Designation: E 478 – 03

Standard Test Methods for

Chemical Analysis of Copper Alloys1
This standard is issued under the fixed designation E 478; 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 Tin by the Phenylfluorone Photometric Test

Method [0.01 to 1.0 %] 112-122
1.1 These test methods cover the chemical analysis of Zinc by Atomic Spectrometry [0.2 to 2 %] 78-88
copper alloys having chemical compositions within the follow- Zinc by the (Ethylenedinitrilo)tetraacetic Acid
ing limits:2 (EDTA) Titrimetric Test Method [2 to 40 %] 46-53

Element Concentration, % 1.3 This standard does not purport to address all of the
Aluminum 12.0 max
safety concerns, if any, associated with its use. It is the
Antimony 1.0 max responsibility of the user of this standard to establish appro-
Arsenic 1.0 max priate safety and health practices and determine the applica-
Cadmium 1.5 max
Cobalt 1.0 max
bility of regulatory limitations prior to use.
Copper 40.0 min
Iron 6.0 max 2. Referenced Documents
Lead 27.0 max
Manganese 6.0 max
2.1 ASTM Standards:
Nickel 50.0 max E 29 Practice for Using Significant Digits in Test Data to
Phosphorus 1.0 max Determine Conformance with Specifications3
Silicon 5.0 max
Sulfur 0.1 max
E 50 Practices for Apparatus, Reagents, and Safety Precau-
Tin 20.0 max tions for Chemical Analysis of Metals4
Zinc 50.0 max E 60 Practice for Photometric and Spectrophotometric
1.2 The test methods appear in the following order: Methods for Chemical Analysis of Metals4
Sections
E 173 Practice for Conducting Interlaboratory Studies of
Aluminum by the Carbamate Extraction-(Ethyl- Methods for Chemical Analysis of Metals4
enedinitrilo) Tetraacetate Titrimetric Test E 255 Practice for Sampling Copper and Copper Alloys for
Method [2 to 12 %] 70-77
Copper by the Combined Electrodeposition
Determination of Chemical Composition4
Gravimetric and Oxalyldihydrazide Photomet- E 1024 Guide for Chemical Analysis of Metals and Metal
ric Test Method [50 %, minimum] 9-17 Bearing Ores by Flame Atomic Absorption Spectropho-
Iron by the 1,10-Phenanthroline Photometric
Test Method [0.003 to 1.25 %] 18-27 tometry4
Lead by the Atomic Absorption Test Method E 1601 Practice for Conducting an Interlaboratory Study to
[0.002 to 15 %] 89-99 Evaluate the Performance of an Analytical Method4
Lead by the (Ethylenedinitrilo)tetraacetic Acid
(EDTA) Titrimetric Test Method [2.0 to
30.0 %] 28-35
3. Significance and Use
Nickel by the Dimethylglyoxime Extraction Pho- 3.1 These test methods for the chemical analysis of metals
tometric Test Method [0.03 to 5.0 %] 36-45
Nickel by the Dimethylglyoxime Gravimetric and alloys are primarily intended as referee methods to test
Test Method [4 to 50 %] 54-61 such materials for compliance with compositional specifica-
Silver in Silver-Bearing Copper by the Atomic tions. It is assumed that all who use these methods will be
Absorption Test Method [0.01 to 0.12 %] 100-111
Tin by the Iodatimetric Titration Test Method trained analysts capable of performing common laboratory
[0.5 to 20 %] 62-69 procedures skillfully and safely. It is expected that work will be
performed in a properly equipped laboratory.
1
These test methods are under the jurisdiction of ASTM Committee E01 on 4. Apparatus, Reagents, and Photometric Practice
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct 4.1 Apparatus and reagents required for each determination
responsibility of Subcommittee E01.05 on Cu, Pb, Zn, Cd, Sn, Be, their Alloys and
Related Metals.
are listed in separate sections preceding the procedure. The
Current edition approved August 10, 2003. Published September 2003. Origi-
nally approved in 1973. Last previous edition approved in 1996 as
3
E 478 – 89a (1996). Annual Book of ASTM Standards, Vol 14.02.
2 4
The actual limits of application of each test method are presented in 1.2. Annual Book of ASTM Standards, Vol 03.05.

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

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 E 478 – 03
apparatus, standard solutions, and certain other reagents used 12.3 Electrodes for Electroanalysis—Platinum electrodes of
in more than one procedure are referred to by number and shall the stationary type are recommended as described in 12.3.1 and
conform to the requirements prescribed in Practices E 50, 12.3.2, but strict adherence to the exact size and shape of the
except that photometers shall conform to the requirements electrodes is not mandatory. When agitation of the electrolyte
prescribed in Practice E 60. is permissible in order to decrease the time of deposition, one
4.2 Photometric practice prescribed in these test methods of the types of rotating forms of electrodes, generally available,
shall conform to Practice E 60. may be employed. The surface of the platinum electrodes
should be smooth, clean and bright to promote uniform
5. Hazards deposition and good adherence. Sandblasting is not recom-
5.1 Specific hazard statements are given in Section 5, Note mended.
4, and Section 106. 12.3.1 Cathodes—Platinum cathodes may be formed either
5.2 For other precautions to be observed in the use of certain from plain or perforated sheets or from wire gauze, and may be
reagents in these test methods, refer to Practices E 50. either open or closed cylinders. Gauze cathodes are recom-
mended, and shall be made preferably from 50-mesh gauze
6. Sampling woven from wire approximately 0.21 mm (0.0085 in.) in
6.1 For procedures for sampling the material, refer to diameter. The cathode should be stiffened by doubling the
Practice E 255. However, this method does not supersede any gauze for about 3 mm at the top and the bottom of the cylinder
sampling requirements specified in a specific ASTM material or by reinforcing the gauze at the top and bottom with a
specification. platinum band or ring. The cylinder should be approximately
30 mm in diameter and 50 mm in height. The stem should be
7. Rounding Calculated Values made from a platinum alloy wire such as platinum-iridium,
7.1 Calculated values shall be rounded to the desired num- platinum-rhodium, or platinum-ruthenium, having a diameter
ber of places as directed in Practice E 29. of approximately 1.30 mm. It should be flattened and welded
the entire length of the gauze. The over-all height of the
8. Interlaboratory Studies cathode should be approximately 130 mm. A cathode of these
dimensions will have a surface area of 135 cm2 exclusive of the
8.1 These test methods were evaluated in accordance with
stem.
Practice E 173 unless otherwise noted in the precision section.
12.3.2 Anodes—Platinum anodes may be of the spiral type
E 173 has been replaced by Practice E 1601. The Reproduc-
when anodic deposits are not being determined, or if the
ibility Index R2 corresponds to the Reproducibility Index R of
deposits are small (as in the electrolytic determination of lead
Practice E 1601. Likewise the Repeatability Index R1 of E 173
when it is present in amounts not over 0.2 %). When used in
corresponds to Repeatablility Index r of Practice E 1601.
analyses where both cathodic and anodic plates are to be
COPPER BY THE COMBINED determined, the anodes should be of wire gauze. Spiral anodes
ELECTRODEPOSITION GRAVIMETRIC AND should be made from 1.00-mm or larger platinum wire formed
OXALYLDIHYDRAZIDE PHOTOMETRIC TEST into a spiral of seven turns having a height of approximately 50
METHOD mm and a diameter of 12 mm, the over-all height being
approximately 130 mm. A spiral anode of this description will
9. Scope have a surface area of 9 cm2. Platinum gauze anodes should be
made of the same material and of the same general design as
9.1 This test method covers the determination of copper in
platinum gauze cathodes. The anode cylinder should be ap-
concentrations greater than 50 %.
proximately 12 mm in diameter and 50 mm in height and the
10. Summary of Test Method over-all height of the anode should be approximately 130 mm.
A gauze anode of these dimensions will have a surface area of
10.1 After dissolution of the sample in nitric and hydrof- 54 cm2. Both areas are exclusive of the stem.
luoric acids, the oxides of nitrogen are reduced with hydrogen 12.3.3 Gauze cathodes are recommended where rapid elec-
peroxide, and the copper deposited electrolytically. Loss of trolysis is used.
platinum from the anode is minimized by the addition of lead.
The copper oxalyldihydrazide complex is formed with the 13. Reagents
copper remaining in the electrolyte. Photometric measurement 13.1 Ammonium Chloride Solution (0.02 g/L)—Dissolve
is made at approximately 540 nm. 0.02 g of ammonium chloride (NH4Cl) in water and dilute to 1
L.
11. Interferences
13.2 Hydrogen Peroxide (3 %)—Dilute 100 mL of 30 %
11.1 The elements ordinarily present do not interfere if their hydrogen peroxide to 1 L.
concentrations are under the maximum limits shown in 1.1. 13.3 Lead Nitrate Solution (10 g/L)—Dissolve 10.0 g of
lead nitrate (Pb(NO3)2) in water and dilute to 1 L.
12. Apparatus
12.1 Polytetrafluoroethylene or Polypropylene Beakers, 14. Procedure
250-mL capacity. 14.1 Transfer a 2.000-g sample, weighed to the nearest 0.1
12.2 Polytetrafluoroethylene or Polypropylene Split Covers. mg, to a 250-mL poly(tetrafluoroethylene) or polypropylene

2
 E 478 – 03
beaker, add 2 mL of HF, and 30 mL of HNO3 (1 + 1). Cover (1 + 1). Evaporate till nearly to dryness. Add 5 mL of water to
with a cover glass and allow to stand for a few minutes until the dissolve the residue. Transfer to a 1-L volumetric flask, dilute
reaction has nearly ceased. Warm but do not heat over 80°C. to volume, and mix.
When dissolution is complete, add 25 mL of 3 % H2O2 and 3 16.4.5 Copper, Standard Solution B (1 mL = 0.010 mg
mL of Pb(NO3)2 solution. Rinse the cover glass and dilute to Cu)—Using a pipet, transfer 10 mL of copper solution A (1
approximately 150 mL with NH4Cl solution. mL = 1.0 mg Cu) to a 1-L volumetric flask, dilute to volume
14.2 With the electrolyzing current off, position the anode and mix.
and the accurately weighed cathode in the solution so that the 16.4.6 Oxalyldihydrazide Solution (2.5 g/L)—Dissolve 2.5
gauze is completely immersed. Cover the beaker with a split g of oxalyldihydrazide in warm water and dilute to 1 L.
plastic cover. 16.5 Preparation of Calibration Curve:
14.3 Start the electrolysis and increase the voltage until the 16.5.1 Calibration Solutions:
ammeter
2
indicates a current which is equivalent to about 1.0 16.5.1.1 Transfer 25 mL of boric acid solution to a 250-mL
A/dm and electrolyze overnight. Alternatively electrolyze at a volumetric flask and then add a solution containing 150 mL of
current density of 4 A/dm2 for 1.5 h. (The more rapid procedure water, 2 mL of HF, and 30 mL of HNO3 (1 + 1). Dilute to
requires the use of gauze electrodes). volume, and mix.
14.4 Slowly withdraw the electrodes (or lower the beaker) 16.5.1.2 Transfer 10 mL of this solution to each of four
with the current still flowing, and rinse with a stream of water 50-mL volumetric flasks. Using pipets, transfer 1, 3, 5, and 7
from a wash bottle. Quickly remove the cathode, rinse it in mL of copper solution B (1 mL = 0.010 mg Cu) to the flasks.
water, and then dip into two successive baths of ethanol or Proceed as directed in 16.5.3.
methanol. Dry in an oven at 110°C for 3 to 5 min.
16.5.2 Reference Solution—Add 10 mL of boric acid solu-
14.5 Return the voltage to zero, and turn off the switch.
tion prepared as directed in 16.5.1.1 to a 50-mL volumetric
Reserve the electrolyte.
flask and proceed as directed in 16.5.3.
14.6 Allow the electrode to cool to room temperature, and
16.5.3 Color Development—Add in order, and with mixing
weigh.
after each addition, 5 mL of citric acid solution, 6 mL of
NH4OH, 10 mL of acetaldehyde solution, and 10 mL of
15. Calculation
oxalyldihydrazide solution. Cool, dilute to volume, and mix.
15.1 Calculate the percentage of copper as follows: Allow to stand for 30 min and proceed as directed in 16.5.4.
Copper, % 5 [~A 1 B/C] 3 100 (1) 16.5.4 Photometry:
16.5.4.1 Multiple-Cell Photometer—Measure the cell cor-
where: rection using absorption cells with a 2-cm light path and a light
A = deposited copper, g, band centered at approximately 540 nm. Using the test cell,
B = copper in the electrolyte as calculated in 16.10, g, and take the photometric readings of the calibration solutions.
C = sample used, g. 16.5.4.2 Single-Cell Photometer—Transfer a suitable por-
tion of the reference solution to an absorption cell with a 2-cm
16. Photometric Determination of the Residual Copper in light path and adjust the photometer to the initial setting using
the Electrolyte a light band centered at approximately 540 nm. While main-
taining this adjustment, take the photometric readings of the
16.1 Interferences—The elements ordinarily present do not
calibration solutions.
interfere if their concentrations are under the maximum limits
shown in 1.1. 16.5.5 Calibration Curve—Plot the net photometric-
16.2 Concentration Range—The recommended concentra- readings of the calibration solutions against milligrams of
tion range is from 0.0025 to 0.07 mg of copper per 50 mL of copper per 50 mL of solution.
solution, using a 2-cm cell. 16.6 Test Solution—Transfer the reserved electrolyte to a
250-mL volumetric flask containing 25 mL of boric acid
NOTE 1—This procedure has been written for cells having a 2-cm light solution, dilute to volume, and mix. Using a pipet, transfer 10
path. Cells having other dimensions may be used, provided suitable mL to a 50-mL volumetric flask (Note 2). Proceed as directed
adjustments can be made in the amounts of sample and reagents used.
in 16.8.
16.3 Stability of Color—The color fully develops in 20 min,
NOTE 2—If the solution shows a permanganate color, add sodium
and is stable for 1 h. nitrite solution (20 g/L) dropwise until the color is discharged, and then
16.4 Reagents: proceed as directed in 16.8.
16.4.1 Acetaldehyde Solution (40 %)—Dilute 400 mL of
acetaldehyde to 1 L with water. 16.7 Reference Solution—Proceed as directed in 16.5.2.
16.4.2 Boric Acid Solution (50 g/L)—Dissolve 50 g of boric 16.8 Color Development—Proceed as directed in 16.5.3.
acid (H3BO3) in hot water, cool, and dilute to 1 L. 16.9 Photometry—Take the photometric reading of the test
16.4.3 Citric Acid Solution (200 g/L)—Dissolve 200 g of solution as directed in 16.5.4.
citric acid in water and dilute to 1 L. 16.10 Calculation—Convert the net photometric reading of
16.4.4 Copper, Standard Solution A (1 mL = 1.0 mg Cu)— the test solution to milligrams of copper by means of the
Transfer a 1.000-g sample of electrolytic copper (purity: calibration curve. Calculate the grams of copper in the total
99.9 % minimum) to a 250-mL beaker and add 10 mL of HNO3 electrolyte as follows:

3
 E 478 – 03
Copper, g 5 ~A 3 25!/1000 (2) 23. Reagents
23.1 Hydroxylamine Hydrochloride Solution (10 g/L)—
where: Dissolve 5.0 g of hydroxylamine hydrochloride (NH2OH·HCl
A = copper found in 50 mL of the final test solution, mg. in 500 mL of water. Prepare fresh as needed.
23.2 Iron, Standard Solution A (1 mL = 0.125 mg Fe)—
Transfer 0.125 g of iron (purity: 99.9 % min) to a 100 mL
17. Precision and Bias beaker. Add 10 mL of HCl (1 + 1) and 1 mL of bromine water.
17.1 Precision—Eight laboratories cooperated in testing Boil gently until the excess bromine is removed. Add 20 mL of
this test method and obtained the data summarized in Table 1. HCl, cool, transfer to a 1-L volumetric flask, dilute to volume,
and mix.
23.3 Iron, Standard Solution B (1 mL = 0.00625 mg Fe)—
TABLE 1 Statistical Information Using a pipet, transfer 50 mL of iron solution A to a 1-L
Copper Repeatability Reproducibility
volumetric flask, dilute to volume with HCl (1 + 49), and mix.
Test Specimen 23.4 Methyl Isobutyl Ketone-Benzene Mixture—Mix 200
Found, % (R1, E 173) (R2, E 173)
1. Bronze ounce metal (NIST 83.56 0.09 0.13 mL of methyl isobutyl ketone (MIBK) and 100 mL of benzene.
124d, 83.60 Cu) 23.5 1,10-Phenanthroline-Ammonium Acetate Buffer
2. AAB 521 91.98 0.03 0.08
Solution—Dissolve 1.0 g of 1,10-phenanthroline monohydrate
3. AAB 655 95.38 0.09 0.14
4. AAB 681 57.60 0.10 0.09 in 5 mL of HCl in a 600-mL beaker. Add 215 mL of acetic acid,
5. AAB 715 68.95 0.08 0.21 and, while cooling, carefully add 265 mL of NH4OH. Cool to
room temperature. Using a pH meter, check the pH; if it is not
between 6.0 and 6.5, adjust it to that range by adding acetic
acid or NH4OH as required. Dilute to 500 mL.
17.2 Bias—The accuracy of this method has been deemed
satisfactory based upon the data for the standard reference 24. Preparation of Calibration Curve
material in Table 1. Users are encouraged to use this or similar 24.1 Calibration Solutions:
reference materials to verify that the method is performing 24.1.1 Using pipets, transfer 1, 2, 5, 10, 15, and 20 mL of
accurately in their laboratories. iron solution B (1 mL = 0.00625 mg Fe) to 50-mL volumetric
flasks. Dilute to 20 mL.
IRON BY THE 1,10-PHENANTHROLINE 24.1.2 Add 20 mL of NH2OH·HCl solution, mix, and allow
PHOTOMETRIC TEST METHOD to stand 1 min. Proceed as directed in 24.3.
24.2 Reference Solution—Transfer 20 mL of water to a
18. Scope
50-mL volumetric flask and proceed as directed in 24.1.2.
18.1 This test method covers the determination of iron in 24.3 Color Development—Add 5 mL of 1,10-
concentrations from 0.003 to 1.25 %. phenanthroline-ammonium acetate buffer solution, dilute to
volume, and mix. Allow to stand at least 5 min but not more
19. Summary of Test Method than 4 h.
19.1 The sample is dissolved in hydrochloric acid and 24.4 Photometry:
hydrogen peroxide, and the excess oxidant removed by evapo- 24.4.1 Multiple-Cell Photometer—Measure the cell correc-
ration. The iron is extracted with methyl isobutyl ketone- tion using absorption cells with a 2-cm light path and a light
benzene mixture. The iron is extracted from the organic phase band centered at approximately 510 nm. Using the test cell,
into a hydroxylamine hydrochloride solution and the red- take the photometric readings of the calibration solutions.
colored 1,10-phenanthroline complex is formed. Photometric 24.4.2 Single-Cell Photometer—Transfer a suitable portion
measurement is made at approximately 510 nm. of the reference solution to an absorption cell with a 2-cm light
path and adjust the photometer to the initial setting, using a
20. Concentration Range light band centered at approximately 510 nm. While maintain-
20.1 The recommended concentration range is from 0.005 ing this adjustment, take the photometric readings of the
to 0.125 mg of iron per 50 mL of solution, using a 2-cm cell. calibration solutions.
24.5 Calibration Curve—Plot the net photometric readings
NOTE 3—This test method has been written for cells having a 2-cm of the calibration solutions against milligrams of iron per 50
light path. Cells having other dimensions may be used, provided suitable
mL of solution.
adjustments can be made in the amounts of sample and reagents used.

21. Stability of Color 25. Procedure

21.1 The color develops within 5 min and is stable for at 25.1 Test Solution:
least 4 h. 25.1.1 Select and weigh a sample in accordance with the
following:
22. Interferences Tolerance in
Sample Sample Aliquot
22.1 Elements ordinarily present do not interfere if their Iron, % Weight, g Weight, mg Volume, mL
concentrations are under the maximum limits shown in 1.1.

4
 E 478 – 03
0.003 to 0.02 2.0 2.0 25 TABLE 2 Statistical Information
0.02 to 0.10 1.0 1.0 10 Repeatability Reproducibility (R2,
0.05 to 0.20 0.5 0.5 10 Test Specimen Iron Found, %
(R1, E 173) E 173)
0.10 to 0.40 0.5 0.5 5
0.25 to 1.25 0.2 0.5 5 1. Cast bronze (NIST 52c, 0.0034 0.0005 0.0010
0.004 Fe)
Transfer it to a 400-mL beaker, or to a poly(tetrafluoroeth- 2. Ounce metal (NIST 0.187 0.012 0.017
124d,
ylene) beaker if HF is to be used. 0.18 Fe)
3. Cupro Nickel, 30 Ni 0.60 0.015 0.044
25.1.2 Carry a reagent blank through the entire procedure,
using the same amounts of all reagents but with the sample 4. Silicon bronze (NIST 1.24 0.019 0.037
omitted. 158a, 1.23 Fe)

25.1.3 Add 12 mL of HCl (7 + 3) per gram of sample, and

then H2O2 as needed to completely dissolve the alloy. Add HF
as needed to decompose high-silicon alloys. When dissolution LEAD BY THE
is complete, add 10 mL of concentrated HCl per gram of (ETHYLENEDINITRILO)TETRAACETIC ACID
sample and heat carefully to decompose excess peroxide. Cool (EDTA) TITRIMETRIC TEST METHOD
to room temperature, transfer to a 100-mL volumetric flask,
dilute to volume with HCl (1 + 1), and mix. 28. Scope
25.1.4 Using a pipet, transfer an aliquot in accordance with 28.1 This test method covers the determination of lead in
25.1.1 to a 125-mL conical separatory funnel. Add HCl (1 + 1), concentrations from 2.0 to 30.0 %.
as required, to adjust the volume to 25 mL.
29. Summary of Test Method
25.1.5 Add 20 mL of MIBK-benzene mixture to the sepa-
ratory funnel and shake 1 min. Allow the phases to separate, 29.1 Lead diethyldithiocarbamate is extracted with chloro-
discard the aqueous phase, wash the organic phase 3 times with form from an alkaline tartrate-cyanide solution. After the
3 to 5-mL portions of HCl (1 + 1) to remove copper, and removal of organic material, lead is titrated with disodium
discard the washings. Extract the iron from the organic phase (ethylenedinitrilo) tetraacetic acid (EDTA) solution.
by shaking vigorously 30 s with 10 mL of NH2OH·HCl
30. Interferences
solution. Transfer the aqueous phase to a 50-mL volumetric
flask. Repeat the extraction with a second 10-mL portion of 30.1 Elements ordinarily present do not interfere if their
NH2OH·HCl solution, and transfer the extract to the 50-mL concentrations are under the maximum limits shown in 1.1.
flask.
31. Apparatus
25.2 Reference Solution—Use the reagent blank solution
prepared as directed in 25.1.2. 31.1 Separatory Funnels, 250-mL capacity.
31.2 Magnetic Stirrer and Poly(tetrafluoroethylene)-
25.3 Color Development—Proceed as directed in 24.3.
Covered Magnetic Stirring Bar.
25.4 Photometry—Proceed as directed in 24.4.
32. Reagents
26. Calculation 32.1 Ascorbic Acid.
26.1 Convert the net photometric reading of the test solution 32.2 Chloroform (CHCl3).
to milligrams of iron by means of the calibration curve. 32.3 Disodium (Ethylenedinitrilo) tetraacetic Acid (EDTA),
Calculate the percentage of iron as follows: Standard Solution (0.025 M)—Dissolve 9.3 g of disodium
(ethylenedinitrilo) tetraacetate dihydrate in water, transfer to a
Iron, % 5 A/~B 3 10! (3)
1-L volmetric flask, dilute to volume, and mix. The solution is
stable for several months when stored in plastic or borosilicate
where: glass bottles. Standardize as follows: Using a pipet, transfer 25
A = iron found in 50 mL of the final test solution, mg, and mL of lead solution (1 mL = 6.0 mg Pb) to a 250-mL beaker
B = sample represented in 50 mL of the final test solution, and dilute to 100 mL. Proceed as directed in 33.7. Calculate the
g. lead equivalent of the solution as follows:
Lead equivalent, g/mL 5 A/B (4)
27. Precision and Bias
where:
27.1 Precision—Seven laboratories cooperated in testing A = weight of lead, g, and
this method, submitting nine pairs of values, and obtained the B = EDTA solution required for titration of the lead
data summarized in Table 2. solution, mL.
27.2 Bias—The accuracy of this method has been deemed 32.4 Fluoboric Acid (37 to 40 %).
satisfactory based upon the data for the standard reference 32.5 Hexamethylenetetramine.
materials in Table 2. Users are encouraged to use these or 32.6 Lead, Standard Solution (1 mL = 6.0 mg Pb)—
similar reference materials to verify that the method is per- Transfer 1.500 g of lead (purity 99.9 % minimum) to a 150-mL
forming accurately in their laboratories. beaker. Add 10 mL of HNO3 (1 + 1) and heat until dissolution

5
 E 478 – 03
is complete. Boil to remove oxides of nitrogen, cool, transfer to (Caution, Note 4) and titrate with the EDTA solution. When a
a 250-mL volumetric flask, dilute to volume, and mix. yellow color begins to appear, stop the titration and add 2 to 3
32.7 Sodium Cyanide Solution (200 g/L)—Dissolve 200 g g of hexamethylenetetramine and a drop of xylenol orange
of sodium cyanide (NaCN) in water and dilute to 1 L. Store in solution. Titrate dropwise until the color changes from
a plastic bottle. purplish-red to yellow.
NOTE 4—Caution: The preparation, storage, and use of NaCN solu- NOTE 5—The titration may be performed in either a hot or cold
tions require care and attention. Avoid inhalation of fumes and exposure solution.
of skin to the chemical and its solutions. Work in a well-ventilated hood.
Refer to Section 6 of Practices E 50. 34. Calculation
32.8 Sodium Diethyldithiocarbamate Solution (100 g/L)— 34.1 Calculate the percentage of lead as follows:
Dissolve 10 g of sodium diethyldithiocarbamate in water and Lead, % 5 [~C 3 D!/E] 3 100 (5)
dilute to 100 mL. Do not use a solution that has stood more
than 24 h.
32.9 Sodium Hydroxide Solution (250 g/L)—Dissolve 250 g where:
of sodium hydroxide (NaOH) in water and dilute to 1 L. Store C = standard EDTA solution used, mL,
D = equivalent of EDTA solution, g/mL, and
in a plastic bottle.
E = sample used, g.
32.10 Sodium Tartrate Solution (250 g/L)—Dissolve 250 g
of sodium tartrate dihydrate in water and dilute to 1 L. 35. Precision and Bias
32.11 Xylenol Orange Indicator Solution (1 g/L)—Dissolve
35.1 Precision—Due to limited data, a precision statement
0.050 g of xylenol orange powder in a mixture of 25 mL of
conforming to the requirements of Practices E 173 cannot be
water and 25 mL of ethanol.
furnished. However, in a cooperative program conducted by
33. Procedure six laboratories, the between-laboratory range was 3.13 to
33.1 Select a sample in accordance with the following: 3.20 % lead on a sample averaging 3.16 %, and 14.05 to
Lead, % Sample Weight, g
14.23 % on a sample averaging 14.15 %.
35.2 Bias—No information on the accuracy of this method
2.0 to 20.0 1.00 is known, because at the time it was tested, no standard
20.0 to 30.0 0.60
reference materials were available. Users are encouraged to
Weigh the sample to the nearest 0.5 mg, and transfer it to a employ suitable reference materials, if available, to verify the
250-mL beaker. accuracy of the method in their laboratories.
33.2 Add 5 mL of HBF4 and then 10 mL of HNO3 (1 + 1).
Cover the beaker and heat until dissolution is complete. Boil NICKEL BY THE DIMETHYLGLYOXIME-
until oxides of nitrogen have been expelled, and cool. EXTRACTION PHOTOMETRIC TEST METHOD
33.3 Wash the cover and walls of the beaker. Add 25 mL of
36. Scope
sodium tartrate solution, 25 mL of NaOH solution, and 25 mL
of NaCN solution (Caution, Note 4), mixing after each 36.1 This test method covers the determination of nickel in
addition. Cool to room temperature. concentrations from 0.03 to 5.0 %.
33.4 Transfer to a 250-mL separatory funnel. Add 15 mL of
sodium diethyldithiocarbamate solution and 15 mL of CHCl3, 37. Summary of Test Method
and shake for 30 s. Allow the layers to separate; draw off the 37.1 A dimethylglyoxime complex of nickel is formed in
lower organic layer into a 250-mL beaker, retaining the the presence of copper, and extracted with chloroform. Photo-
aqueous layer. Add 5 mL more of diethyldithiocarbamate metric measurement is made at approximately 405 nm.
solution to the separatory funnel and mix. If no precipitate
forms, proceed as directed in 33.5. If a precipitate does form, 38. Concentration Range
add 5 mL of diethyldithiocarbamate solution and 10 mL of 38.1 The recommended concentration range is 0.015 to 0.3
CHCl3, shake for 30 s, and draw off the organic layer into the mg of nickel per 20 mL of solution, using a 2-cm cell.
250-mL beaker containing the extract. NOTE 6—This procedure has been written for a cell having a 2-cm light
33.5 Extract twice with additional 10-mL portions of path. Cells having other dimensions may be used, provided suitable
CHCl3, adding the extracts to the extracts in the 250-mL adjustments can be made in the amounts of sample and reagents used.
beaker.
33.6 Add 10 mL of HCl (1 + 1) to the combined extracts, 39. Stability of Color
and place on a hot plate. Cover the beaker with a raised cover 39.1 The color is stable for at least 2 h.
glass, and evaporate the solution to a volume of 2 to 3 mL.
Wash the cover and walls of the beaker, dilute to 100 mL, and 40. Interferences
heat to dissolve salts. 40.1 The elements ordinarily present do not interfere if their
33.7 Place the beaker on a magnetic stirrer and stir (Note 5). concentrations are under the maximum limits shown in 1.1.
Add 10 to 20 mg of ascorbic acid and 3 or 4 drops of xylenol
orange solution. Add enough hexamethylenetetramine to color 41. Reagents
the solution purple. Add 4 or 5 drops of NaCN solution 41.1 Chloroform (CHCl3).

6
 E 478 – 03
41.2 Complexing Solution—Mix 240 mL of sodium tartrate 42.3.2 Transfer the yellow-colored chloroform phase to a
solution, 90 mL of NaOH solution, 480 mL of sodium acetate 25-mL Erlenmeyer flask fitted with a ground-glass stopper and
solution, and 200 mL of Na2S2O3 solution. containing about 1 g of Na2SO4. Shake to stir the Na2SO4 into
41.3 Dimethylglyoxime Solution (10 g/L in alcohol)— the CHCl3. Decant the clear CHCl3 solution into an absorption
Dissolve 10 g of dimethylglyoxime in ehtanol, methanol, or cell, and cover immediately to prevent loss of solvent.
No. 30 specially denatured alcohol and dilute to 1 L with 42.4 Photometry:
alcohol. Filter before using. This solution keeps almost indefi- 42.4.1 Multiple-Cell Photometer—Measure the cell correc
nitely. tion using absorption cells with a 2-cm light path and a light
41.4 Hydroxylamine Hydrochloride Solution (10 g/L)— band centered at approximately 405 nm. Using the test cell,
Dissolve 10 g of hydroxylamine hydrochloride (NH2OH·HCl) take the photometric readings of the calibration solutions.
in water, and dilute to 1 L. Adjust the pH to 7.0 with NH4OH. 42.4.2 Single-Cell Photometer—Transfer a suitable portion
41.5 Nickel, Standard Solution A (1 mL = 1.0 mg Ni)— of the reference solution to an absorption cell with a 2-cm light
Dissolve 1.000 g of nickel metal (purity, 99.8 % min) in 10 mL path and adjust the photometer to the initial setting, using a
of HNO3. When dissolution is complete, boil gently to expel light band centered at approximately 405 nm. While maintain-
oxides of nitrogen, cool, transfer to a 1-L volumetric flask, ing this adjustment, take the photometric readings of the
dilute to volume, and mix. calibration solutions.
41.6 Nickel, Standard Solution B (1 mL = 0.2 mg Ni)—
42.5 Calibration Curve—Plot the net photometric readings
Using a pipet, transfer 100 mL of nickel solution A (1 mL = 1.0
of the calibration solutions against milligrams of nickel per 20
mg Ni) to a 500-mL volumetric flask, dilute to volume, and
mL of solution.
mix.
41.7 Sodium Acetate Solution (200 g/L)—Dissolve 200 g of
43. Procedure
sodium acetate trihydrate (CH3COONa·3H2O) in about 600
mL of water, filter, and dilute to 1 L. 43.1 Test Solution:
41.8 Sodium Hydroxide Solution (1 N)—Dissolve 40 g of 43.1.1 Select and weigh a sample in accordance with the
sodium hydroxide (NaOH) in water, cool, transfer to a 1-L following:
volumetric flask, dilute to volume, and mix. Store in a plastic Tolerance in
bottle. Sample Sample Weight, Weight of Aliquot Vol-
Nickel, % Weight, g mg Copper, g ume, mL
41.9 Sodium Sulfate, anhydrous (Na2SO4).
41.10 Sodium Tartrate Solution (100 g/L)—Dissolve 100 g 0.03 to 0.6 1.0 1.0 ... 25
of sodium tartrate dihydrate in water, and dilute to 1 L. 0.55 to 1.5 0.4 0.5 0.6 25
1.45 to 3.5 0.4 0.5 0.6 10
41.11 Sodium Thiosulfate Solution (200 g/L)—Dissolve 200 3.45 6 5.0 0.25 0.2 0.75 10
g of sodium thiosulfate pentahydrate (Na2S2O3· 5H2O) in
water, and dilute to 1 L. Transfer it to a 250-mL beaker. Add to the beaker the weight
of copper (purity, 99.99 % min) indicated in the table.
42. Preparation of Calibration Curve 43.1.2 Add 20 mL of HCl (1 + 1), and add 10 mL of H2O2
42.1 Calibration Solutions: solution in small portions. Cool until the violent reaction has
42.1.1 Transfer 1.000 g of copper (purity, 99.99 % min) to ceased. When dissolution is complete, boil for approximately 1
each of five 250-mL beakers, add 20 mL of HCl (1 + 1), and min to destroy excess peroxide. Cool, transfer to a 500-mL
add 10 mL of H2O2 solution in small portions. When dissolu- volumetric flask, dilute to volume, and mix.
tion is complete, boil for 1 min to destroy excess peroxide, and 43.1.3 Proceed as directed in 42.1.3, using an aliquot
cool. volume in accordance with 43.1.1. If a 10-mL aliquot is used,
42.1.2 Using pipets, transfer 2, 5, 10, 20, and 30 mL of add 3 mL of HCl (1 + 9) to the aliquot in the separatory funnel.
nickel solution B (1 mL = 0.2 mg Ni) to the beakers. Transfer 43.2 Reference Solution—Proceed as directed in 42.2.
the solutions to 500-mL volumetric flasks, dilute to volume, 43.3 Color Development—Proceed as directed in 42.3.
and mix.
43.4 Photometry—Proceed as directed in 42.4.
42.1.3 Using a pipet, transfer 25 mL to a 250-mL conical
separatory funnel. Add 5 mL of NH2OH·HCl solution and 50
44. Calculation
mL of complexing solution, shaking after each addition. Using
indicator paper, check the pH, which should be between 6.5 44.1 Convert the net photometric readings of the test solu-
and 7.2. If necessary, adjust the pH with HCl (1 + 1) or dilute tion to milligrams of nickel by means of the calibration curve.
NaOH solution. Calculate the percentage of nickel as follows:
42.2 Reference Solution—Transfer 1.000 g of copper (pu- Nickel, % 5 A/~B 3 10! (6)
rity, 99.99 % min) to a 250-mL beaker and proceed as directed
in 41.1, omitting the addition of nickel solution.
42.3 Color Development: where:
42.3.1 Add 3 mL of dimethylglyoxime solution, and shake A = nickel found in 20 mL of the final test solution, mg,
for 1 min. Using a pipet, transfer 20 mL of CHCl3 to the and
B = sample represented in 20 mL of the final test solution,
solution, and shake again for 40 s. Allow the phases to
g.
separate.

7
 E 478 – 03
45. Precision and Bias 50.5 Buffer Solution (pH 10)—Dissolve 54 g of ammonium
45.1 Precision—Eight laboratories cooperated in testing chloride (NH4Cl) in 200 mL of water. Add 350 mL of NH4OH
this test method and obtained the data summarized in Table 3. and dilute to 1 L. Store in a polyethylene bottle.
45.2 Bias—The accuracy of this method has been deemed 50.6 Disodium —(Ethylenedinitrilo) Tetraacetic Acid
satisfactory based upon the data for the standard reference (EDTA), Standard Solution (0.05 M):
materials in Table 3. Users are encouraged to use these or 50.6.1 Dissolve 18.6125 g of disodium (ethylenedinitrilo)
similar reference materials to verify that the method is per- tetraacetate dihydrate in water, transfer to a 1-L volumetric
forming accurately in their laboratories. flask, dilute to volume, and mix. The solution is stable for
several months when stored in plastic or borosilicate glass
TABLE 3 Statistical Information bottles.
50.6.2 Standardization—Dissolve 0.1 g of zinc in 10 mL of
Nickel Repeatability (R1, Reproducibility
Test Specimen HNO3 (1 + 1) in a 400-mL beaker. Dilute the solution to 150
Found, % E 173) (R2, E 173)
1. 816-12 0.107 0.010 0.028
mL and proceed as directed in 51.4-51.7.
2. Sheet Brass (NIST 37c, 0.531 0.010 0.036 Zinc equivalent, mg/mL 5 ~A 3 1000!/~B 2 C! (7)
0.53 Ni)
3. Ounce Metal (NIST 124d, 0.997 0.021 0.037
0.99 Ni)
4. 844-J 4.90 0.071 0.33 where:
A = grams of zinc,
B = final buret reading, mL, and
ZINC BY THE ETHYLENEDIAMINE C = initial buret reading, mL.
TETRAACETATE (TITRIMETRIC) TEST METHOD 50.7 Eriochrome Black-T Indicator Solution—Dissolve 0.4
g of the sodium salt to 1-(1-hydroxy-2 naphtholazo)-5 nitro-2
46. Scope naphthol-4 sulfonic acid in a mixture of 20 mL of ethanol and
46.1 This test method covers the determination of zinc in 30 mL of triethanolamine. Store in a tightly closed polyethyl-
the range from 2 to 40 %. ene dropping bottle. Do not use a solution that has stood for
more than 3 months.
47. Summary of Test Method 50.8 Formaldehyde Solution (37 %).
47.1 The zinc is converted to the zinc thiocyanate complex 50.9 Hydrogen Peroxide Solution (3 %)—Dilute 100 mL of
and extracted with methyl isobutyl ketone. The zinc is then 30 % H2O2 to 1 L.
stripped from the organic phase as the ammonia complex, 50.10 Indicator Ion Solution (0.05 M MgCl2 Solution)—
which is further treated with potassium cyanide to complex Dissolve 1.02 g of magnesium chloride hexahydrate (MgCl2·
bivalent metals as well as the zinc. Finally, the zinc is released 6 H2O) in water and dilute to 100 mL.
from the cyanide complex by means of formaldehyde and 50.11 Lead Nitrate Solution (10 g/L)—Dissolve 10 g of lead
titrated with disodium (ethylenedinitrilo) tetraacetic acid nitrate (Pb(NO3)2) in water and dilute to 1 L.
(EDTA) solution. 50.12 Methyl Isobutyl Ketone.
50.13 Potassium Cyanide Solution (100 g/L)—Dissolve 100
48. Interferences g of potassium cyanide (KCN) in water and dilute to 1 L. Store
48.1 None of the elements ordinarily present interfere. The in a polyethylene bottle.
extraction procedure also affords a separation of the zinc from NOTE 7—Caution: The preparation, storage, and use of KCN solutions
cadmium. require care and attention. Avoid inhalation of fumes and exposure of the
skin to the chemical and its solutions. Do not allow solutions containing
49. Apparatus cyanide to come in contact with strongly acidic solutions: Work in a
49.1 Electrodes for Electroanalysis—Platinum anode and well-ventilated hood. (Refer to Section 6 of Practices E 50.
cathode described in 12.3. 50.14 Sodium Hydroxide Solution (200 g/L)—Dissolve 200
49.2 Separatory Funnels, conical, 500-mL capacity. g of sodium hydroxide (NaOH) in water, cool, and dilute to 1
49.3 Magnetic Stirrer, with poly(tetrafluoroethylene)- L. Store the solution in a polyethylene bottle.
covered magnetic stirring bar. 50.15 Thiocyanate Wash Solution—Dissolve 100 g of so-
dium chloride (NaCl) in 600 mL of water. Add 10 mL of the
50. Reagents NH4SCN solution, and mix. Add 10 mL of HCl and dilute to 1
50.1 Ammonium Chloride Solution (0.02 g/L)—Dissolve L.
0.20 g of ammonium chloride (NH4Cl) in water and dilute to 50.16 Zinc Metal (purity: 99.9 % min)—Do not use finely
10 L. divided powder, or surface oxidized material.
50.2 Ammonium Fluoride Solution (200 g/L)—Dissolve 200
g of ammonium fluoride (NH4F) in water and dilute to 1 L. 51. Procedure
Store in a polyethylene bottle. 51.1 Transfer a 2.00-g sample, weighed to the nearest 1 mg,
50.3 Ammonium Thiocyanate Solution (500 g/L)—Dissolve to a 250-mL polytetrafluoroethylene or polypropylene beaker
500 g of ammonium thiocyanate (NH4SCN) in water and dilute and add 2 mL of HF followed by 30 mL of HNO3 (1 + 1).
to 1 L. Filter, if necessary, and store in a polyethylene bottle. Cover the beaker with a plastic cover and allow the sample to
50.4 Ascorbic Acid, powdered. dissolve. Do not place the beaker on a hot plate unless the

8
 E 478 – 03
temperature is less than 80°C. When dissolution is complete, Zinc, % 5 ~A 2 B!C/~D 3 10! (8)
add 25 mL of H2O2 solution and 3 mL of Pb(NO3)2 solution.
Rinse the plastic cover glass and dilute to approximately 150
where:
mL with NH4Cl solution. A = final buret reading, mL,
51.2 Insert the electrodes into the solution and cover the B = initial buret reading, mL,
beaker with a pair of split cover glasses. Electrolyze for 2 h at C = zinc equivalent of standard EDTA solution, mg/mL,
a current density of 4 A/dm2 using gauze electrodes. When and
deposition is complete, slowly withdraw the electrodes (or D = grams of sample represented in portion of electrolyte
lower the beaker) with the current still flowing and rinse them taken.
with a stream of water from a wash bottle. Reserve the
electrolyte. 53. Precision and Bias
51.3 Depending on the amount of zinc present, transfer the 53.1 Precision—Eight laboratories cooperated in testing
whole electrolyte or an aliquot portion, containing not more this method and obtained the data shown in Table 4.
than 100 mg of zinc, to a 400-mL beaker. If an aliquot of the 53.2 Bias—The accuracy of this method has been deemed
sample is to be taken, add 25 mL of saturated boric acid satisfactory based upon the data for the standard reference
(H3BO3) solution to the volumetric flask, add the electrolyte, materials in Table 4. Users are encouraged to use these or
dilute to volume, and mix. Dilute the aliquot to 150 mL and similar reference materials to verify that the method is per-
proceed as directed in 51.4. If the entire electrolyte is to be forming accurately in their laboratories.
used, proceed directly with the neutralization.
51.4 Neutralize with NaOH solution using litmus paper as
an indicator; then add 10 mL of HCl (1 + 1), and cool. TABLE 4 Statistical Information
51.5 Transfer to a 500-mL separatory funnel and dilute to Test Specimen Zinc Found, %
Repeatability Reproducibility
(R1, E 173) (R2, E 173)
about 250 mL. Add 30 mL of NH4SCN solution, and 20 mL of
NH4F solution, and mix. Add 50 mL of methyl isobutyl ketone 1. Ounce Metal (NIST 124d, 5.08 0.02 0.18
5.06 Zn)
and shake vigorously for 1 min. Allow the layers to separate; 2. Sheet Brass (NIST 37c, 27.87 0.13 0.27
then draw off the lower aqueous layer into a second separatory 27.85 Zn)
funnel. Retain the organic layer. Add an additional 50 mL of 3. AAB Alloy 681 40.84 0.23 0.40
methyl isobutyl ketone to the second funnel and shake for 1
min. Allow the layers to separate. Draw off and discard the
aqueous layer. Add the organic layer to that retained in the first
separatory funnel. To the combined extracts, add 40 mL of NICKEL BY THE DIMETHYLGLYOXIME
thiocyanate wash solution, shake, and allow the layers to GRAVIMETRIC TEST METHOD
separate. Draw off and discard the aqueous layer.
54. Scope
51.6 To the organic layer add 20 mL buffer solution, and 30
mL of water, and shake to strip the zinc from the organic phase. 54.1 This test method covers the determination of nickel in
Allow the layers to separate, and drain off the lower ammo- concentrations from 4 to 50 %.
niacal layer into a 600-mL beaker. Repeat the extraction of zinc
with another 20 mL of buffer solution and 30 mL of water, 55. Summary of Test Method
followed by a final wash with 50 mL of water, combining all 55.1 After dissolution of the sample, the nickel is precipi-
the aqueous extracts in the 600-mL beaker. Discard the organic tated from an alkaline citrate solution with sodium dimethylg-
layer. lyoximate; this precipitate is subsequently weighed as nickel
51.7 Dilute to about 300 mL. Place a poly dimethylglyoxime.
(tetrafluoroethylene)-covered stirring bar into the beaker, add
20 mL of KCN solution, and then add 10 to 20 mg of ascorbic 56. Interferences
acid powder. Add 1.0 mL of indicator ion solution and about 5 56.1 The elements ordinarily present do not interfere if their
drops of eriochrome black-T indicator. Transfer the beaker to concentrations are under the maximum limits shown in 1.1.
the magnetic stirring apparatus and titrate with EDTA solution
to a pure blue end point. Record the initial buret reading. 57. Apparatus
Cautiously add formaldehyde solution, 1 to 2 mL at a time, 57.1 Electrodes for Electroanalysis—Platinum anode and
until the color has changed again to wine red. Titrate with cathode described in 12.3.
EDTA solution to a pure blue end point. Make further additions 57.2 Filtering Crucibles—Gooch crucible (35 mL) fitted
of formaldehyde and each time titrate to the blue end point to with a glass microfibre pad, or fritted glass crucible (30 mL) of
ensure that all the zinc has been released. Avoid adding medium porosity.
excessive amounts of formaldehyde. Record the final buret
reading. 58. Reagents
58.1 Citric Acid (250 g/L)—Dissolve 250 g of citric acid in
52. Calculation water and dilute to 1 L. The addition of 1 g of benzoic acid per
52.1 Calculate the percentage of zinc as follows: litre will prevent bacterial growth.

9
 E 478 – 03
58.2 Sodium Dimethylglyoximate Solution (25 g/L)— of sodium dimethylglyoximate solution to the filtrate and let
Dissolve 25 g of sodium dimethylglyoximate [(CH3)2C2- stand overnight to make certain that the separation of the nickel
(NONa)2·8H2O], in water and dilute to 1 L. Do not use a is complete.
solution that has stood more than 24 h. 59.9 Dry the precipitate at 150°C to constant weight. Cool
58.3 Sulfamic Acid Solution (100 g/L)—Dissolve 100 g of in a desiccator and weigh as nickel dimethylglyoxime.
sulfamic acid [H(NH2)SO3] in water and dilute to 1 L.
60. Calculation
59. Procedures 60.1 Calculate the percentage of nickel as follows:
59.1 Transfer a sample, weighed to the nearest 0.1 mg, Nickel, % 5 [~A 3 0.2032!/B] 3 100 (9)
which contains between 40 and 150 mg of nickel, to a 250-mL
beaker. Dissolve the sample in 25 mL of HNO3 (1 + 1) and
where:
when dissolution is complete, boil gently to expel oxides of
A = nickel dimethylglyoxime, g, and
nitrogen. Add 50 mL of hot water and, if the solution is clear, B = sample used, g.
proceed as described in 59.4. If enough tin is present at this
point to cause turbidity, proceed as directed to 59.2 and 59.3. 61. Precision and Bias
59.2 Maintain the temperature of the solution at about 80°C 61.1 Precision—Eight laboratories cooperated in testing
for 1 h, or until the precipitate has coagulated. Add paper pulp this test method, submitting eight pairs of values, and obtained
and filter through a fine paper into a 250-mL beaker to remove the data summarized in Table 5. Although samples with the
the metastannic acid. Wash several times with hot HNO3 nickel concentration near the upper limit of the scope were not
(1 + 99), and reserve the filtrate and washings. available for testing, the precision data obtained for the other
59.3 Transfer the filter paper and precipitate to the original specimens should apply.
beaker, add 15 to 20 mL of HNO3 and 10 to 15 mL of HClO4. 61.2 Bias—No information on the accuracy of this method
Heat to copious white fumes and boil to destroy organic matter. is known, because at the time it was tested, no standard
Cool, wash the cover glass and sides of the beaker, and add 15 reference materials were available. Users are encouraged to
mL of HBr. Heat to copious white fumes to volatilize the tin. employ suitable reference materials, if available, to verify the
If the solution is not clear, repeat the treatment with HBr. accuracy of the method in their laboratories.
Evaporate the solution to near dryness, cool, and dissolve the
residue in a few millilitres of water. Combine with the filtrate
TABLE 5 Statistical Information
reserved in 59.2.
Nickel Repeatability Reproducibility
59.4 Add 1 drop of HCl (1 + 99) and 5 mL of sulfamic acid Test Specimen
Found, % (R1, E 173) (R2, E 173)
solution. Insert the electrodes into the solution, cover with a 1. Cupro-nickel 29.74 0.12 0.14
pair of split cover glasses, and electrolyze overnight at a 2. Nickel-aluminum bronze 5.00 0.05 0.04
current density of 0.5 A/dm2, or for a short period at a current
density of 4 A/dm2 while stirring. After the blue color due to
copper has disappeared, wash the cover glasses, electrodes, and TIN BY THE IODATIMETRIC TITRATION TEST
the sides of the beaker, and continue the electrolysis until METHOD
deposition of the copper is complete, as indicated by failure to
62. Scope
plate on a new surface when the level of the solution is raised.
62.1 This test method covers the determination of tin in
NOTE 8—Rotating electrodes must be used at the higher current concentrations from 0.5 to 20 %.
densities. The more rapid procedure requires the use of gauze electrodes.
59.5 When deposition of the copper is complete, with the 63. Summary of Test Method
current still flowing, lower the beaker slowly while washing 63.1 After dissolution of the sample in hydrochloric and
the electrodes with water. Reserve the electrolyte. nitric acids, iron is added as a collector and tin is separated
59.6 Add 5 mL of HNO3 and 10 mL of HClO4 to the from copper by double precipitation with ammonium hydrox-
reserved electrolyte and evaporate to copious white fumes. ide. The precipitate is dissolved in hydrochloric acid and the tin
Cool, add 100 mL of water, and heat to dissolve the soluble is reduced with iron and nickel and titrated with a standard
salts. If insoluble matter is present, filter the solution through a potassium iodate solution in an inert atmosphere. Starch is used
medium paper into a 600-mL beaker. If there is no insoluble to indicate the end point.
matter, transfer the solution to a 600-mL beaker.
59.7 Add 10 mL of citric acid solution. Add NH4OH until 64. Interferences
the blue color is formed, and then add 1 mL in excess. Dilute 64.1 The elements ordinarily present do not interfere if their
to 400 mL and heat to 60 to 70°C. concentrations are under the maximum limits shown in 1.1.
59.8 Add 0.4 mL of sodium dimethylglyoximate solution
for each milligram of nickel, plus 10 mL in excess. Stir the 65. Apparatus
mixture vigorously and allow to cool to room temperature 65.1 Apparatus for Reduction of Tin—When tin is to be
while stirring occasionally. Filter on a Gooch or fritted glass reduced to the stannous state and determined by titration with
crucible of medium porosity which has been dried at 150°C for standard iodine or iodate solution, air must be excluded during
1 h and weighed. Wash with water 10 to 12 times. Add 5 mL the reduction and titration to prevent oxidation of the stannous

10
 E 478 – 03
tin. This exclusion of air is usually accomplished by keeping potassium chlorate (KClO3). Cool, transfer to a 1-L volumetric
the solution under a blanket of gaseous CO2 and may be flask, dilute to volume, and mix.
accomplished in a variety of ways. One of the simplest
methods is by means of the apparatus in which the reduction of 67. Procedure
the tin solution is made in a flask capped with a rubber stopper 67.1 Select and weigh a sample in accordance with the
containing an L-shape siphon tube. When reduction is com- following:
plete, the end of the siphon is dipped into a saturated solution Tolerance in Sample
of NaHCO3 and set aside to cool. When cool, the stopper is Tin, % Sample Weight, g Weight, mg
removed and the solution titrated.
0.5 to 2.5 2 4
2.5 to 10.0 1 2
66. Reagents 10.0 to 20.0 0.5 1

66.1 Ammonium Chloride Solution (10 g/L)—Dissolve 10 g Transfer it to a 400-mL beaker.

of ammonium chloride (NH4Cl) in water and dilute to 1 L. 67.2 Carry a reagent blank through the entire procedure
66.2 Ferric Chloride Solution (50 g/L)—Dissolve 50 g of using the same amount of all reagents, but with the sample
ferric chloride hexahydrate (FeCl3·6H2O) in 5 mL of HCl and omitted.
995 mL of water. 67.3 Add 5 mL of HCl and 20 mL of HNO3 (1 + 1), plus an
66.3 Iron, metal powder, containing less than 0.001 % tin. additional 5 mL of HCl and 5 mL of HNO3 (1 + 1) for each
66.4 Nickel, sheet, containing less than 0.001 % tin and gram of sample. Heat until dissolution is complete and then
having a total (exposed) surface area of at least 65 cm2. boil the solution for 2 to 3 min. Add 100 mL of water and 10
66.5 Potassium Iodate, Standard Solution (0.05 N)—Dry mL of FeCl3 solution.
the crystals of potassium iodate (KIO3) at 180ºC to constant 67.4 Add NH4OH (1 + 1) until the salts, which initially
weight. Dissolve 1.785 g of the KIO3 in 200 mL of water form, have been dissolved and the solution becomes clear dark
containing 1 g of sodium hydroxide (NaOH) and 10 g of blue. Heat to boiling to coagulate the precipitate. Filter on a
potassium iodide (KI). When dissolution is complete, transfer 12.5-cm coarse paper and wash the beaker and paper alter-
to a 1-L volumetric flask, dilute to volume, and mix. Standard- nately five times each with hot slightly ammoniacal NH4Cl
ize the solution as follows: solution and water. Discard the filtrate. Place the original
66.5.1 Using a pipet, transfer 50 mL of the tin solution (1 beaker beneath the funnel and dissolve the precipitate with hot
mL = 0.001 g Sn) to a 500-mL Erlenmeyer flask. Add 75 mL of HCl (1 + 1). Wash the paper several times with hot water and
HCl, 200 mL of water, and 2 to 3 g of iron powder. Insert a roll reserve the filter paper. Precipitate the iron and tin as before
of sheet nickel. Stopper the flask as described in 65.1. Boil the and heat to boiling to coagulate the precipitate. Wash the
solution gently for 45 min. reserved filter paper three times with hot NH4OH (1 + 99),
66.5.2 Cool to about 10°C while maintaining an atmosphere collecting the washings in a 400-mL beaker, and then filter the
of CO2 as described under the apparatus for the reduction of hot solution containing the precipitated hydroxides of iron and
tin. tin into the 400-mL beaker containing the NH4OH washings.
66.5.3 Add 5 mL of starch solution and titrate with KIO3 Wash alternately five times each with hot, slightly ammoniacal
solution until a blue color persists. NH4Cl solution and water. Discard the filtrate. Transfer the
paper and precipitate to a 500-mL Erlenmeyer flask.
66.5.4 Determine a blank using the same amounts of all
67.5 Add 75 mL of HCl and gently swirl the flask to
reagents but with the tin omitted. Calculate the tin equivalent
partially disintegrate the paper and to dissolve the precipitate.
of the KIO3 solution as follows:
Add 200 mL of water and 2 to 3 g of iron powder. Insert a roll
Tin equivalent, g Sn/mL 5 A/~B 2 C! (10) of sheet nickel. Stopper the flask as described under Apparatus
No. 7A. Boil the solution gently for 45 min.
where: 67.6 Cool the solution to about 10°C while maintaining an
A = tin titrated, g, atmosphere of CO2 as described under Apparatus No. 7A. Add
B = KIO3 solution required to titrate tin, mL, and 5 mL of KI solution and 5 mL of starch solution and titrate with
C = KIO3 solution required to titrate the blank, mL. KIO3 solution until a blue color persists.
66.6 Potassium Iodide Solution (100 g/L)—Dissolve 10 g of
potassium iodide (KI) in water, and dilute to 100 mL. Prepare 68. Calculation
fresh as needed. 68.1 Calculate the percentage of tin as follows:
66.7 Starch Solution (10 g/L)—Add about 5 mL of water ~A 2 B! 3 C
gradually to 1 g of soluble (or arrowroot) starch, with stirring, Tin, % 5 D 3 100 (11)
until a paste is formed, and add this to 100 mL of boiling water.
Cool, add 5 g of potassium iodide (KI), and stir until the KI is where:
dissolved. Prepare fresh as needed. A = KIO3 solution required to titrate the tin in the sample,
66.8 Tin, Standard Solution (1 mL = 0.001 g Sn)—Transfer mL,
1.0000 g of tin (purity, 99.9 % min) to a 400-mL beaker, and B = KIO3 solution required to titrate the blank, mL,
cover. Add 300 mL of HCl (1 + 1) and warm gently until the C = the tin equivalent of the KIO3 solution, and
D = sample used, g.
metal is dissolved. If dissolution is difficult, add 0.5 to 1.0 g of

11
 E 478 – 03
69. Precision and Bias 74.3 (Disodium) (Ethylenedinitrilo) Tetraacetate Dihydrate
69.1 Precision—Eight laboratories cooperated in testing (EDTA), Standard Solution (0.05 M)—Dissolve 18.613 g of
this test method and obtained the data summarized in Table 6. disodium (ethylenedinitrilo) Tetraacetate dihydrate in water,
Although samples with tin concentration near the upper limit of transfer to a 1-L volumetric flask, dilute to volume, and mix.
the scope were not available for testing, the precision data The solution is stable for several months when stored in plastic
obtained for the other specimens should apply. or borosilicate glass bottles. Standardize the solution as fol-
69.2 Bias—No information on the accuracy of this method lows:
is known, because at the time it was tested, no standard 74.3.1 Using a pipet, transfer 25 mL of the EDTA solution
reference materials were available. Users are encouraged to to a 400-mL beaker. Add 150 mL of water and 30 mL of the
employ suitable reference materials, if available, to verify the buffer solution. Add 6 to 8 drops of xylenol orange indicator
accuracy of the method in their laboratories. solution and titrate with standard zinc solution until the color
changes from yellow to orange or pink.
74.3.2 Calculate the volume of EDTA standard solution
TABLE 6 Statistical Information equivalent to 1 mL of zinc standard solution as follows:
Repeatability Reproducibility EDTA equivalent 5 ~A/B! (12)
Test Specimen Tin Found, %
(R1, E 173) (R2, E 173)
1. Tin bronze AAB521 7.51 0.14 0.23
2. Yellow brass AAB681 0.93 0.04 0.04 where:
3. Yellow brass AAB681 + 0.93 0.03 0.05 A = EDTA solution, mL, and
20 % Pb
B = zinc solution (0.0500 M), mL.
74.3.3 Calculate the molarity of the EDTA solution as
follows:
ALUMINUM BY THE CARBAMATE Molarity, EDTA solution 5 C 3 0.002 (13)
EXTRACTION-(ETHYLENEDINITRILO)
TETRAACETATE TITRIMETRIC TEST METHOD
where:
C = millilitres of zinc standard solution required to titrate
70. Scope
25.00 mL of EDTA standard solution.
70.1 This test method covers the determination of aluminum 74.4 Sodium Tartrate Solution (250 g/L)—Dissolve 250 g of
in concentrations from 2 to 12 %. sodium tartrate (Na2C4H4O6·2H2O) in water. Dilute to 1 L, and
mix.
71. Summary of Test Method 74.5 Xylenol Orange Indicator Solution (2 g/L)—Dissolve
71.1 A diethyldithiocarbamate extraction at pH 5.5 removes 0.100 g of xylenol orange tetrasodium salt in 50 mL of water.
antimony, cadmium, copper, iron, lead, manganese, nickel, tin, Store in and dispense from a polyethylene dropping bottle.
and zinc. Aluminum is chelated with an excess of a standard 74.6 Zinc, Standard Solution (0.0500 M)—Transfer 3.2690
solution of disodium (ethylenedinitrilo) tetraacetate (EDTA) g of zinc (purity: 99.9 % min) to a 1 L borosilicate volumetric
and then determined by back-titration with standard zinc flask. Add 50 mL of water and 20 mL of HCl and heat to
solution. dissolve. Cool, dilute to volume, and mix.

72. Interferences 75. Procedure

72.1 The elements ordinarily present do not interfere if their 75.1 Select and weigh a sample in accordance with the
concentrations are under the maximum limits shown in 1.1. following:
Tolerance in Sample
73. Apparatus Aluminum, % Sample Weight, g Weight, mg

73.1 Separatory Funnels, 250-mL capacity with poly(tet- 2.0 to 3.0 1.0 3.0
rafluoroethylene) stopcocks. 2.9 to 4.3 0.7 2.0
4.0 to 6.0 0.5 1.0
5.0 to 7.5 0.4 0.5
74. Reagents 7.0 to 10.0 0.3 0.5
8.0 to 12.0 0.25 0.5
74.1 Buffer Solution—Dissolve 250 g of ammonium acetate
(CH3COONH4) in 600 mL of water and add 30 mL of glacial 75.2 Transfer the sample to a 250-mL beaker, and add 5 mL
acetic acid (CH3COOH). Dilute to 1 L and mix. Add 10 mL of of HCl (1 + 1), plus an additional 1 mL for each 0.1 g of
buffer solution to 100 mL of water. Using a pH meter, check sample over 0.25 g. Add H2O2 in 1-mL portions until the
the pH of the solution which should be between 5.3 and 5.6. If sample has been completely dissolved. Cover the beaker with
it is not in the range, add sufficient CH3COOH or NH4OH to a ribbed cover glass.
provide the desired pH. 75.3 Boil gently and evaporate the excess acid until the
74.2 Diethyldithiocarbamate (DDC) Solution (100 g/L)— color turns from a clear green to a brown-green. Cool. Remove
Dissolve 100 g of diethyldithiocarbamic acid, disodium salt, in and rinse the cover glass.
water, dilute to 1 L, and mix. Do not use a solution that has 75.4 Add 50 mL of water and 5 mL of sodium tartrate
stood more than 24 h. solution. With swirling, add NH4OH dropwise until the color

12
 E 478 – 03
changes from a clear green to a turquoise-green color (pH TABLE 7 Statistical Information
approximately 5.5). Add 30 mL of the buffer solution, and mix. Test Specimen
Aluminum Repeatability (R1, Reproducibility
75.5 Transfer the solution to a 500-mL separatory funnel Found, % E 173) (R2, E 173)

and dilute to approximately 125 to 150 mL. Add 8 mL of the High tensile brass (BCS 2.52 0.05 0.08
179/1, 2.54 Al)
DDC solution for each 0.1 g of sample used. Add 50 mL of Manganese bronze, high 5.29 0.04 0.08
CHCl3. Shake the separatory funnel vigorously for 30 s and ten-
allow the phases to separate. Draw off the organic phase and sile
Nickel-aluminum bronze 11.58 0.05 0.18
discard, being careful to avoid any losses of the aqueous
solution in this operation and the subsequent phase separations.
75.6 Add 5 mL of the DDC solution and 25 mL of CHCl3 to
the separatory funnel. Shake the separatory funnel vigorously employ suitable reference materials, if available, to verify the
for 30 s and allow the phases to separate. Add an additional 2 accuracy of the method in their laboratories.
to 3 mL of the DDC solution to ensure that an excess of DDC
has been added. (If a precipitate appears, shake again, add 5 ZINC BY ATOMIC SPECTROMETRY TEST
mL of the DDC solution, shake vigorously for 30 s and allow METHOD
the phases to separate. Repeat this extraction until no further
precipitation occurs. Draw off and discard the organic phase. 78. Scope
75.7 Add 25 mL of the CHCl3, and shake the separatory 78.1 This test method covers the determination of zinc in
funnel for 15 s. Allow the phases to separate. Draw off and concentrations from 0.02 to 2 %.
discard the organic phase. Repeat this step.
75.8 Transfer the aqueous layer quantitatively to a 500-mL 79. Summary of Test Method
Erlenmeyer flask. Rinse the separatory funnel with distilled 79.1 An acid solution of the sample is aspirated into the
water and transfer the rinsings to the flask. air-acetylene flame of an atomic absorption spectrophotometer.
75.9 Using a pipet, add 25 mL of EDTA solution, and mix. The absorption by the sample solution of the zinc resonance
Boil gently for 3 to 5 min to completely decompose any line energy of 2138 Å is measured and compared with the
residual DDC and to chelate the aluminum. Cool to below absorption of calibration solutions containing known amounts
20°C. of zinc.
75.10 Add 6 to 8 drops of xylenol orange indicator solution,
and mix. 80. Concentration Range
75.10.1 If the solution is red, add CH3COOH dropwise until 80.1 The concentration range of zinc must be determined
the color just turns from red to yellow. Proceed as directed in experimentally because the optimum range will depend on the
75.11. characteristics of the instrument used. Determine the appropri-
75.10.2 If the solution is yellow, add NH4OH dropwise just ate concentration range as directed in 80.1.1-80.1.5.
to the transition color from yellow to red. Then add acetic acid 80.1.1 Prepare a dilute standard solution as directed in 83.3.
dropwise until the color just turns from red to yellow. 80.1.2 Prepare the instrument for use as directed in 86.1.
75.11 Titrate the excess EDTA with the standard zinc Measure the instrument response while aspirating a reference
solution (0.0500 M) to the first color change from yellow to solution, the lowest, and the two highest calibration solutions.
orange or pink. Apply the sensitivity test and curve linearity test as directed in
82.1.1 and 82.1.2, respectively.
76. Calculation 80.1.3 If the criteria of sensitivity and of curve linearity are
76.1 Calculate the percentage of aluminum as follows: met, the initial concentration range may be considered accept-
@25.00 2 ~A 3 B!# 3 C 3 2.698
able. Proceed as directed in 80.1.5.
Aluminum, % 5 D (14) 80.1.4 If the minimum response is not obtained, prepare a
dilute standard solution to provide a higher concentration range
where: and repeat 80.1.1 and 80.1.2. If the linearity criterion is not
A = zinc solution required to titrate the excess EDTA in met, prepare a dilute standard solution to provide a concentra-
74.11, mL, tion range lower than that of the original standard solution and
B = EDTA equivalent to 1.00 millilitre of zinc standard repeat 80.1.1 and 80.1.2. If a concentration range cannot be
solution, mL, 73.3.2, found for which both criteria are met, the instrument’s perfor-
C = molarity of EDTA solution, and mance must be improved before this method is used.
D = sample used, g. 80.1.5 Perform the stability test as directed in 82.1.3. If the
minimum requirements are not met with the selected calibra-
77. Precision and Bias tion solutions, do not use this method until the desired stability
77.1 Precision—Eight laboratories cooperated in testing is obtained.
this test method and obtained the data summarized in Table 7.
77.2 Bias—No information on the accuracy of this method 81. Interferences
is known, because at the time it was tested, no standard 81.1 The elements ordinarily present do not interfere if their
reference materials were available. Users are encouraged to concentrations are under the maximum limits shown in 1.1

13
 E 478 – 03
82. Apparatus covered 600-mL beaker with 50 mL of dissolving solution.
82.1 Atomic Absorption Spectrophotometer—Determine Boil gently to remove gases, cool, transfer to a 1-L volumetric
that the atomic absorption spectrophotometer is satisfactory for flask, dilute to volume, and mix. Store in a plastic bottle.
use in this test method by proceeding as directed in 82.1.1- 83.3 Zinc, Standard Solution B (1 mL = 0.004 mg Zn)—
82.1.3. Using a pipet, transfer 4 mL of Zinc Solution A to a 1-L
volumetric flask, add 10 mL of dissolving solution, dilute to
NOTE 9—Optimum settings for the operating parameters of the atomic volume, and mix. Store in a plastic bottle. Do not use a solution
absorption spectrophotometer vary with the instrument used; use the 2138
that has stood more than 24 h.
Å zinc line, a band pass of approximately 5 Å, and a lean air-acetylene
flame.
84. Calibration
82.1.1 Sensitivity—The difference between the readings of 84.1 Calibration Solutions—Using a 50-mL buret, transfer
the two highest of eight equally spaced calibration solutions 4, 8, 12, 16, 20, 24, 28, and 32 mL of Zinc Solution B to
must be sufficient to permit an estimation equivalent to one 100-mL volumetric flasks. Add 2 mL of dissolving solution to
fifth of the difference between the concentrations of the two each flask, dilute to volume, and mix.
solutions. 84.2 Reference Solution—Add 2 mL of dissolving solution
82.1.2 Curve Linearity—The difference between the read- to a 100-mL volumetric flask, dilute to volume, and mix.
ings of the two highest of eight equally spaced calibration 84.3 Determine the suitability of the selected concentration
solutions must be more than 0.7 times the difference between range and apparatus as directed in Section 82.
the reference solution and the lowest of the calibration solu-
tions. Absorbance values are to be used in this calculation. 85. Procedure
82.1.3 Minimum Stability—Obtain the readings of the ref-
85.1 Test Solution:
erence solution and the highest calibration solution. Repeat at
85.1.1 Transfer a 1.00-g sample to a 400-mL beaker, cover,
least twice with no change in parameters. The variability of the
and add 20 mL of dissolving solution. Allow the initial reaction
readings of the highest calibration solution and of the reference
to subside. Heat gently to remove gases and to complete the
solution must be less than 3.0 % and 1.5 %, respectively, as
dissolution. Cool, transfer to a 1-L volumetric flask, dilute to
calculated as follows:
volume, and mix. Store in a plastic bottle.
VC 5
100
C̄
3 Œ (~C 2 C̄! 2
n21 (15)
85.1.2 Select the appropriate aliquot in accordance with the
following, and, using a pipet, transfer it to a 100-mL volumet-
ric flask, add 2 mL of dissolving solution, dilute to volume, and
mix.
VO 5
100
C̄
3 Œ (~O 2 Ō! 2
n21 (16) Zinc Concentration, % Aliquot

0.02 to 0.1 use as prepared

0.1 to 0.25 50 mL
where: 0.25 to 1.0 10 mL
1.0 to 2.0 5 mL
VC = percent variability of the highest calibration
readings, 86. Measurements
C̄ = average absorbance value for the highest
calibration solution, 86.1 Instrument Adjustments:
( (C − C̄)2 = sum of the squares of the n differences 86.1.1 Set the parameters to the values suggested in 82.1
between the absorbance readings of the high- and light the burner.
est calibration solution and their average, 86.1.2 Aspirate the highest calibration solution and opti-
Ō = average absorbance value of the reference mize all adjustments to obtain maximum absorption.
solution, 86.1.3 Aspirate the reference solution to ensure stability and
VO = percent variability of the readings on the set the initial reading above, but near, zero.
reference solution relative to C̄, 86.2 Aspirate the test solution to determine its place in the
( (O − = sum of the squares of the n difference be- order of increasing concentration of the calibration solutions.
Ō)2 tween the absorbance readings of the refer- 86.3 Aspirate the reference solution and adjust to the base
ence solution and their average, and reading. Aspirate the reference solution, the test solution, and
n = number of determinations. calibration solutions, in the order of increasing readings.
86.4 Repeat 86.3 at least twice.
83. Reagents
87. Calculation
83.1 Dissolving Solution—Add 250 mL of HNO3 to 500 mL
of water, mix, add 250 mL of HCl, and mix. Store in a plastic 87.1 Calculate the variability of the readings for the refer-
bottle. ence solution and the highest calibration solution as directed in
82.1.3 to determine whether they are less than 1.5 and 3.0 %,
NOTE 10—All plastic bottles used in the method must be well rinsed respectively. If they are not, disregard the data, readjust the
with the dissolving solution before use. instrument, and proceed again as directed in 86.2.
83.2 Zinc, Standard Solution A (1 mL = 1.00 mg Zn)— 87.2 If necessary, convert the average of the readings for
Dissolve 1.00 g of zinc metal (purity: 99.95 % min) in a each calibration solution to absorbance.

14
 E 478 – 03
87.3 Prepare a calibration curve by plotting the average 92. Interferences
absorbance values for the calibration solutions against milli- 92.1 The elements normally present do not interfere if their
grams of zinc/100 mL. concentrations are under the maximum limits shown in 1.1.
87.4 Convert the absorbance value of the test solution to
milligrams of zinc per 100 mL by means of the calibration 93. Apparatus
curve.
87.5 Calculate the percentage of zinc as follows: 93.1 Atomic Absorption Spectrophotometer—Determine
that the instrument is suitable for use as prescribed in the
A
Zinc, % 5 B 3 100 (17) operational guide. The percent of variability for the highest
calibration solution (Vc) should be less than 1.0 %.
where: 93.1.1 Operating Parameters:
A = zinc/100 mL of the final test solution, mg, and
B = sample represented in 100 mL of the test solution Wavelength 2833 Å (Note 11)
taken for analysis, mg. Bandpass about 5 Å
Gas mixture air-acetylene
Flame type lean
88. Precision and Bias
NOTE 11—For very low concentrations of lead, the resonance line
88.1 Precision—Eight laboratories cooperated in the testing energy at 2170Å may be used provided the criteria set forth in 93.1 are
of this test method and obtained the data summarized in Table met.
8. Supporting data are available from ASTM Headquarters.
Request RR:E03-1012. 94. Reagents
88.2 Bias—The accuracy of this method has been deemed 94.1 Fluoboric Acid (37 to 40 %).
satisfactory based upon the data for the standard reference 94.2 Lead, Standard Solution A (1 mL = 1.00 mg Pb)—
materials in Table 8. Users are encouraged to use these or Dissolve 1.000 g of lead metal (purity: 99.9 % min) in a
similar reference materials to verify that the method is per- covered 150-mL beaker with 15 mL of HNO3 (1 + 2). Transfer
forming accurately in their laboratories. to a 1-L volumetric flask, add 100 mL of HNO3 (1 + 2), dilute
to volume, and mix. Store in a plastic bottle.
94.3 Lead, Standard Solution B (1 mL = 0.200 mg Pb)—
TABLE 8 Statistical Information
Using a pipet, transfer 50 mL of Standard Lead Solution A to
Zinc Repeatability (R1, Reproducibility
Test Specimen
Found, % E 173) (R2, E 173)
a 250-mL volumetric flask. Dilute to volume and mix.
1. 70-30 cupro-nickel alloy 0.965 0.0306 0.0391
2. Aluminum-bronze alloy 0.034 0.0009 0.003 95. Calibration
(78 Cu-9 Al-5 Fe-5 Ni)
3. NIST 52c, 2.12 % zinc 2.10 0.025 0.078
95.1 Select a convenient value, Q µg/mL, less than the
4. NIST 158a, 2.08 % zinc 2.09 0.039 0.108 maximum obtained in 91.1. Using pipets, transfer into indi-
5. 70-30 cupro-nickel alloy 0.129 0.007 0.017 vidual 100-mL volumetric flasks 0.1Q, 0.2Q, 0.3Q, 0.4Q, and
0.5Q mL of Standard Lead Solution B. Add 5 mL of HNO3
(1 + 2) to each flask, dilute to volume, and mix.
95.2 Reference Solution—Add 5 mL of HNO3 (1 + 2) to a
LEAD BY THE ATOMIC ABSORPTION TEST 100-mL volumetric flask, dilute to volume, and mix.
METHOD 95.3 Determine the suitability of the selected concentration
range and apparatus as directed in the operational guide.
89. Scope
89.1 This test method covers the determination of lead in 96. Procedure
concentrations from 0.002 to 15 %. 96.1 Test Solution:
96.1.1 Transfer a 1-g sample, weighed to the nearest 1 mg,
90. Summary of Test Method to a 150-mL beaker, add 5 mL of HBF4 and 15 mL of HNO3
90.1 An acid solution of the sample is aspirated into the (1 + 2), and cover. Allow the initial reaction to subside. Heat
air-acetylene flame of an atomic absorption spectrophotometer. gently to complete the dissolution and remove gases. Cool,
The absorption by the sample solution of the lead resonance transfer to a 100-mL volumetric flask, dilute to volume, and
line energy at 2833 Å is measured and compared with the mix.
absorption of calibration solutions containing known amounts 96.1.2 Select an appropriate aliquot (nominal values) in
of lead. accordance with the following, and, using a pipet, transfer it to
a 100-mL volumetric flask, add 5 mL HNO3 (1 + 2), dilute to
91. Concentration Range volume, and mix.
91.1 If the optimum concentration range is not known; Lead Concentration, % Aliquot

determine it as directed in Guide E 1024, here in after referred 0.002 to 0.60 use as prepared
to as the operational guide. A sensitivity of 0.5 µg/mL of 0.50 to 3.00 20 mL
0.0044 absorbance is widely obtained. 2.0 to 12.0 5 mL

15
 E 478 – 03
97. Measurements 103. Interferences
97.1 Optimize the response of the instrument (adjustments) 103.1 Elements normally present in silver-bearing copper
and take preliminary readings; complete the analysis and do not interfere. Contamination of the calibration or test
calculate the concentration of lead in the test solution as in the solutions by halides may lead to the loss of silver. (Note that
graphical, ratio, or single point procedures, as described in the copper that has been soldered may contain a flux residue with
operational guide. For low levels of lead, expanded scale a chloride constituent).
readout is advisable.
104. Apparatus
98. Calculation
104.1 Atomic Absorption Spectrophotometer—Determine
98.1 Calculate the percentage of lead as follows: that the instrument is suitable for use as prescribed in the
A Operational Guide. The percent variability for the highest
Lead, % 5 B 3 100 (18)
calibration solution should be less than 1.0.
104.1.1 Operating Parameters:
where:
A = lead/100 mL of the final test solution, mg, and
B = sample represented in 100 mL of the test solution Wavelength 328.1 nm
Gas mixture air – acetylene
taken for analysis, mg. Flame type lean

99. Precision and Bias 105. Reagents

99.1 Precision—Due to limited data, a precision statement
105.1 Mercury Solution (3 g/L)—Dissolve 3 g of mercury in
conforming to the requirements of Practices E 173 cannot be
10 mL of HNO3 (1 + 1). Warm gently to remove fumes, cool,
furnished. However, in a cooperative program conducted by
add 25 mL HNO3, and dilute to 1 L. Store in a plastic bottle.
six laboratories, the results reported in Table 9 were obtained.
105.2 Silver, Standard Solution A (1 mL = 0.2 mg Ag)—
Supporting data are available from ASTM Headquarters. Re-
Dissolve 0.3150 g of silver nitrate (AgNO3) (purity, 99.7 %
quest RR: E03-1013.
min) in water. Transfer to a 1-L volumetric flask, add 100 mL
99.2 Bias—No information on the accruacy of this method
of mercury solution (3 g/L) and 25 mL of HNO3. Dilute to
is known, because at the time it was tested, no standard
volume and mix. Store in a tightly sealed plastic bottle in a
reference materials were available. Users are encouraged to
dark place. The solution is stable for one year.
employ suitable reference materials, if available to verify the
105.3 Silver, Standard Solution B (1 mL = 0.02 mg Ag)—
accuracy of the method in their laboratories.
Using a pipet, transfer 25 mL of silver Solution A to a 250-mL
volumetric flask. Dilute to volume and mix. Prepare fresh prior
TABLE 9 Statistical Information to use.
% Pb, Highest
Average of Lowest Value of Lead
Material Value of Lead
Lead, % Obtained, %
Obtained, %
106. Hazards
Copper (C102) 0.0037 0.0028 0.0052 106.1 Caution—Mercury is a health hazard. Handling and
Bronze (C544) 4.22 4.14 4.35 disposal should be done in a safe manner.
Bronze (C922) 2.00 1.93 2.06
Bronze (C939) 14.43 14.27 14.67
107. Calibration
107.1 Calibration Solutions—Select a convenient value, Q
SILVER IN SILVER-BEARING COPPER BY THE µg/mL, less than the range maximum obtained in 101.1. Using
ATOMIC ABSORPTION TEST METHOD pipets, transfer Q, 2Q, 3Q, 4Q, and 5Q mL of silver Solution
B to 100-mL volumetric flasks. Add 10 mL of mercury solution
100. Scope (3 g/L) and 5 mL of HNO3(1 + 1) to each flask, dilute to
100.1 This test method covers the determination of silver in volume, and mix. Store away from the light.
concentrations from 0.01 to 0.12 %. 107.2 Reference Solution—Add 10 mL of mercury solution
(3 g/L) and 5 mL HNO3 (1 + 1) to a 100-mL volumetric flask.
101. Summary of Test Method Dilute to the mark and mix.
101.1 An acid solution of the sample is aspirated into the 107.3 Determine the suitability of the selected concentration
air-acetylene flame of an atomic absorption spectrophotometer. range and apparatus as directed in the Operational Guide.
The absorption by the sample solution of the silver resonance
line energy at 328.1 nm is measured and compared with the 108. Procedure
absorption by calibration solutions containing known amounts 108.1 Test Solution—Accurately weigh a sample (0.5 g or
of silver. less) to contain up to 100 Q µg Ag. Transfer to a 150-mL
beaker, add 8 mL of HNO3 (1 + 1), and allow to dissolve.
102. Concentration Range Warm gently to remove gasses, cool, and transfer to a 100-mL
102.1 If the optimum concentration range is not known volumetric flask. Add 10 mL of mercury solution (3 g/L), dilute
determine it as directed in the Operational Guide. to volume, and mix.

16
 E 478 – 03
109. Measurements 116. Interferences
109.1 Optimize the response of the instrument and take 116.1 The elements ordinarily present do not interfere if
preliminary readings; complete the analysis and calculate the their concentrations are under the maximum limits shown in
concentration of silver in the test solution as described in the 1.1.
Operational Guide.
117. Apparatus
110. Calculation 117.1 pH Meter.
110.1 Calculate the percentage of silver as follows:
118. Reagents
A
Silver, % 5 B 3 100 (19) 118.1 Ascorbic Acid, Powder.
118.2 Boric Acid Solution (50 g/L)—Dissolve 50 g of boric
where: acid (H3BO3) in hot water, cool, and dilute to 1 L.
A = silver per 100 mL of the final test solution, mg, and 118.3 Copper, High-Purity—Use copper containing less
B = sample represented in 100 mL of the test solution than 0.0001 % tin.
taken for analysis, mg. 118.4 Fluoboric Acid (HBF4) (49 to 50 %).
110.2 If required, convert to troy ounces per short ton: 118.5 Gelatin Solution (10 g/L)—While stirring, add 1 g of
Silver, % 3 291.7 5 silver, oz/ton (20) gelatin to 100 mL of boiling water. Do not use a solution that
has stood more than 1 day.
118.6 Perchloric Acid Solution (9 + 31)—Slowly add 225
111. Precision and Bias mL of HClO4 to a 1-L volumetric flask containing 500 mL of
111.1 Precision—Seven laboratories cooperated in testing water, cool, dilute to volume, and mix.
this test method and obtained 9 sets of data summarized in 118.7 Phenylfluorone Solution (0.2 g/L)—Dissolve 0.200 g
Table 10. Supporting data are available from ASTM Headquar- of phenylfluorone (2,6,7-trihydroxy-9-phenylisoxanthene3-
ters. Request RR: E03-1032. one)5 in a mixture of 600 mL of 2-ethoxy-ethanol (ethylene
111.2 Bias—No information on the accuracy of this method glycol monoethyl ether), 30 mL of water, and 30 mL of HClO4,
is known, because at the time it was tested, no standard while stirring with a magnetic stirrer. Dilute to 1 L with water.
reference materials were available. Users are encouraged to Do not use a solution that has stood more than 1 week.
employ suitable reference materials, if available, to verify the 118.8 Potassium Permanganate Solution (20 g/L)—
accuracy of the method in their laboratories. Dissolve 20 g of potassium permanganate (KmnO4) in water
and dilute to 1 L.
TABLE 10 Statistical Information 118.9 Sodium Citrate Solution (100 g/L)—Dissolve 100 g of
Test Specimen Repeatability Reproducibility (R2, sodium citrate dihydrate in water and dilute to 1 L.
Silver Found, %
(Alloy Number) (R1, E 173) E 173) 118.10 Sodium Hydroxide Solution (250 g/L)—Dissolve
1. C11600 0.0959 0.0039 0.0077 250 g of sodium hydroxide (NaOH) in about 100 mL of water.
2. C11400 0.0383 0.0020 0.0038
When dissolution is complete, cool, and dilute to 1 L. Store in
a plastic bottle.
118.11 Tin, Standard Solution A (1 mL = 1.0 mg Sn)—
TIN BY THE PHENYLFLUORONE Dissolve 1.000 g of tin (purity: 99.9 % min) in a mixture of 25
PHOTOMETRIC TEST METHOD mL of HNO3, 25 mL of HCl, and 25 mL of HBF4. When
112. Scope dissolution is complete, boil gently to expel oxides of nitrogen,
cool, transfer to a 1-L volumetric flask, dilute to volume, and
112.1 This test method covers the determination of tin in mix. Store in a polyethylene bottle.
concentrations from 0.01 to 1.0 %. 118.12 Tin, Standard Solution (1 mL = 0.005 mg Sn)—
113. Summary of Method Using a pipet, transfer 5 mL of tin Solution A (1 mL = 1.0 mg
of Sn) to a 1-L volumetric flask, add 25 mL of HBF4 (1 + 9),
113.1 The sample is dissolved in fluoboric and nitric acids. dilute to volume, and mix. Do not use a solution that has stood
Phenylfluorone in a perchloric acid-sodium citrate-buffered more than 1 week.
solution reacts with the tin to form an orange-red complex. 118.13 Tin, Standard Solution C (1 mL = 0.010 mg Sn)—
Photometric measurement is made at approximately 510 nm. Using a pipet, transfer 10 mL of tin Solution A (1 mL = 1.0 mg
114. Concentration Range Sn) to a 1-L volumetric flask, add 25 mL of HBF4 (1 + 9),
dilute to volume, and mix. Do not use a solution that has stood
114.1 The recommended concentration range is from 0.02 more than 1 week.
to 0.16 mg of tin in 100 mL of solution, using a 1-cm cell.
NOTE 12—This test method has been written for cells having a 1-cm 119. Preparation of Calibration Curve
light path. Cells having other dimensions may be used, provided suitable 119.1 Calibration Solutions—Using pipets, transfer 5, 10,
adjustments can be made in the amounts of sample and reagents used. and 15 mL of tin Solution B (1 mL = 0.005 mg Sn), and 10 and
115. Stability of Color
115.1 Photometric measurement is made after 75 6 10 min. 5
Eastman No. 6346 has been found satisfactory for this purpose.

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TABLE 11 Statistical Information 120.1.1 Select and weigh a sample in accordance with the
Test Specimen Tin Found, %
Repeatability Reproducibility following:
(R1E 173) (R2E 173)
Toler-
1. Copper-zinc-nickel 0.023 0.002 0.004 ance in
(NIST 157a 0.021 Sn) Sample Sample Aliquot
2. Tin-copper alloy 0.201 0.013 0.031 Weight, Weight, Dilution, Volume,
(Kennecott 1784) Tin, % g mg mL mL
3. High tensile brass 0.528 0.016 0.085
(BCS 179/1) 0.01 to 0.035 2.00 1.0 100 15
4. Silicon bronze (NIST 158a 0.962 0.024 0.120 0.03 to 0.10 1.00 1.0 100 15
0.96 Sn) 0.09 to 0.16 1.00 1.0 100 10
5. Anaconda brass 0.952 0.042 0.114 0.15 to 0.32 0.50 0.5 100 10
(AABC 681) 0.30 to 0.64 0.25 0.25 100 10
0.60 to 1.00 0.25 0.25 100 5

Transfer it to a 100-mL borosilicate volumetric flask.

120.1.2 Add 10 mL of HBF4 (1 + 9) and 10 mL of HNO3
15 mL of tin solution C (1 mL = 0.010 mg Sn) to 150-mL (1 + 1). When dissolution is complete, heat the solution to
beakers. Proceed as directed in 119.3. boiling and continue to boil until oxides of nitrogen are
119.2 Reference Solution—Transfer 15 mL of water to a removed. Cool, dilute to volume, and mix.
150-mL beaker. Proceed as directed in 119.3. 120.1.3 Using a pipet, transfer 5 to 15 mL portions, as
119.3 Color Development—Adjust the volume to 15 mL specified in 120.1.1, to 150-mL beakers. Proceed as directed in
with water and add 15 mL of sodium citrate solution. Using a 120.3.
pH meter, adjust the pH to 12 6 0.25 with NaOH solution. 120.2 Reference Solution—Transfer a weight of copper
Using a pipet, add 10 mL of HClO4 (9 + 31) and, while stirring, taken in 120.1.1 to a 100-mL borosilicate volumetric flask.
add KMnO4 solution until a pink color persists. Add 25 mL of Treat an aliquot the same size as that of the test solution as
H3BO3 solution and 5 mL of gelatin solution, 25 to 50 mg of directed in 120.1.2. Proceed as directed in 120.3.
ascorbic acid, and 10 mL of phenylfluorone solution. Transfer 120.3 Color Development—Proceed as directed in 119.3.
the solution to a 100-mL volumetric flask, dilute to volume, 120.4 Photometry—Proceed as directed in 119.4.
and mix. Allow to stand 75 6 10 min.
119.4 Photometry: 121. Calculation
119.4.1 Multiple-Cell Photometer—Measure the cell cor- 121.1 Convert the net photometric reading of the test
rection using absorption cells with a 1-cm path and a light band solution to milligrams of tin by means of the calibration curve.
centered at approximately 510 nm. Using the test cell, take Calculate the percentage of tin as follows:
photometric readings of the calibration solutions. A
Tin, % 5 B 3 10 (21)
NOTE 13—Test absorption cells must be cleaned after each reading in a
solution of dilute nitric acid (1 + 4) to remove the colored complex that
may adhere to the windows. where:
A = tin found in 100 mL of the final test solution, mg, and
119.4.2 Single-Cell Photometer—Transfer a suitable por- B = sample represented in 100 mL of the final test solu-
tion of the reference solution to an absorption cell with a 1-cm tion, g.
light path and adjust the photometer to the initial setting, using
a light band centered at approximately 510 nm. While main- 122. Precision and Bias
taining this adjustment, take photometric readings of the 122.1 Precision—Eight laboratories cooperated in testing
calibration solutions (Note 13). this test method with one laboratory reporting a second pair of
119.5 Calibration Curve—Plot the net photometric readings values. The data are summarized in Table 11.
of the calibration solutions against milligrams of tin per 100 122.2 Bias—The accuracy of this method has been deemed
mL of solution. satisfactory based upon the data for the standard reference
material in Table 11. Users are encouraged to use these or
120. Procedure similar reference materials to verify that the method is per-
120.1 Test Solution: forming accurately in their laboratories.

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