL sample omitted.
beaker and evaporate to dryness, but do not bake. Proceed as 26.3 Reference Solution—Isopropyl ether, washed.
directed in 33.4. 26.4 Color Development—Proceed as directed in 33.4.

4
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26.5 Photometry—Take the photometric readings of the 28. Precision and Bias
reagent blank and test solutions as directed in 33.5. 28.1 Data on this test method were obtained by six labora-
tories, with two laboratories providing a second pair of values.
27. Calculation The data are summarized in Table 2.
27.1 Convert the net photometric readings of the test and 28.2 The accuracy of this test method could not be evalu-
reagent blank solutions to milligrams of antimony by means of ated because adequate certified standard reference materials
the calibration curve. Calculate the percent of antimony as were unavailable at the time of testing. The user is cautioned to
verify by the use of certified reference materials, if available,
follows:
that the accuracy of this method is adequate for the contem-
Antimony, % 5 ~A – B!/~C 3 10! (3) plated use.
where: 29. Keywords
A 5 milligrams of antimony found in 20 mL of the final 29.1 antimony; atomic absorption; bismuth; colorimetry;
test solution, copper; lead; silver; zinc
B 5 milligrams of antimony found in 20 mL of final
TABLE 2 Statistical Information
reagent blank solution, and
C 5 grams of sample represented in 20 mL of the final test Test Specimen Element Found, %
Repeatability (R1, Reproducibility (R2,
E 173) E 173)
solution. 1 0.0008 0.0002 0.0002
2 0.0045 0.0003 0.0007

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