ASTM E396-17

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
´1
Designation: E396 − 12 E396 − 17
Standard Test Methods for
Chemical Analysis of Cadmium
This standard is issued under the fixed designation E396; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
ε NOTE—Editorial corrections were made throughout in August 2012.
1. Scope
1.1 These test methods cover the chemical analysis of cadmium having chemical compositions with the following limits:
Element Composition, max, %
Antimony 0.001
Arsenic 0.003
Copper 0.015
Lead 0.025
Silver 0.010
Thallium 0.003
Tin 0.010
Zinc 0.035
1.2 The test methods appear in the following order:
Sections
Antimony by the Rhodamine B Spectrophotometric Method 62 – 72
[0.0002 % to 0.0010 %]
Arsenic by the Molybdenum Blue Spectrophotometric Method 40 – 50
[0.001 % to 0.005 %]
Copper by the Neocuproine Spectrophotometric Method [0.002 % to 10 – 19
0.030 %]
Copper, Lead, Silver, and Zinc by the Atomic Absorption Spectrom- 51 – 61
etry Method [0.004 % to 0.02 % Cu, 0.01 % to 0.05 % Pb, 0.004 %
to 0.02 % Ag,
and 0.01 % to 0.05 % Zn]
Lead by the Dithizone Spectrophotometric Method [0.001 % to 20 – 29
0.05 %]
Lead by the Dithizone Spectrophotometric Method [0.001 % to 0.05 20 – 29
%]
Thallium by the Rhodamine B Spectrophotometric Method 30 – 39
[0.0003 % to 0.005%]
Thallium by the Rhodamine B Spectrophotometric Method 30 – 39
[0.0003 % to 0.005 %]
Tin by the 8-Quinolinol Spectrophotometric Method [0.0025 % to 73 – 82
0.0150 %]
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use. Specific precautionary information is given in Section 6, , , and .
1.4 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:
B440 Specification for Cadmium
These test methods are under the jurisdiction of ASTM Committee E01 on Analytical Chemistry for Metals, Ores, and Related Materials and are the direct responsibility
of Subcommittee E01.05 on Cu, Pb, Zn, Cd, Sn, Be, Precious Metals, their Alloys, and Related Metals.
Current edition approved Jan. 27, 2012Dec. 15, 2017. Published February 2012January 2017. Originally approved in 1970. Last previous edition approved in 20112012
ɛ1
as E396 – 05E396 – 12 (2011). DOI: 10.1520/E0396-12.10.1520/E0396-17.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E396 − 17
D1193 Specification for Reagent Water
E29 Practice for Using Significant Digits in Test Data to Determine Conformance with Specifications
E50 Practices for Apparatus, Reagents, and Safety Considerations for Chemical Analysis of Metals, Ores, and Related Materials
E55 Practice for Sampling Wrought Nonferrous Metals and Alloys for Determination of Chemical Composition
E60 Practice for Analysis of Metals, Ores, and Related Materials by Spectrophotometry
E88 Practice for Sampling Nonferrous Metals and Alloys in Cast Form for Determination of Chemical Composition
E135 Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
E173 Practice for Conducting Interlaboratory Studies of Methods for Chemical Analysis of Metals (Withdrawn 1998)
E1601 Practice for Conducting an Interlaboratory Study to Evaluate the Performance of an Analytical Method
3. Terminology
3.1 For definitions of terms used in this test method, refer to Terminology E135.
4. Significance and Use
4.1 These test methods for the chemical analysis of cadmium are primarily intended to test such material for compliance with
compositional specifications in Specification B440. It is assumed that all who use these test methods will be trained analysts
capable of performing common laboratory procedures skillfully and safely. It is expected that work will be performed in a properly
equipped laboratory.
5. Apparatus, Reagents, and Spectrophotometric Practice
5.1 Apparatus and reagents required for each determination are listed in separate sections preceding the procedure. The
apparatus, standard solutions, and reagents shall conform to the requirements prescribed in Practices E50. Spectrophotometers shall
conform to the requirements prescribed in Practice E60.
5.2 Spectrophotometric practice prescribed in these methods shall conform to Practice E60.
5.3 Reagents—
5.3.1 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water conforming
to Type II of Specification D1193. Type III or Type IV may be used if they effect no measurable change in the blank or sample.
5.3.2 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society where such
specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
6. Safety Hazards
6.1 For precautions to be observed in the use of certain reagents in these test methods, refer to Practices E50.
7. Sampling
7.1 Wrought products shall be sampled in accordance with Practice E55. Cast products shall be sampled in accordance with
Practice E88. However, these test methods do not supersede any sampling requirements specified in a specific ASTM material
specification.
8. Rounding Calculated Values
8.1 Calculated values shall be rounded to the desired numberRounding of test results obtained using this test method shall be
performed in accordance with Practice E29of places as directed in Practice, Rounding Method, unless an alternative E29.rounding
method is specified by the customer or applicable material specification.
9. Interlaboratory Studies
9.1 These test methods have been evaluated in accordance with Practices E173, unless otherwise noted in the precision section.
9.2 Practice E173 has been replaced by Practice E1601. The reproducibility index, R , of Practice E173 corresponds to the
reproducibility index, R, of Practice E1601. The repeatability index, R , of Practice E173, corresponds to the repeatability index,
r, of Practice E1601.
COPPER BY THE NEOCUPROINE SPECTROPHOTOMETRIC METHOD
10. Scope
10.1 This test method covers the determination of copper content from 0.002 % to 0.030 %.
The last approved version of this historical standard is referenced on www.astm.org.
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by
the American Chemical Society, see the United States Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD
E396 − 17
10. Scope
10.1 This test method covers the determination of copper content from 0.002 % to 0.030 %.
11. Summary of Test Method
11.1 Copper is separated as cuprous copper from other metals by extraction of the copper-neocuproine complex with
chloroform. Spectrophotometric absorbance measurement is made at approximately 455 nm.
12. Concentration Range
12.1 The recommended concentration range is from 0.01 mg to 0.15 mg of copper for each 25 mL of solution, using a 1-cm
cell.
NOTE 1—This test method has been written for cells having a 1-cm light path. Cells having other dimensions may be used, provided suitable
adjustments can be made in the amounts of sample and reagents used.
13. Stability of Color
13.1 The color develops within 5 min and the extracted complex is stable. However, because of the volatile nature of the solvent,
it is advisable to take spectrophotometric readings promptly.
14. Interferences
14.1 The elements ordinarily present do not interfere if their contents are under the maximum limits shown in 1.1.
15. Reagents
15.1 Chloroform (CHCl ).
15.2 Copper, Standard Solution (1 mL = 0.01 mg Cu)—Dissolve 0.1000 g of copper (purity: 99.9 % min) in 10 mL of HNO
(1 + 1). Add 25 mL of water, heat to boiling, and boil gently for 2 min to eliminate oxides of nitrogen. Cool, transfer to a 100-mL
volumetric flask, dilute to volume, and mix. Transfer 5.00 mL to a 500-mL volumetric flask. Add 1 mL of HNO (1 + 1), dilute
to volume, and mix.
15.3 Hydroxylamine Hydrochloride Solution (100 g/L)—Dissolve 5.0 g of hydroxylamine hydrochloride
(NH OH · HCl)OH·HCl) in 50 mL of water. Prepare fresh as needed.
15.4 Metacresol Purple Indicator Solution (1 g/L)—Dissolve 0.100 g of metacresol purple together with 1 pellet of sodium
hydroxide (NaOH) NaOH in about 10 mL of water by warming. Dilute to 100 mL, and mix.
15.5 Neocuproine Solution (1 g/L)—Dissolve 0.10 g of neocuproine (2,9-dimethyl-1,10-phenanthroline hemihydrate) in 100 mL
of either methanol or 95 % ethanol.
15.6 Sodium Citrate Solution (300 g/L)—Dissolve 300 g of sodium citrate dihydrate in water, dilute to 1 L, and mix.
15.7 Purity of Water—Unless otherwise indicated, reference to water shall be understood to mean reagent water as defined by
Type II of Specification D1193. Other Types may be used if they effect no measurable change in the reference solution or sample.
16. Preparation of Calibration Curve
16.1 Calibration Solution:
16.1.1 Using pipets, transfer (2, 5, 10, 15, and 20) mL of copper solution (1 mL = 0.01 mg Cu) to five 150-mL beakers, and
dilute to about 40 mL.
16.1.2 Add 2 drops of metacresol purple indicator solution, and then add HNO (1 + 1) dropwise to the red color change of the
indicator. Proceed as directed in 16.3.
16.2 Reference Solution—Add 40 mL of water to a 150- mL beaker. Proceed as directed in 16.1.2.
16.3 Color Development:
16.3.1 Add 10 mL of NH OH · HCl OH·HCl solution, and stir. Add 10 mL of sodium citrate solution, and stir. Add NH OH
2 4
to the purple color of the indicator (pH about 8.5). Add 5.0 mL of neocuproine solution, stir, and allow to stand for 5 min.
NOTE 2—The precipitate that may form upon addition of sodium citrate solution will redissolve when the pH is raised to 8.5 with NH OH.
16.3.2 Transfer to a 125-mL separatory funnel marked at 80 mL, and dilute to the mark with water. Add 25.0 mL of CHCl .
Shake vigorously for 45 s, and allow the layers to separate. Draw off and discard about 1 mL of the CHCl layer to rinse the stem
of the separatory funnel.
16.4 Spectrophotometry:
16.4.1 Multiple-Cell Spectrophotometer—Measure the cell correction using absorption cells with a 1-cm light path and a light
band centered at approximately 455 nm (nm. Note 3). Using the test cell, take the spectrophotometric absorbance readings of the
calibration solutions.
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NOTE 3—Avoid transfer of water to the absorption cell in the following manner. Insert a loose plug of sterilized absorbent cotton into the stem of each
separatory funnel. Just prior to filling the absorption cell with the solution in the separatory funnel, discard about 1 mL of the CHCl layer through the
cotton plug and immediately transfer a suitable portion of the CHCl layer into the dry absorption cell.
16.4.1.1 Avoid transfer of water to the absorption cell in the following manner: Insert a loose plug of sterilized absorbent cotton
into the stem of each separatory funnel. Just prior to filling the absorption cell with the solution in the separatory funnel, discard
about 1 mL of the CHCl layer through the cotton plug and immediately transfer a suitable portion of the CHCl layer into the
3 3
dry absorption cell.
16.4.2 Single-Cell Spectrophotometer—Transfer a suitable portion of the reference solution to an absorption cell with a 1-cm
light path and adjust the spectrophotometer to the initial setting, using a light band centered at approximately 455 nm (Note 1).
While maintaining this adjustment, take the spectrophotometric absorbance readings of the calibration solutions.
16.5 Calibration Curve—Plot the net spectrophotometric absorbance readings of the calibration solutions against milligrams of
copper per 25 mL of solution.
17. Procedure
17.1 Test Solution—Transfer a 0.5-g sample, weighed to the nearest 1 mg, to a 150-mL beaker. Add 5 mL of HNO (1 + 1).
When dissolution is complete, add 20 mL of water and boil gently to eliminate oxides of nitrogen. Cool, dilute to about 40 mL,
and add 2 drops of metacresol purple indicator solution. Proceed as directed in 17.3.
17.2 Reference Solution—Carry a reagent blank through the entire procedure using the same amount of all reagents with the
sample omitted, for use as the reference solution.
17.3 Color Development—Proceed as directed in 16.3.
17.4 Spectrophotometry—Proceed as directed in 16.4.
18. Calculation
18.1 Convert the net spectrophotometric absorbance reading of the test solution to milligrams of copper by means of the
calibration curve. Calculate the percentage of copper as follows:
Copper,%5 A/ B 310 (1)
~ !
where:
A = copper found in the 25 mL of final test solution, mg, and
B = sample represented in 25 mL of final test solution, g.
19. Precision and Bias
19.1 Precision—Eight laboratories cooperated in testing this test method and obtained the data summarized in Table 1.
19.2 Accuracy—Bias—No certified reference materials suitable for testing this test method were available when the
interlaboratory testing program was conducted. The user of this test method is encouraged to employ accepted reference materials,
if available, to determine the accuracy of this test method as applied in a specific laboratory.
19.3 E173 has been replaced by Practice E1601. The reproducibility Index R corresponds to the Reproducibility Index R of
Practice E1601. Likewise the Repeatability Index R corresponds to the Repeatability Index r of Practice E1601.
LEAD BY THE DITHIZONE SPECTROPHOTOMETRIC METHOD
20. Scope
20.1 This test method covers the determination of lead in content from 0.001 % to 0.05 %.
20. Scope
20.1 This test method covers the determination of lead in content from 0.001 % to 0.05 %.
21. Summary of Test Method
21.1 Lead dithizonate is extracted with chloroform from a buffered cyanide solution at a pH of 8.5. The excess dithizone in the
chloroform is then removed by extraction with an ammoniacal sulfite solution. spectrophotometric Spectrophotometric absorbance
measurement is made at approximately 515 nm.
TABLE 1 Statistical Information
Copper Found, Repeatability Reproducibility
Specimen
% (R , E173) (R , E173)
1 2
1 0.0074 0.003 0.0013
2 0.0173 0.0018 0.0031
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22. Concentration Range
22.1 The recommended concentration range is from 0.005 mg to 0.050 mg of lead for each 25 mL of solution, using a 1-cm
cell (Note 1).
23. Stability of Color
23.1 The color is stable for at least 2 h if protected from direct sunlight; however, because of the volatile nature of the solvent,
it is advisable to take spectrophotometric readings promptly.
24. Interferences
24.1 The elements ordinarily present in cadmium do not interfere if their contents are under the maximum limits shown in 1.1.
25. Reagents
25.1 Ascorbic Acid.Acid (C H O ).
6 8 6
25.2 Bromine Water, (saturated.Saturated).
25.3 Chloroform (CHCl ).
25.4 Dithizone Solution (0.01 g/L ofin CHCl )—Dissolve 0.05 g of dithizone (diphenylthiocarbazone) in a freshly opened 700-g
bottle of CHCl . Mix several times over a period of several hours. Store in a cool, dark place. Just before use, dilute 50 mL of
this solution to 500 mL with CHCl in a dry borosilicate bottle or flask, and mix.
25.5 Lead, Standard Solution (1 mL = 0.005 mg Pb)—Dissolve 0.1000 g of lead (purity: 99.9 % min) in 20 mL of HNO (1 + 1),
and boil gently to eliminate oxides of nitrogen. Cool, transfer to a 200-mL volumetric flask, dilute to volume, and mix. Transfer
5.00 mL to a 500-mL volumetric flask, dilute to volume, and mix. Prepare the final solution fresh as needed.
25.6 Metacresol Purple Indicator Solution (1 g/L)—Proceed as directed in 15.4.
25.7 Potassium Cyanide Solution (200 g/L)—Dissolve 200 g of potassium cyanide (KCN) (low in lead and sulfide) (Warning
—See ) in water, and dilute to 1 L. Bring to a boil and boil for 2 min. Cool, and store in a polyethylene bottle.
25.8 Sodium Sulfite Wash Solution—Dissolve 1 g of sodium sulfite (Na SO ) in about 300 mL of water in a 1-L volumetric flask.
2 3
Add 20 mL of the KCN solution and 475 mL of NH OH (1 + 1) which has been prepared from a freshly opened bottle. Dilute to
volume, and mix. Store in a polyethylene bottle. (Warning—The preparation, storage, and use of KCN solutions require care and
attention. Avoid inhalation of fumes and exposure of the skin to the chemical and its solutions. Do not allow solutions containing
cyanide to come in contact with strongly acidic solutions. Work in a well-ventilated hood. Refer to Section 8 of Practices E50.)
25.9 Sodium Tartrate Solution (250 g/L)—Dissolve 50 g of sodium tartrate dihydrate in water, and dilute to 200 mL.
25.10 Thioglycolic Acid Solution (1 + 99)—Dilute 1.0 mL of thioglycolic acid (mercaptoacetic acid) to 100 mL with water.
Refrigerate both the concentrated and diluted acid solutions. Do not use concentrated acid that is more than 1 year old, nor diluted
acid that has stood for more than 1 week.
25.11 Purity of Water—Unless otherwise indicated, reference to water shall be understood to mean reagent water as defined by
Type II of Specification D1193. Other Types may be used if they effect no measurable change in the reference solution or sample.
26. Preparation of Calibration Curve
26.1 Calibration Solutions—Using pipets, transfer (1, 2, 3, 5, and 10)-mL volumes of lead solution (1 mL = 0.005 mg Pb) to
125-mL separatory funnels (set No. 1). Dilute to 15 mL with water and add 1 drop of metacresol purple indicator solution.solution
(Note 3).
26.2 Reference Solution—Transfer 15 mL of water to a 125-mL separatory funnel (one of set No. 1), and add 1 drop of
metacresol purple indicator solution.
26.3 Color Development:
26.3.1 Add NH OH (1 + 1) dropwise, with swirling, until the indicator color begins to change from red to yellow. Add 2 drops
of HNO . Extract with successive 10-mL portions of dithizone solution until the color of the dithizone remains unchanged. Discard
all extracts.
26.3.2 Add 2 mL of sodium tartrate solution, about 20 mg of ascorbic acid, and 2 drops of thioglycolic acid solution (1 + 99).
Add NH OH (1 + 1), while mixing, until the solution turns yellow. Add 20 mL of KCN solution (Warning—see ) and mix. Add
10 mL of acetic acid (1 + 4), and mix.
NOTE 3—The indicator color should be purple and the pH approximately 8.5. Some lots of KCN may give a pH lower than 8.0 or higher than 9.0.
Should this occur, use NH OH (1 + 1) or acetic acid (1 + 4) to adjust the pH to 8.5 6 0.5.
26.3.3 Dilute to 60 mL with water, add 15.0 mL of dithizone solution, and shake vigorously for 1 min. Allow the layers to
separate for 1 min. Transfer the lower layer to another 125-mL separatory funnel (set No. 2) containing 50 mL of the sodium sulfite
E396 − 17
wash solution. Add an additional 10.0 mL of dithizone solution to the original separatory funnel (set No. 1) and shake for 1 min.
Again allow the layers to separate for 1 min and add this second portion to the No. 2 separatory funnel.
26.3.4 Shake the combined organic layers in the No. 2 funnel for 1 min and allow the layers to separate for 1 min. Draw off
and discard a few millilitres of the lower layer to rinse out the stem of the funnel.
26.4 Spectrophotometry:
26.4.1 Multiple-Cell Spectrophotometer—Measure the cell correction using absorption cells with a 1-cm light path and a light
band centered at approximately 515 nm. Using the test cell, take the spectrophotometric absorbance readings of the calibration
solutions.
26.4.2 Single-Cell Spectrophotometer—Transfer a suitable portion of the reference solution to an absorption cell with a 1-cm
light path and adjust the spectrophotometer to the initial setting, using a light band centered at approximately 515 nm. While
maintaining this adjustment, take the spectrophotometric absorbance readings of the calibration solutions.
26.5 Calibration Curve—Plot the net spectrophotometric absorbance readings of the calibration solutions against milligrams of
lead per 25 mL of solution.
27. Procedure
27.1 Test Solution—Transfer a 5-g sample, weighed to the nearest 10 mg, to a 125-mL beaker. Add 25 mL of HNO (1 + 1).
When dissolution is complete, add several drops of HCl and 1 mL of saturated bromine water. Boil gently to eliminate the oxides
of nitrogen and to remove excess bromine. Cool, transfer to a 100-mL volumetric flask, dilute to volume, and mix. Using a pipet,
transfer a 2-mL to 10-mL portion (containing between 0.005 mg and 0.050 mg of Pb) to a 125-mL separatory funnel. Dilute to
15 mL with water, and add 1 drop of metacresol purple indicator solution. Proceed as directed in 27.3.
27.2 Reference Solution—Carry a reagent blank through the entire procedure using the same amount of all reagents, with the
sample omitted for use as the reference solution.
27.3 Color Development—Proceed as directed in 26.3.
27.4 Spectrophotometry—Proceed as directed in 26.4.
28. Calculation
28.1 Convert the net spectrophotometric absorbance reading of the test solution to milligrams of lead by means of the calibration
curve. Calculate the percentage of lead as follows:
Lead,%5 A/~B 310! (2)
where:
A = lead in the 25 mL of final test solution, mg, and
B = sample represented in 25 mL of final test solution, g.
29. Precision and Bias
29.1 Precision—Eight laboratories cooperated in testing this test method and obtained the data summarized in Table 2.
29.2 Accuracy—Bias—No certified reference materials suitable for testing this test method were available when the
interlaboratory testing program was conducted. The user of this test method is encouraged to employ accepted reference materials,
if available, to determine the accuracy of this test method as applied in a specific laboratory.
29.3 E173 has been replaced by Practice E1601. The reproducibility Index R corresponds to the Reproducibility Index R of
Practice E1601. Likewise the Repeatability Index R corresponds to the Repeatability Index r of Practice E1601.
THALLIUM BY THE RHODAMINE B
SPECTROPHOTOMETRIC METHOD
30. Scope
30.1 This test method covers the determination of thallium in concentrations from 0.0003 % to 0.005 %. Higher and lower
amounts can be determined by varying the sample size or the dilution within reasonable limits. However, the standard solutions
used to establish the calibration curve must contain about the same amount of cadmium as the test solution.
TABLE 2 Statistical Information
Lead Found, Repeatability Reproducibility
Specimen
% (R , E173) (R , E173)
1 2
1 0.0066 0.0009 0.0020
2 0.0236 0.0025 0.0053
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30. Scope
30.1 This test method covers the determination of thallium from 0.0003 % to 0.005 %. Higher and lower amounts can be
determined by varying the sample size or the dilution within reasonable limits. However, the calibration solutions used to establish
the calibration curve must contain about the same amount of cadmium as the test solution.
31. Summary of Test Method
31.1 The bromothallate (III) ion is extracted from a 1-M hydrobromic acid solution with isopropyl ether and the red rhodamine
B complex of thallium is then formed. spectrophotometric Spectrophotometric absorbance measurement is made at approximately
540 nm.
32. Concentration Range
32.1 The recommended concentration range is from 0.002 mg to 0.025 mg of thallium for each 25 mL of solution using a 1-cm
cell (Note 1).
33. Stability of Color
33.1 The color develops immediately and is stable. However, transfers of the organic layer should be carried out quickly and
the spectrophotometric absorbance measurements made in stoppered cells to minimize evaporation of the isopropyl ether.
34. Interferences
34.1 The elements normally present do not interfere if their contents are under the maximum limits shown in 1.1.
35. Reagents
35.1 Cadmium Bromide Solution (1 mL = 0.05 g Cd)—Dissolve 5.0 g of cadmium metal (thallium, max 0.001 %) with 35 mL
of the HBr-Br mixture. Warm, if necessary, to effect dissolution. Evaporate just to dryness but do not bake; dissolve in water, and
cool. Transfer to a 100-mL volumetric flask, dilute to volume, and mix.
35.2 Hydrobromic Acid-Bromine Mixture—
(Warning —Add 50 mL of bromine to 950 mL of HBr and mix. (Handle liquid bromine with care. The vapors are poisonous and
the liquid causes severe burns.))
35.3 Isopropyl Ether—(Warning —Isopropyl ether that has been improperly stored or that has been stored for many years may
contain peroxides. Small amounts of peroxide can cause violent explosions when the ether is distilled; larger amounts can be
detonated by ordinary handling of the liquid.)
35.4 Rhodamine B Solution (0.1 g/L)—Dissolve 0.10 g of rhodamine B in water. Add 40 mL of HCl, and dilute to 1 L.
35.5 Sulfatoceric Acid Solution (2 g/L)—Dissolve 0.2 g of sulfatoceric acid (ceric sulfate) (H Ce(SO ) ), in 50 mL of water and
4 4 4
4 mL of H SO (1 + 1). Dilute to 100 mL.
2 4
35.6 Thallium Standard Solution (1 mL = 0.005 mg Tl)—Remove the surface oxide from a piece of thallium metal (purity:
99.9 % min). Dissolve 0.100 g in 10 mL of H SO (1 + 1). Transfer to a 200-mL volumetric flask, dilute to volume, and mix.
2 4
Transfer 5.00 mL to a 500-mL volumetric flask containing 250 mL of water. Add 25 mL of H SO (1 + 1), cool, dilute to volume,
2 4
and mix.
35.7 Purity of Water—Unless otherwise indicated, reference to water shall be understood to mean reagent water as defined by
Type II of Specification D1193. Other Types may be used if they effect no measurable change in the reference solution or sample.
36. Preparation of Calibration Curve
36.1 Calibration Solutions—Using pipets, transfer 1,(1, 2, 3, and 55) mL of thallium solution (1 mL = 0.005 mg Tl) to 100-ml
beakers. Add 10.0 mL of cadmium bromide solution, 5 mL of HBr-Br mixture, and sufficient water to bring the volume of each
solution to about 20 mL. Boil gently to eliminate excess bromine. Cool the solution (Note 54). Proceed as directed in 36.3.
NOTE 4—The solution should be colorless or at most faintly yellow and the volume should be not less than 8 mL.
36.2 Reference Solution—Transfer 10 mL of cadmium bromide solution, 5 mL of HBr-Br mixture, and 5 mL of water to a
100-mL beaker. Boil gently to eliminate excess bromine (Note 54). Cool the solution.
36.3 Color Development—Transfer the solution to a 125-mL separatory funnel, add 1.0 mL of sulfatoceric acid solution, and
dilute to approximately 30 mL. Mix thoroughly, and allow to stand 10 min. Add 25.0 mL of isopropyl ether. Shake for 60 s and
then allow the layers to separate completely. Drain off and discard the aqueous (lower) layer. Add 20 mL of rhodamine B solution
and shake for 30 s. Allow the layers to separate and again discard the aqueous (lower) layer.
36.4 Spectrophotometry:
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36.4.1 Multiple-Cell Spectrophotometer—Measure the cell correction using absorption cells with a 1-cm light path and a light
band centered at approximately 540 nm (Note 1). Using the test cell, take the spectrophotometric absorbance readings of the
calibration solutions.
NOTE 6—Eliminate water droplets in the organic solvent by drawing the isopropyl ether layer into a clean, dry test tube before transferring to the
absorption cell.
36.4.1.1 Eliminate water droplets in the organic solvent by drawing the isopropyl ether layer into a clean, dry test tube before
transferring to the absorption cell.
36.4.2 Single-Cell Spectrophotometer—Transfer a suitable portion of the reference solution to an absorption cell with a 1-cm
light path and adjust the spectrophotometer to the initial setting, using a light band centered at approximately 540 nm (Note 1).
While maintaining this adjustment, take the spectrophotometric absorbance readings of the calibration solutions.
36.5 Calibration Curve—Plot the net spectrophotometric absorbance readings of the calibration solutions against milligrams of
thallium per 25 mL of solution.
37. Procedure
37.1 Test Solution—Transfer a 0.5-g sample, weighed to the nearest 1 mg, to a 100-mL beaker. Add 6 mL of HBr-Br mixture,
and heat gently to dissolve the sample. Add 15 mL of water, and boil (Note 54). Cool the solution. Proceed as directed in 37.3.
37.2 Reference Solution—Carry a reagent blank through the entire procedure using the same amount of all reagents with the
sample omitted for use as the reference solution.
37.3 Color Development—Proceed as directed in 36.3.
37.4 Spectrophotometry—Proceed as directed in 36.4.
38. Calculation
38.1 Convert the net spectrophotometric absorbance reading of the test solution to milligrams of thallium by the means of the
calibration curve. Calculate the percentage of thallium as follows:
Thallium,%5 A/~B 310! (3)
where:
A = thallium in 25 mL of final test solution, mg, and
B = sample represented in 25 mL of final test solution, g.
39. Precision and Bias
39.1 Precision—Nine laboratories cooperated in testing this test method and obtained the data summarized in Table 3.
39.2 Accuracy—Bias—No certified reference materials suitable for testing this test method were available when the
interlaboratory testing program was conducted. The user of this test method is encouraged to employ accepted reference materials,
if available, to determine the accuracy of this test method as applied in a specific laboratory.
39.3 E173 has been replaced by Practice E1601. The reproducibility Index R corresponds to the Reproducibility Index R of
Practice E1601. Likewise the Repeatability Index R corresponds to the Repeatability Index r of Practice E1601.
TABLE 3 Statistical Information
Thallium Found, Repeatability Reproducibility
Specimen
% (R , E173) (R , E173)
1 2
1 0.0011 0.0001 0.0002
2 0.0030 0.0006 0.0007
ARSENIC BY THE MOLYBDENUM BLUE
SPECTROPHOTOMETRIC METHOD
40. Scope
40.1 This test method covers the determination of arsenic content from 0.001 % to 0.005 %. Higher and lower contents can be
determined by varying the sample size within reasonable limits.
40. Scope
40.1 This test method covers the determination of arsenic content from 0.001 % to 0.005 %. Higher and lower contents can be
determined by varying the sample size within reasonable limits.
E396 − 17
41. Summary of Test Method
41.1 Arsenic is reduced to As (III) with stannous chloride and potassium iodide, and extracted into benzene. The arsenic is
stripped from the organic layer and oxidized to As (V) with potassium permanganate. The heteropoly acid is formed with
molybdate and extracted into methyl isobutyl ketone. Excess molybdate is removed with sulfuricH SO acid solution. The yellow
2 4
molybdoarsenate is reduced with stannous chloride. spectrophotometric Spectrophotometric absorbance measurement of the blue
complex is made at approximately 725 nm.
42. Concentration Range
42.1 The recommended concentration range is from 10 μg to 80 μg of arsenic per 25 mL of solution using a 1-cm cell (see Note
1).
43. Stability of Color
43.1 The color develops immediately and is stable for at least 1 h.
44. Interferences
44.1 The elements ordinarily present do not interfere if their contents are under the maximum limits shown in 1.1. More than
20 μg of germanium in the final sample solution will interfere. A procedure is given for eliminating this possible interference.
45. Apparatus
45.1 Glassware, borosilicate, having low arsenic content should be used. Before use, clean all glassware with HNO or cleaning
solution and rinse with water. Do not use soaps or detergents because they may contain phosphates or silicates.
46. Reagents
46.1 Ammonium Molybdate Solution (25 g/L)—Dissolve 25 g of ammonium molybdate tetrahydrate (NH)[(NH ) Mo O · 4
4 6 7 2244
H4H O)O] in about 900 mL of water. Add 70 mL of H SO (1 + 1). Dilute to 1L, and mix. Store in a polyethylene bottle.
2 2 4
46.2 Ammonium Oxalate Solution (Saturated)—Add 10 g of ammonium oxalate monohydrate to 100 mL of water.
46.3 Arsenic, Standard Solution (1 mL = 50 μg As)—Weigh 0.0661 g of arsenic trioxide (As O ) and transfer to a polyethylene
2 3
beaker. Add 1 pellet of NaOH and 10 mL of water. Swirl to dissolve. Transfer to a glass beaker and dilute to about 90 mL. Add
2 mL of H SO . Heat to boiling and add KMnO solution dropwise until a precipitate or a pink color persists. Cool the solution
2 4 4
for 15 min. Add ammonium oxalate solution dropwise, with stirring, until a clear, colorless solution is obtained. Transfer to a 1-L
volumetric flask, add 60 mL of H SO (1 + 1), and cool. Dilute to volume, and mix. Store in a polyethylene bottle.
2 4
46.4 Benzene.Benzene (C H ).
6 6
46.5 Carbon Tetrachloride (CCl ).
46.6 Methanol.
46.7 Methylene Isobutyl Ketone.
46.8 Potassium Iodide Solution (100 g/L)—Dissolve 10 g of potassium iodide (KI) in water, and dilute to 100 mL. Prepare fresh
as needed.
46.9 Potassium Permanganate Solution (10 g/L)—Dissolve 1 g of potassium permanganate (KMnO ) in water and dilute to 100
mL.
46.10 Stannous Chloride Solution A (50 g/L)—Dissolve 5 g of stannous chloride dihydrate (SnCl · 2H O) in 10 mL HCl, and
2 2
dilute to 100 mL with water. Prepare just before use.
46.11 Stannous Chloride Solution B (1 g/L)—Transfer 2.0 mL of stannous chloride Solution A (50 g/L) to a 100-mL volumetric
flask. Add 20 mL of HCl, dilute to volume, and mix. Do not use a solution that has stood more than 24 h.
46.12 Sulfuric-Hydrochloric Acid Wash Solution—Add 160 mL of H SO (1 + 1) to 90 mL of water, and cool. Add 750 mL of
2 4
HCl, and mix.
46.12 Purity of Water—Unless otherwise indicated, reference to water shall be understood to mean reagent water as defined by
Type II of Specification D1193. Other Types may be used if they effect no measurable change in the reference solution or sample.
47. Preparation of Calibration Curve
47.1 Calibration Solution—Using pipets, transfer 1,(1, 2, 3, 5, and 1010) mL of arsenic solution (1 mL = 50 μg As) to 100-mL
volumetric flasks. Add 10 mL of HNO , dilute to volume, and mix. Using a pipet, transfer 20 mL of each solution to 150-mL
beakers. Proceed as directed in 47.3.1.
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47.2 Reference Solution—Add 10 mL of HNO to a 100-mL volumetric flask. Dilute to volume, and mix. Using a pipet, transfer
20 mL to a 150-mL beaker. Proceed as directed in 47.3.1.
47.3 Color Development:
47.3.1 Add 4 mL of H SO . Evaporate the solution to sulfurSO trioxide fumes (surface temperature of hot plate 250°C) 250
2 4 3
°C) and heat for 5 min to 10 min. Cool. Add 5 mL of ammonium oxalate solution, again evaporate to sulfurSO trioxide fumes
and heat for at least 5 min. Cool. Add 15 mL of water and boil for 3 min.
NOTE 7—If more than 20 μg of germanium is present, it is removed at this time. Transfer the solution to a 125-mL separatory funnel. Add 20 mL of
HCl, 1 drop of H O (10 %), and mix. Add 25 mL of carbon tetrachloride (CCl ) and shake for 1 min. Discard the CCl layer. Continue as directed in
2 2 4 4
47.3.2 but add 10 mL of water instead of 10 mL of HCl.
47.3.1.1 If more than 20 μg of germanium is present, it is removed at this time. Transfer the solution to a 125-mL separatory
funnel. Add 20 mL of HCl, 1 drop of H O (10 %), and mix. Add 25 mL of CCl and shake for 1 min. Discard the CCl layer.
2 2 4 4
Continue as directed in 47.3.2 but add 10 mL of water instead of 10 mL of HCl.
47.3.2 Add 10 mL of HCl, 1 mL of KI solution, and 2 mL of SnCl Solution A. Mix and allow to stand for 15 min. Transfer
the solution to a 125-mL separatory funnel and add 50 mL of HCl in three portions using the HCl to rinse the beaker. Add 20 mL
of benzene and shake for 1 min. Drain the aqueous phase into a 125-mL separatory funnel and extract with a second 20-mL portion
of benzene. Discard the aqueous solution and combine the benzene extracts. To the organic solution, add 4 drops of SnCl Solution
A and 25 mL of H SO -HCl acid wash solution. Shake for 5 s. Allow the layers to separate for 15 min, and discard the aqueous
2 4
phase. Allow the benzene layer to stand for 5 min and discard any aqueous solution that separates. Add 25 mL of water and shake
for 1 min. After 15 min, transfer the aqueous layer to a 150-mL beaker.
47.3.3 Add 1 mL of H SO (1 + 1) and 4 drops of KMnO solution. Mix and heat for about 15 min (surface temperature of hot
2 4 4
plate 150°C). 150 °C). Cool to room temperature and add 1 drop of ammonium oxalate solution. Swirl and allow to stand for 5
min. Repeat the addition of ammonium oxalate solution until a clear, colorless solution is obtained. Transfer the solution to a
125-mL separatory funnel. Rinse the beaker with two 25-mL portions of ammonium molybdate solution, add the rinsings to the
funnel, and mix. Using a pipet, add 20 mL of methyl isobutyl ketone. MlBK. Shake for 1 min. Allow the phases to separate and
discard the aqueous phase. Add 50 mL of H SO (1 + 9) washing the stopper and the ground glass with the acid. Shake for 30 s.
2 4
Allow the layers to separate and discard the aqueous layer. Repeat the extraction with a second 50-mL portion of H SO (1 + 9).
2 4
Allow the layers to separate and discard the aqueous layer. Allow to stand for 10 min. Drain off and discard the last few drops of
the aqueous phase. Add 10 mL of SnCl Solution B and shake for 30 s. Allow the layers to separate for 10 min and discard the
aqueous phase. Using a pipet, add 5 mL of methanol, and mix. Flush a small portion of the organic solution through the stopcock
and stem of the separatory funnel. Dry the stem with a cotton swab.
47.4 Spectrophotometry:
47.4.1 Multiple-Cell Spectrophotometer—Measure the cell correction using absorption cells with a 1-cm light path and a light
band centered at approximately 725 nm. Using the test cell, take the spectrophotometric absorbance readings of the calibration
solutions.
47.4.2 Single-Cell Spectrophotometer—Transfer a suitable portion of the reference solution to an absorption cell with a 1-cm
light path and adjust the photometerspectrophotometer to the initial setting, using a light band centered at approximately 725 nm.
While maintaining this adjustment, take the spectrophotometric absorbance readings of the calibration solutions.
47.5 Calibration Curve—Plot the net spectrophotometric readings of the calibration solutions against micrograms of arsenic per
25 mL of solution.
48. Procedure
48.1 Test Solution:
48.1.1 Transfer a 5.0-g or 10.0-g sample, weighed to the nearest 5 mg, to a 250-mL beaker. Add 35 mL of HNO (1 + 1) and
cover. When dissolution is complete, add 20 mL of water and several boiling chips. Boil for 15 min, and cool. Transfer to a 100-mL
volumetric flask, dilute to volume, and mix. Using a pipet, transfer a portion of the solution containing about 50 μg of arsenic to
a 150-mL beaker.
48.2 Reference Solution—Add 4 mL of HNO to a 150-mL beaker and proceed as directed in 47.3.
48.3 Color Development—Proceed as directed in 47.3.
48.4 Spectrophotometry—Take the spectrophotometric absorbance readings of the test solution as directed in 47.4.
49. Calculation
49.1 Convert the net spectrophotometric absorbance readings of the test solution to micrograms of arsenic by means of the
calibration curve. Calculate the percentage of arsenic as follows:
Arsenic,%5 A/ B 310 000 (4)
~ !
E396 − 17
where:
A = arsenic found in 25 mL of the final test solution, μg and
B = sample in 25 mL of the final test solution, g.
50. Precision and Bias
50.1 Precision—Eight laboratories cooperated in testing this test method and obtained the data summarized in Table 4.
50.2 Accuracy—Bias—No certified reference materials suitable for testing this test method were available when the
interlaboratory testing program was conducted. The user of this test method is encouraged to employ accepted reference materials,
if available, to determine the accuracy of this test method as applied in a specific laboratory.
50.3 E173 has been replaced by Practice E1601. The Reproducibility Index R , corresponds to the Reproducibility Index R of
Practice E1601. Likewise the Repeatability Index R , corresponds to the Repeatability Index r of Practice E1601.
TABLE 4 Statistical Information
Repeatability Reproducibility
Specimen Arsenic Found,
(R , E173) (R , E173)
1 2
D60 0.0012 0.0002 0.0003
D61 0.0052 0.0010 0.0010
COPPER, LEAD, SILVER, AND ZINC BY THE ATOMIC
ABSORPTION SPECTROMETRY METHOD
51. Scope
51.1 This test method covers the determination of copper in contents from 0.004 % to 0.02 %; lead in contents from 0.01 % to
0.05 %; silver in contents from 0.004 % to 0.02 %; and zinc in contents from 0.01 % to 0.05 %.
51. Scope
51.1 This test method covers the determination of copper in contents from 0.004 % to 0.02 %; lead in contents from 0.01 % to
0.05 %; silver in contents from 0.004 % to 0.02 %; and zinc in contents from 0.01 % to 0.05 %.
52. Summary of Test Method
52.1 A nitricHNO acid solution of the sample is aspirated into the flame of the atomic absorption apparatus.spectrometer. The
absorption of the resonance line energy from the spectrum of each element is measured and compared with that of calibration
solutions of the same element.
53. Concentration Range
53.1 The concentration range of each element in the test solutions must be determined experimentally because the optimum
range will depend upon the individual instrument. Higher or lower concentration ranges may be required for different instruments
and with different radiation sources. Determine the appropriate concentration ranges of the elements as described in 53.1.1 –
53.1.5.
53.1.1 Prepare a dilute standardcalibration solution (see Table 5 for suggested initial concentrations).
53.1.2 Prepare the instrument for use as directed in 59.1.1 – 59.1.4. Measure the instrument response of the “zero,” the lowest,
and the two highest calibration solutions. Apply the minimum sensitivity (55.1.1) and curve linearity (55.1.2) tests.
53.1.3 If the instrument meets or surpasses the minimum sensitivity and curve linearity criteria, the initial concentration range
chosen is suitable for use, and the sample size should be selected to bring the anticipated concentration of the unknown element
within that range. If both criteria are met, proceed as described in 53.1.5. If either fails, proceed to 53.1.4.
TABLE 5 Preparation of Typical Calibration Solutions
Dilute
Equivalent
StandardCalibration Concentration Cadmium
WeightMass
Solution, Range of the Solution,
of Cadmium,
(5 mL to 25 Element, μg/mL mL/100 mL
g
mL)
Copper 1.0 to 5.0 25.0 2.50
Lead 1.0 to 5.0 10.0 1.00
Silver 0.5 to 2.5 10.0 1.00
Zinc 0.2 to 1.0 2.00 0.200
E396 − 17
53.1.4 If the minimum sensitivity is not achieved, prepare another dilute standardcalibration solution to provide a higher
concentration range and repeat 53.1.2 and 53.1.3. If the calibration curve does not meet the linearity criterion, prepare another
dilute standardcalibration solution to provide a lower concentration range and repeat 53.1.2 and 53.1.3. If a concentration range
cannot be found for which both criteria can be met, the performance of the apparatusspectrometer must be improved before this
test method may be employed.
53.1.5 Apply the stabi
...