ASTM E478-08(2017)

Standard Test Methods for Chemical Analysis of Copper Alloys

SIGNIFICANCE AND USE
4.1 These test methods for the chemical analysis of metals and alloys are primarily intended as referee methods to test such materials for compliance with composition specifications. It is assumed that all who use these 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.
SCOPE
1.1 These test methods cover the chemical analysis of copper alloys having chemical ranges within the following limits:2    
Element  
Composition, %  
Aluminum  
12.0 max  
Antimony  
1.0 max  
Arsenic  
1.0 max  
Cadmium  
1.5 max  
Cobalt  
1.0 max  
Copper  
40.0 min  
Iron  
6.0 max  
Lead  
27.0 max  
Manganese  
6.0 max  
Nickel  
50.0 max  
Phosphorus  
1.0 max  
Silicon  
5.0 max  
Sulfur  
0.1 max  
Tin  
20.0 max  
Zinc  
50.0 max  
1.2 The test methods appear in the following order:    
Sections  
Aluminum by the Carbamate Extraction-Ethyl-
enedinitrilotetraacetate Titrimetric Test Method [2 % to 12 %]  
71 – 78  
Copper by the Combined Electrodeposition Gravimetric and Oxalyldihydrazide Spectrophotometric Test Method [50 %, minimum]  
10 – 18  
Iron by the 1,10-Phenanthroline Spectrophotometric Test Method [0.003 % to 1.25 %]  
19 – 28  
Lead by Atomic Absorption Spectrometry [0.002 % to 15 %]  
90 – 100  
Lead by the Ethylenedinitrilotetraacetic Acid (EDTA) Titrimetric Test Method [2.0 % to 30.0 %]  
29 – 36  
Nickel by the Dimethylglyoxime Extraction Sprectophotometric Test Method [0.03 % to 5.0 %]  
37 – 46  
Nickel by the Dimethylglyoxime Gravimetric Test Method [4 % to 50 %]  
55 – 62  
Silver in Silver-Bearing Copper by Atomic Absorption Spectrometry [0.01 % to 0.12 %]  
101 – 112  
Tin by the Iodotimetric Titration Test Method [0.5 % to 20 %]  
63 – 70  
Tin by the Phenylfluorone Spectrophotometric Test Method [0.01 % to 1.0 %]  
113 – 123  
Zinc by Atomic Absorption Spectrometry [0.2 % to 2 %]  
79 – 89  
Zinc by the Ethylenedinitrilotetraacetic Acid (EDTA) Titrimetric Test Method [2 % to 40 %]  
47 – 54  
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.4 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 and health practices and determine the applicability of regulatory limitations prior to use.  
1.5 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.

General Information

• Status: Published
• Publication Date: 14-Jan-2017
• ICS: 77.040.30 - Chemical analysis of metals
• ICS: 77.120.30 - Copper and copper alloys
• Technical Committee: E01 - Analytical Chemistry for Metals, Ores, and Related Materials
• Drafting Committee: E01.05 - Cu, Pb, Zn, Cd, Sn, Be, Precious Metals, their Alloys, and Related Metals

Relations

• Refers: ASTM E135-20 - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 01-Jan-2020
• Refers: ASTM E1601-19 - Standard Practice for Conducting an Interlaboratory Study to Evaluate the Performance of an Analytical Method
• Effective Date: 01-Nov-2019
• Refers: ASTM E135-19 - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-May-2019
• Refers: ASTM E50-17 - Standard Practices for Apparatus, Reagents, and Safety Considerations for Chemical Analysis of Metals, Ores, and Related Materials
• Effective Date: 01-Sep-2017
• Refers: ASTM E50-11(2016) - Standard Practices for Apparatus, Reagents, and Safety Considerations for Chemical Analysis of Metals, Ores, and Related Materials
• Effective Date: 01-Aug-2016
• Refers: ASTM E135-16 - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-May-2016
• Refers: ASTM E135-15a - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 01-Jul-2015
• Refers: ASTM E135-15 - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-May-2015
• Refers: ASTM E135-14b - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-Aug-2014
• Refers: ASTM E135-14a - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 01-Apr-2014
• Refers: ASTM E135-14 - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-Feb-2014
• Refers: ASTM E135-13a - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 01-Dec-2013
• Refers: ASTM E1601-12 - Standard Practice for Conducting an Interlaboratory Study to Evaluate the Performance of an Analytical Method
• Effective Date: 15-Dec-2012
• Refers: ASTM E50-11 - Standard Practices for Apparatus, Reagents, and Safety Considerations for Chemical Analysis of Metals, Ores, and Related Materials
• Effective Date: 15-Oct-2011
• Refers: ASTM E135-11b - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-Sep-2011

Overview

ASTM E478-08(2017), "Standard Test Methods for Chemical Analysis of Copper Alloys," is a vital international standard published by ASTM International. The standard specifies a comprehensive suite of referee methods for determining the chemical composition of copper alloys, providing authoritative guidance for verifying conformance to material specifications. Laboratories and trained analysts regularly rely on ASTM E478 for accurate and reproducible results when characterizing copper alloy samples in accordance with internationally recognized standardization principles.

ASTM E478 covers copper alloys with a wide range of permitted elemental compositions, including but not limited to copper, aluminum, antimony, arsenic, cadmium, cobalt, iron, lead, manganese, nickel, phosphorus, silicon, sulfur, tin, and zinc. Each designated test method within the standard is tailored for specific elements and concentration ranges, supporting the rigorous demands of quality assurance and regulatory compliance in metals industries.

Key Topics

• Compositional Range: The standard applies to copper alloys with elemental compositions typically ranging from 40% minimum copper, with other elements such as aluminum (up to 12%), lead (up to 27%), nickel and zinc (up to 50%), and others within specified limits.
• Referee Test Methods: Designed as referee analytical procedures, the methods ensure high confidence in results, suitable for resolving compliance disputes or certification needs. The range includes:
  • Gravimetric, titrimetric, and spectrophotometric analyses
  • Atomic absorption spectrometry
  • Standardized preparation, dissolution, and sample handling procedures
• Analytical Accuracy: Emphasizes the requirement for skilled analysts using well-equipped laboratories, following prescribed apparatus, reagents, and protocols for reliable chemical analysis.
• Safety and Quality: The document highlights the importance of laboratory safety and the application of appropriate health and regulatory practices when handling chemicals and hazardous substances during analysis.
• International Principles: Developed per WTO Technical Barriers to Trade (TBT) guidelines, facilitating global harmonization in trade and industry.

Applications

• Quality Control in Metallurgy: Essential for manufacturers and suppliers of copper alloys to certify material compositions and ensure compliance with customer and regulatory requirements.
• Referee Analysis in Disputes: Serves as the authoritative method for resolving disputes over alloy composition between buyer and seller, or during third-party inspections.
• Research and Development: Supports metallurgists and researchers in accurate characterization of copper alloys during process refinement, alloy development, and material selection.
• Regulatory and Export Compliance: Used by testing laboratories to meet international standards required for certification, customs clearance, and participation in global supply chains.
• Calibration of Instrumental Methods: Provides reference points for verifying and calibrating newer, faster instrumental techniques, reinforcing traceability to established wet-chemistry methods.

Related Standards

• ASTM E29 – Significant digits in test data for assessing conformance.
• ASTM E50 – Apparatus, reagents, and laboratory safety in chemical analysis.
• ASTM E60 – Spectrophotometric analysis of metals, ores, and related materials.
• ASTM E135 – Terminology for analytical chemistry in metals analysis.
• ASTM E255 – Sampling practices for copper and copper alloys.
• ASTM E1601 – Interlaboratory studies for evaluating analytical methods performance.

In summary, ASTM E478-08(2017) is a cornerstone reference for laboratories and organizations involved in copper alloy production and analysis, supporting precise chemical characterization, regulatory compliance, and international trade. Widespread adoption of this standard promotes consistency, reliability, and global interoperability in the chemical analysis of copper alloys.

Standards Content (Sample)

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.
Designation: E478 − 08 (Reapproved 2017)
Standard Test Methods for
Chemical Analysis of Copper Alloys
This standard is issued under the fixed designation E478; 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.
This standard has been approved for use by agencies of the U.S. Department of Defense.
1. Scope
Tin by the Iodotimetric Titration Test Method
[0.5 % to 20 %] 63–70
1.1 These test methods cover the chemical analysis of
Tin by the Phenylfluorone Spectrophotometric
copper alloys having chemical ranges within the following Test Method [0.01 % to 1.0 %] 113 – 123
Zinc by Atomic Absorption Spectrometry [0.2 %
limits:
to 2 %] 79–89
Element Composition, % Zinc by the Ethylenedinitrilotetraacetic Acid
(EDTA) Titrimetric Test Method [2 % to 40 %] 47–54
Aluminum 12.0 max
1.3 The values stated in SI units are to be regarded as
Antimony 1.0 max
Arsenic 1.0 max standard. No other units of measurement are included in this
Cadmium 1.5 max
standard.
Cobalt 1.0 max
Copper 40.0 min 1.4 This standard does not purport to address all of the
Iron 6.0 max
safety concerns, if any, associated with its use. It is the
Lead 27.0 max
responsibility of the user of this standard to establish appro-
Manganese 6.0 max
Nickel 50.0 max priate safety and health practices and determine the applica-
Phosphorus 1.0 max
bility of regulatory limitations prior to use.
Silicon 5.0 max
1.5 This international standard was developed in accor-
Sulfur 0.1 max
Tin 20.0 max
dance with internationally recognized principles on standard-
Zinc 50.0 max
ization established in the Decision on Principles for the
1.2 The test methods appear in the following order:
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
Sections
Aluminum by the Carbamate Extraction-Ethyl-
Barriers to Trade (TBT) Committee.
enedinitrilotetraacetate Titrimetric Test
Method [2 % to 12 %] 71–78
2. Referenced Documents
Copper by the Combined Electrodeposition
Gravimetric and Oxalyldihydrazide Spectro-
2.1 ASTM Standards:
photometric Test Method [50 %, minimum] 10–18
Iron by the 1,10-Phenanthroline Spectrophoto- E29 Practice for Using Significant Digits in Test Data to
metric Test Method [0.003 % to 1.25 %] 19–28
Determine Conformance with Specifications
Lead by Atomic Absorption Spectrometry
E50 Practices for Apparatus, Reagents, and Safety Consid-
[0.002%to15%] 90 – 100
Lead by the Ethylenedinitrilotetraacetic Acid erations for Chemical Analysis of Metals, Ores, and
(EDTA) Titrimetric Test Method [2.0 % to
Related Materials
30.0 %] 29–36
E60 Practice for Analysis of Metals, Ores, and Related
Nickel by the Dimethylglyoxime Extraction
Sprectophotometric Test Method [0.03 % to
Materials by Spectrophotometry
5.0 %] 37–46
E135 Terminology Relating to Analytical Chemistry for
Nickel by the Dimethylglyoxime Gravimetric
Metals, Ores, and Related Materials
Test Method [4 % to 50 %] 55–62
Silver in Silver-Bearing Copper by Atomic Ab-
E173 Practice for Conducting Interlaboratory Studies of
sorption Spectrometry [0.01 % to 0.12 %] 101 – 112
Methods for Chemical Analysis of Metals (Withdrawn
1998)
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, For referenced ASTM standards, visit the ASTM website, www.astm.org, or
their Alloys, and Related Metals. contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Current edition approved Jan. 15, 2017. Published March 2017. Originally Standards volume information, refer to the standard’s Document Summary page on
approved in 1973. Last previous edition approved in 2008 as E478 – 08. DOI: the ASTM website.
10.1520/E0478-08R17. The last approved version of this historical standard is referenced on
The actual limits of application of each test method are presented in 1.2. www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E478 − 08 (2017)
E255 Practice for Sampling Copper and Copper Alloys for 10.2 This international standard was developed in accor-
the Determination of Chemical Composition dance with internationally recognized principles on standard-
E1601 Practice for Conducting an Interlaboratory Study to ization established in the Decision on Principles for the
Evaluate the Performance of an Analytical Method Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
3. Terminology
Barriers to Trade (TBT) Committee.
3.1 For definitions of terms used in these test methods, refer
11. Summary of Test Method
to Terminology E135.
11.1 After dissolution of the sample in HNO and HF, the
4. Significance and Use
oxidesofnitrogenarereducedwithhydrogenperoxide,andthe
4.1 These test methods for the chemical analysis of metals copper deposited electrolytically. Loss of platinum from the
anode is minimized by the addition of lead. The copper
and alloys are primarily intended as referee methods to test
such materials for compliance with composition specifications. oxalyldihydrazide complex is formed with the copper remain-
ing in the electrolyte. Photometric measurement is made at
It is assumed that all who use these methods will be trained
approximately 540 nm.
analysts capable of performing common laboratory procedures
skillfully and safely. It is expected that work will be performed
12. Interferences
in a properly equipped laboratory.
12.1 The elements ordinarily present do not interfere if their
5. Apparatus, Reagents, and Spectrophotometric Practice
concentrations are under the maximum limits shown in 1.1.
5.1 Apparatus, standard solutions, and other reagents re-
13. Apparatus
quired for each determination are listed in separate sections
preceding the procedure. Spectrophotometers shall conform to 13.1 Polytetrafluoroethylene or Polypropylene Beakers,
250-mL capacity.
the requirements prescribed in Practice E60.
5.2 Spectrophotometric practice prescribed in these test 13.2 PolytetrafluoroethyleneorPolypropyleneSplitCovers.
methods shall conform to Practice E60.
13.3 Electrodes for Electroanalysis—Recommended sta-
tionary type platinum electrodes are described in 13.3.1 and
6. Hazards
13.3.2. The surface of the platinum electrode should be
6.1 Specific hazard statements are given in 33.7, 51.13, and
smooth, clean, and bright to promote uniform deposition and
107.1.
good adherence. Deviations from the exact size and shape are
6.2 Forotherprecautionstobeobservedintheuseofcertain allowable. In instances where it is desirable to decrease the
time of deposition and agitation of the electrolyte is
reagents in these test methods, refer to Practices E50.
permissible, a generally available rotating type of electrode
7. Sampling
may be employed. Cleaning of the electrode by sandblasting is
not recommended.
7.1 For procedures for sampling the material, refer to
13.3.1 Cathodes—Platinum cathodes may be either open or
Practice E255. However, this practice does not supersede any
closed cylinders formed from sheets that are plain or
sampling requirements specified in a specific ASTM material
perforated, or from gauze. Gauze cathodes are recommended;
specification.
preferably from 50-mesh gauze woven from approximately
8. Rounding Calculated Values
0.21-mm diameter wire. The top and bottom of gauze cathodes
should be reinforced by doubling the gauze about 3 mm onto
8.1 Calculated values shall be rounded to the desired num-
itself, or by the use of platinum bands or rings. The cylinder
ber of places as directed in Practice E29.
should be approximately 30 mm in diameter and 50 mm in
9. Interlaboratory Studies
height. The stem should be made from a platinum alloy wire
such as platinum-iridium, platinum-rhodium, or platinum-
9.1 These test methods were evaluated in accordance with
ruthenium, having a diameter of approximately 1.3 mm. It
Practice E173 unless otherwise noted in the precision section.
should be flattened and welded the entire length of the gauze.
Practice E173 has been replaced by Practice E1601. The
The overall height of the cathode should be approximately
Reproducibility R corresponds to the Reproducibility Index R
130 mm. A cathode of these dimensions will have a surface
of Practice E1601. The Repeatability R of Practice E173
area of 135 cm exclusive of the stem.
corresponds to the Repeatability Index r of Practice E1601.
13.3.2 Anodes—Platinum anodes may be a spiral type when
COPPER BY THE COMBINED
anodic deposits are not being determined, or if the deposits are
ELECTRODEPOSITION GRAVIMETRIC AND small (as in the electrolytic determination of lead when it is
OXALYLDIHYDRAZIDE SPECTROPHOTOMETRIC
present in compositions below 0.2 %). Spiral anodes should be
TEST METHOD
made from 1.0 mm or larger platinum wire formed into a spiral
of seven turns having a height of approximately 50 mm and a
10. Scope
diameter of 12 mm with an overall height of approximately
10.1 This test method covers the determination of copper in 130 mm.Aspiralanodeofthesedimensionswillhaveasurface
compositions greater than 50 %. area of 9 cm . When both cathode and anode plates are to be
E478 − 08 (2017)
determined,theanodeshouldbemadeofthesamematerialand 17. Spectrophotometric Determination of the Residual
design as the electrode described in 13.3.1. The anode cylinder Copper in the Electrolyte
should be approximately 12 mm in diameter and 50 mm in
17.1 Interferences—The elements ordinarily present do not
height and the overall height of the anode should be approxi-
interfere if their composition is under the maximum limits
mately 130 mm. A gauze anode of these dimensions will have
shown in 1.1.
a surface area of 54 cm exclusive of the stem.
17.2 Concentration Range—The recommended concentra-
13.3.3 Gauze cathodes are recommended where rapid elec-
tion is from 0.0025 mg to 0.07 mg of copper per 50 mL of
trolysis is used.
solution, using a 2-cm cell.
14. Reagents
NOTE 1—This procedure has been written for cells having a 2-cm light
path. Cells having other dimensions may be used, provided suitable
14.1 Ammonium Chloride Solution (0.02 g⁄L)—Dissolve
adjustments can be made in the amounts of sample and reagents used.
0.02 g of ammonium chloride (NH Cl) in water and dilute to
17.3 Stability of Color—The color fully develops in 20 min
1L.
and is stable for 1 h.
14.2 Hydrogen Peroxide (3 %)—Dilute 100 mL of 30 %
17.4 Reagents:
hydrogen peroxide to 1 L.
17.4.1 Acetaldehyde Solution (40 %)—Dilute 400 mL of
14.3 Lead Nitrate Solution (10 g⁄L) —Dissolve 10.0 g of
acetaldehyde to 1 L with water.
lead nitrate (Pb(NO ) ) in water and dilute to 1 L.
3 2
17.4.2 BoricAcidSolution(50g⁄L)—Dissolve 50 g of boric
acid (H BO ) in hot water, cool, and dilute to 1 L.
3 3
15. Procedure
17.4.3 Citric Acid Solution (200g⁄L)—Dissolve 200 g of
15.1 Transfer a 2.000-g sample, weighed to the nearest
citric acid in water and dilute to 1 L.
0.1 mg, to a 250-mL polytetrafluoroethylene or polypropylene
17.4.4 Copper, Standard Solution A (1mL=1.0mg Cu)—
beaker, add 2 mL of HF, and 30 mL of HNO (1 + 1). Cover
Transfer a 1.000-g sample of electrolytic copper (purity:
withacoverglassandallowtostandforafewminutesuntilthe
99.9 % minimum) to a 250-mL beaker and add 10 mL of
reaction has nearly ceased. Warm but do not heat over 80 °C.
HNO (1 + 1). Evaporate nearly to dryness.Add 5 mLof water
When dissolution is complete, add 25 mL of 3 % H O and
2 2
to dissolve the residue. Transfer to a 1-L volumetric flask,
3 mLof Pb(NO ) solution. Rinse the cover glass and dilute to
3 2
dilute to volume, and mix.
approximately 150 mL with NH Cl solution.
17.4.5 Copper, Standard Solution B (1 mL = 0.010 mg
15.2 With the electrolyzing current off, position the anode
Cu)—Using a pipet, transfer 10 mL of Copper Solution A
and the accurately weighed cathode in the solution so that the
(1 mL = 1.0 mgCu)toa1-Lvolumetricflask,dilutetovolume,
gauze is completely immersed. Cover the beaker with a split
and mix.
plastic cover.
17.4.6 OxalyldihydrazideSolution(2.5g/L)—Dissolve2.5 g
of oxalyldihydrazide in warm water and dilute to 1 L.
15.3 Start the electrolysis and increase the voltage until the
ammeter indicates a current which is equivalent to about
17.5 Preparation of Calibration Curve:
1.0 A⁄dm and electrolyze overnight.Alternatively electrolyze
17.5.1 Calibration Solutions:
at a current density of 4 A⁄dm for 1.5 h. (The more rapid
17.5.1.1 Transfer 25 mL of boric acid solution to a 250-mL
procedure requires the use of gauze electrodes).
volumetric flask and then add a solution containing 150 mL of
15.4 Slowly withdraw the electrodes (or lower the beaker)
water, 2 mL of HF, and 30 mL of HNO (1 + 1). Dilute to
with the current still flowing, and rinse with a stream of water
volume and mix.
from a wash bottle. Quickly remove the cathode, rinse it in
17.5.1.2 Transfer 10 mL of this solution to each of four
water, and then dip into two successive baths of ethanol or
50-mL volumetric flasks. Using pipets, transfer (1, 3, 5, and
methanol. Dry in an oven at 110 °C for 3 min to 5 min.
7) mL of Copper Solution B (1 mL = 0.010 mg Cu) to the
flasks. Proceed as directed in 17.5.3.
15.5 Return the voltage to zero and turn off the switch.
17.5.2 Reference Solution—Add 10 mL of boric acid solu-
Reserve the electrolyte.
tion prepared as directed in 17.5.1.1 to a 50-mL volumetric
15.6 Allow the electrode to cool to room temperature and
flask and proceed as directed in 17.5.3.
weigh.
17.5.3 Color Development—Add in order, and with mixing
after each addition, 5 mL of citric acid solution, 6 mL of
16. Calculation
NH OH, 10 mL of acetaldehyde solution, and 10 mL of ox-
16.1 Calculate the percentage of copper as follows:
alyldihydrazide solution. Cool, dilute to volume, and mix.
Allow to stand for 30 min and proceed as directed in 17.5.4.
Copper, % 5 @~A1B!/C# 3100 (1)
17.5.4 Spectrophotometry:
where:
17.5.4.1 Multiple-Cell Spectrophotometer—Measure the
A = deposited copper, g,
cellcorrectionusingabsorptioncellswitha2-cmlightpathand
B = copper in the electrolyte as calculated in 17.10,g,and
a light band centered at approximately 540 nm. Using the test
cell, take the spectrophotometric readings of the calibration
C = sample used, g.
solutions.
E478 − 08 (2017)
17.5.4.2 Single-Cell Spectrophotometer—Transfer a suit- ization established in the Decision on Principles for the
able portion of the reference solution to an absorption cell with Development of International Standards, Guides and Recom-
a2-cmlightpathandadjustthespectrophotometertotheinitial mendations issued by the World Trade Organization Technical
setting using a light band centered at approximately 540 nm. Barriers to Trade (TBT) Committee.
While maintaining this adjustment, take the spectrophotomet-
20. Summary of Test Method
ric readings of the calibration solutions.
17.5.5 Calibration Curve—Plot the net spectrophotometric-
20.1 The sample is dissolved in HCl and hydrogen
readings of the calibration solutions against milligrams of
peroxide, and the excess oxidant removed by evaporation. The
copper per 50 mL of solution.
iron is extracted with methyl isobutyl ketone-benzene mixture.
The iron is extracted from the organic phase into a hydrox-
17.6 Test Solution—Transfer the reserved electrolyte to a
ylamine hydrochloride solution and the red-colored 1,10-
250-mL volumetric flask containing 25 mL of boric acid
phenanthroline complex is formed. Spectrophotometric mea-
solution, dilute to volume, and mix. Using a pipet, transfer
surement is made at approximately 510 nm.
10 mL to a 50-mL volumetric flask. Proceed as directed in
17.8. If the solution shows a permanganate color, add sodium
21. Concentration Range
nitrite solution (20 g⁄L) dropwise until the color is discharged,
and then proceed as directed in 17.8.
21.1 The recommended concentration range is from
0.005 mg to 0.12 mg of iron per 50 mL of solution, using a
17.7 Reference Solution—Proceed as directed in 17.5.2.
2-cm cell.
17.8 Color Development—Proceed as directed in 17.5.3.
NOTE2—Thistestmethodhasbeenwrittenforcellshavinga2-cmlight
17.9 Spectrophotometry—Take the spectrophotometric
path. Cells having other dimensions may be used, provided suitable
reading of the test solution as directed in 17.5.4.
adjustments can be made in the amounts of sample and reagents used.
17.10 Calculation—Convert the net spectrophotometric
22. Stability of Color
reading of the test solution to milligrams of copper by means
22.1 The color develops within 5 min and is stable for at
of the calibration curve. Calculate the grams of copper in the
least 4 h.
total electrolyte as follows:
Copper, g 5 A 325 /1000 (2)
~ !
23. Interferences
where:
23.1 Elements ordinarily present do not interfere if their
A = copper found in 50 mL of the final test solution, mg.
composition range is under the maximum limits shown in 1.1.
18. Precision and Bias
24. Reagents
18.1 Precision—Eightlaboratoriescooperatedintestingthis
24.1 Hydroxylamine Hydrochloride Solution (10 g⁄L)—
test method and obtained the data summarized in Table 1.
Dissolve 5.0 g of hydroxylamine hydrochloride (NH OH·HCl)
in 500 mL of water. Prepare fresh as needed.
18.2 Bias—The accuracy of this method has been deemed
satisfactory based upon the data for the certified reference
24.2 Iron, Standard Solution A (1mL=0.125mg Fe)—
material in Table 1. Users are encouraged to use this or similar
Transfer 0.125 g of iron (purity: 99.9 % minimum) to a
reference materials to verify that the method is performing
100-mL beaker. Add 10 mL of HCl (1 + 1) and 1 mL of
accurately in their laboratories.
bromine water. Boil gently until the excess bromine is re-
moved. Add 20 mL of HCl, cool, transfer to a 1-L volumetric
IRON BY THE 1,10-PHENANTHROLINE
flask, dilute to volume, and mix.
SPECTROPHOTOMETRIC TEST METHOD
24.3 Iron, Standard Solution B (1mL=0.00625mg Fe)—
19. Scope
Using a pipet, transfer 50 mL of Iron Solution A to a 1-L
volumetric flask, dilute to volume with HCl (1 + 49), and mix.
19.1 This test method covers the determination of iron in
compositions from 0.003 % to 1.25 %.
24.4 Methyl Isobutyl Ketone-Benzene Mixture—Mix
200 mL of methyl isobutyl ketone (MIBK) and 100 mL of
19.2 This international standard was developed in accor-
benzene.
dance with internationally recognized principles on standard-
24.5 1,10-Phenanthroline-Ammonium Acetate Buffer
Solution—Dissolve 1.0 g of 1,10-phenanthroline monohydrate
TABLE 1 Statistical Information
in5 mLofHClina600-mLbeaker.Add215 mLofaceticacid,
Repeatability Reproducibility
Copper
and, while cooling, carefully add 265 mL of NH OH. Cool to
Test Specimen (R , Practice (R , Practice
1 2 4
Found, %
E173) E173)
room temperature. Using a pH meter, check the pH; if it is not
1. Bronze ounce metal (NIST 83.56 0.09 0.13
between 6.0 and 6.5, adjust it to that range by adding acetic
124d, 83.60 Cu)
acid or NH OH as required. Dilute to 500 mL.
2. AAB 521 91.98 0.03 0.08
3. AAB 655 95.38 0.09 0.14
24.6 Sodium Nitrite Solution (20g/L)—Dissolve 20.0 g of
4. AAB 681 57.60 0.10 0.09
dry sodium nitrite (NaNO ) in approximately 500 mLof water,
5. AAB 715 68.95 0.08 0.21 2
transfer to a 1-L volumetric flask, dilute to volume and mix.
E478 − 08 (2017)
25. Preparation of Calibration Curve with 3-mL to 5-mL portions of HCl (1 + 1) to remove copper,
and discard the washings. Extract the iron from the organic
25.1 Calibration Solutions:
phase by shaking vigorously 30 s with 10 mL of NH OH·HCl
25.1.1 Using pipets, transfer (1, 2, 5, 10, 15, and 20) mL of
solution. Transfer the aqueous phase to a 50-mL volumetric
Iron Solution B (1 mL = 0.00625 mg Fe) to 50-mL volumetric
flask. Repeat the extraction with a second 10-mL portion of
flasks. Dilute to 20 mL.
NH OH·HCl solution, and transfer the extract to the 50-mL
25.1.2 Add 20 mL of NH OH·HCl solution, mix, and allow
flask.
to stand 1 min. Proceed as directed in 25.3.
26.2 Reference Solution—Use the reagent blank solution
25.2 Reference Solution—Transfer 20 mL of water to a
prepared as directed in 26.1.2.
50-mL volumetric flask and proceed as directed in 25.1.2.
26.3 Color Development—Proceed as directed in 25.3.
25.3 Color Development—Add 5 mL of 1,10-
phenanthroline-ammonium acetate buffer solution, dilute to 26.4 Spectrophotometry—Proceed as directed in 25.4.
volume, and mix. Allow to stand at least 5 min but not more
27. Calculation
than 4 h.
27.1 Convert the net spectrophotometric reading of the test
25.4 Spectrophotometry:
solution to milligrams of iron by means of the calibration
25.4.1 Multiple-Cell Spectrophotometer—Measure the cell
curve. Calculate the percentage of iron as follows:
correction using absorption cells with a 2-cm light path and a
light band centered at approximately 510 nm. Using the test
Iron, % 5 A/ B 310 (3)
~ !
cell, take the spectrophotometric readings of the calibration
where:
solutions.
A = iron found in 50 mL of the final test solution, mg, and
25.4.2 Single-Cell Spectrophotometer—Transfer a suitable
portion of the reference solution to an absorption cell with a
B = sample represented in 50 mL of the final test solution,
2-cm light path and adjust the photometer to the initial setting,
g.
using a light band centered at approximately 510 nm. While
maintaining this adjustment, take the spectrophotometric read-
28. Precision and Bias
ings of the calibration solutions.
28.1 Precision—Seven laboratories cooperated in testing
25.5 Calibration Curve—Plot the net spectrophotometric
this method, submitting nine pairs of values, and obtained the
readings of the calibration solutions against milligrams of iron
data summarized in Table 2.
per 50 mL of solution.
28.2 Bias—The accuracy of this method has been deemed
26. Procedure
satisfactory based upon the data for the certified reference
26.1 Test Solution:
materials in Table 2. Users are encouraged to use these or
26.1.1 Select and weigh a sample as follows:
similar reference materials to verify that the method is per-
Tolerance in forming accurately in their laboratories.
Sample Sample Aliquot
Iron, % Weight, g Weight, mg Volume, mL
LEAD BY THE
ETHYLENEDINITRILOTETRAACETIC ACID
0.003 to 0.02 2.0 2.0 25
0.02 to 0.10 1.0 1.0 10 (EDTA)TITRIMETRIC TEST METHOD
0.05 to 0.20 0.5 0.5 10
0.10 to 0.40 0.5 0.5 5
29. Scope
0.25 to 1.25 0.2 0.5 5
29.1 This test method covers the determination of lead in
Transfer it to a 400-mL beaker or to a polytetrafluoroethyl-
composition range from 2.0 % to 30.0 %.
ene beaker if HF is to be used.
26.1.2 Carry a reagent blank through the entire procedure,
29.2 This international standard was developed in accor-
using the same amounts of all reagents but with the sample
dance with internationally recognized principles on standard-
omitted.
ization established in the Decision on Principles for the
26.1.3 Add 12 mL of HCl (7 + 3) per gram of sample, and
then H O as needed to completely dissolve the alloy.Add HF
2 2
as needed to decompose high-silicon alloys. When dissolution
TABLE 2 Statistical Information
is complete, add 10 mL of concentrated HCl per gram of
Repeatability Reproducibility
sample and heat carefully to decompose excess peroxide. Cool
Test Specimen Iron Found, % (R , Practice (R , Practice
1 2
to room temperature, transfer to a 100-mL volumetric flask, E173) E173)
dilute to volume with HCl (1 + 1), and mix.
1. Cast bronze (NIST 52c, 0.0034 0.0005 0.0010
0.004 Fe)
26.1.4 Using a pipet, transfer an aliquot in accordance with
2. Ounce metal (NIST 0.187 0.012 0.017
26.1.1toa125-mLconicalseparatoryfunnel.AddHCl (1 + 1),
124d, 0.18 Fe)
as required, to adjust the volume to 25 mL. 3. Cupro Nickel, 30 Ni 0.60 0.015 0.044
26.1.5 Add 20 mL of MIBK-benzene mixture to the sepa-
4. Silicon bronze (NIST 1.24 0.019 0.037
ratory funnel and shake 1 min. Allow the phases to separate,
158a, 1.23 Fe)
discard the aqueous phase, wash the organic phase three times
E478 − 08 (2017)
Development of International Standards, Guides and Recom- 33.9 NaOH (250g⁄L)—Dissolve 250 g of NaOH in water
mendations issued by the World Trade Organization Technical and dilute to 1 L. Store in a plastic bottle.
Barriers to Trade (TBT) Committee.
33.10 Sodium Tartrate Solution (250g⁄L)—Dissolve 250 g
of sodium tartrate dihydrate in water and dilute to 1 L.
30. Summary of Test Method
33.11 Xylenol Orange Indicator Solution (1g⁄L)—Dissolve
30.1 Lead diethyldithiocarbamate is extracted with chloro-
0.050 g of xylenol orange powder in a mixture of 25 mL of
form from an alkaline tartrate-cyanide solution. After the
water and 25 mL of ethanol.
removal of organic material, lead is titrated with disodium
ethylenedinitrilotetraacetic acid (EDTA) solution.
34. Procedure
34.1 Select a sample as follows:
31. Interferences
Lead, % Sample Weight, g
31.1 Elements ordinarily present do not interfere if their
compositions are under the maximum limits shown in 1.1.
2.0 to 20.0 1.00
20.0 to 30.0 0.60
32. Apparatus
Weigh the sample to the nearest 0.5 mg, and transfer it to a
250-mL beaker.
32.1 Separatory Funnels, 250-mL capacity.
34.2 Add 5 mL of HBF and then 10 mL of HNO (1 + 1).
32.2 Magnetic Stirrer and Polytetrafluoroethylene-Covered 4 3
Cover the beaker and heat until dissolution is complete. Boil
Magnetic Stirring Bar.
until oxides of nitrogen have been expelled and cool.
33. Reagents
34.3 Wash the cover and walls of the beaker.Add 25 mL of
sodium tartrate solution, 25 mL of NaOH solution, and 25 mL
33.1 Ascorbic Acid.
of NaCN solution (Warning—See 33.7.), mixing after each
33.2 Chloroform (CHCl ).
addition. Cool to room temperature.
33.3 Disodium Ethylenedinitrilotetraacetic Acid (EDTA),
34.4 Transfer to a 250-mLseparatory funnel.Add 15 mLof
Standard Solution (0.025 M)—Dissolve 9.3 g of disodium
sodium diethyldithiocarbamate solution and 15 mL of CHCl ,
ethylenedinitrilo tetraacetate dihydrate in water, transfer to a
and shake for 30 s. Allow the layers to separate; draw off the
1-L volmetric flask, dilute to volume, and mix. The solution is
lower organic layer into a 250-mL beaker, retaining the
stable for several months when stored in plastic or borosilicate
aqueous layer. Add 5 mL more of diethyldithiocarbamate
glass bottles. Standardize as follows: Using a pipet, transfer
solution to the separatory funnel and mix. If no precipitate
25 mLofleadsolution(1 mL = 6.0 mgPb)toa250-mLbeaker
forms, proceed as directed in 34.5. If a precipitate does form,
anddiluteto100 mL.Proceedasdirectedin34.7.Calculatethe
add 5 mL of diethyldithiocarbamate solution and 10 mL of
lead equivalent of the solution as follows:
CHCl , shake for 30 s, and draw off the organic layer into the
Lead equivalent, g/mL 5 A/B (4)
250-mL beaker containing the extract.
where:
34.5 Extract twice with additional 10-mL portions of
CHCl , adding the extracts to the extracts in the 250-mL
A = weight of lead, g, and
B = EDTA solution required for titration of the lead beaker.
solution, mL.
34.6 Add 10 mL of HCl (1 + 1) to the combined extracts
33.4 Fluoroboric Acid (37 % to 40 %). and place on a hot plate. Cover the beaker with a raised cover
glass, and evaporate the solution to a volume of 2 mLto 3 mL.
33.5 Hexamethylenetetramine.
Wash the cover and walls of the beaker, dilute to 100 mL, and
33.6 Lead, Standard Solution (1 mL = 6.0 mg Pb)—
heat to dissolve salts.
Transfer 1.500 g of lead (purity 99.9 % minimum) to a 150-mL
34.7 Place the beaker on a magnetic stirrer and stir (Note 3).
beaker. Add 10 mL of HNO (1 + 1) and heat until dissolution
Add 10 mg to 20 mg of ascorbic acid and three or four drops
iscomplete.Boiltoremoveoxidesofnitrogen,cool,transferto
of xylenol orange solution. Add enough hexamethylenete-
a 250-mL volumetric flask, dilute to volume, and mix.
tramine to color the solution purple. Add four or five drops of
33.7 Sodium Cyanide Solution (200g⁄L)—Dissolve 200 g
NaCN solution (Warning—See 33.7.) and titrate with the
of sodium cyanide (NaCN) in water and dilute to 1 L. Store in
EDTAsolution.When a yellow color begins to appear, stop the
a plastic bottle. (Warning—The preparation, storage, and use
titration and add 2 g to 3 g of hexamethylenetetramine and a
of NaCN solutions require care and attention.Avoid inhalation
drop of xylenol orange solution. Titrate dropwise until the
offumesandexposureofskintothechemicalanditssolutions.
color changes from purplish-red to yellow.
Workinawell-ventilatedhood.RefertotheHazardsSectionof
NOTE3—Thetitrationmaybeperformedineitherahotorcoldsolution.
Practices E50.)
33.8 Sodium Diethyldithiocarbamate Solution (100g⁄L)—
35. Calculation
Dissolve 10 g of sodium diethyldithiocarbamate in water and
35.1 Calculate the percentage of lead as follows:
dilute to 100 mL. Do not use a solution that is more than 24 h
old. Lead,% 5 C 3D /E 3100 (5)
@~ ! #
E478 − 08 (2017)
where: 42.3 Dimethylglyoxime Solution (10 g⁄L in alcohol)—
Dissolve 10 g of dimethylglyoxime in ethanol, methanol, or
C = standard EDTA solution used, mL,
denatured alcohol and dilute to 1 L with alcohol. Filter before
D = equivalent of EDTA solution, g/mL, and
E = sample used, g. using. This solution keeps almost indefinitely.
42.4 Hydroxylamine Hydrochloride Solution (10 g⁄L)—
36. Precision and Bias
Dissolve 10 g of hydroxylamine hydrochloride (NH OH·HCl)
36.1 Precision—Due to limited data, a precision statement
in water and dilute to 1 L. Adjust the pH to 7.0 with NH OH.
conforming to the requirements of Practice E173 cannot be
42.5 Nickel, Standard Solution A (1mL=1.0mg Ni)—
furnished. However, in a cooperative program conducted by
Dissolve 1.000 g of nickel metal (purity, 99.8 % minimum) in
six laboratories, the between-laboratory range was 3.13 % to
10 mL of HNO . When dissolution is complete, boil gently to
3.20 % lead on a sample averaging 3.16 %, and 14.05 % to
expel oxides of nitrogen, cool, transfer to a 1-L volumetric
14.23 % on a sample averaging 14.15 %.
flask, dilute to volume, and mix.
36.2 Bias—No information on the accuracy of this method
42.6 Nickel, Standard Solution B (1mL=0.2mg Ni)—
is known, because at the time it was tested, no certified
Using a pipet, transfer 100 mL of Nickel Solution A
reference materials were available. Users are encouraged to
(1 mL = 1.0 mg Ni) to a 500-mL volumetric flask, dilute to
employ suitable reference materials, if available, to verify the
volume, and mix.
accuracy of the method in their laboratories.
42.7 Sodium Acetate Solution (200g⁄L)—Dissolve 200 g of
NICKEL BY THE DIMETHYLGLYOXIME-
sodium acetate trihydrate (CH COONa·3H O) in about
3 2
EXTRACTION SPECTROPHOTOMETRIC TEST
600 mL of water, filter, and dilute to 1 L.
METHOD
42.8 NaOH (1 N)—Dissolve 40 g of NaOH in water, cool,
transfer to a 1-L volumetric flask, dilute to volume, and mix.
37. Scope
Store in a plastic bottle.
37.1 This test method covers the determination of nickel in
42.9 Sodium Sulfate, anhydrous (Na SO ).
2 4
composition range from 0.03 % to 5.0 %.
42.10 Sodium Tartrate Solution (100g⁄L)—Dissolve 100 g
37.2 This international standard was developed in accor-
of sodium tartrate dihydrate in water and dilute to 1 L.
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
42.11 Sodium Thiosulfate Solution (200 g⁄L)—Dissolve
Development of International Standards, Guides and Recom-
200 g of sodium thiosulfate pentahydrate (Na S O ·5H O) in
2 2 3 2
mendations issued by the World Trade Organization Technical
water and dilute to 1 L.
Barriers to Trade (TBT) Committee.
43. Preparation of Calibration Curve
38. Summary of Test Method
43.1 Calibration Solutions:
38.1 A dimethylglyoxime complex of nickel is formed in
43.1.1 Transfer 1.000 g of copper (purity, 99.99 % mini-
the presence of copper and extracted with chloroform. Spec-
mum) to each of five 250-mL beakers, add 20 mL of
trophotometric measurement is made at approximately
HCl (1 + 1), and add 10 mL of H O in small portions. When
2 2
405 nm.
dissolution is complete, boil for 1 min to destroy excess
peroxide, and cool.
39. Concentration Range
43.1.2 Using pipets, transfer (2, 5, 10, 20, and 30) mL of
39.1 The recommended concentration range is 0.015 mg to
Nickel Solution B (1 mL = 0.2 mg Ni) to the beakers. Transfer
0.3 mg of nickel per 20 mL of solution, using a 2-cm cell.
the solutions to 500-mL volumetric flasks, dilute to volume,
and mix.
NOTE 4—This procedure has been written for a cell having a 2-cm light
43.1.3 Using a pipet, transfer 25 mL to a 250-mL conical
path. Cells having other dimensions may be used, provided suitable
adjustments can be made in the amounts of sample and reagents used.
separatory funnel. Add 5 mL of NH OH·HCl solution and
50 mL of complexing solution, shaking after each addition.
40. Stability of Color
Using indicator paper, check the pH, which should be between
6.5 and 7.2. If necessary, adjust the pH with HCl (1 + 1) or
40.1 The color is stable for at least 2 h.
dilute NaOH solution.
41. Interferences
43.2 Reference Solution—Transfer 1.000 g of copper
41.1 The elements ordinarily present do not interfere if their
(purity, 99.99 % minimum) to a 250-mLbeaker and proceed as
composition is under the maximum limits shown in 1.1.
directed in 43.1, omitting the addition of nickel solution.
43.3 Color Development:
42. Reagents
43.3.1 Add 3 mL of dimethylglyoxime solution and shake
42.1 Chloroform (CHCl ).
for 1 min. Using a pipet, transfer 20 mL of CHCl to the
42.2 Complexing Solution—Mix 240 mL of sodium tartrate solution and shake again for 40 s.Allow the phases to separate.
solution, 90 mL of NaOH solution, 480 mL of sodium acetate 43.3.2 Transfer the yellow-colored chloroform phase to a
solution, and 200 mL of Na S O solution. 25-mLErlenmeyer flask fitted with a ground-glass stopper and
2 2 3
E478 − 08 (2017)
TABLE 3 Statistical Information
containing about 1 g of Na SO . Shake to stir the Na SO into
2 4 2 4
the CHCl . Decant the clear CHCl solution into an absorption Repeatability Reproducibility
3 3
Nickel
Test Specimen (R , Practice (R , Practice
1 2
cell and cover immediately to prevent loss of solvent.
Found, %
E173) E173)
43.4 Spectrophotometry:
1. 816-12 0.107 0.010 0.028
2. Sheet Brass (NIST 37c, 0.531 0.010 0.036
43.4.1 Multiple-Cell Spectrophotometer—Measure the cell
0.53 Ni)
correction using absorption cells with a 2-cm light path and a
3. Ounce Metal (NIST 124d, 0.997 0.021 0.037
light band centered at approximately 405 nm. Using the test
0.99 Ni)
4. 844-J 4.90 0.071 0.33
cell, take the spectrophotometric readings of the calibration
solutions.
43.4.2 Single-Cell Spectrophotometer—Transfer a suitable
portion of the reference solution to an absorption cell with a
2-cm light path and adjust the spectrophotometer to the initial
46.2 Bias—The accuracy of this method has been deemed
setting, using a light band centered at approximately 405 nm.
satisfactory based upon the data for the certified reference
While maintaining this adjustment, take the spectrophotomet-
materials in Table 3. Users are encouraged to use these or
ric readings of the calibration solutions.
similar reference materials to verify that the method is per-
43.5 Calibration Curve—Plot the net spectrophotometric forming accurately in their laboratories.
readings of the calibration solutions against milligrams of
ZINC BY THE ETHYLENEDIAMINE
nickel per 20 mL of solution.
TETRAACETATE (TITRIMETRIC) TEST METHOD
44. Procedure
47. Scope
44.1 Test Solution:
47.1 This test method covers the determination of zinc in
44.1.1 Select and weigh a sample as follows:
the range from 2 % to 40 %.
Tolerance in
Sample Sample Weight, Weight of Aliquot
47.2 This international standard was developed in accor-
Nickel, % Weight, g mg Copper, g Volume, mL
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
0.03 to 0.6 1.0 1.0 . 25
0.55 to 1.5 0.4 0.5 0.6 25
Development of International Standards, Guides and Recom-
1.45 to 3.5 0.4 0.5 0.6 10
mendations issued by the World Trade Organization Technical
3.45 to 5.0 0.25 0.2 0.75 10
Barriers to Trade (TBT) Committee.
Transfer it to a 250-mLbeaker.Add to the beaker the weight
of copper (purity, 99.99 % minimum) indicated in the table.
48. Summary of Test Method
44.1.2 Add 20 mL of HCl (1 + 1), and add 10 mL of H O
2 2
48.1 The zinc is converted to the zinc thiocyanate complex
in small portions. Cool until the violent reaction has ceased.
and extracted with methyl isobutyl ketone. The zinc is then
When dissolution is complete, boil for approximately 1 min to
stripped from the organic phase as the ammonia complex,
destroy excess peroxide. Cool, transfer to a 500-mLvolumetric
which is further treated with potassium cyanide to complex
flask, dilute to volume, and mix.
bivalent metals as well as the zinc. Finally, the zinc is released
44.1.3 Proceed as directed in 43.1.3, using an aliquot
from the cyanide complex by means of formaldehyde and
volume in accordance with 44.1.1. If a 10-mL aliquot is used,
titrated with disodium ethylenedinitrilotetraacetic acid (EDTA)
add 3 mLof HCl (1 + 9) to the aliquot in the separatory funnel.
solution.
44.2 Reference Solution—Proceed as directed in 43.2.
44.3 Color Development—Proceed as directed in 43.3.
49. Interferences
44.4 Spectrophotometry—Proceed as directed in 43.4.
49.1 None of the elements ordinarily present interfere. The
extraction procedure also affords a separation of the zinc from
45. Calculation
cadmium.
45.1 Convert the net spectrophotometric readings of the test
50. Apparatus
solution to milligrams of nickel by means of the calibration
curve. Calculate the percentage of nickel as follows:
50.1 Electrodes for Electroanalysis—Platinum anode and
cathode described in 13.3.
Nickel,% 5 A/~B 310! (6)
50.2 Separatory Funnels, conical, 500-mL capacity.
where:
50.3 Magnetic Stirrer, with polytetrafluoroethylene-covered
A = nickelfoundin20 mLofthefinaltestsolution,mg,and
magnetic stirring bar.
B = sample represented in 20 mL of the final test solution,
g.
51. Reagents
46. Precision and Bias
51.1 Ammonium Chloride Solution (0.02g⁄L)—Dissolve
46.1 Precision—Eightlaboratoriescooperatedintestingthis 0.20 g of ammonium chloride (NH Cl) in water and dilute to
test method and obtained the data summarized in Table 3. 10 L.
E478 − 08 (2017)
51.2 Ammonium Fluoride Solution (200 g⁄L)—Dissolve 51.15 Thiocyanate Wash Solution—Dissolve 100 g of so-
200 gofammoniumfluoride(NH F)inwateranddiluteto1 L. dium chloride (NaCl) in 600 mL of water. Add 10 mL of the
Store in a polyethylene bottle. NH SCN solution and mix. Add 10 mL of HCl and dilute to
1L.
51.3 Ammonium Thiocyanate Solution (500g⁄L)—Dissolve
51.16 Zinc Metal (purity: 99.9 % minimum)—Do not use
500 gofammoniumthiocyanate(NH SCN)inwateranddilute
finely divided powder or surface oxidized material.
to 1 L. Filter, if necessary, and store in a polyethylene bottle.
51.4 Ascorbic Acid, powdered.
52. Procedure
51.5 Buffer Solution (pH 10)—Dissolve 54 g of ammonium
52.1 Transfer a 2.00-g sample, weighed to the nearest 1 mg,
chloride (NH Cl) in 200 mL of water.Add 350 mL of NH OH
4 4
to a 250-mL polytetrafluoroethylene or polypropylene beaker
and dilute to 1 L. Store in a polyethylene bottle.
and add 2 mL of HF followed by 30 mL of HNO (1 + 1).
Cover the beaker with a plastic cover and allow the sample to
51.6 Disodium—Ethylenedinitrilotetraacetic Acid (EDTA),
dissolve. Do not place the beaker on a hot plate unless the
Standard Solution (0.05M) :
temperature is less than 80 °C. When dissolution is complete,
51.6.1 Dissolve 18.6125 g of disodium ethylenedinitrilo
add 25 mL of H O solution and 3 mL of Pb(NO ) solution.
2 2 3 2
tetraacetate dihydrate in water, transfer to a 1-L volumetric
Rinse the plastic cover glass and dilute to approximately
flask, dilute to volume, and mix. The solution is stable for
150 mL with NH Cl solution.
several months when stored in plastic or borosilicate glass
bottles.
52.2 Insert the electrodes into the solution and cover the
beaker with a pair of split cover glasses. Electrolyze for 2 h at
51.6.2 Standardization—Dissolve 0.1 g of zinc in 10 mL of
a current density of 4 A⁄dm using gauze electrodes. When
HNO (1 + 1) in a 400-mL beaker. Dilute the solution to
deposition is complete, slowly withdraw the electrodes (or
150 mL and proceed as directed in 52.4 – 52.7.
lower the beaker) with the current still flowing and rinse them
Zinc equivalent, mg/mL 5 A 31000 / B 2 C (7)
~ ! ~ !
with a stream of water from a wash bottle. Reserve the
where:
electrolyte.
A = grams of zinc,
52.3 Depending on the amount of zinc present, transfer the
B = final buret reading, mL, and
whole electrolyte or an aliquot portion, containing not more
C = initial buret reading, mL.
than 100 mg of zinc, to a 400-mL beaker. If an aliquot of the
51.7 Eriochrome Black-T Indicator Solution—Dissolve sample is to be taken, add 25 mL of saturated boric acid
(H BO ) solution to the volumetric flask, add the electrolyte,
0.4 g of the sodium salt of 1-(1-hydroxy-2 naphtholazo)-5
3 3
nitro-2 naphthol-4 sulfonic acid in a mixture of 20 mL of dilute to volume, and mix. Dilute the aliquot to 150 mL and
proceed as directed in 52.4. If the entire electrolyte is to be
ethanol and 30 mLof triethanolamine. Store in a tightly closed
used, proceed directly with the neutralization.
polyethylene dropping bottle. Do not use a solution that is
older than three months.
52.4 Neutralize with NaOH solution using litmus paper as
an indicator; then add 10 mL of HCl (1 + 1) and cool.
51.8 Formaldehyde Solution (37 %).
52.5 Transfer to a 500-mL separatory funnel and dilute to
51.9 Hydrogen Peroxide Solution (3%)—Dilute 100 mL of
about 250 mL. Add 30 mL of NH SCN solution, 20 mL of
30 % H O to1L.
2 2
NH F solution, and mix.Add 50 mLof methyl isobutyl ketone
51.10 Indicator Ion Solution (0.05M MgCl Solution)—
2 and shake vigorously for 1 min. Allow the layers to separate;
Dissolve 1.02 g of magnesium chloride hexahydrate (MgCl ·6
2 then draw off the lower aqueous layer into a second separatory
H O) in water and dilute to 100 mL.
2 funnel. Retain the organic layer. Add an additional 50 mL of
methyl isobutyl ketone to the second funnel and shake for 1
51.11 LeadNitrateSolution(10g/L)—Dissolve 10 g of lead
min. Allow the layers to separate. Draw off and discard the
nitrate (Pb(NO ) ) in water and dilute to 1 L.
3 2
aqueous layer.Add the organic layer to that retained in the first
51.12 Methyl Isobutyl Ketone.
separatory funnel. To the combined extracts, add 40 mL of
thiocyanate wash solution, shake, and allow the layers to
51.13 Potassium Cyanide Solution (100 g⁄L)—Dissolve
separate. Draw off and discard the aqueous layer.
100 g of potassium cyanide (KCN) in water and dilute to 1 L.
Store in a polyethylene bottle. (Warning—The preparation,
52.6 To the organic layer add 20 mL buffer solution, 30 mL
storage, and use of KCN solutions require care and attention.
of water, and shake to strip the zinc from the organic phase.
Avoid inhalation of fumes and exposure of the skin to the
Allow the layers to separate, and drain off the lower ammo-
chemical and its solutions. Do not allow solutions containing
niacallayerintoa600-mLbeaker.Repeattheextractionofzinc
cyanidetocomeincontactwithstronglyacidicsolutions.Work
with another 20 mL of buffer solution and 30 mL of water,
in a well-ventilated hood. (Refer to the Hazards Section of
followed by a final wash with 50 mL of water, combining all
Practices E50.))
the aqueous extracts in the 600-mLbeaker. Discard the organic
layer.
51.14 NaOH (200g⁄L)—Dissolve 200 g of NaOH in water,
cool, and dilute to 1 L. Store the solution in a polyethylene 52.7 Dilute to about 300 mL. Place a
bottle. polytetrafluoroethylene-covered stirring bar into the beaker,
E478 − 08 (2017)
add 20 mL of KCN solution, and then add 10 mg to 20 mg of 56. Summary of Test Method
ascorbic acid powder.Add 1.0 mLof indicator
...