Designation: E53 − 07 (Reapproved 2013)

Standard Test Method for

Determination of Copper in Unalloyed Copper by
Gravimetry1
This standard is issued under the fixed designation E53; 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 Department of Defense.

1. Scope E255 Practice for Sampling Copper and Copper Alloys for
1.1 This test method covers the chemical analysis of copper the Determination of Chemical Composition
having minimum purity of 99.75 % to 99.95 %. E1024 Guide for Chemical Analysis of Metals and Metal
Bearing Ores by Flame Atomic Absorption Spectropho-
1.2 This test method covers the electrolytic determination of tometry (Withdrawn 2004)3
copper in chemical, electrolytic, and fire refined copper. In this E1601 Practice for Conducting an Interlaboratory Study to
method silver is deposited with the copper, and is reported as Evaluate the Performance of an Analytical Method
copper.
1.3 This standard does not purport to address all of the 3. Terminology
safety concerns, if any, associated with its use. It is the 3.1 Definitions—For definitions of terms used in this test
responsibility of the user of this standard to establish appro- method, refer to Terminology E135.
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. Specific precau- 4. Summary of Test Method
tionary statements are given in 8.4 and Section 9. 4.1 The sample is dissolved in an acid mixture and the
copper is electrolytically deposited and weighed on a tared
2. Referenced Documents platinum cathode. Copper remaining in the electrolyte is
2.1 ASTM Standards:2 determined by atomic absorption spectroscopy.
E29 Practice for Using Significant Digits in Test Data to
Determine Conformance with Specifications 5. Significance and Use
E50 Practices for Apparatus, Reagents, and Safety Consid- 5.1 This test method for the chemical analysis of copper is
erations for Chemical Analysis of Metals, Ores, and primarily intended to test for compliance with compositional
Related Materials specifications. It is assumed that all who use this method will
E121 Test Methods for Chemical Analysis of Copper- be trained analysts capable of performing common laboratory
Tellurium Alloys (Withdrawn 2010)3 procedures skillfully and safely. It is expected that work will be
E135 Terminology Relating to Analytical Chemistry for performed in a properly equipped laboratory.
Metals, Ores, and Related Materials
E173 Practice for Conducting Interlaboratory Studies of 6. Interferences
Methods for Chemical Analysis of Metals (Withdrawn 6.1 Elements normally present in refined copper with a
1998)3 minimum purity of 99.85 % do not interfere.
6.2 Approximately one-half of any selenium or tellurium
1
present will co-deposit. If interfering amounts are present,
This test method is under the jurisdiction of ASTM Committee E01 on
proceed in accordance with Test Methods E121.
Analytical Chemistry for Metals, Ores, and Related Materials and is the direct
responsibility of Subcommittee E01.05 on Cu, Pb, Zn, Cd, Sn, Be, Precious Metals,
their Alloys, and Related Metals. 7. Apparatus
Current edition approved Oct. 1, 2013. Published October 2013. Originally 7.1 Electrodes for Electroanalysis:
approved in 1946. Last previous edition approved in 2007 as E53 – 07. DOI:
10.1520/E0053-07R13. 7.1.1 Electrodes—Recommended stationary type platinum
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or electrodes are described in 7.1.2 and 7.1.3. The surface of the
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM platinum electrodes should be smooth, clean, and bright to
Standards volume information, refer to the standard’s Document Summary page on
promote uniform deposition and good adherence. Deviations
the ASTM website.
3
The last approved version of this historical standard is referenced on from the exact size and shape are allowable. In instances where
www.astm.org. it is desirable to decrease the time of deposition and agitation

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

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 E53 − 07 (2013)
of the electrolyte is permissible, a generally available, rotating a 250-mL beaker, add 10 mL of HNO3 (1 + 1) and cover. After
type of electrode may be employed. Cleaning of the electrode dissolution, warm to dispel fumes, cool, transfer to a 1-L
by sandblasting is not recommended. volumetric flask, dilute to volume, and mix.
7.1.2 Cathodes—Platinum cathodes may be either open or 8.2 Copper, Standard Solution B (1 mL = 0.20 mg Cu)—
closed cylinders formed from sheets that are plain or Using a pipet, transfer 20 mL of copper Solution A to a 100-mL
perforated, or from gauze. Gauze cathodes are recommended; volumetric flask, dilute to volume, and mix.
preferably from 50-mesh gauze woven from approximately
0.21 mm diameter wire. The top and bottom of gauze cathodes 8.3 Sulfuric-Nitric Acid Mixture—While stirring, slowly add
should be reinforced by doubling the gauze about 3 mm onto 300 mL of H2SO4 to 750 mL of H2O. Cool to ambient
itself, or by the use of platinum bands or rings. The cylinder temperature, and while stirring, add 210 mL of HNO3.
should be approximately 30 mm in diameter and 50 mm in 8.4 Potassium Cyanide Solution (100 g/L)—Dissolve 100 g
height. The stem should be made from a platinum alloy wire of KCN in water and dilute to 1 L. (Warning—The
such as platinum-iridium, platinum-rhodium, or platinum- preparation, storage, and use of KCN require care and atten-
ruthenium, having a diameter of approximately 1.3 mm. It tion. Avoid inhalation of fumes and exposure of the skin to the
should be flattened and welded the entire length of the gauze. chemical and its solutions. Work in a well-ventilated hood.
The overall height of the cathode should be approximately 130 Refer to the applicable section of Practices E50.)
mm. A cathode of these dimensions will have a surface area of 8.5 Sulfamic Acid Solution (100 g/L)—Dissolve 10 g of
135 cm2 exclusive of the stem. sulfamic acid (HNH2SO3) in water and dilute to 100 mL.
7.1.3 Anodes—Platinum anodes may be a spiral type when Prepare fresh daily.
anodic deposits are not being determined, or if the deposits are
small (as in the electrolytic determination of lead when it is 9. Hazards
present in concentrations below 0.2 %). Spiral anodes should 9.1 For precautions to be observed in this method, refer to
be made from 1.0-mm or larger platinum wire formed into a Practices E50.
spiral of seven turns having a height of approximately 50 mm
and a diameter of 12 mm with an overall height of approxi- 9.2 Cyanides must be disposed of with care, avoiding
mately 130 mm. A spiral anode of these dimensions will have contact with acids that release hydrogen cyanide gas.
a surface area of 9 cm2. When both cathode and anode plates 10. Sampling
are to be determined, the anodes should be made of the same
material and design as the electrode described in 7.1.2. The 10.1 For procedures in sampling refer to Practice E255.
anode cylinder should be approximately 12 mm in diameter However, this practice does not supersede any sampling
and 50 mm in height and the overall height of the anode should requirements specified in a specific ASTM material specifica-
be approximately 130 mm. A gauze anode of these dimensions tion nor preclude a procedure agreed upon by the producer and
will have a surface area of 54 cm2 exclusive of the stem. consumer.
7.2 Atomic Absorption Spectrometer: 10.2 For all trace element determinations, care must be
7.2.1 Determine that the atomic absorption spectrometer is taken to limit sample exposure to contaminations, and to
suitable for use as described in Guide E1024. The variability remove any contaminations that occur.
for the highest calibration solution should not exceed 1 %. 10.3 Wherever possible, non-metallic tools shall be used to
7.2.2 Operating Parameters: obtain chips (millings, drillings, sawings, nibblings, and so
Wavelength 327.5 nm forth) from the sample.
Bandpass About 0.2 nm
Gas mixture Air-acetylene 10.4 Except for the estimation of oxygen or hydrogen, or
Flame type Lean when analyzing standard reference materials that forbid
7.2.3 Instrument Response—Adequate instrument response cleaning, the chips shall be cleaned prior to weighing a portion
is obtained if the difference between the readings of the two for analysis. Immerse in HNO3 (1 + 3), rinse in running water
highest of five equally spaced calibration solutions is sufficient followed by distilled or deionized water and alcohol, and allow
to permit an estimation equivalent to one twentieth of the to air-dry. Exercise great care to prevent re-contamination of
difference. the specimen by metal tools, or from zinc in rubber stoppers, or
7.2.4 Curve Linearity—The upper limit of the usable por- chlorides from HCl vapor, and so forth.
tion of a calibration curve is normally set such that the 10.5 In methods for the determination of impurities in
difference between the readings of the two highest of five copper, particular care must be taken to prevent specimen
equally spaced calibration solutions is more than 0.7 times the contamination by reagents or glassware.
difference between the lowest of the calibration solutions.
Absorbance values are used in this calculation. 10.6 The interior of glassware shall be cleaned immediately
prior to use by a rinse in HNO3 (1 + 3) followed by running
7.3 Glassware, shall be borosilicate glass unless otherwise water and by distilled or deionized water, all in an area free
stated. from HCl fumes.
8. Reagents 10.7 Reagent acid should be taken from a bottle reserved for
8.1 Copper, Standard Solution A (1 mL = 1.0 mg Cu)— trace metal analysis. Extra-purity acids, intended for trace
Transfer 1.000 g of electrolytic copper (purity: 99.9 % min) to metal analysis are recommended but not required.

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 E53 − 07 (2013)
11. Rounding Calculated Values TABLE 1 Statistical Information—Copper
Test Copper S min R %R
11.1 Calculated values shall be rounded to the desired Specimen Found, % (E1601) (E1601) (E1601)
number of places, as directed in Practice E29, including as an 1. Copper 99.959 0.008 0.023 0.02
option, the special rounding off to a nearest final number of 2. Copper 99.723 0.009 0.051 0.05
five.

12. Interlaboratory Studies

12.1 This test method has been evaluated in accordance 14.6.1 Calibration:
with Practice E173 unless otherwise noted in the precision and 14.6.1.1 Calibration Solutions—Using pipets, transfer 5, 10,
bias section. 15, 20, and 25 mL portions of copper Solution B to 250-mL
volumetric flasks. Add 20 mL of H2SO4 (1 + 1), dilute to
13. Preparation of Electrodes volume, and mix. These are equivalent to 0.001, 0.002, 0.003,
13.1 Cathode—Clean the cathode in hot nitric acid (HNO3), 0.004, and 0.005 g of Cu/250 mL.
(1 + 1), rinse with distilled water, rinse in two separate baths of 14.6.1.2 Reference Solution—Transfer 20 mL of H2SO4 to a
ethanol or acetone. Dry at a low temperature (110 °C for 3 to 250-mL volumetric flask, dilute to volume, and mix.
5 min), and cool to room temperature in a desiccator. 14.6.2 Analysis:
13.2 Anode—Clean in hydrochloric acid (HCl), (1 + 1), 14.6.2.1 Test Solution—If necessary evaporate the spent
rinse with distilled water. electrolyte from 14.5 to below 250 mL and cool. Transfer to a
250-mL volumetric flask, dilute to volume, and mix.
13.3 Weigh the cathodes to the nearest 0.1 mg and record 14.6.2.2 Measurements—Optimize the response of the
the weight. The anode does not have to be weighed. instrument, take preliminary readings, and complete the analy-
sis and determine the grams of copper in 250 mL by one of the
14. Procedure procedures, graphical, ratio, or single point in accordance with
14.1 Clean the metal that is to be analyzed in KCN solution. Guide E1024.
Rinse with water, then alcohol, and air-dry thoroughly at
ambient temperature. 15. Calculations
14.2 Transfer 5 g of the cleaned metal, weighed to the 15.1 Calculate the weight of deposited copper as follows:
nearest 0.1 mg, to a 400-mL tall-form beaker. Add 45 mL of the Copper, g 5 A 2 B (1)
H2SO4-HNO3 mixture and immediately cover with a close
fitting cover glass. Cool as required to prevent the reaction where:
from becoming violent. When the reaction has subsided, heat A = weight of cathode plus deposited copper, g, and
moderately until dissolution is complete. Continue heating at B = weight of cathode, g.
approximately 90 °C until the brown fumes are expelled. Never 15.2 Calculate the percentage of copper as follows:
boil. Cool slightly and carefully wash down the cover glass and
Copper, % 5 ~~ C1D ! /E ! 3 100 (2)
sides of the beaker. Add 10 mL of sulfamic acid solution, stir,
and dilute to approximately 175 to 200 mL. where:
14.3 With the electrolyzing current off, position the anode C = grams of deposited copper found in 15.1,
and the tared cathode, weighed to the nearest 0.1 mg, in the D = grams of copper in 250 mL of electrolyte found in
solution and add water so that the gauze is completely 14.6.2.2, and
immersed. Cover the beaker with a split cover glass. E = grams of sample used.
14.4 Electrolyze at a current density of about 0.6 A/dm2 16. Precision and Bias4
(Note 1). When the solution becomes colorless, wash down the
cover glass, electrode stems, and sides of the beaker, add 10 16.1 Precision—Six laboratories cooperated in testing this
mL of sulfamic acid, and continue the electrolysis until method and obtained the data summarized in Table 1. The
deposition is essentially complete, as indicated by failure to interlaboratory test was conducted in accordance with Practice
plate on a new surface of the cathode stem when the solution E173 and calculated using Practice E1601 software.
level is raised. 16.2 Bias—No certified reference materials suitable for
testing this test method were available when the interlaboratory
NOTE 1—When a current density of 0.6 A/dm2 is used, the electrolysis
requires about 16 h and is conveniently carried out overnight. testing program was conducted. The user of this test method is
encouraged to employ accepted reference materials, if
14.5 Wash the cathode with a stream of water as it is being
available, to validate the test method as implemented in a
removed from the spent solution. Immediately wash succes-
specific laboratory and to obtain estimates of uncertainty due to
sively in two baths of water and two baths of ethanol or
bias.
methanol. Reserve the electrolyte. Dry at 110 °C for 3 to 5 min,
cool to ambient temperature, and weigh.
14.6 Determination of the Residual Copper in the Electro- 4
Supporting data have been filed at ASTM International Headquarters and may
lyte by Atomic Absorption Spectrometry: be obtained by requesting Research Report RR:E01-1089.

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 E53 − 07 (2013)
17. Keywords
17.1 copper; copper concentration

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