Astm E34 - 2011

Designation: E34 – 11
Standard Test Methods for

Chemical Analysis of Aluminum and Aluminum-Base Alloys1
This standard is issued under the fixed designation E34; 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 Procedure Sections

1e
Boron by the Carmine (Photometric) Test Method
1.1 These test methods cover the chemical analysis of Cadmium:
aluminum and aluminum-base alloys having compositions Cadmium by the Atomic Absorption Test Method 167 to 177
within the following limits: Chromium:
1e
Chromium by the Diphenylcarbazide (Photometric)
Beryllium, ppm 0.3 to 100
Test Method
Bismuth, % 0.02 to 1.0 1b
Chromium by the Persulfate Oxidation (Titrimetric)
Boron, % 0.005 to 0.060
Test Method
Cadmium, % 0.001 to 0.50
Chromium by the Atomic Absorption Test Method 199 to 209
Chromium, % 0.01 to 1.0
Copper:
Copper, % 0.01 to 20.0 1c
Copper and Lead by the Electrolytic (Gravimetric)
Gallium, % 0.001 to 0.05
Test Method
Iron, % 0.01 to 3.0
Copper and Zinc by the Atomic Absorption 210 to 220
Lead, % 0.01 to 1.0
Spectometry Test Method
Lithium, % 0.001 to 4.0
Copper by the Electrolytic (Gravimetric) Test Method 303 to 311
Magnesium, % 0.002 to 12.0 1a
Copper by the Neocuproine (Photometric)
Manganese, % 0.005 to 2.0
Test Method
Nickel, % 0.01 to 4.0
Gallium:
Silicon, % 0.05 to 20.0
Gallium by the Ion Exchange-Atomic Absorption 312 to 323
Tin, % 0.03 to 1.0
Test Method
Titanium, % 0.002 to 0.30
Iron:
Vanadium, % 0.002 to 0.16
Iron by the 1,10-Phenanthroline (Photometric) Method 73 to 81
Zinc, % 0.003 to 12.0
Iron and Manganese by the Atomic Absorption 221 to 231
Zirconium, % 0.01 to 0.30
Spectometry Method
1.2 The analytical procedures appear in the following sec- Lead:
1c
Copper and Lead by the Electrolytic (Gravimetric)
tions: Test Method
Procedure Sections Bismuth and Lead by the Atomic Absorption 188 to 198
Beryllium: Spectrometry Test Method
Beryllium by Argon Plasma Optical Emission 283 to 292 Lithium:
Spectroscopy Lithium by the Atomic Absorption Test Method 324 to 334
Beryllium by the Morin (Fluorometric) Test 1e Magnesium:
1b
Method Magnesium by the Pyrophosphate (Gravimetric)
Bismuth: Method
1e
Bismuth by the Thiourea (Photometric) Method 1a Magnesium by the Ethylenediamine Tetraacetate
Bismuth and Lead by the Atomic Absorption 188 to 198 (Titrimetric) Test Method
Test Method Magnesium by the Atomic Absorption Spectrometry 232 to 242
Boron: Test Method
Manganese:
Iron and Manganese by the Atomic Absorption 221 to 231
Spectrometry Test Method
1
These test methods are under the jurisdiction of ASTM Committee E01 on Manganese by the Periodate (Photometric) 293 to 302
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct Test Method
responsibility of Subcommittee E01.04 on Aluminum and Magnesium. Nickel:
1a
Current edition approved July 1, 2011. Published August 2011. Originally Nickel by the Dimethylglyoxime (Photometric)
published as E34 – 60 T. Last previous edition E34 – 94 (Reapproved 2002). Test Method
1b
1a
Discontinued as of Feb. 25, 1983. Nickel by the Dimethylglyoxime (Gravimetric)
1b
Discontinued as of May 29, 1981. Test Method
1c
Discontinued as of Oct. 25, 1985. Nickel by the Atomic Absorption Spectrometry 243 to 253
1d
Discontinued as of March 25, 1983. DOI: 10.1520/E0034-11. Test Method
1e
Discontinued as of July 1, 2011. DOI: 10.1520/E0034-11. Silicon:
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
1
E34 – 11
Silicon by the Molybdisilicic Acid (Photometric) 1e E1601 Practice for Conducting an Interlaboratory Study to
Test Method Evaluate the Performance of an Analytical Method
1e
Silicon by the Sodium Hydroxide-Perchloric Acid
(Gravimetric) Method
Tin: 3. Terminology
1e
Tin by the Iodate (Titrimetric) Test Method
Titanium:
3.1 Definitions—For definitions of terms used in this test
Titanium by the Chromotropic Acid (Photometric) 141 to 150 method, refer to Terminology E135.
Test Method
Titanium by the Diantipyrylmethane Photometric 254 to 263 4. Significance and Use
Test Method
Vanadium: 4.1 These test methods for the chemical analysis of metals
Vanadium by an Extraction-Photometric Test Method 264 to 273 and alloys are primarily intended to test such materials for
using N-Benzoyl-N-Phenylhydroxylamine
Zinc: compliance with compositional specifications. It is assumed
Zinc by the Ammonium Mercuric Thiocyanate or the 1b
that all who use these test methods will be trained analysts
Zinc Oxide (Gravimetric) Test Method
Zinc by the Ethylenediamine Tetraacetate 1d capable of performing common laboratory procedures skill-
(Titrimetric) Test Method fully and safely. It is expected that work will be performed in
Copper and Zinc by the Atomic Absorption 210 to 220 a properly equipped laboratory.
Spectrometry Test Method
Zinc by the Ion Exchange-EDTA Titrimetric 274 to 282
Test Method 5. Apparatus, Reagents, and Photometric Practice
Zirconium: 5.1 Apparatus and reagents required for each determination
Zirconium by the Arsenazo III (Photometric) Method 178 to 187
1.3 The values stated in SI units are to be regarded as the are listed in separate sections preceding the procedure.
standard. 5.2 Photometric practice prescribed in these test methods
1.4 This standard does not purport to address all of the shall conform to Practice E60.
safety problems, if any, associated with its use. It is the 5.3 Calculated values shall be rounded to the desired num-
responsibility of the user of this standard to establish appro- ber of places in accordance with the rounding method of
priate safety and health practices and determine the applica- Practice E29.
bility of regulatory limitations prior to use. Specific hazard
statements are given throughout these test methods.
2. Referenced Documents
2.1 ASTM Standards: 2
E29 Practice for Using Significant Digits in Test Data to
Determine Conformance with Specifications 3
E50 Practices for Apparatus, Reagents, and Safety Consid-
erations for Chemical Analysis of Metals, Ores, and
Related Materials 3
E55 Practice for Sampling Wrought Nonferrous Metals and
Alloys for Determination of Chemical Composition 3
E60 Practice for Analysis of Metals, Ores, and Related
Materials by Spectrophotometry 3
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 Metals3 4
E716 Practices for Sampling and Sample Preparation of
Aluminum and Aluminum Alloys for Determination of
Chemical Composition by Spectrochemical Analysis 4
E1024 Guide for Chemical Analysis of Metals and Metal
Bearing Ores by Flame Atomic Absorption Spectropho-
tometry5
E1479 Practice for Describing and Specifying Inductively-
Coupled Plasma Atomic Emission Spectrometers
2
Annual Book of ASTM Standards, Vol 14.02.
3
4
5
Withdrawn. The last approved version of this historical standard is referenced NOTE 1—Shaded areas are suitable for sampling.
on www.astm.org. FIG. 1 Type A and Type B Disks
2
E34 – 11
6. Precautions CHROMIUM BY THE DIPHENYLCARBAZIDE
6.1 For precautions to be observed in the use of certain (PHOTOMETRIC) TEST METHOD
reagents in these test methods, reference shall be made to (This test method, which consisted of Sections 39 through 47
Practices E50. of this standard, was discontinued in 2008.)
7. Sampling CHROMIUM BY THE PERSULFATE OXIDATION

7.1 Wrought products shall be sampled in accordance with (TITRIMETRIC) TEST METHOD
Practice E55. Cast products shall be sampled in accordance (This test method, which consisted of Sections 48 through 53
with Practice E88. of this standard, was discontinued in 1981.)
7.2 Chill cast disks produced for analysis by spectrochemi-
cal methods (see Practices E716) shall be sampled by drilling COPPER BY THE NEOCUPROINE
or milling through the entire thickness. Drill bits or milling (PHOTOMETRIC) TEST METHOD
cutters should be carbide to avoid iron contamination.
(This test method, which consisted of Sections 54 through 63
NOTE 1—The use of a machined disk may result in the exclusion of an of this standard, was discontinued in 1983.)
element-rich portion of the sample. This practice should be avoided
wherever possible, especially for analyses affecting product acceptance.
COPPER AND LEAD BY THE ELECTROLYTIC
7.2.1 If samples are produced by drilling, use a minimum of (GRAVIMETRIC) TEST METHOD
two positions approximately opposite each other and combine (This test method, which consisted of Sections 64 through 72
the drillings. of this standard, was discontinued in 1985.)
7.2.2 The outer edges of the holes shall be approximately
0.48 cm (3⁄16 in.) from the edge of the disk. Drill bits shall be
IRON BY THE 1,10-PHENANTHROLINE
not less than 0.95 cm (3⁄8 in.) in diameter and not larger than
(PHOTOMETRIC) TEST METHOD
1.27 cm (1⁄2 in.) in diameter.6
7.2.3 If samples are produced by milling, mill disks at (This test method, which consisted of Sections 73 through 81
similar points to a distance of 40 % of the sample diameter or of this standard, was discontinued in 2008.)
other methods that provide a representative sample such as
quarter of half milling. A 0.95-cm (3⁄8 in.) milling cutter has MAGNESIUM BY THE PYROPHOSPHATE
been shown to provide acceptable chips.6 (GRAVIMETRIC) TEST METHOD
7.2.4 Center pour (Type B, Practices E716) and vacuum cast (This test method, which consisted of Sections 82 through 87
disks may be sampled around the entire circumference. Fig. 1 of this standard, was discontinued in 1981.)
illustrates the areas suitable for sampling Type B disks.
Vacuum cast disks are sampled in the same manner as Type B MAGNESIUM BY THE ETHYLENEDIAMINE
disks.6 TETRAACETATE (TITRIMETRIC) TEST METHOD
7.2.5 Drilling or milling techniques ideally should produce
(This test method, which consisted of Sections 88 through 93
uniformly small chips. Break large continuous pieces into
of this standard, was discontinued in 2008.)
smaller pieces 0.64 cm (1⁄4 in.) to 0.95 cm (3⁄8 in.) long. Drilling
or milling techniques should minimize production of fine,
MANGANESE BY THE PERIODATE
dust-like material.6
BERYLLIUM BY THE MORIN (FLUOROMETRIC) (This test method, which consisted of Sections 94 through
TEST METHOD 102 of this standard, was replaced in 1984 by Sections 293
(This test method, which consisted of Sections 8 through 19 through 302.)
NICKEL BY THE DIMETHYLGLYOXIME
BISMUTH BY THE THIOUREA (PHOTOMETRIC) TEST METHOD
(PHOTOMETRIC) TEST METHOD (This test method, which consisted of Sections 103 through
(This test method, which consisted of Sections 20 through 29 111 of this standard, was discontinued in 1983.)
NICKEL BY THE DIMETHYLGLYOXIME
BORON BY THE CARMINE (PHOTOMETRIC) (GRAVIMETRIC) TEST METHOD
TEST METHOD (This test method, which consisted of Sections 112 through
(This test method, which consisted of Sections 30 through 38 117 of this standard, was discontinued in 1981.)
SILICON BY THE MOLYBDISILICIC ACID
6
Olson, H. A., and Macy, D. W., “Metallurgical Approach to Evaluating (This test method, which consisted of Sections 118 through
Chemical Sample Disks,” Light Metals, Vol 2, 1978, pp. 301–311. 127 of this standard, was discontinued in 2008.)
3
E34 – 11
SILICON BY THE SODIUM HYDROXIDE- 146.5 Sodium Hydroxide Solution A (200 g/L)—Dissolve
PERCHLORIC ACID (GRAVIMETRIC) 200 g of sodium hydroxide (NaOH) in about 500 mL of water,
TEST METHOD dilute to about 900 mL, and cool. Transfer to a 1-L volumetric
(This test method, which consisted of Sections 128 through flask, dilute to volume, and mix. Immediately transfer to a
133 of this standard, was discontinued in 2008.) plastic bottle.
146.6 Sodium Hydroxide Solution B (80 g/L)—Dissolve 80
TIN BY THE IODATE (TITRIMETRIC) g of sodium hydroxide (NaOH) in about 200 mL of water,
TEST METHOD dilute to about 900 mL, and cool. Transfer to a 1-L volumetric
(This test method, which consisted of Sections 134 through flask, dilute to volume, and mix. Immediately transfer to a
140 of this standard, was discontinued in 2008.) plastic bottle.
146.7 Sodium Metadisulfite (Na2S 2O5).
TITANIUM BY THE CHROMOTROPIC ACID 146.8 Sodium Monochloroacetic Acid Buffer Solution—
(PHOTOMETRIC) TEST METHOD Dissolve 189 g of monochloroacetic acid in 150 mL of water.
141. Scope Dissolve 40 g of sodium hydroxide (NaOH) in about 100 mL
141.1 This test method covers the determination of titanium of water, and cool. Add the NaOH solution to the monochlo-
in concentrations from 0.002 to 0.3 %. roacetic acid solution, mix thoroughly, and cool. If turbid, filter
142. Summary of Test Method through a fine paper and wash the filter with water. Transfer to
142.1 The sample is dissolved in a sodium hydroxide a 500-mL volumetric flask, dilute to volume, and mix. (The pH
solution and acidified with nitric and sulfuric acids. Iron is should be about 2.9.)
reduced with ascorbic acid. The yellow complex of titanium 146.9 Sodium Sulfite Solution (20 g/L)—Dissolve 2 g of
with chromotropic acid is formed at a pH between 3.1 and 3.2. sodium sulfite (Na2SO 3) in water and dilute to 100 mL. Do not
Photometric measurement is made at approximately 470 nm. use a solution that has stood more than 8 h.
143. Concentration Range 146.10 Sulfurous Acid Solution (saturated).
143.1 The recommended concentration range is from 0.002 146.11 Titanium, Standard Solution A (1 mL = 0.4 mg
to 0.10 mg of titanium per 50 mL of solution, using a 2-cm cell. Ti)—Dissolve 0.400 g of titanium (purity: 99.5 % minimum) in
NOTE 2—This test method has been written for cells having a 2-cm 125 mL of H2SO4(1+4). When dissolution is complete, oxidize
light path. Cells having other dimensions may be used, provided suitable with 10 drops of HNO3, and boil gently to expel fumes of
adjustments can be made in the amounts of sample and reagents used. nitrous oxide. Cool, transfer to a 1-L volumetric flask, dilute to
144. Stability of Color volume, and mix.
144.1 The color develops within 5 min and is stable for 40 146.12 Titanium, Standard Solution B (1 mL = 0.02 mg
min. Ti)—Using a pipet, transfer 50 mL of Titanium Solution A to
145. Interferences a 1-L volumetric flask, dilute to volume, and mix.
145.1 Chromium, if present, interferes because of the back- 146.13 Titanium, Standard Solution C (1 mL = 0.002 mg
ground color of the solution. Provision is made to correct for Ti)—Using a pipet, transfer 100 mL of Titanium Solution B to
this interference. a 1-L volumetric flask. Add 2.5 mL of H 2SO4 (1+4), cool,
146. Reagents dilute to volume, and mix. Do not use a solution that has stood
146.1 Ascorbic Acid Solution (40 g/L)—Dissolve 1 g of more than 1 day.
ascorbic acid in 25 mL of water. Do not use a solution that has
stood more than 1 h. 147. Preparation of Calibration Curve
146.2 Chromotrophic Acid Solution (Disodium Salt) (20
147.1 Calibration Solutions:
g/L)—Dissolve 2 g of chromotropic acid (4,5-dihydroxy-2,7-
naphthalenedisulfonic acid, disodium salt) in 70 mL of water 147.1.1 Using pipets, transfer 1, 2, 5, 10, and 15 mL of
containing 0.75 mL of acetic acid. Add 0.2 g of sodium Titanium Solution C to 100-mL beakers containing 10 mL of
metadisulfite (Na2S2O5) and stir until completely dissolved. the reagent mixture.
Filter through a fine paper into a 100-mL volumetric flask. 147.1.2 Using pipets, transfer 1, 2, 3, 4, and 5 mL of
Wash with water, dilute to volume, and mix. Select a lot of Titanium Solution B to 100-mL beakers containing 10 mL of
reagent that meets the following criteria: The solution must be the reagent mixture.
light, clear yellow and have an absorbance reading of 0.3 or 147.1.3 Add KMnO4 solution dropwise until a permanent
less when measured at 470 nm in a 2-cm cell, using distilled red color is developed. Add Na2SO3 solution dropwise, while
water as the reference. Do not use a solution that has stood mixing the solution thoroughly, until the permanganate is
more than 3 weeks. decomposed, and then add 1 drop in excess. Add 10 mL of
146.3 Potassium Permanganate Solution (1 g/L)—Dissolve monochloroacetic acid buffer solution and mix. Add 1.0 mL of
0.1 g of potassium permanganate (KMnO 4) in water and dilute ascorbic acid solution and mix. Adjust the volume to about 35
to 100 mL. mL. Using a pH meter, adjust the pH from 2.1 to 2.2 with
146.4 Reagent Mixture—Transfer 300 mL of water to a 1-L H2SO4 (1+4) or NaOH Solution B, as required. Proceed as
volumetric flask, add in order 250 mL of NaOH Solution A, directed in 147.3.
250 mL of H2SO4 (1+4), and 18 mL of HNO3 and mix. Cool, 147.2 Reference Solution—Transfer 10 mL of reagent mix-
dilute to volume, and mix. (The pH should be about 0.50.) ture to a 100-mL beaker and proceed as directed in 147.1.3.
4
E34 – 11
147.3 Color Development—Using a pipet, add 5 mL of 148.6 Photometry—Take the photometric reading of the test
chromotropic acid solution, transfer to a 50-mL volumetric solution and background color solution, if necessary, as di-
flask, dilute to volume, and mix. rected in 147.4.
147.4 Photometry: 149. Calculation
147.4.1 Multiple–Cell Photometer—Measure the cell correc- 149.1 Convert the net photometric readings of the test
tion using absorption cells with a 2-cm light path and a light solution and the background color solution to milligrams of
band centered at approximately 470 nm. Using the test cell, titanium by means of the calibration curve. Calculate the
take the photometric readings of the calibration solutions. percentage of titanium as follows:
147.4.2 Single–Cell Photometer—Transfer a suitable portion Titanium, % 5 ~A 2 B!/~C 3 10! (1)
of the reference solution to an absorption cell with a 2-cm light
where:
path and adjust the photometer to the initial setting, using a
A = titanium found in 50 mL of the final test solution, mg,
light band centered at approximately 470 nm. While maintain- B = background color correction, mg of titanium, and
ing this adjustment, take the photometric readings of the C = sample represented in 50 mL of the final test solution,
calibration solutions. g.
147.5 Calibration Curve—Plot the net photometric readings
of the calibration solutions against milligrams of titanium per 150. Precision
50 mL of solution. 150.1 Six laboratories cooperated in testing this test method
148. Procedure and obtained eight sets of data summarized in Table 1.
148.1 Test Solution:
148.1.1 Select and weigh a sample in accordance with the TABLE 1 Statistical Information
following table and transfer it to a 250-mL beaker. Titanium Repeatability (R1, Reproducibility
Test Specimen
Sample Tolerance in Sample Found, % E173) (R2, E173)
Titanium, % Weight, g Weight, mg 1. 1075 alloy 0.003 0.001 0.001
0.001 to 0.03 1.000 0.5 2. 356 alloy 0.112 0.006 0.006
0.02 to 0.30 0.500 0.2
148.1.2 Add 25 mL of NaOH Solution A, cover, and, if

necessary, heat gently to start reaction. When reaction slows, ZINC BY THE AMMONIUM MERCURIC
wash the cover and sides of the beaker with hot water. Boil THIOCYANATE OR THE ZINC OXIDE
gently for a few minutes to complete the dissolution, and cool. (GRAVIMETRIC) TEST METHOD
(This test method, which consisted of Sections 151 through
NOTE 3—For alloys containing more than 3 % silicon, proceed as
follows: Transfer the sample to a platinum dish and cover with a platinum 159 of this standard, was discontinued in 1981.)
cover. Add 25 mL of NaOH solution A. When the major reaction ceases,
wash down the sides of the dish and the cover with hot water, and ZINC BY THE ETHYLENEDIAMINE
evaporate the solution to a syrupy paste. Proceed as directed in 148.1.3. TETRAACETATE
(TITRIMETRIC) TEST METHOD
148.1.3 Dilute to about 50 mL. Add 2 mL of HNO3 and 40
mL of H2SO4(1+4). Mix and boil gently until the salts dissolve. (This test method, which consisted of Sections 160 through
If manganese dioxide has separated, add a few drops of H2SO 166 of this standard, was discontinued in 1983.)
3 solution and boil for 3 to 5 min. Cool, transfer to a 100-mL
CADMIUM BY THE ATOMIC ABSORPTION TEST
volumetric flask, dilute to volume, and mix. METHOD
148.1.4 Filter through a fine, dry paper, discard the first 10 to
167. Scope
20 mL, and collect about 50 mL. Using a pipet, transfer 10 mL
167.1 This test method covers the determination of cadmium
if the expected titanium concentration is less than 0.15 %, or 5
in concentrations from 0.001 to 0.5 %.
mL if the expected titanium concentration is greater than
168. Summary of Test Method
0.15 %, to a 100-mL beaker. Proceed as directed in 147.1.3.
168.1 An acid solution of the sample is aspirated into the
148.2 Reference Solution—Carry a reagent blank through the air-acetylene flame of an atomic absorption spectrophotometer.
entire procedure, using the same amounts of all reagents with The absorption by the sample of the cadmium resonance line at
the sample omitted. 2288 Å is measured and compared with that of calibration
148.3 Color Development—Proceed as directed in 147.3. solutions containing known amounts of cadmium and alumi-
148.4 Background Color Solution—If the test solution con- num.
tains chromium or other elements which form colored ions, 169. Concentration Range
transfer a second aliquot of the filtered solution obtained in 169.1 If the optimum concentration range is not known,
148.1.4 and proceed as directed in 147.1.3. After the pH determine it as directed in Guide E1024. A sensitivity of 0.02
adjustment, transfer to a 50-mL volumetric flask, dilute to µg/mL at 0.0044 absorbance is frequently obtained.
volume, and mix. 170. Interferences
148.5 Background Color Reference Solution—Use a portion 170.1 Elements normally present do not interfere if their
of the reagent blank to which no chromotropic acid has been concentrations are less than the maximum limits shown in 1.1.
added. 171. Apparatus
5
E34 – 11
171.1 Atomic Absorption Spectrophotometer—Determine dissolution. Cool for 5 min, add 2 mL of HNO 3, and boil
that the instrument is suitable for use as prescribed in Guide gently for 3 to 5 min.
E1024. The percent variability for the highest calibration NOTE 5—If insoluble silicon is present, dilute to 50 mL with hot water,
solution (Vc) should not exceed 2 %. filter using a medium paper into a 250-mL beaker, and wash the residue
171.1.1 Operation Parameters: with hot water. Reserve the filtrate. Transfer the paper and residue to a
Wavelength 2288Å platinum crucible, dry, and ignite at 600°C. Cool, add 5 drops of HNO3
Bandpass about 6 Å and 5 mL of HF, and evaporate carefully to dryness. Cool, add 1 mL of
Gas mixture air-acetylene HCl (1+1) and 5 mL of hot water. Heat to dissolve the salts and add the
Flame type lean solution to the reserved filtrate.
174.1.2 For 0.001 to 0.05 % cadmium, transfer the solution
172. Reagents to a 100-mL volumetric flask, dilute to volume, and mix. Use
172.1 Aluminum Solution (1 mL = 50 mg Al)—Transfer 10 g a 500-mL volumetric flask for 0.05 and 0.5 % cadmium.
of aluminum (purity: 99.999 % min) to a 400-mL beaker. Add 175. Measurements
50 mL of water and a small drop of mercury. Add 110 mL of 175.1 Optimize the response of the instrument and take
HCl in small increments, heating moderately to accelerate the preliminary readings; complete the analysis and calculate the
dissolution. When dissolution is complete, add 2 mL of HNO3 cadmium concentration as in the graphical, ratio, or single-
and boil gently for 5 min. Cool, transfer to a 200-mL point procedures, as described in Guide E1024.
volumetric flask, dilute to volume, and mix. Store in a NOTE 6—A three-slot burner is recommended for the lower range, and
polyethylene bottle. a 5-cm single slot burner for the higher range.
NOTE 4—The high purity aluminum is necessary when determining 176. Calculation
cadmium in concentrations less than 0.01 %. 176.1 Calculate the percentage of cadmium as follows:
172.2 Cadmium, Standard Solution A (1 mL = 1.00 mg A
Cadmium, % 5 B 3 100 (2)
Cd)—Transfer 1.00 g of cadmium (purity: 99.9 % min) to a
400-mL beaker. Add 5 mL of water, 10 mL of HCl, and 2 mL
where:
of HNO3. Cover, heat gently until dissolution is complete, cool,
A = cadmium in the final test solution, mg, and
and add 50 mL of water. Transfer to a 1-L volumetric flask, B = sample represented in the test solution, mg.
dilute to volume, and mix. Store in a polyethylene bottle.
172.3 Cadmium, Standard Solution B (1 mL = 0.08 mg 177. Precision7
Cd)—Using a pipet, transfer 20 mL of Cadmium Solution A to 177.1 Eight laboratories cooperated in testing this test
a 250-mL volumetric flask. Add 10 mL HCl, dilute to volume, method. The data are summarized in Table 2.
and mix. Store in a polyethylene bottle.
172.4 Cadmium, Standard Solution C (1 mL = 0.02 mg
Cd)—Using a pipet, transfer 20 mL of Cadmium Solution A to TABLE 2 Statistical Information
a 250-mL volumetric flask. Add 10 mL HCl, dilute to volume, Reproduci-
Cadmium Repeatability
Test Specimen bility
and mix. Store in a polyethylene bottle. Found, % (R1, E173)
(R2, E173)
Pure aluminum (Aluminum As- 0.0018 0.00008 0.0005
173. Calibration sociation 1080 alloy, 99.80 %
Al)
173.1 Calibration Solutions: A
Pure aluminum (Aluminum As- 0.011 0.002
173.1.1 0.001 to 0.05 % Cadmium—Using pipets, transfer 0, sociation 1075 alloy, 99.75 %
5, 10, 15, 20, and 25 mL of Cadmium Solution C to 100-mL Al)
Aluminum-copper alloy (Alumi- 0.191 0.007 0.025
volumetric flasks. Add 20 mL of aluminum solution (171.1) to num Association X2020 Al-
each flask, dilute to volume, and mix. loy, 4 Cu-1 Li-0.6 Mn-0.2 Cd)
173.1.2 0.05 to 0.50 % Cadmium—Using pipets, transfer 0, A
R1 is indeterminate because no deviations were observed in the pairs of
5, 10, 15, 20, and 25 mL of Cadmium Solution B to 200-mL determinations, which were carried to only three decimal places.
volumetric flasks. Add 8 mL of aluminum solution (171.1) to
each flask, dilute to volume, and mix.
ZIRCONIUM BY THE ARSENAZO III
173.2 Since sensitivity may vary among instruments, deter- PHOTOMETRIC
mine the suitability of the selected concentration range and TEST METHOD
apparatus as directed in Guide E1024. Scale expansion may be
required to meet the minimum response criteria for some
ranges. Sample and calibration solutions always must contain 178. Scope
the same quantity of aluminum per millilitre. 178.1 This test method covers the determination of zirco-
nium in concentrations from 0.01 to 0.3 %.
174. Procedure
174.1.1 Transfer a 1.00-g sample, weighed to the nearest 1
mg, to a 400-mL beaker. Add 22 mL of HCl (1+1) in small 7
Supporting data are available from ASTM Headquarters. Request RR:E01-
increments. After the reaction has subsided, heat to hasten 1066.
6
E34 – 11
179.1 Zirconium in hydrochloric acid reacts with Arsenazo (1+3) and heat gently until dissolution of the salts is complete.
III to form a complex suitable for photometric measurement at Cool, transfer to a 1-L volumetric flask, dilute to volume with
approximately 665 nm. HCl (1+3), and mix.
180. Concentration Range 183.5.2 Transfer 0.354 g of zirconyl chloride octahydrate
180.1 The recommended concentration range is from 0.002 (ZrOCl 2·8H2O) to a 250-mL beaker and add 100 mL of HCl
to 0.030 mg of zirconium per 50 mL of solution, using a 1-cm (1+3). Boil for 5 min. Cool, transfer to a 1-L volumetric flask,
cell. dilute to volume with HCl (1+3), and mix. Standardize as
NOTE 7—This test method has been written for cells having a 1-cm follows: Using a pipet, transfer 200 mL to a 400-mL beaker.
light path. Cells having other dimensions may be used, provided suitable Add 2 mL of H2O2 and 25 mL of the (NH4)2HPO4 solution. An
adjustments can be made in the amounts of sample and reagents used. excess of H 2O2 must be present at all times. Filter using a 9-cm
medium paper containing ashless paper pulp and wash thor-
181. Stability of Color
oughly with cold NH 4NO3 solution. Transfer the paper to a
181.1 The color develops within 5 min and is stable for 3 h;
platinum crucible, dry, and ignite carefully so that the paper
however, because of the possible loss of hydrochloric acid, it is
chars but does not flame. When the paper is charred, gradually
advisable to take photometric readings promptly and to use
increase the temperature until all the carbon is gone, and then
covered absorption cells.
heat at 1050°C for 15 min. Cool in a desiccator and weigh as
182. Interferences
zirconium pyrophosphate (ZrP2O7).
182.1 Strong oxidants, reductants, sulfates, and fluorides
interfere. Concentrations of fluoride and sulfate in the final 183.6 Zirconium, Standard Solution B (1 mL = 0.005 mg
solution must be less than 2 µg/mL and 1 mg/mL, respectively. Zr)—Using a pipet, transfer 5 mL of Zirconium Solution A to
The elements ordinarily present in aluminum and aluminum- a 100-mL volumetric flask. Add 2.5 mL of HCl, cool, dilute to
base alloys do not interfere if their concentrations are under the volume with HCl (1+1), and mix. Do not use a solution which
maximum limits shown in 1.1. has stood for more than 8 h.
183. Reagents
183.1 Aluminum Solution (1 mL = 25 mg Al)—Dissolve 45 184. Preparation of Calibration Curve
g of aluminum chloride hexahydrate (AlCl3·6H2O) in about 184.1 Calibration Solutions—Using pipets, transfer 1, 2, 3,
150 mL of HCl (1+1). Transfer to a 200-mL volumetric flask, 4, 5, and 6 mL of Zirconium Solution B to six 50-mL
dilute to volume with HCl (1+1), and mix. volumetric flasks containing 10 mL of HCl (1+1). Add 2 mL of
183.2 Ammonium Nitrate Wash Solution (50 g/L)—Dissolve aluminum solution (1 mL = 25 mg Al). Proceed as directed in
25 g of ammonium nitrate (NH4NO 3) in about 400 mL of 184.3.
water and dilute to 500 mL. 184.2 Reference Solution—Transfer 2 mL of aluminum
183.3 Arsenazo III Solution (2.5 g/L)—Dissolve 0.250 g of solution (1 mL = 25 mg Al) to a 50-mL volumetric flask
Arsenazo III [2,28-(1,8-dihydroxy-3,6-disulfonaphthylene2,7- containing 10 mL of HCl (1+1). Proceed as directed in 184.3.
diazodibenzenearsonic acid)] in 90 mL of water containing 300 184.3 Color Development—Using a pipet, add 1 mL of
mg of sodium carbonate (Na2CO 3), and heat gently. Using a Arsenazo III solution, dilute to volume with HCl (1+1), and
pH meter, adjust the pH to 4.0 6 0.1 with HCl (1+1), and cool. mix.
Transfer to a 100-mL volumetric flask, dilute to volume, and 184.4 Photometry:
mix. This solution is stable at least 6 months.
184.4.1 Determine the wavelength of maximum absorbance
NOTE 8—Some lots of reagent have been found to be completely (Note 8) by taking photometric readings of the calibration
unsatisfactory. Therefore, the reagent should be checked with a standard solution containing 0.020 mg of zirconium over the range from
zirconium solution before use in this test method. A satisfactory reagent
600 to 700 nm. Between 630 and 670 nm, take 5-nm
should give an absorbance of about 0.8 for the high standard (0.6 µg/mL
Zr) at 665 nm using 1-cm cells.8 increments. Using the reference solution, adjust the photometer
to the initial setting before each reading.
183.4 Diammonium Phosphate Solution (120 g/L)—
Dissolve 60 g of diammonium phosphate ((NH4)2HPO4) in NOTE 9—The maximum absorbance of the zirconium-Arsenazo III
about 400 mL of water and dilute to 500 mL. complex normally occurs at 665 nm. It is advisable to verify this
183.5 Zirconium, Standard Solution A (1 mL = 0.100 mg absorption maximum for each new lot of Arsenazo III.
Zr)—Prepare as described in 183.5.1 or 183.5.2. Store in a 184.4.2 Multiple Cell Photometer—Measure the cell correc-
polyethylene bottle. tion using stoppered absorption cells with a 1-cm light path and
183.5.1 Transfer 0.100 g of zirconium (purity: 99.5 % min) a light band centered at the wavelength determined in 184.4.1.
to a 250-mL beaker. Add 30 mL of methanol (CH3OH) and, Using the test cell, take the photometric readings of the
while cooling, 5 mL of bromine (Br2). When the reaction has calibration solutions.
ceased, heat gently to complete the attack. Add 20 mL of HCl 184.4.3 Single Cell Photometer—Transfer a suitable portion
and evaporate to moist salts but do not bake. Add 75 mL of HCl of the reference solution to a stoppered absorption cell having
a 1-cm light path and adjust the photometer to the initial setting
using a light band centered at the wavelength determined in
8
Aldrich Chemical Co. Reagent No. A9277-5 and G. Frederick Smith Chemical 184.4.1. While maintaining this adjustment, take the photomet-
Co. Reagent No. 594 have been found to be suitable for this purpose. ric readings of the calibration solutions.
7
E34 – 11
184.5 Calibration Curve—Plot the net photometric readings 189. Summary of Test Method
of the calibration solutions against milligrams of zirconium per 189.1 An acid solution of the sample is aspirated into the
50 mL of solution. air-acetylene flame of an atomic absorption spectrophotometer.
185. Procedure The absorption by the sample solution of the bismuth reso-
185.1 Test Solution: nance line at 2230Å and the lead resonance line at 2833 Å is
185.1.1 Transfer a 0.200-g sample, weighed to the nearest measured and compared with the absorption of calibration
0.5 mg, to a 250-mL beaker. solutions containing known amounts of bismuth and lead. The
185.1.2 Add 20 mL of HCl (1+1), heat until dissolution is 2170-Å lead resonance line may be used successfully on some
complete, and evaporate carefully to moist salts. Cool, add instruments, especially if an electrodeless discharge lamp is
about 180 mL of HCl (1+1), and heat gently to dissolve salts. employed.
185.1.3 Cool and transfer to a 200-mL volumetric flask, 190. Concentration Range
ignoring any remaining residue. Dilute to volume with HCl 190.1 If the optimum concentration range is not known,
(1+1), and mix. Allow any residue to settle. determine it as directed in Guide E1024. A sensitivity of 0.4 to
185.1.4 Using a pipet, transfer to a 50-mL volumetric flask, 0.8 µg/mL for 0.0044 absorbance for bismuth, and 0.4 to 0.8
20 mL if the expected zirconium concentration is less than µg/mL for 0.0044 absorbance for lead using the 2833-Å line is
0.10 %, 10 mL if the expected zirconium concentration is widely obtained. At 2170Å, the sensitivity for lead is 0.2
between 0.10 and 0.20 %, or 5 mL if the expected zirconium µg/mL for 0.0044 absorbance.
concentration is between 0.20 and 0.30 %. Add 2 mL of 191. Interferences
aluminum solution (1 mL = 25 mg Al). 191.1 Elements normally present do not interfere if their
185.2 Reference Solution—Proceed as directed in 184.2. concentrations are less than the maximum limits shown in 1.1.
185.3 Color Development—Proceed as directed in 184.3. 192. Apparatus
185.4 Photometry—Take the photometric reading of the test 192.1 Atomic Absorption Spectrophotometer—Determine
solution as directed in 184.4.2 or 184.4.3. that the instrument is suitable for use as prescribed in Guide
186. Calculation E1024. The percent variability for the highest calibration
186.1 Convert the net photometric reading of the test solution (Vc) should not exceed 1 %.
solution to milligrams of zirconium by means of the calibration 193. Reagents
curve. Calculate the percentage of zirconium as follows:
193.1 Aluminum Solution (1 mL = 50 mg Al)—Transfer 25 g
A of aluminum (purity: 99.99 % min) to a 1-L beaker. Add 100
Zirconium, % 5 B 3 10 (3)
mL of water and a small drop of mercury. Add 315 mL of HCl
where: in small increments, heating moderately to accelerate the
A = zirconium found in 50 mL of the final test solution, dissolution. When dissolution is complete, add 2 mL of H2O2
mg, and (30 %) and boil gently for 5 min. Cool, transfer to a 500-mL
B = sample represented in 50 mL of the final test solution, volumetric flask, dilute to volume, and mix. Store in a
g. polyethylene bottle.
193.2 Bismuth, Standard Solution A (1 mL = 0.40 mg
187. Precision9 Bi)—Transfer 0.400 g of bismuth (purity: 99.9 % min) to a
185.1 Seven laboratories cooperated in testing this test 400-mL beaker and dissolve in 50 mL of HNO3 (1+1), heating
method and obtained eight sets of data summarized in Table 3. gently if necessary. When dissolution is complete, boil for 5
min, cool, and transfer to a 1-L volumetric flask. Add 100 mL
TABLE 3 Statistical Information of HNO3 (1+1), dilute to volume, and mix. Store in a
Zirconium Repeatability Reproducibility
polyethylene bottle.
Test Specimen 193.3 Bismuth, Standard Solution B (1 mL = 0.04 mg
Found, % (R1, E173) (R2, E173)
1. 6151 alloy 0.023 0.0027 0.0033 Bi)—Using a pipet, transfer 25 mL of Bismuth Standard
2. 2219 alloy 0.152 0.0097 0.019 Solution A to a 250-mL volumetric flask. Dilute to volume and
3. 7046 alloy 0.282 0.0278 0.060 mix. Do not use a solution that has stood for more than 24 h.
193.4 Lead, Standard Solution A (1 mL = 0.40 mg Pb)—
Transfer 0.400 g of lead (purity: 99.9 % min) to a 400-mL
BISMUTH AND LEAD BY THE ATOMIC beaker and proceed in accordance with 193.2.
ABSORPTION 193.5 Lead, Standard Solution B (1 mL = 0.04 mg Pb)—
TEST METHOD Dilute Lead Standard Solution A as directed in 193.3.
188. Scope 194. Calibration

188.1 This test method covers the determination of bismuth 194.1 Calibration Solutions:
in concentrations from 0.02 to 1.0 %, and lead in concentra- 194.1.1 0.01 to 0.10 % Bi or Pb—Using pipets, transfer 5,
tions from 0.01 to 1.0 %. 10, 15, 20, and 25-mL portions of the appropriate Standard
Solution B to 100-mL volumetric flasks. Add 20 mL of
9
Supporting data are available from ASTM Headquarters. Request RR:E01- aluminum solution and 10 mL of HNO3 (1+1). Cool, dilute to
1070. volume, and mix.
8
E34 – 11
194.1.2 0.10 to 1.0 % Bi or Pb—Using pipets, transfer 5, 10, TABLE 4 Statistical Information
15, 20, and 25-mL portions of the appropriate Standard Test Specimen
Bismuth Repeatability Reproducibility
Solution A to 250-mL volumetric flasks. Add 20 mL of Found, % (R1, E173) (R2, E173)
1000 0.033 0.0046 0.008
aluminum solution and 10 mL of HNO3 (1+1). Cool, dilute to KS-0010-12 6262 alloy 0.60 0.0089 0.024
volume, and mix.
194.2 Reference Solution—Prepare a reference solution by
adding the appropriate amount of aluminum solution and 10 TABLE 5 Statistical Information
mL of HNO3 (1+1) to the appropriate size volumetric flask. Lead Repeatability Reproducibil-
Test Specimen
Dilute to volume and mix. Found, % (R1, E173) ity (R2, E173)
194.3 Since sensitivity may vary among instruments, deter- NBS 85b 2024 alloy 0.021 0.0014 0.003
mine the suitability of the selected concentration range and (0.021 % Pb)
BCS No. 181/2 2218 alloy 0.041 0.0029 0.005
apparatus as directed in Guide E1024. Scale expansion may be (0.04 % Pb)
required to meet the minimum response criteria for some KS-0010-12 6262 alloy 0.55 0.015 0.044
ranges. Sample and calibration solutions always must contain
the same quantity of aluminum per millilitre.
195. Procedure comparing accepted reference values with the corresponding
195.1 Test Solution: arithmetic averages obtained by interlaboratory testing.
195.1.1 Transfer a 1.000-g sample, weighed to the nearest 1
mg, to a 400-mL beaker. Add 20 mL of water and 25 mL of CHROMIUM BY THE ATOMIC ABSORPTION
HCl (1+1) in small increments, and cover with a borosilicate TEST METHOD
cover glass. When the reaction subsides, add 10 mL of HNO3
(1+1) and boil for 5 min. 199. Scope
195.1.2 Filter using a medium paper into a 100-mL volu- 199.1 This test method covers the determination of chro-
metric flask when the bismuth or lead content is expected to be mium in concentrations from 0.01 to 1.0 %.
0.10 % or less, or into a 250-mL volumetric flask when the 200. Summary of Test Method
bismuth or lead content is expected to be greater than 0.10 %. 200.1 An acid solution of the sample is aspirated into the
Wash the residue with hot water and reserve the filtrate. nitrous oxide-acetylene flame of an atomic absorption spectro-
195.1.3 When the silicon content is 0.5 % or greater, transfer photometer. The absorption of the chromium resonance line at
the filter paper and residue to a platinum crucible, dry, and 3579 Å is measured and compared with the absorption of
ignite at 550°C. Cool, add 5 mL of HF, and then add HNO3 calibration solutions containing known amounts of chromium.
dropwise until a clear solution is obtained. Evaporate to 201. Concentration Range
dryness, cool, and dissolve the residue in 5 drops of HCl (1+1) 201.1 If the optimum concentration range is not known,
and a minimum amount of water. Add this solution to the determine it as directed in Guide E1024. A sensitivity of 0.1 to
reserved filtrate obtained in 195.1.2. 0.2 µg/mL for 0.0044 absorbance is widely obtained.
195.1.4 Cool the solution obtained in 195.1.2 or the com- 202. Interferences
bined filtrates obtained in 195.1.3. Dilute to volume and mix. 202.1 Elements normally present do not interfere if their
196. Measurements concentrations are less than the maximum limits shown in 1.1.
196.1 Optimize the response of the instrument and take 203. Apparatus
preliminary readings; then complete the analysis and determine 203.1 Atomic Absorption Spectrophotometer—Determine
the concentration of bismuth or lead using the graphical, ratio, that the instrument is suitable for use as prescribed in Guide
or single-point procedure, as described in Guide E1024. E1024. The percent variability for the highest calibration
197. Calculations solution (Vc) should not exceed 1 %.
197.1 Calculate the percentage of bismuth or lead as follows: 204. Reagents
A
204.1 Aluminum Solution (1 mL = 50 mg Al)—Transfer 25 g
Bismuth or lead, % 5 B 3 100 (4) of aluminum (purity: 99.99 % min) to a 1-L beaker. Add 100
mL of water and a small drop of mercury. Add 275 mL of HCl
where: in small increments, heating moderately to accelerate the
A = bismuth or lead in the final test solution, mg, and dissolution. When dissolution is complete, add 2 mL of H2O2
B = sample represented in the test solution taken for (30 %) and boil gently for 5 min. Cool, transfer to a 500-mL
analysis, mg. volumetric flask, dilute to volume, and mix. Store in a polyeth-
198. Precision and Bias10 ylene bottle.
198.1 Precision—Eight laboratories cooperated in testing 204.2 Chromium Standard Solution A (1 mL = 0.40 mg
this test method. The precision of this test method can be Cr)—Transfer 0.400 g of chromium (purity: 99.9 % min) to a
estimated by examining the data in Tables 4 and 5 400-mL beaker containing 50 mL of water. Dissolve the metal
198.2 Bias—No information on the accuracy of this test with 15 mL of HCl. Transfer the solution to a 1-L volumetric
method is available. The accuracy may be judged, however, by flask, dilute to volume, and mix. Store in a polyethylene bottle.
204.3 Chromium Standard Solution B (1 mL = 0.04 mg
10
Supporting data are available from ASTM Headquarters. Request RR:E01- Cr)— Using a pipet, transfer 25 mL of Chromium Solution A to
1073. a 250-mL volumetric flask. Dilute to volume and mix.
9
E34 – 11
205. Calibration A = chromium in the final test solution, mg, and
205.1 Calibration Solutions: B = sample represented in the test solution taken for
205.1.1 0.01 to 0.10 % Cr—Using pipets, transfer 0, 5, 10, analysis, mg.
15, 20, and 25 mL of the Chromium Standard Solution B to
100-mL volumetric flasks. Add 20 mL of aluminum solution,
dilute to volume, and mix.
TABLE 6 Statistical Information
205.1.2 0.1 to 1.0 % Cr—Using pipets, transfer 0, 5, 10, 15,
Reproduci-
20, and 25 mL of Chromium Standard Solution B to 100-mL Test Specimen
Chromium Repeatability
bility (R2,
volumetric flasks. Add 2 mL of aluminum solution and 5 mL of Found, % (R1, E173)
E173)
HCl (1+1). Cool, dilute to volume, and mix. MD 184 0.010 0.0009 0.002
205.2 Reference Solution—The 0 calibration solution is used NBS 85b 2024 alloy (0.211 % Cr) 0.21 0.008 0.014
KNB 793-96 0.80 0.015 0.032
as the reference solution.
205.3 Since sensitivity may vary among instruments, deter-
mine the suitability of the selected concentration range and
apparatus as directed in Guide E1024. Scale expansion may be 209. Precision and Bias11
required to meet the minimum response criteria for some 209.1 Precision—Nine laboratories cooperated in testing this
ranges. Sample and calibration solutions always must contain test method. The precision of the test method can be estimated
the same quantity of aluminum per millilitre. by examining the data in Table 6.
209.2 Bias—No information on the accuracy of this test
206. Procedure method is available. The accuracy may be judged, however, by
206.1 Test Solution: comparing the accepted reference values with the correspond-
206.1.1 Transfer a 1.000-g sample, weighed to the nearest 1 ing arithmetic averages obtained by interlaboratory testing.
mg, to a 400-mL beaker. Add 20 mL of water and 22 mL of
HCl (1+1) in small increments. Cover with a ribbed cover glass COPPER AND ZINC BY THE ATOMIC ABSORPTION
and when the reaction subsides, add 2 mL of H2O2 (30 %) and TEST METHOD
boil for 5 min. 210. Scope
206.1.2 Filter through a medium paper into a 100-mL 210.1 This test method covers the determination of copper in
volumetric flask. Wash with hot water and reserve the filtrate. concentrations from 0.01 to 10 %, and zinc in concentrations
206.1.3 When the silicon content is 0.5 % or greater, transfer from 0.003 to 10 %.
the filter paper and residue to a platinum crucible, dry, and 211. Summary of Test Method
ignite at 500°C. Cool, add 5 mL of HF, and then add HNO3 211.1 An acid solution of the sample is aspirated into the
dropwise until a clear solution is obtained. Evaporate to air-acetylene flame of an atomic absorption spectrophotometer.
dryness, cool, and dissolve the residue in 5 drops of HCl (1+1) The absorption by the sample of the copper resonance line at
and a minimum amount of water. Add this solution to the 3247 Å and the zinc resonance line at 2139 Å is measured and
reserved filtrate obtained in 206.1.2. compared with the absorption of calibration solutions contain-
206.1.4 Cool the solution obtained in 206.1.2 or the com- ing known amounts of copper or zinc.
bined filtrates obtained in 206.1.3. Dilute to volume and mix. 212. Concentration Range
This is Sample Solution A. 212.1 If the optimum concentration range is not known,
206.1.5 Pipet 10 mL of Sample Solution A into a 100-mL determine it as directed in Guide E1024. A sensitivity of 0.05
volumetric flask containing 5 mL of HCl (1+1). Dilute to to 0.10 µg/mL for 0.0044 absorbance is widely obtained for
volume and mix. This is Sample Solution B. copper and 0.02 to 0.06 µg/mL for zinc.
206.1.6 When the chromium concentration is less than 213. Interferences
0.10 %, aspirate Sample Solution A into the flame using the 213.1 Elements normally present do not interfere when their
standards from 205.1.1 concentrations are less than the maximum limits shown in 1.1.
206.1.7 When the chromium content is between 0.10 and 214. Apparatus
1.0 %, aspirate Sample Solution B into the flame using 214.1 Atomic Absorption Spectrophotometer—Determine
standards from 205.1.2. that the instrument is suitable for use as prescribed in Guide
207. Measurements E1024. The percent variability for the highest calibration
207.1 Optimize the response of the instrument and take solution (Vc) should not exceed 1 %.
preliminary readings; then complete the analysis and determine 215. Reagents
the chromium concentration using the graphical, ratio, or 215.1 Aluminum Solution A (1 mL = 50 mg Al)—Transfer 25
single-point procedure, as described in Guide E1024. g of aluminum chips (purity: 99.99 % min) to a 1-L beaker.
208. Calculation Add 100 mL of water and a small drop of mercury. Add 275
208.1 Calculate the percentage of chromium as follows: mL of HCl in small increments, heating moderately to accel-
erate dissolution. When dissolution is complete, add 2 mL of
A
Chromium, % 5 B 3 100 (5)
11
where:
1074.
10
E34 – 11
H2O2 (30 %) and boil gently for 5 min. Cool, transfer to a 217.1.3 When the silicon content is 0.5 % or greater, transfer
500-mL volumetric flask, dilute to volume, and mix. Store in a the filter paper and residue to a platinum crucible, dry, and
polyethylene bottle. ignite at 500°C. Cool, add 5 mL of HF, and then add HNO3
215.2 Aluminum Solution B (1 mL = 2.50 mg Al)—Pipet 25 dropwise until a clear solution is obtained. Evaporate carefully
mL of Aluminum Solution A into a 500-mL volumetric flask, to dryness, cool, and dissolve the residue in 5 drops of HCl
dilute to volume, and mix. Store in a polyethylene bottle. (1+1) and minimum amount of water. Heat to dissolve the salts
215.3 Copper Solution A (1 mL = 1.00 mg Cu)—Transfer and add this solution to the filtrate reserved in 217.1.2.
1.000 g of copper (purity: 99.9 % min) to a 250-mL beaker. 217.1.4 Cool the solution from 217.1.2 or the combined
Add 5 mL of water, cover, and dissolve in 3 mL of HNO3. After filtrates obtained in 217.1.3. Dilute to volume and mix. This is
dissolution is complete, boil to remove oxides of nitrogen, Sample Solution A.
cool, transfer to a 1-L volumetric flask, dilute to volume, and 217.1.5 Pipet 10 mL of Sample Solution A into a 100-mL
mix. Store in a polyethylene bottle. volumetric flask containing 8 mL of HCl (1+1), dilute to
215.4 Zinc Solution A (1 mL = 1.00 mg Zn)—Transfer 1.000 volume, and mix. This is Sample Solution B.
g of zinc (purity: 99.9 % min) to a 400-mL beaker containing 217.1.6 For copper or zinc concentrations less than 0.1 %,
50 mL of water. Dissolve in 3 mL of HCl. Transfer the solution pipet 50 mL of Sample Solution A into a 100-mL volumetric
to a 1-L volumetric flask, dilute to volume, and mix. Store in flask containing 6.5 mL of HCl (1+1), dilute to volume, and
a polyethylene bottle. mix. Use standards prepared in accordance with 216.1.1.
215.5 Copper and Zinc Standard Solution B (1 mL = 0.04 217.1.7 If the copper or zinc content is between 0.1 and
mg Cu and 0.04 mg Zn)—Pipet 10 mL of Copper Solution A 0.5 %, use Sample Solution B. Use standards prepared in
and 10 mL of Zinc Solution A into a 250-mL volumetric flask, 216.1.2.
dilute to volume, and mix. Store in a polyethylene bottle. 217.1.8 If the copper or zinc content is between 0.5 and
2.5 %, pipet 20 mL of Sample Solution B into a 100-mL
216. Calibration volumetric flask containing 6.5 mL of HCl (1+1), dilute to
216.1 Calibration Solutions: volume, and mix. Use standards prepared in accordance with
216.1.1 0.02 to 0.1 % Cu and Zn—Using pipets, transfer 0, 216.1.3.
5, 10, 15, 20, and 25 mL of Copper-Zinc Standard Solution B 217.1.9 If the copper or zinc content is between 2 and 10 %,
to 200-mL volumetric flasks. Add 20 mL of Aluminum pipet 10 mL of Sample Solution B into a 200-mL volumetric
Solution A and 13 mL of HCl (1+1). Dilute to volume and mix. flask containing 16 mL of HCl (1+1), dilute to volume, and
216.1.2 0.1 to 0.5 % Cu and Zn—Using pipets, transfer 0, 5, mix. Use standards prepared in accordance with 216.1.4.
10, 15, 20, and 25 mL of Copper-Zinc Standard Solution B to 218. Measurements
200-mL volumetric flasks. Add 4 mL of Aluminum Solution A 218.1 Optimize the instrument response and take prelimi-
and 16 mL of HCl (1+1). Cool, dilute to volume, and mix. nary readings; then complete the analysis and determine the
216.1.3 0.5 to 2.5 % Cu and Zn—Using pipets, transfer 0, 5, copper or zinc concentration using the graphical, ratio, or
10, 15, 20, and 25 mL of Copper-Zinc Standard Solution B to single-point procedure, as described in Guide E1024.
200-mL volumetric flasks. Add 16 mL of Aluminum Solution 219. Calculation
B and 16 mL of HCl (1+1). Cool, dilute to volume, and mix. 219.1 Calculate the percentage of copper or zinc as follows:
216.1.4 2.0 to 10 % Cu and Zn—Using pipets, transfer 0, 5,
A
10, 15, 20, and 25-mL of Copper-Zinc Standard Solution B to Copper or zinc, % 5 B 3 100 (6)
200-mL volumetric flasks. Add 4 mL of Aluminum Solution B
and 17 mL of HCl (1+1). Cool, dilute to volume, and mix.
216.2 Reference Solution—The 0 calibration solution is used where:
for the reference solution for each range of calibration. A = copper or zinc in the final test solution, mg, and
216.3 Since sensitivity may vary among instruments, deter- B = sample represented in the test solution taken for
mine the suitability of the selected concentration range and analysis, mg.
required to meet the minimum response criteria for some 220. Precision and Bias12
ranges. Sample and calibration solutions always must contain 220.1 Precision—Eight laboratories cooperated in testing
the same quantity of aluminum per millilitre. this test method. The precision of this test method can be
217. Procedure estimated by examining the data in Tables 7 and 8.
217.1 Test Solution: 220.2 Bias—No information on the accuracy of this test
217.1.1 Transfer a 1.000-g sample, weighed to the nearest 1 method is available. The accuracy may be judged, however, by
mg, to a 400-mL beaker. Add 20 mL of water and 22 mL of comparing accepted reference values with the corresponding
HCl (1+1). Warm, if necessary, to complete dissolution. When arithmetic averages obtained by interlaboratory testing.
the reaction subsides, add 2 mL of H2O 2(30 %) and boil for 5
min.
217.1.2 Filter on a medium paper into a 100-mL volumetric 12
flask. Wash the residue with hot water. Reserve the filtrate. 1075.
11
E34 – 11
TABLE 7 Statistical Information metal with 15 mL of HCl. Transfer the solution to a 1-L
Test Specimen
Copper Repeatability Reproducibil- volumetric flask, dilute to volume, and mix. Store in a polyeth-
Found, % (R1, E173) ity (R2, E173) ylene bottle.
1. 5082 alloy 0.050 0.0019 0.0035 226.3 Manganese Standard Solution B (1 mL = 0.04 mg
2. 7049 alloy 1.16 0.058 0.075
3. BCS No. 216/2 2014 4.52 0.054 0.24
Mn)—Using a pipet, transfer 25 mL of Manganese Standard
alloy (4.56 % Cu) Solution A to a 250-mL volumetric flask. Dilute to volume and
4. 2219 alloy 6.18 0.093 0.26 mix.
226.4 Iron Standard Solution A (1 mL = 0.40 mg Fe)—
Transfer 0.400 g of iron wire (purity: 99.9 % min) to a 400-mL
TABLE 8 Statistical Information
beaker and proceed in accordance with 226.2.
Zinc Repeatability Reproducibil-
Test Specimen
Found, % (R1, E173) ity (R2, E173)
226.5 Iron Standard Solution B (1 mL = 0.04 mg Fe)—
Dilute Iron Standard Solution A in accordance with 226.3.
1. 5082 alloy 0.0028 0.0013 0.0016
2. 2219 alloy 0.036 0.0031A 0.0028
3. BCS No. 216/2 2014 0.20 0.0021 0.0094 227. Calibration
alloy (0.20 % Zn)
4. 7049 alloy 7.60 0.25 0.25
227.1 Calibration Solutions:
A
227.1.1 0.01 to 0.10 % Mn or Fe—Using pipets, transfer 0,
R1 appears higher than R2 because one of the eight laboratories that
participated showed much poorer repeatability than the others for this sample. 5, 10, 15, 20, and 25 mL of the appropriate Standard Solution
B to 100-mL volumetric flasks. Add 20 mL of aluminum
solution. Cool, dilute to volume, and mix.
IRON AND MANGANESE BY THE ATOMIC 227.1.2 0.1 to 1.0 % Mn or Fe—Using pipets, transfer 0, 5,
ABSORPTION 10, 15, 20, and 25 mL of the appropriate Standard Solution B
TEST METHOD to 100-mL volumetric flasks. Add 2 mL of aluminum solution
and 5 mL HCl (1+1). Cool, dilute to volume, and mix.
221. Scope
227.1.3 1.0 to 2.0 % Mn or Fe—Using pipets, transfer 0, 5,
221.1 This test method covers the determination of iron in
10, 15, 20, and 25 mL of the appropriate Standard Solution B
concentrations from 0.02 to 2.0 %, and manganese in concen-
to 100-mL volumetric flasks. Add 1 mL of aluminum solution
trations from 0.01 to 2.0 %.
and 5 mL HCl (1+1). Cool, dilute to volume, and mix.
222.1 An acid solution of the sample is aspirated into the 227.2 Reference Solution—The 0 calibration solution is used
air-acetylene flame of an atomic absorption spectrophotometer. as the reference solution.
The absorption of the iron resonance line at 2483 Å and the 227.3 Since sensitivity may vary among instruments, deter-
manganese resonance line at 2795 Å is measured and com- mine the suitability of the selected concentration range and
pared with the absorption of calibration solutions containing apparatus as directed in Guide E1024. Scale expansion may be
known amounts of manganese or iron. required to meet the minimum response criteria for some
223. Concentration Range ranges. Sample and calibration solutions always must contain
223.1 If the optimum concentration range is not known, the same quantity of aluminum per millilitre.
determine it as directed in Guide E1024. A sensitivity of 0.1 to 228. Procedure
0.2 µg/mL for 0.0044 absorbance for manganese and iron is 228.1 Test Solution:
widely obtained. 228.1.1 Transfer a 1.000-g sample, weighed to the nearest 1
224. Interferences mg, to a 400-mL beaker. Add 20 mL of water and 22 mL of
224.1 Elements normally present do not interfere if their HCl (1+1) in small increments, and cover with a ribbed cover
concentrations are less than the maximum limits shown in 1.1. glass. When the reaction subsides, add 2 mL of H2O2 (30 %)
225. Apparatus and boil for 5 min.
225.1 Atomic Absorption Spectrophotometer—Determine 228.1.2 Filter through a medium paper into a 100-mL
that the instrument is suitable for use as prescribed in Guide volumetric flask. Wash the residue with hot water and reserve
E1024. The percent variability for the highest calibration the filtrate.
solution (Vc) should not exceed 1 %. 228.1.3 When the silicon content is 0.5 % or greater, transfer
226. Reagents the filter paper and residue to a platinum crucible, dry, and
226.1 Aluminum Solution (1 mL = 50 mg Al)—Transfer 25 g ignite at 500°C. Cool, add 5 mL of HF, and then add HNO3,
of aluminum chips (purity: 99.99 % min) to a 1-L beaker. Add dropwise, until a clear solution is obtained. Evaporate to
100 mL of water and a small drop of mercury. Add 275 mL of dryness, cool, and dissolve the residue in 5 drops of HCl (1+1)
HCl in small increments, heating moderately to accelerate and a minimum amount of water. Add this solution to the
dissolution. When dissolution is complete, add 2 mL of H2O2 reserved filtrate obtained in 228.1.2.
(30 %) and boil gently for 5 min. Cool, transfer to a 500-mL 228.1.4 Cool the solution obtained in 228.1.2 or the com-
volumetric flask, dilute to volume, and mix. Store in a polyeth- bined filtrates obtained in 228.1.3. Dilute to volume and mix.
ylene bottle. This is Sample Solution A.
226.2 Manganese Standard Solution A (1 mL = 0.40 mg 228.1.5 Pipet 10 mL of Sample Solution A into a 100-mL
Mn)—Transfer 0.400 g of manganese metal (purity: 99.9 % volumetric flask containing 5 mL of HCl (1+1), dilute to
min) to a 400-mL beaker containing 50 mL water. Dissolve the volume, and mix. This is Sample Solution B.
12
E34 – 11
228.1.6 Pipet 5 mL of Sample Solution A into a 100-mL MAGNESIUM BY THE ATOMIC ABSORPTION TEST
volumetric flask containing 5 mL of HCl (1+1), dilute to METHOD
volume, and mix. This is Sample Solution C 232. Scope
228.1.7 When the manganese or iron concentration is less 232.1 This test method covers the determination of magne-
than 0.10 %, aspirate Sample Solution A and use calibration sium in concentrations from 0.002 to 5.0 %.
solutions prepared in accordance with 227.1.1. 233. Summary of Test Method
228.1.8 When the manganese or iron concentration is be- 233.1 An acid solution of the sample is aspirated into the
tween 0.10 and 1.0 %, aspirate Sample Solution B and use nitrous oxide-acetylene flame of an atomic absorption spectro-
calibration solutions prepared in accordance with 227.1.2. photometer. The absorption of the magnesium resonance line at
228.1.9 When the manganese or iron concentration is be- 2852 Å is measured and compared with the absorption of
tween 1.0 and 2.0 %, aspirate Sample Solution C and use calibration solutions containing known amounts of magne-
calibration solutions prepared in accordance with 227.1.3. sium.
229. Measurements 234. Concentration Range
229.1 Optimize the instrument response and take prelimi- 234.1 If the optimum concentration range is not known,
nary readings, then complete the analysis and determine the determine it as directed in Guide E1024. A sensitivity of 0.01
manganese or iron concentration using the graphical, ratio, or to 0.03 µg/mL for 0.0044 absorbance is widely obtained for
single-point procedure described in Guide E1024. magnesium.
230. Calculation
235. Interferences
230.1 Calculate the percentage of manganese or iron as
235.1 Elements normally present do not interfere if their
follows:
concentrations are less than the maximum limits shown in 1.1.
A 236. Apparatus
Manganese or iron, % 5 B 3 100 (7)
236.1 Atomic Absorption Spectrophotometer—Determine
where: that the instrument is suitable for use as prescribed in Guide
A = manganese or iron in the final test solution, mg, and E1024. The percent variability for the highest calibration
B = sample represented in the test solution taken for solution (Vc) should not exceed 1 %.
analysis, mg. 237. Reagents
237.1 Aluminum Solution A (1 mL = 50 mg Al)—Transfer 25
231. Precision and Bias13 g of aluminum chips (purity: 99.999 % min) to a 1-L beaker.
231.1 Precision—Ten laboratories cooperated in testing this Add 100 mL of water and a small drop of mercury. Add 275
test method. The precision of this test method can be estimated mL of HCl in small increments, heating moderately to accel-
by examining the data in Tables 9 and 10. erate dissolution. When dissolution is complete, add 2 mL of
H2O2 (30 %) and boil gently for 5 min. Cool, transfer to a
500-mL volumetric flask, dilute to volume, and mix. Store in a
TABLE 9 Statistical Information polyethylene bottle.
Repeatability Reproducibil- 237.2 Aluminum Solution B (1 mL = 2.50 mg Al)—Pipet 25
Test Specimen Iron Found, %
(R1, E173) ity (R2, E173) mL of Aluminum Solution A into a 500-mL volumetric flask,
7075 alloy 0.046 0.0036 0.009 dilute to volume, and mix. Store in a polyethylene bottle.
BCS No. 181/2 2218 alloy 0.41 0.024 0.024 237.3 Aluminum Solution C (1 mL = 1.00 mg Al)—Pipet 10
(0.42 % Fe)
MD 184 1.60 0.039 0.051 mL of Aluminum Solution A into a 500-mL volumetric flask,
dilute to volume, and mix. Store in a polyethylene bottle.
237.4 Magnesium Standard Solution A (1 mL = 1.00 mg
TABLE 10 Statistical Information Mg)—Transfer 1.000 g of magnesium (purity: 99.9 % min) to
Reproduci- a 400-mL beaker. Dissolve by adding carefully, in small
Manganese Repeatability
Test Specimen bility (R2, portions, 30 mL of HCl (1+1). Transfer the solution to a 1-L
Found, % (R1, E173)
E173)
volumetric flask, dilute to volume, and mix. Store in a
MD 184 0.015 0.0009 0.003
NBS 85b 2024 alloy (0.61 % Mn) 0.60 0.015 0.023
3004 alloy 1.16 0.047 0.070 237.5 Magnesium Standard Solution B (1 mL = 0.010 mg
Mg)—Pipet 10 mL of Magnesium Solution A into a 1-L
volumetric flask, dilute to volume, and mix. Store in a
231.2 Bias—No information on the accuracy is available.
The accuracy may be judged, however, by comparing accepted 238. Calibration
reference values with the corresponding arithmetic averages 238.1 Calibration Solutions:
obtained by interlaboratory testing. 238.1.1 0.01 to 0.05 % Mg—Using pipets, transfer 0, 5, 10,
15, 20, and 25-mL portions of Magnesium Standard Solution B
to 250-mL volumetric flasks. Add 10 mL of Aluminum
13
Supporting data are available from ASTM Headquarters. Request RR:E01- Solution A and 20 mL of HCl (1+1). Cool, dilute to volume,
1076. and mix.
13
E34 – 11
238.1.2 0.05 to 0.25 % Mg—Using pipets, transfer 0, 5, 10, volume, and mix. Use the calibration solutions prepared in
15, 20, and 25-mL portions of Magnesium Standard Solution B accordance with 238.1.3.
to 250-mL volumetric flasks. Add 40 mL of Aluminum 239.1.9 When the magnesium content is between 1 and 5 %,
Solution B and 21 mL of HCl (1+1). Cool, dilute to volume, pipet 5 mL of Sample Solution B into a 250-mL volumetric
and mix. flask containing 20 mL of HCl (1+1), dilute to volume, and
238.1.3 0.2 to 1 % Mg—Using pipets, transfer 0, 5, 10, 15, mix. Use the calibration solutions prepared in accordance with
20, and 25-mL portions of Magnesium Standard Solution B to 238.1.4.
250-mL volumetric flasks. Add 10 mL of Aluminum Solution 240. Measurements
B and 21 mL of HCl (1+1). Cool, dilute to volume, and mix. 240.1 Optimize the instrument response and take prelimi-
238.1.4 1 to 5 % Magnesium—Using pipets, transfer 0, 5, 10, nary readings; then complete the analysis and determine the
15, 20, and 25-mL portions of Magnesium Standard Solution B magnesium concentration using the graphical, ratio, or single-
to 250-mL volumetric flasks. Add 5 mL of Aluminum Solution point procedure, as described in Guide E1024.
C and 21 mL of HCl (1+1). Cool, dilute to volume, and mix. 241. Calculation
238.2 Reference Solution—The 0 calibration solution is used 241.1 Calculate the percentage of magnesium as follows:
as the reference solution. A
Magnesium, % 5 B 3 100 (8)
238.3 Since sensitivity may vary among instruments, deter-
mine the suitability of the selected concentration range and
apparatus as directed in Guide E1024. Scale expansion may be where:
A = magnesium in the final test solution, mg, and
required to meet the minimum response criteria for some
B = sample represented in the test solution taken for
ranges. Sample and calibration solutions always must contain
analysis, mg.
the same quantity of aluminum per millilitre.
239. Procedure
242. Precision and Bias14
239.1 Test Solution: 242.1 Precision—Eight laboratories cooperated in testing
239.1.1 Transfer a 1.000-g sample, weighed to the nearest 1 this test method. The precision of this test method can be
mg, to a 400-mL beaker. Add 20 mL of water and 22 mL of estimated by examining the data in Table 11.
HCl (1+1). Warm, if necessary, to complete dissolution. When
the reaction subsides, add 2 mL of H2O 2 (30 %) and boil for 5
min. TABLE 11 Statistical Information
239.1.2 Filter through a medium paper into a 100-mL Reproduci-
Magnesium Repeatability
Test Specimen bility (R2,
volumetric flask. Wash the residue with hot water and reserve Found, % (R1, E173)
E173)
the filtrate. 1. 2219 alloy 0.0066 0.0008 0.001
239.1.3 When the silicon content is 0.5 % or greater, transfer 2. BCS No. 216/2 2014 alloy 0.75 0.013 0.030
the filter paper and residue to a platinum crucible, dry, and (0.74 % Mg)
3. 7049 alloy 2.78 0.042 0.15
ignite at 500°C. Cool, add 5 mL of HF, and then add HNO3 4. 5082 alloy 4.25 0.14 0.18
dropwise until a clear solution is obtained. Evaporate carefully
to dryness, cool, and dissolve the residue in 5 drops of HCl
(1+1) and a minimum amount of water. Heat to dissolve the
salts and add this solution to the reserved filtrate obtained in 242.2 Bias—No information is available on the accuracy of
237.1.2. this test method. The accuracy may be judged, however, by
comparing accepted reference values with the corresponding
239.1.4 Cool the solution obtained in 239.1.2 or the com-
arithmetic averages obtained by interlaboratory testing.
bined filtrates obtained in 239.1.3. Dilute to volume and mix.
This is Sample Solution A. NICKEL BY THE ATOMIC ABSORPTION TEST
239.1.5 Pipet 10 mL of Sample Solution A into a 100-mL METHOD
volumetric flask containing 8 mL of HCl (1+1), dilute to
volume, and mix. This is Sample Solution B.
243. Scope
239.1.6 For magnesium concentrations less than 0.05 %,
243.1 This test method covers the determination of nickel in
pipet 20 mL of Sample Solution A into a 100-mL volumetric
concentrations from 0.01 to 4 %.
flask containing 8 mL of HCl (1+1), dilute to volume, and mix.
Use the calibration solutions prepared in accordance with
244.1 An acid solution of the sample is aspirated into the
238.1.1.
air-acetylene flame of an atomic absorption spectrophotometer.
239.1.7 When the magnesium content is between 0.05 and The absorption of the nickel resonance line at 2320 Å is
0.25 %, pipet 10 mL of Sample Solution A into a 250-mL measured and compared with the absorption of calibration
volumetric flask containing 21 mL of HCl (1+1), dilute to solutions containing known amounts of nickel.
volume, and mix. Use the calibration solutions prepared in 245. Concentration Range
accordance with 238.1.2.
239.1.8 When the magnesium content is between 0.2 and
1.0 %, pipet 25 mL of Sample Solution B into a 250-mL 14
volumetric flask containing 19 mL of HCl (1+1), dilute to 1077.
14
E34 – 11
245.1 If the optimum concentration range is not known, 250.1.2 When the silicon content is 0.5 % or greater, transfer
determine it as directed in Guide E1024. A sensitivity of 0.2 the filter paper and residue to a platinum crucible, dry, and
µg/mL for 0.0044 absorbance is widely obtained. ignite at 550°C. Cool, add 5 mL HF, and then add HNO3
246. Interferences dropwise until a clear solution is obtained. Evaporate to
246.1 Elements normally present do not interfere if their dryness, cool, and dissolve the salts in 5 drops of HCl (1+1)
concentrations are less than the maximum limits shown in 1.1. and a minimum amount of water. Add this solution to the
247. Apparatus reserved filtrate obtained in 250.1.1.
250.1.3 Cool the solution obtained in 250.1.1 or the com-
247.1 Atomic Absorption Spectrophotometer—Determine
bined filtrates obtained in 250.1.2. Dilute to volume and mix.
that the instrument is suitable for use as prescribed in Guide
This is Sample Solution A.
E1024. The percent variability for the highest calibration
250.1.4 Pipet 10 mL of Sample Solution A into a 100-mL
solution (Vc) should not exceed 1 %.
volumetric flask containing 8 mL of HCl (1+1), dilute to
248. Reagents volume, and mix. This is Sample Solution B.
248.1 Aluminum Solution A (1 mL = 50 mg Al)—Transfer 250.2 Prepare the test solution for aspiration according to the
25.00 g of aluminum (purity: 99.99 % min) to a 1-L beaker. following:
Add 100 mL of water, a small drop of mercury, and 275 mL of 250.2.1 When the nickel concentration is less than 0.2 %,
HCl in increments, heating moderately to accelerate the disso- pipet 50 mL of Sample Solution A into a 100-mL volumetric
lution. When dissolution is complete, add 2 mL of H2O2 (30 %) flask containing 7 mL of HCl (1+1), dilute to volume, and mix.
and boil for 5 min. Cool, transfer to a 500-mL volumetric flask, Use the 0.01 to 0.20 % nickel set of calibration solutions.
dilute to volume, and mix. Store in a polyethylene bottle. 250.2.2 When the nickel concentration is between 0.20 and
248.2 Aluminum Solution B (1 mL = 2.5 mg Al)—Using a 2.00 %, pipet 10 mL of Sample Solution A into a 200-mL
pipet, transfer 25 mL of Aluminum Solution A to a 500-mL volumetric flask containing 16 mL of HCl (1+1), dilute to
volumetric flask, dilute to volume, and mix. volume, and mix. Use the 0.20 to 2.00 % nickel set of
248.3 Nickel, Standard Solution A (1 mL = 1.00 mg Ni)— calibration solutions.
Transfer 1.000 g of nickel (purity: 99.9 % min) to a 400-mL 250.2.3 When the nickel concentration is between 2.00 and
beaker. Dissolve in 50 mL of HNO3 (1+1), boil for 5 min, cool, 4.00 %, pipet 25 mL of Sample Solution B into a 100-mL
and transfer to a 1-L volumetric flask. Dilute to volume and volumetric flask containing 6 mL of HCl (1+1), dilute to
mix. Store in a polyethylene bottle. volume, and mix. Use the 2.00 to 4.00 % nickel set of
248.4 Nickel, Standard Solution B (1 mL = 0.04 mg Ni)— calibration solutions.
Using a pipet, transfer 10 mL of Nickel Standard Solution A to 251. Measurements
a 250-mL volumetric flask, dilute to volume, and mix. 251.1 Optimize the response of the instrument and take
preliminary readings; complete the analysis and determine the
249. Calibration concentration of nickel in the test solution by the graphical
procedure, as described in Guide E1024.
249.1 Calibration Solutions—Using pipets, transfer 0, 5, 10,
15, 20, and 25 mL of Nickel Standard Solution B to 100-mL NOTE 10—The graphical procedure is preferred because of the nonlin-
volumetric flasks. Add Aluminum Solution A or B and HCl earity of nickel response at 232.0 nm.
(1+1) as indicated as follows, dilute to volume, and mix. 252. Calculation
Nickel Concentration, % Aluminum Solution, mL HCl (1+1), mL 252.1 Calculate the percentage of nickel as follows:
0.01 to 0.20 10 Solution A 7
0.20 to 2.00 20 Solution B 8 A
2.00 to 4.00 10 Solution B 8 Nickel, % 5 B 3 100 (9)
249.2 Reference Solution—The 0 calibration solution is used where:

as the reference solution. A = nickel per 100 mL of final test solution, mg, and
249.3 Since sensitivity may vary among instruments, deter- B = sample represented in 100 mL of the final test solution
mine the suitability of the selected concentration range and taken for analysis, mg.
required to meet the minimum response criteria for some 253. Precision and Bias15
ranges. Sample and calibration solutions always must contain 253.1 Precision—Nine laboratories cooperated in testing this
the same quantity of aluminum per millilitre. test method. The precision of this test method can be estimated
250. Procedure by examining the data in Table 12.
250.1 Test Solution: 253.2 Bias—No information on the accuracy of this test
250.1.1 Transfer a 1.0-g sample, weighed to the nearest 1 method is available. The accuracy may be judged, however, by
mg, to a 400-mL beaker. Add 20 mL of water and 22 mL of comparing the accepted reference values with the correspond-
HCl (1+1) in small increments. When the reaction subsides, ing arithmetic averages obtained by interlaboratory testing.
add 2 mL of H2O2(30 %), heat until dissolution is complete,
and boil gently for 5 min. Filter through a medium paper into
a 100-mL volumetric flask, wash the residue with hot water, 15
and reserve the filtrate. 1078.
15
E34 – 11
TABLE 12 Statistical Information 259.6 Titanium, Standard Solution B (1 mL = 0.015 mg
Nickel Repeatability
Reproduci- Ti)—Using a pipet, transfer 15 mL of Titanium Solution A to
Test Specimen bility a 500-mL volumetric flask, dilute to volume, and mix.
Found, % (R1, E173)
(R2, E173)
MD 184 0.011 0.0012 0.004
NBS 85b 2024 alloy (0.084 % Ni) 0.087 0.0053 0.009 260. Preparation of Calibration Curve
BCS No. 181/2 2218 alloy (1.91 % 1.88 0.042 0.101 260.1 Calibration Solutions—Using pipets, transfer 1, 2, 4,
Ni)
6, 8, and 10 mL of Titanium Solution B to 100-mL volumetric
flasks. Add 20 mL of aluminum solution. Proceed as directed in
260.3.
TITANIUM BY THE DIANTIPYRYLMETHANE 260.2 Reference Solution—Transfer 20 mL of aluminum
PHOTOMETRIC TEST METHOD solution to a 100-mL volumetric flask. Proceed as directed in
260.3.
254. Scope 260.3 Color Development—Using a pipet, add 25 mL of
254.1 This test method covers the determination of titanium H2SO4 (1+1), dilute to 75 mL, and cool. Add 2 drops of copper
in concentrations from 0.003 to 0.3 %. sulfate solution and 2 mL of ascorbic acid solution, and mix.
255. Summary of Test Method Using a pipet, add 10 mL of diantipyrylmethane solution,
255.1 The sample is dissolved in hydrochloric acid. Iron and dilute to volume, and mix. Allow the color to develop for 1 h.
vanadium are reduced with ascorbic acid in the presence of 260.4 Photometry:
copper sulfate. The yellow titanium complex is formed with 260.4.1 Multiple–Cell Photometer—Measure the cell correc-
diantipyrylmethane. Photometric measurement is made at ap- tion using absorption cells with a 1-cm light path and a light
proximately 400 nm. band centered at approximately 400 nm. Using the test cell,
256. Concentration Range take the photometric readings of the calibration solutions.
256.1 The recommended concentration is from 0.015 to 0.15 260.4.2 Single–Cell Photometer—Transfer a suitable portion
mg of titanium per 100 mL, using a 1-cm cell. of the reference solution to an absorption cell with a 1-cm light
NOTE 11—This test method has been written for cells having a 1-cm path and adjust the photometer to the initial setting, using a
light path. Cells having other dimensions may be used, provided suitable light path centered at approximately 400 nm. While maintain-
adjustments can be made in the amounts of sample and reagents used. ing this adjustment, take the photometric readings of the
257. Stability of Color calibration solutions.
257.1 The color is developed within 1 h and is then stable for 260.5 Calibration Curve—Plot the net photometric readings
8 h. of the calibration solutions against milligrams of titanium per
258. Interferences 100 mL of solution.
258.1 The elements ordinarily present in aluminum and 261. Procedure
aluminum-base alloys do not interfere if their concentrations 261.1 Test Solution:
are under the maximum limits shown in 1.1. 261.1.1 Transfer a 1.00-g sample, weighed to the nearest 1
259. Reagents mg, to a 400-mL beaker. Cover with a ribbed cover glass.
259.1 Aluminum Solution (1 mL = 25 mg Al)—Transfer 25 g 261.1.2 Add 30 mL of water, and 30 mL of HCl (1+1) in
of aluminum (purity 99.99 % min) to a 1-L beaker. Add 100 small increments. Warm if necessary to complete dissolution.
mL of water and a small drop of mercury. Add 275 mL of HCl When the reaction subsides, add 2 mL of H2O2 (30 %), and boil
in small increments, heating moderately to accelerate dissolu- for 5 min.
tion. When dissolution is complete, add 2 mL of H2O2(1+1), 261.1.3 Filter, using a medium paper, into a 100-mL volu-
and boil gently for 5 min. Cool, transfer to a 1-L volumetric metric flask. Wash with hot water and reserve the filtrate.
flask, dilute to volume, and mix. Store in a polyethylene
261.1.4 When a visible silicon residue is present, transfer the
container.
filter paper and residue to a platinum crucible, dry, and ignite
259.2 Ascorbic Acid Solution (20 g/L)—Dissolve 2 g of
at 600°C until the carbon is removed, Cool, add 5 mL of HF,
ascorbic acid (C6H 8O6) in 100 mL of water. Do not use a
and add HNO3 dropwise until a clear solution is obtained.
solution that has stood for more than 1 h.
Evaporate to dryness, cool, add 5 drops of HCl (1+1), and a
259.3 Copper Sulfate Solution (48 g/L)—Dissolve 7.5 g of
minimum amount of water. Heat to dissolve the salts, and add
copper sulfate (CuSO4·5H 2O) in water and dilute to 100 mL.
the solution to the filtrate reserved in 261.1.3.
259.4 Diantipyrylmethane Solution (50 g/L)—Dissolve 10.0
g of diantipyrylmethane (CH 2[C:(CH3)N(CH3)N(C6H5)CO] 261.1.5 Cool the solution from 261.1.3 or 261.1.4, dilute to
2), in 34 mL of HCl (1+1), and 150 mL of water. Dilute to 200
volume, and mix.
mL. 261.1.6 According to the expected titanium content, proceed
259.5 Titanium, Standard Solution A (1 mL = 0.5 mg Ti)— with the volumes of test solution and aluminum solution listed
Dissolve 0.500 g of titanium (purity 99.5 % min) in 125 mL of in the following:
H2SO4. When dissolution is complete, cool, add 10 drops of Volume of Test Volume of Aluminum Solution,
Expected Titanium, % Solution, mL mL
HNO3, and boil gently for 5 min. Cool and dilute to about 800 0.003 to 0.030 50.0 ...
mL. Cool, transfer to a 1-L volumetric flask, dilute to volume, 0.020 to 0.070 20.0 12
and mix. 0.060 to 0.30 5.0 18
16
E34 – 11
261.1.7 Using a clean, dry pipet, transfer the appropriate VANADIUM BY AN EXTRACTION-PHOTOMETRIC
volume of test solution to a 100-mL volumetric flask. Add the TEST
appropriate volume of aluminum solution. Reserve the remain- METHOD USING N-BENZOYL-N-
ing test solution for use in 261.4. PHENYLHYDROXYLAMINE
261.2 Reference Solution—Proceed as directed in 260.2.
261.3 Color Development—Proceed as directed in 260.3. 264. Scope
261.4 Background Color Solution (Correction for elements 264.1 This test method covers the determination of vana-
in the test solution present as colored ions)—Pipet an addi- dium in concentrations from 0.002 to 0.16 %.
tional aliquot of the test solution to a 100-mL volumetric flask
and add aluminum solution equal to that selected in 261.1.7.
265.1 After dissolution of the sample in acids, the vanadium
For a 50-mL aliquot, use the remaining test solution without
is oxidized with potassium permanganate. The vanadium (V) is
pipetting. Proceed as in 260.3, but omit the diantipyrylmethane
complexed with N-benzoyl-N-phenylhydroxylamine, the com-
solution.
plex is extracted with chloroform and photometric measure-
261.5 Background Color Reference Solution—Proceed as in
ment is made at approximately 530 nm.
260.3 and 260.3, but omit the diantipyrylmethane solution.
266. Concentration Range
261.6 Photometry—Take the photometric readings of the test
solution and background color solution as directed in 260.4, 266.1 The recommended concentration range is from 0.02 to
each with its appropriate reference solution. 0.40 mg of vanadium per 50 mL of chloroform solution, using
262. Calculation a 1-cm cell.
262.1 Convert the net photometric readings of the test NOTE 12—This test method has been written for cells having a 1-cm
solution and the background color solution to milligrams of light path. Cells having other dimensions may be used, provided suitable
titanium by means of the calibration curve. Calculate the adjustments can be made in the amounts of sample and reagents used.
percentage of titanium as follows: 267. Stability of Color
Titanium, % 5 [~A 2 B!/C] 3 10 (10) 267.1 The color is stable for at least 48 h.
where: 268. Interferences
A = titanium found in 100 mL of final test solution, mg, 268.1 Other than titanium, the elements ordinarily present in
B = background color correction, equivalent milligrams of aluminum alloys do not interfere when concentrations are less
titanium, and than the maximum limits shown in 1.1. Titanium, at concen-
C = sample represented in 100 mL of the final test solution, trations above 2 mg in the sample solution will produce a
g. positive interference. This becomes significant only when
operating near the lower limit of the scope of this test method
263. Precision and Bias with samples having a high Ti-to-V ratio. It is evidenced by an
263.1 Precision16—Ten laboratories cooperated in testing off color in the test solution.
this test method on ISO-9 and ISO-22, and nine laboratories 269. Reagents
tested ISO-30. Seven of the laboratories analyzed each of the 269.1 Chloroform (CHCl3), spectrophotometric grade.
samples on five separate days while the other three laboratories 269.2 N-benzoyl-N-phenylhydroxylamine(BPHA) Solution
analyzed their samples on either four or five separate days. (1g/L)—Dissolve 0.250 g of BPHA (C 6H5CON(OH)C6H5) in
Repeatability ( R1) and reproducibility (R2) were calculated by 100 mL of CHCl 3. Transfer to a dry 250-mL volumetric flask,
analysis of variance (Practice E173) using M = 1. The data dilute to volume with CHCl3, and mix. When stored in a brown
obtained are summarized in Table 13. glass bottle in the dark, this reagent is stable for at least 2
months.
269.3 Vanadium, Standard Solution A (1 mL = 0.100 mg
TABLE 13 Statistical Information V)—Dissolve 0.1785 g of reagent grade V2O5, which has been
Titanium
Repeatability Reproducibility ignited at 300°C for 1 to 2 h, in 20 mL of NaOH (5 g/100 mL)
Test Specimen (R1, E173; (R2, E173; solution. Add 25 mL of H 2SO4 (1+1) and cool to room
Found, %
M = 1) M = 1)
temperature. Transfer to a 1-L volumetric flask, dilute to
ISO-30 (5182 alloy) 0.0076 0.00085 0.00089
ISO-22 (7005 alloy) 0.0168 0.0013 0.0016
volume with water, and mix. Store in a polyethylene bottle.
ISO-9 (10 Cu-1 Ni alloy) 0.155 0.0067 0.013 269.4 Vanadium, Standard Solution B (1 mL + 0.010 mg
V)—Using a pipet, transfer 25 mL of Vanadium Solution A to
a 250-mL volumetric flask, dilute to volume, and mix. Store in
a polyethylene bottle.
263.2 Bias—No information on the accuracy of the test 269.5 Potassium Permanganate Solution (2 g/L)—Dissolve
method is available. 0.20 g of KMnO4 in water and dilute to 100 mL.
270. Preparation of Calibration Curve

16
Supporting data are available from ASTM Headquarters. Request RR:E01- 270.1 Calibration Solutions—Using pipets, transfer 5, 10,
1087. 20, 30, and 40 mL of Vanadium Solution B to a series of
17
E34 – 11
250-mL separatory funnels. Add to each 27 mL of H2SO4 271.1.5 To filtrate from 271.1.3 or 271.1.4, add 20 mL of
(1+1), dilute to about 100 mL with water, and proceed as H2SO 4 (1+1), cover with a ribbed cover glass, and carefully
directed in 270.3. evaporate to fumes of H2SO4. Reduce the heat to avoid
270.2 Reference Solution—Transfer 27 mL of H2SO4 bumping and continue fuming for 15 min to remove chloride.
(1 + 1), to a 250-mL separatory funnel, dilute to about 100 mL After cooling, wash down with about 30 mL of water and heat
with water, and proceed as directed in 270.3. to dissolve any salts. Dilute to 75 mL and boil the solution for
270.3 Color Development: 5 min. Cool and transfer to a 250-mL separatory funnel. Dilute
270.3.1 To the solutions in the separatory funnels, add to about 100 mL and proceed as directed in 270.3.
KMnO4 solution dropwise with mixing until a slight pink color 271.2 Reference Solution—Prepare a reference solution as
persists for at least 10 min. described in 270.2.
271.3 Color Development—Proceed as directed in 270.3.
270.3.2 Add 30 mL BPHA solution and 34 mL of HCl.
271.4 Photometry—Take the photometric reading of the test
Immediately after addition of the HCl, shake for 1 min and
solution as described in 270.4.1 or 270.4.2.
allow the layers to separate. Collect the CHCl3 layer in a dry
272. Calculation
50-mL volumetric flask.
272.1 Convert the net photometric reading of the test
270.3.3 Re-extract with 10 mL of BPHA solution and solution to milligrams of vanadium by means of the calibration
combine with the extract obtained in 270.3.2. Dilute to volume curve. Calculate the percentage of vanadium as follows:
with CHCl3 and mix. Allow the extracts to stand for at least 1
h before taking photometric readings. Vanadium, % 5 ~A/B 3 10! (11)
270.4 Photometry: where:
270.4.1 Multiple Cell Photmeter—Measure the cell correc- A = vanadium found in 50 mL of the final test solution, mg,
tion using stoppered absorption cells with a 1-cm light path and and
a light band centered at approximately 530 nm. Using the test B = sample represented in 50 mL of the final test solution,
cell, take the photometric readings of the calibration solutions. g.
270.4.2 Single–Cell Photometer—Transfer a suitable portion
of the reference solution to a stoppered absorption cell having 273. Precision and Bias
a 1-cm light path and adjust the photometer to the initial 220.1 Precision—Nine laboratories cooperated in testing this
setting, using a light band centered at approximately 530 nm. test method. The precision of this test method can be estimated
While maintaining this adjustment, take the photometric read- by examining the data in Table 14.
ings of the calibration solutions. 220.2 Bias—No information on the accuracy of this test
270.4.3 Calibration Curve—Plot the net photometric read- method is available.
ings of the calibration solutions against milligrams of vana-
dium per 50 mL of solution. ZINC BY THE ION EXCHANGE-EDTA
TITRIMETRIC
271. Procedure
TEST METHOD
274. Scope
271.1.1 Select a sample weight in accordance with the
274.1 This test method covers the determination of zinc in
following table:
concentrations from 0.1 to 12 %.
Vanadium, % Sample Weight, g
0.002–0.025 1.0
0.025–0.070 0.5 275.1 The sample is dissolved in acid, and excess acid is
0.07–0.16 0.25 removed by evaporation. The residue is dissolved in dilute
271.1.2 Transfer the portion, weighed to the nearest 0.5 mg, hydrochloric acid and passed through a strongly basic anion
to a 250-mL beaker. Add 25 mL of water, 7 mL of H2SO4 exchange resin. The adsorbed zinc is eluted from the column
(1+1), and 2 mL HCl. Cover with a watch glass and, if and titrated with disodium (ethylenedinitrilo) tetraacetate
necessary, heat gently to start reaction. When reaction slows, (EDTA), using dithizone as the indicator.
boil gently until reaction is completed and cool. 276. Interferences
271.1.3 Filter, using a medium paper, into a 250-mL beaker. 276.1 Cadmium remains with zinc, and will be titrated.
Wash with hot water and reserve the filtrate. Cadmium is rarely encountered in other than negligible
amounts in alloys containing zinc. Other elements ordinarily
271.1.4 If a visible residue is present, transfer the filter paper
present do not interfere if their concentrations are less than the
and residue to a platinum crucible, dry, and ignite at 500°C
maximum limits shown in 1.1.
(Note 13). Cool, add 5 mL of HF, and add HNO3 dropwise until
a clear solution is obtained. Evaporate to dryness, cool, and
dissolve the residue in 5 drops of H2SO4 (1+1) and a minimum TABLE 14 Statistical Information
amount of water. Heat to dissolve the salts and add the solution Vanadium Repeatibility Reproducibility
Test Specimen
to the filtrate reserved in 271.1.3. Found, % (R1, E173) (R2, E173)
1070 Alloy 0.0032 0.00018 0.00095
NOTE 13—Experimental data on alloys containing up to 6 % silicon 7029 Alloy 0.056 0.0017 0.0072
have shown that this test method yields the same results for vanadium 2219 Alloy 0.140 0.0045 0.0085
even when this recovery step is omitted.
18
E34 – 11
277. Apparatus (1 + 1) diluted with 50 mL of water. Cool, transfer to a 1-L
277.1 Anion Exchange Column—A glass column 20 mm in volumetric flask, dilute to volume, and mix.
diameter and approximately 400-mm long, provided with a
fritted disk and a stopcock. A modification of Apparatus No. 8 279. Hazards
may be adapted to this test method. A reservoir for reagents 279.1 Dilute acid concentrations are expressed as molarities
may be added at the top of the column. However, reagents must in the sections pertaining to the ion exchange steps to empha-
be added according to the procedure described in 280.1. size the need for careful dilution of concentrated acids.
278. Reagents Standardization is not required.
278.1 Acetic Acid (1 M)—Add 58 mL of glacial acetic acid
280. Procedure
(CH3COOH) to water and make up to a volume of 1 L.
278.2 Ammonium Acetate Solution (500 g/L)—Dissolve 50 g 280.1 Test Procedure:
of ammonium acetate (CH3COONH4) in water, and dilute to 280.1.1 Transfer a 2.0-g sample, weighed to the nearest 1
100 mL. mg, to a 400-mL beaker. Cover with a ribbed cover glass.
278.3 Anion Exchange Resin. 280.1.2 Carry a reagent blank through the entire procedure,
278.3.1 Use a strongly basic anion exchange resin of the using the same amounts of all reagents, but with the sample
polystyrene-quaternary-ammonium type, chloride form, hav- omitted.
ing a crosslinkage of 2 to 3 % and a 50 to 100 nominal mesh 280.1.3 Carefully add 50 mL of HCl (1+1) in small incre-
size.17 Wash the resin with successive portions of HCl (0.005 ments. When the reaction subsides, wash down the sides of the
M), decanting until a clear solution is obtained. Allow to stand beaker and the cover glass, and add 2 mL of H2O2 (30 %) to
for 12 h in HCl (0.005 M). dissolve copper. Warm gently to complete the dissolution, and
278.3.2 Preparation of the Ion Exchange Column—Stir the carefully evaporate just to crystallization. Cool, and dissolve
resin, and add a sufficient amount of the suspension to obtain the salts with 100 mL HCl (2 M). Heat to complete the
a column approximately 150-mm high after the resin has dissolution.
settled. Precautions should be taken to avoid air bubbles or 280.1.4 Filter, using a medium-porosity paper previously
channels (Note 14). Wash the column with 100 mL of HCl washed with hot HCl (6 M) and hot water, into a 250-mL
(0.005 M) at a flow rate of 5 to 7 mL/min. beaker. Wash with 30 to 50 mL of hot HCl (2 M), and reserve
NOTE 14—When not in use, the resin bed in the column should always the filtrate.
be covered with HCl (0.005 M). 280.1.5 When a visible silicon residue is present, wash the
278.4 Disodium Ethylenedinitrilo Tetraacetate (EDTA), paper and residue with hot water and discard the washings.
Standard Solution. Transfer the filter paper and residue to a platinum crucible, dry,
278.4.1 Dissolve 7.5 g of disodium (ethylenedinitrilo) tet- and ignite at 600°C until the carbon is removed. Cool, add 5
raacetate dihydrate (EDTA) in water. Transfer to a 1-L volu- mL of HF, and add HNO3 dropwise until a clear solution is
metric flask, dilute to volume, and mix. Store in a plastic bottle. obtained. Evaporate to dryness, cool, and add 5 mL of HCl (2
278.4.2 Standardize as follows: Using a pipet, transfer 25 M). Heat to dissolve the salts, add the solution to the filtrate
mL of zinc standard solution to a 400-mL beaker and dilute to reserved in 280.1.4, and cool.
100 mL. Proceed as directed in 280.1.11 and 280.1.12. Calcu- 280.1.6 For samples containing more than 1.5 % zinc,
late the zinc equivalent of the EDTA solution as follows: transfer the solution to a 200-mL volumetric flask, using HCl
Zinc equivalent, g/mL 5 A/~B 2 C! (12) (2 M) as the transfer solution. Dilute to volume with HCl (2 M)
and mix. Using the following table as a guide, select the
where: appropriate portion of the test solution for ion exchange.
A = zinc represented in 25 mL of zinc solution, g, Aliquot
B = EDTA solution required for titration of the zinc solu- Zn, % Volume, mL
tion, mL, and 0.1 to 1.5 Solution from 280.1.5
1.5 to 3 100
C = EDTA solution required for titration of the blank, mL. 3 to 6 50
278.5 Dithizone Solution (0.25 g/L)—Dissolve 0.025 g of 6 to 12 25
diphenyl thiocarbazone (C6H 5NHNHCSN:NC6H5) in ethanol
(CH3·CH 2OH) and dilute to 100 mL with ethanol. 280.1.7 Transfer the aliquot selected into a beaker, dilute to
278.6 Hydrochloric Acid (2 M)—Add 170 mL of HCl to approximately 150 mL with HCl (2 M), and add 0.5 mL of
water and dilute to 1 L. HNO 3.
278.7 Hydrochloric Acid (1 M)—Add 85 mL of HCl to water 280.1.8 Condition the ion exchange column by passing 200
and dilute to 1 L. mL of HCl (2 M), containing 0.5 mL of HNO3, through the
278.8 Hydrochloric Acid (0.005 M)—Dilute 5 mL of HCl (1 column at a rate of 5 to 7 mL/min
M) with water and make up to a volume of 1 L. 280.1.9 Pass the test solution through the column at a rate of
278.9 Zinc, Standard Solution (1 mL = 2.00 mg Zn)— 5 to 7 mL/min. Wash the beaker and the column with five
Dissolve 2.000 g of zinc (purity 99.95 % min) in 50 mL of HCl successive 25-mL portions of HCl (2 M), and then wash the
column with 125 mL of HCl (1 M), maintaining the flow rate.
17
Dowex 1 3 2, manufactured by the Dow Chemical Co., Midland, MI, has NOTE 15—If more than 6 mg of lead (Pb) are present, wash with 200
been found satisfactory for this purpose. mL of HCl (1 M).
19
E34 – 11
280.1.10 Elute the zinc from the column with 300 mL of HCl 283.1 This test method covers the analysis of aluminum and
(0.005 M), at a flow rate of 5 to 7 mL/min, collecting the eluate aluminum alloys having beryllium composition within the
in a 400-mL beaker. Cover with a ribbed cover glass, and limits of 0.3 to 100 ppm.
evaporate carefully to approximately 100 mL. 284. Summary of Test Method
NOTE 16—When bismuth (Bi) is present in the alloy, it will be retained
284.1 An acid solution of the sample is aspirated into the jet
on the column and will be seen as a light-colored band at the top of the of an argon plasma optical emission spectrometer. The beryl-
column. Remove by washing the column with 200 mL of HNO3 (7.5 M), lium concentration is measured at 234.86 nm by comparing it
followed by 200 mL of water. Condition the column for further samples with matched matrix calibration solutions.
as directed in 280.1.8. 285. Interferences
280.1.11 Neutralize the evaporated eluate with ammonium 285.1 Elements normally present do not interfere if their
hydroxide using a pH meter. Add 10 mL of acetic acid (1 M), concentrations are less than the maximum limits shown in 1.1.
and 10 mL of ammonium acetate solution. Adjust the pH to 5.3 286. Apparatus
6 0.2 with ammonium hydroxide or acetic acid (1 M). Add 50 286.1 Argon Plasma Optical Emission Spectrometer—
mL of acetone, and cool to approximately 5°C. Follow manufacturer’s instruction manual for installation and
280.1.12 Add 2 mL of dithizone solution, and titrate imme- operation.
diately with the EDTA solution, until the color changes from 287. Reagents
red to yellow. The color should not vary after the addition of 287.1 Argon—Purity: 99.998 %, min.
two additional drops of EDTA. 287.2 Aluminum Solution (1 mL = 20 mg Al)—Transfer 20 g
281. Calculation of aluminum (purity: 99.999 % min) into a 1-L beaker. Add
281.1 Calculate the percentage of zinc as follows: 400 mL of HCl (1+1) in which 20 mg of HgCl 2 have been
Zinc, % 5 [~A 2 B!C/D] 3 100 (13) dissolved and heat moderately to accelerate dissolution (Note
17). When dissolution is complete, add 2 mL of H2O2 (30 %)
where: and boil gently for 5 min. Cool, transfer to a 1-L volumetric
A = EDTA solution required for titration of the test solu- flask, dilute to volume, and mix. Store in a polyethylene bottle.
tion, mL,
B = EDTA solution required for titration of the blank, mL, NOTE 17—High purity aluminum is difficult to dissolve. An alternative
procedure is to allow the aluminum and acid mixture to stand overnight in
C = zinc equivalent of the EDTA solution, g/mL, and
the covered beaker. After 16 h, only a minimum amount of heating is
D = sample represented in the final test solution, g. usually required to complete the dissolution.
282. Precision and Bias18 287.3 Beryllium, Standard Solution A (1 mL = 0.1 mg

282.1 Precision—Sixteen laboratories cooperated in testing Be)—Transfer 100 mg beryllium metal (purity: 99.95 %) into
this test method on sample ISO-10 and fourteen laboratories a 100-mL beaker. Add 20 mL of HCl (1+1) and warm gently to
tested sample ISO-15. All but one of the laboratories analyzed just dissolve the metal. Transfer into a 1-L volumetric flask,
the samples on a minimum of five separate days. One labora- dilute to volume, and mix. Store in a polyethylene bottle.
tory analyzed ISO-15 on four separate days. Repeatability (R1) 287.4 Beryllium, Standard Solution B (1 mL = 0.01 mg
and reproducibility (R2) were calculated by analysis of vari- Be)—Pipet 50 mL of Beryllium Standard Solution A into a
ance (Practice E173) using M = 1. The data obtained are 500-mL volumetric flask, dilute to volume, and mix. Store in a
summarized in Table 15. polyethylene bottle.
287.5 Beryllium, Standard Solution C (1 mL = 0.001 mg
Be)—Pipet 10 mL of Beryllium Standard Solution B into a
TABLE 15 Statistical Information 100-mL volumetric flask. Add 2 mL of HCl (1+1), dilute to
Repeatability Reproducibility volume with distilled water, and mix. Prepare fresh daily as
Test Specimen Zinc Found, % (R1, E173, (R2, E173, needed.
M = 1) M = 1)
ISO–10 5.97 0.255 0.305
287.6 Beryllium, Standard Solution D (1 mL = 0.0001 mg
ISO–15 0.432 0.0155 0.0193 Be)—Pipet 10 mL of Beryllium Standard Solution C into a
100-mL volumetric flask. Add 2 mL of HCl (1+1), dilute to
volume with distilled water, and mix. Prepare fresh daily as
needed.
282.2 Bias—No information on the accuracy of this test 288. Hazards
method is available. 288.1 Beryllium and its compounds are extremely toxic and
care must be exercised in their handling. For precautions to be
BERYLLIUM BY ARGON PLASMA observed, refer to Practices E50. To prevent eye damage, the
OPTICAL EMISSION SPECTROSCOPY ultraviolet radiation from the argon plasma must be shielded at
all times.
283. Scope
289. Calibration
289.1 Calibration Solutions—Using pipets, transfer into
18
Supporting data are available from ASTM Headquarters. Request RR:E01- 100-mL volumetric flasks the volumes of the appropriate
1090. beryllium standard indicated as follows:
20
E34 – 11
mL Beryllium Standard Be in Al, ppm 292.1 Precision—Ten laboratories cooperated in testing this
0 ... 0 test method and obtained twelve sets of data. Five laboratories
2.0 D 0.2
5.0 D 0.5
used ICP spectrometers and seven laboratories used DCP. All
10.0 D 1.0 samples were analyzed on three separate days. Repeatability
5.0 C 5.0 (R1) and reproducibility (R2) were calculated by analysis of
10.0 C 10.0
25.0 C 25.0
variance (Practice E173) using M = 1. The data obtained are
5.0 B 50.0 summarized in Table 16.
10.0 B 100.0
Add 50 mL of aluminum solution to each flask, dilute to TABLE 16 Statistical Information

volume, and mix.
Repeatabil- Reproduci-
289.2 Instrument Optimization—While aspirating the high- Beryllium
ity (R1, bility (R2,
Test Specimen Found, µg/g
est beryllium calibration solution, adjust all instrument param- (ppm)
E173, E173,
eters, argon flow rate, wavelength, photomultiplier tube volt- M = 1) M = 1)
age, viewing height, and sample uptake to optimize response 1145 Alloy 0.18 0.10 0.16
1145 Alloy 6.50 0.58 0.92
according to the instrument manufacturer’s recommended 7075 Alloy (NBS 859) (26 ppm Be) 26.2 2.2 3.3
operating practice. 4032 Alloy 31.0 3.5 3.8
289.3 Standardization—Aspirate each of the calibration
solutions in 289.1 and record the emission intensity as related
to concentration. Aspirate 0.01 M HCl between each run.
292.2 Bias—No information on the accuracy of this test
Prepare an analytical curve by plotting the emission intensity
method is available. The accuracy may be judged, however, by
of each calibration solution versus its concentration or calcu-
comparing the accepted reference value with the corresponding
late a standard curve. If the instrument is equipped for direct
arithmetic average obtained by interlaboratory testing.
reading of concentrations, this method of calibration may be
used provided that the proper blank correction is applied. MANGANESE BY THE PERIODATE
290. Procedure (PHOTOMETRIC) TEST METHOD
290.1.1 Transfer a 1.0-g sample, weighed to the nearest 1 293. Scope
mg, into a 250-mL beaker. Add 20 mL of water and 20 mL of 293.1 This test method covers the determination of manga-
HCl (1+1) in small increments, and cover with a ribbed cover nese in aluminum and aluminum alloys in concentrations from
glass. When the reaction subsides, add 2 mL of H2O2 (30 %) 0.005 to 2.0 %.
and boil for 5 min. 294. Summary of Test Method
290.1.2 Filter, using a 0.45-µ membrane filter, into a 100-mL 294.1 Manganese, in acid solution, is oxidized to perman-
volumetric flask. Wash with hot water and reserve the filtrate. ganate ion by potassium periodate. Photometric measurement
290.1.3 When a visible silicon residue is present, transfer the is made at approximately 525 nm.
membrane filter and residue into a platinum crucible, dry, and 295. Concentration Range
ignite at 500°C until the carbon is removed. Cool, add 5 mL 295.1 The recommended concentration range is from 0.1 to
HF, and add HNO3 dropwise until a clear solution is obtained. 2.0 mg Mn/100 mL of solution using a cell depth of 1 cm (see
Add 4 drops of H2SO4 (1+1), evaporate to fumes, and gently Note 12).
fume for 2 min. Cool, add 5 drops of HCl (1+1) and a 296. Stability of Color
minimum amount of water. Heat to dissolve the salts and 296.1 The color develops within 30 min if the concentration
combine the solution with the filtrate reserved in 290.1.2. is less than 0.2 mg Mn/100 mL of solution and within 15 min
290.1.4 Cool the solution from 290.1.2 or 290.1.3, dilute to if the concentration is greater than this amount. The color is
volume, and mix. stable for several weeks if excess periodate is present.
290.1.5 Aspirate the test solution and record its emission 297. Interferences
intensity or concentration. Verify the calibration by analyzing a 297.1 The elements ordinarily present in aluminum and
calibration standard with beryllium content similar to the test aluminum base alloys do not interfere if their concentrations
solution. If the value obtained is not within 5 % of the expected are under the maximum limits shown in 1.1.
value, repeat the instrument calibration procedure. Wash with 298. Reagents
0.01 M HCl between each run. 298.1 Boric Acid Solution (50 g/L)—Dissolve 50 g of boric
291. Calculation acid (H3BO3) in hot water, cool, and dilute to 1 L.
291.1 Calculate the concentration of beryllium in the test 298.2 Fluoroboric Acid Solution—Add 200 mL of HF to 800
solution in parts per million (µg/g) using the analytical curve mL of boric acid solution (298.1) in a plastic bottle, and mix.
prepared in 289.3. Direct reading instruments will provide the 298.3 Manganese, Standard Solution A (1 mL = 1.0 mg
results in the calibrated concentration units. Mn)—Clean electrolytic manganese metal (purity 99.9 % min)
292. Precision and Bias19 in H2SO4 (1+9). Rinse thoroughly by decantation and dry.
Transfer 1.000 g (weighed to within 1 mg) to a 400-mL beaker.
Dissolve in 100 mL of H2SO4(1+9). When dissolution is
19
Supporting data are available from ASTM Headquarters. Request RR:E01- complete, boil the solution for 5 min and cool. Transfer to a 1-L
1092. volumetric flask, dilute to volume, and mix.
21
E34 – 11
298.4 Manganese, Standard Solution B (1 mL = 0.1 mg E = absorbance of the reagent blank after NaNO2 solution
Mn)—Using a pipet, transfer 100 mL of Manganese Standard addition.
Solution A to a 1-L volumetric flask. Dilute to volume and mix. 299.6 Calibration Curve—Plot the net absorbance readings
298.5 Potassium Periodate Solution (50 g/L)—Dissolve 50 of the calibration solutions against milligrams of manganese
g of potassium periodate (KIO 4) in water, add 200 mL HNO3, per 100 mL of solution.
and dilute to 1 L. 300. Procedure
298.6 Sodium Hydroxide Solution (200 g/L)—In a nickel 300.1 Test Solution:
dish, dissolve 200 g of sodium hydroxide (NaOH) in water.
300.1.1 Manganese Content, 0.1 to 2.0 %—Transfer 1.0 g of
Cool and dilute to 1 L. Store in a plastic container.
the sample, weighed to the nearest 1 mg to a 100-mL platinum
298.7 Sodium Nitrite Solution (20 g/L)—Dissolve 2 g of or tetrafluoroethylene (TFE) vessel and add, in small amounts,
sodium nitrite (NaNO2) in water and dilute to 100 mL. Prepare 40 mL of NaOH solution. Cover with a platinum or TFE lid
fresh daily. and heat gently to facilitate the attack. Move the lid slightly
298.8 Sulfurous Acid Solution—Pass a stream of sulfur and evaporate with care until a syrupy consistency is reached.
dioxide gas (SO2) through water until saturated. Cool, wash the lid and walls of the vessel with about 25 mL of
298.9 Water, Free of Reducing Agents—To 1 L of water, and warm water, and warm gently. Transfer to a 250-mL beaker
10 mL of H2SO4 and heat to boiling. Add a few crystals of containing 30 mL of H2SO4 (1+1) and 10 mL of HNO3. If
KIO4 and continue to boil for 10 min. manganese hydroxide adheres to the vessel, return some of the
test solution and add several drops of sulfurous acid solution.
299. Preparation of Calibration Curve Mix and transfer back to the beaker. Transfer the test solution
299.1 Calibration Solutions—Using pipets or a buret, trans- to the volumetric flask indicated below. Dilute to volume, mix,
fer 1.0, 2.0, 5.0, 10.0, 15.0, and 20.0 mL of Manganese and using a pipet, transfer the indicated aliquot into a 250-mL
Standard Solution B (1 mL = 0.10 mg Mn) to 250-mL beakers. beaker. Add 5 mL of HNO3, 5 mL of H3PO4, and the required
To each add 15 mL of H2SO4 (1+1), 10 mL of HNO3, and 5 mL volume of H2SO4 (1+1). Dilute to about 70 mL.
of H3PO4. Dilute to about 70 mL. Mn, % Volumetric Flask, Aliquot, H2SO4(1+1) Addition,
299.2 Reagent Blank—Transfer 15 mL of H2SO4, 10 mL of (estimated) mL mL mL
0.1 to 0.4 100 50 5
HNO3, and 5 mL of H 3PO4 to a 250-mL beaker and dilute to
0.4 to 1.0 250 50 10
about 70 mL. 1.0 to 2.0 250 25 10
299.3 Color Development—Heat to boiling and add 10 mL
of KIO4 solution. Continue to boil until the characteristic color 300.1.2 Manganese Content, 0.005 to 0.1 %, Silicon Content
develops and for an additional 5 min (an additional 15 to 30 Less Than 10 %—Weigh and dissolve 1.0 g of sample as
min if the manganese content is less than 0.2 mg). Cool and directed in 300.1.1 but do not transfer to a volumetric flask.
transfer to a 100-mL volumetric flask, previously rinsed with Concentrate the solution in the beaker to a volume of about 65
water treated to remove reducing agents (see 298.7). Dilute to mL and add 5 mL of H3PO4.
volume with the treated water. 300.1.3 Manganese Content, 0.005 to 0.1 %, Silicon Content
299.4 Photometry: More Than 10 %—Transfer 1.0 g of sample, weighed to the
nearest 1 mg, to a 250-mL beaker. Add 20 mL of H2SO 4 (1+1),
299.4.1 Multiple Cell Photometer—Measure the cell correc-
10 mL of HNO3, and 2 mL of fluoroboric acid solution and
tion using absorption cells with a 1-cm light path and a light
warm gently to dissolve. Heat to boiling to remove nitrous
band centered at approximately 525 nm. Using the test cell,
fumes. Dilute to about 50 mL, add a little filter pulp, and heat
take photometric readings of the reagent blank and calibration
for several minutes. Filter through closetextured paper, collect-
solutions. After each reading, add 2 drops of NaNO2 solution to
ing the filtrate and washings in a 250-mL beaker. Transfer the
the cell, mix, and repeat the measurement.
filter paper and pulp to a platinum crucible and ignite in a
299.4.2 Single Cell Photometer—Transfer a suitable portion
muffle furnace at 500 to 600°C to complete destruction of the
of water to an absorption cell with a 1-cm light path and adjust
paper. Cool, add several drops of H2SO4, 2 to 5 mL of HF, and
the photometer to the initial setting using a light band centered
HNO3 dropwise until the solution clears. Evaporate to dryness
at approximately 525 nm. While maintaining this adjustment,
over a Meker burner, continue heating for several more
take photometric readings of the reagent blank and calibration
minutes, and cool. Take up the residue in a little H2SO4 (1+1)
solutions. After each reading, add 2 drops of NaNO2 solution to
and warm water with heating. Filter if necessary and combine
the cell, mix, and repeat the measurement.
the solutions. Concentrate to about 65 mL and add 5 mL of
299.5 For each solution, calculate the net absorbance as H3PO4.
follows:
A 5 ~B 2 C! 2 ~D 2 E! (14) NOTE 18—This alternative procedure may be used for silicon-
aluminum alloys, containing more than 0.1 % Mn, by diluting the test
where: solution to volume before the addition of the 5 mL of H3PO4, and taking
A = net absorbance, a suitable aliquot as described in 300.1.1.
B = gross absorbance of the calibration or test solution, 300.2 Reagent Blank—Carry a reagent blank through the
C = absorbance of the solution after NaNO2 solution entire procedure using the same amounts of all reagents.
addition, 300.3 Color Development—Proceed as directed in 299.3.
D = gross absorbance of the reagent blank, and 300.4 Photometry—Proceed as directed in 299.4.
22
E34 – 11
301. Calculation known to be present. This test method should not be applied to
301.1 Calculate net absorbance as directed in 299.5. Convert alloys containing greater than 2.0 % silicon.
the net absorbance of the test solution to milligrams of 306. Apparatus
manganese by means of the calibration curve. Calculate the 306.1 Electrodes for Electroanalysis—Platinum electrodes
percentage of manganese as follows: of the stationary type are recommended as described in 306.1.1
Manganese, % 5 F/~G 3 10! (15) and 306.1.2, but strict adherence to the exact size and shape of
the electrodes is not mandatory. When agitation of the electro-
where: lyte is permissible in order to decrease the time of deposition,
F = manganese in 100 mL of the final test solution, mL, one of the types of rotating forms of electrodes, generally
and available, may be employed. The surface of the platinum
G = sample represented in 100 mL of the final test solu- electrodes should be smooth, clean, and bright to promote
tion, g. uniform deposition and good adherence. Sandblasting is not
recommended.
302. Precision and Bias20 306.1.1 Cathodes— Platinum cathodes may be formed either
302.1 Precision—Eleven laboratories cooperated in testing from plain or perforated sheets or from wire gauze, and may be
this test method using alkaline dissolution on sample ISO–17, either open or closed cylinders. Gauze cathodes are recom-
ten laboratories on ISO–6, and eight on ISO–13. Each labora- mended, and shall be made preferably from 50-mesh gauze
tory analyzed the samples on a minimum of six separate days. woven from wire approximately 0.21 mm (0.0085 in.) in
Six laboratories cooperated in testing the acid dissolution diameter. The cathode should be stiffened by doubling the
procedure on ISO–7 (12.9 % Si). Each laboratory analyzed the gauze for about 3 mm at the top and the bottom of the cylinder
sample on a minimum of four separate days. Repeatability (R1) or by reinforcing the gauze at the top and bottom with a
and reproducibility ( R2) were calculated by analysis of platinum band or ring. The cylinder should be approximately
variance (Practice E173) using M = 1. The data obtained are 30 mm in diameter and 50 mm in height. The stem should be
summarized in Table 17. made from a platinum alloy wire such as platinum-iridium,
platinum-rhodium, or platinum-ruthenium, having a diameter
TABLE 17 Statistical Information of approximately 1.30 mm. It should be flattened and welded
Reproduci- the entire length of the gauze. The over-all height of the
Manganese Repeatability (R1, bility
Test Specimen
Found, % E173, M = 1) (R2, E173,
cathode should be approximately 130 mm. A cathode of these
M = 1) dimensions will have a surface area of 135 cm2 exclusive of the
NaOH Dissolution: stem.
ISO–17 0.848 0.0200 0.0442 306.1.2 Anodes— Platinum anodes may be of the spiral type
ISO–6 0.244 0.00886 0.0157
ISO–13 0.0209 0.00163 0.00362
when anodic deposits are not being determined, or if the
Acid Dissolution: deposits are small (as in the electrolytic determination of lead
ISO–7 (12.9 % Si) 0.0096 0.00072 0.00124 when it is present in amounts not over 0.2 %). When used in
analyses where both cathodic and anodic plates are to be
determined, the anodes should be of wire gauze. Spiral anodes
302.2 Bias—No data relating to the magnitude of the bias of should be made from 1.00-mm or larger platinum wire formed
results obtained using this test method are available. into a spiral of seven turns having a height of approximately 50
mm and a diameter of 12 mm, the over-all height being
COPPER BY THE ELECTROLYTIC approximately 130 mm. A spiral anode of this description will
(GRAVIMETRIC) have a surface area of 9 cm2. Platinum gauze anodes should be
TEST METHOD made of the same material and of the same general design as
303. Scope platinum gauze cathodes. The anode cylinder should be ap-
303.1 This test method covers the determination of copper in proximately 12 mm in diameter and 50 mm in height and the
aluminum and aluminum alloys in concentrations from 0.5 to over-all height of the anode should be approximately 130 mm.
20 %. A gauze anode of these dimensions will have a surface area of
304. Summary of Test Method 54 cm2. Both areas are exclusive of the stem.
304.1 The sample is dissolved in acid, silicon is removed by 307. Hazards
filtration, and copper is recovered from the nonvolatile residue 307.1 Perchloric acid can be safely used as specified in the
remaining after treatment with HF. The sample solution is procedure. It should not be brought into contact with finely
electrolyzed and the cathodic deposit is weighed. divided aluminum, silicon, or organic matter if nitric acid is not
305. Interferences present. Exhaust hoods should be in accordance with Practices
305.1 Of the elements ordinarily present in aluminum and E50.
aluminum alloys, only bismuth, tin, and antimony interfere. 308. Reagents
This test method should not be applied when these elements are 308.1 Sulfamic Acid—NH2SO 3H.
309. Procedure
20
Supporting data are available from ASTM Headquarters. Request RR:E01- 309.1 Select a sample weight in accordance with the
1094. following:
23
E34 – 11
Sample HClO4 ance (Practice E173) using M = 1. The data obtained are
Copper, % Weight, g (1+1), mL HNO3, mL summarized in Table 18.
0.5 to 2.0 5 180 5
2.0 to 5.0 2 75 5
5.0 to 20.0 1 40 5 TABLE 18 Statistical Information
309.2 Transfer the sample, weighed to the nearest 1 mg, to a Test Repeatability (R1, Reproducibility (R2,
Copper Found, %
Specimen E173, M = 1) E173, M = 1)
400-mL beaker. Cover with a ribbed cover glass. Just before
ISO–9 10.03 0.107 0.262
use, mix the quantities of HClO4 (1+1) and HNO3 as specified ISO–12 5.44 0.100 0.183
in 309.1, and add the mixture, in small increments. Moderate ISO–8 1.03 0.048 0.082
heat may be required to start the reaction. When dissolution is
complete, evaporate to dense white fumes and fume for 15 min.
Allow to cool, add 300 mL of hot water, stir, and boil for 5 min. 311.2 Bias—The accuracy of this test method could not be
309.3 Allow the residue to settle, and filter while hot, using evaluated because adequate certified standard reference mate-
a medium-porosity paper and a little paper pulp. Wash well rials were unavailable at the time of testing. The user is
with hot water and collect the filtrate and washings in a cautioned to verify by the use of certified reference materials,
600-mL beaker. if available, that the accuracy of this test method is adequate
309.4 Transfer the filter paper and residue to a platinum for the contemplated use.
crucible, dry, and ignite at 550°C. Cool, add 1 mL of H2SO4
(1+3), 5 mL of HF, and then add HNO3 dropwise until a clear GALLIUM BY THE ION-EXCHANGE-ATOMIC
solution is obtained. Evaporate to dryness and dissolve the ABSORPTION
residue in 1 mL of HClO 4 (1+1) and a minimum amount of TEST METHOD
water. Filter if necessary and add to the solution obtained in 312. Scope
309.3. Adjust the volume to approximately 200 mL or to a 312.1 This test method covers the determination of gallium
volume sufficient to cover the electrodes. in concentrations from 0.001 to 0.05 %.
309.5 Add 10 mL of HNO3 (1+1), and 1 g of sulfamic acid. 313. Summary of Test Method
Use weighed electrodes and a current density from 0.5 to 1 313.1 Gallium is adsorbed on a column of strongly basic
A/dm2 of cathode surface, and electrolyze while stirring until anion exchange resin from a 6 M hydrochloric acid solution of
the solution is colorless. Raise the level of the electrolyte 1 cm the sample. The adsorbed gallium is eluted from the column
by adding water, add 1 g of sulfamic acid, and continue the with 0.5 M hydrochloric acid and the concentrated eluate is
electrolysis for an additional 30 min. If deposition occurs, add aspirated into the nitrous oxide-acetylene flame of an atomic
more water, and continue electrolysis until there is no further absorption spectrophotometer. The absorption of the gallium
deposition. resonance line at 2874 Å is measured and compared with the
309.6 Without interrupting the current, remove the beaker absorption of calibration solutions containing known amounts
containing the electrolyte and quickly replace it with a beaker of gallium.
containing sufficient water to cover the electrodes completely. 314. Concentration Range
Remove the beaker, disconnect the cathode, and rinse in two 314.1 If the optimum concentration range is not known,
successive beakers of ethanol. Dry in an oven at 110°C for 10 determine it as directed in Guide E1024. A sensitivity of 0.5 to
min, cool in a desiccator, and weigh as metallic copper. The 0.8 µg/mL for 0.0044 absorbance is widely obtained.
electrolyte should not contain more than 0.2µ g/mL copper 315. Interferences
when tested with a sensitive method such as the neocuproine 315.1 Elements normally present do not interfere if their
photometric or atomic absorption. concentrations are less than the maximum limits shown in 1.1.
310. Calculation 316. Apparatus
310.1 Calculate the percentage of copper as follows: 316.1 Atomic Absorption Spectrophotometer—Determine
Copper, % 5 ~A/B! 3 100 (16)
that the instrument is suitable for use as prescribed in Guide
E1024. The percent variability for the highest calibration
where: solution (Vc) should not exceed 1 %.
A = copper found, g, and 316.2 Anion Exchange Column—A glass column 20 mm in
B = sample used, g. diameter and approximately 400 mm long, provided with a
fritted disk and a stopcock. A reservoir for reagents may be
311. Precision and Bias21 added at the top of the column. However, reagents must be
311.1 Precision—Eleven laboratories cooperated in testing added in accordance with the procedure described in 320.1.
sample ISO–9; nine laboratories tested ISO–12; and ten 317. Reagents
laboratories tested ISO–8. Each laboratory analyzed the 317.1 Anion Exchange Resin:
samples on a minimum of six separate days. Repeatability (R 1) 317.1.1 Use a strongly basic anion exchange resin of the
and reproducibility (R2) were calculated by analysis of vari- polystyrene-quaternary ammonium type, chloride form, having
a cross linkage of 8 % and a 50 to 100 nominal mesh size.22
21 22
Supporting data are available from ASTM Headquarters. Request RR:E01- Dowex 1-X8 manufactured by Dow Chemical Co., Midland, MI, and AG 1-X8
1044. produced by Bio-Rad, Richmond, CA, have been found satisfactory for this purpose.
24
E34 – 11
Wash the resin with successive portions of water, decanting to filter with 1 mL HNO3(1+1) and heat on a hot plate until the
remove “fines” until a clear supernatant solution is obtained. membrane chars. Ignite in a muffle furnace at 500 to 600°C
317.1.2 Preparation of the Ion Exchange Column—Stir the until the carbon is removed. Cool, add 5 mL of HF, and add
resin slurry and transfer a sufficient amount of the suspension HNO3 dropwise until a clear solution is obtained. Evaporate to
to the glass column to obtain a resin bed approximately 150 dryness, cool, and dissolve the residue in 1 mL of HCl (1+1)
mm high after settling. Using a 19-mm outside diameter and a minimum amount of water. Heat to dissolve the salts and
column, this is about 30 mL of wet resin. Precautions should be add the solution to the reserved filtrate.
taken to avoid air bubbles or channels (Note 19). Wash the 320.1.3 Evaporate the solution from 320.1.1 or 320.1.2,
column with 150 mL of HCl (0.5 M), followed by 200 mL of using a ribbed cover glass, to a volume of about 10 mL or until
water using a flow rate of 3 to 5 mL/min. heavy crystallization occurs. Add 40 mL of HCl (6 M) and
warm to dissolve the salts.
NOTE 19—Precaution: When not in use, the resin bed in the column
should always be covered with water. 320.1.4 Condition the anion exchange resin by passing 50
mL of HCl (6 M) through the column at a flow rate of 3 to 5
317.2 Gallium Solution A (1 mL = 1.00 mg Ga)—Transfer mL/min.
0.500 g of gallium (purity: 99.9 % min) to a 250-mL beaker. 320.1.5 Transfer the cooled solution from 320.1.3 to the
Cover and add 10 mL of HCl (1+1). Cautiously add, in small reservoir of the column and rinse the beaker with small
amounts at a time, 2 mL of 30 % H2O2. When dissolution is portions of HCl (6 M). Pass the test solution through the
complete, boil the solution for about 5 min. After cooling, add column at a flow rate of 3 to 5 mL/min. Wash the column
33 mL of HCl (6 M) and transfer to a 500-mL volumetric flask. reservoir three times with 10-mL portions of HCl (6 M). Allow
Dilute to volume and mix. Store in a polyethylene bottle. each wash to drain before adding the next.
317.3 Gallium Solution B (1 mL = 0.1 mg Ga)—Pipet 50 mL 320.1.6 Wash the column with 200 mL of HCl (4 M)
of Gallium Solution A into a 500-mL volumetric flask, add 33 maintaining the same flow rate. This step separates all the
mL of HCl (6 M), dilute to volume, and mix. Store in a aluminum and those metals not adsorbed by anion exchange,
polyethylene bottle. plus most of the copper, if present. Discard the eluate and
317.4 Hydrochloric Acid (6 M)—Add 510 mL of HCl to washes.
water and dilute to 1 L. 320.1.7 Elute the gallium with 150 mL HCl (0.5 M) at a flow
317.5 Hydrochloric Acid (4 M)—Add 340 mL of HCl to rate of 3 to 5 mL/min, collecting the eluate in a 250-mL beaker.
water and dilute to 1 L. Cover with a ribbed cover glass and evaporate just to dryness.
317.6 Hydrochloric Acid—(0.5 M)—Dilute 125 mL of HCl
(4 M) with water and make up to 1 L. NOTE 20—The only elements present in this eluate are gallium, iron,
and, for copper-containing alloys, a small amount of residual copper.
318. Hazards 320.1.8 Dissolve the residue in 2 to 3 mL of HCl (0.5 M)
318.1 Dilute acid concentrations are expressed as molarities with gentle heating. Cool and transfer to a 10-mL volumetric
in the sections pertaining to the ion exchange steps to empha- flask using HCl (0.5 M). Dilute to volume with HCl (0.5 M)
size the need for careful dilution of concentrated acids. and mix. Complete the analysis as described in 321.1.
Standardization is not required. 320.1.9 To prepare for the next determination, wash the
column with 200 mL of hot water (boiling) using a flow rate of
319. Calibration 5 to 7 mL/min to elute any zinc. Under these conditions, the
319.1 Calibration Solutions—Using pipets, transfer 10, 20, resin bed will maintain a temperature of about 50°C. If
30, 40, and 50 mL of Gallium Solution B to 100-mL volumetric high-zinc alloys, such as the 7000 series, have been analyzed,
flasks. Dilute to volume with HCl (0.5 M) and mix. Store in wash with a second 200-mL portion of hot water. (Note 21).
polyethylene bottles. NOTE 21—For alloys containing bismuth, recondition the column in a
319.2 Reference Solution—Use HCl (0.5 M) as the reference manner similar to that described in Note 16. The final conditioning should
solution. be done in accordance with 320.1.4.
319.3 Since sensitivity may vary among instruments, deter- 321. Measurements
mine the suitability of the selected concentration range and 321.1 Optimize the response of the instrument and take
apparatus in accordance with Guide E1024. preliminary readings using the standards prepared in 319.1.
320. Procedure Complete the analysis and calculate the gallium concentration
320.1 Test Solution: using one of the procedures described in Guide E1024.
320.1.1 Transfer a 1.0-g sample, weighed to the nearest 1 322. Calculation
mg, to a 400-mL beaker. Add 10 mL of water and cover with 322.1 Calculate the percentage of gallium as follows:
a ribbed cover glass. Carefully add 30 mL of HC1 (1+1) in
A
small increments. When the reaction subsides, add 2 mL of Gallium, % 5 B 3 100 (17)
H2O2 (30 %) and boil for 5 min. If no precipitate is observed,
proceed as directed in 320.1.3. where:
320.1.2 When a visible silicon residue is present, filter A = gallium in the final test solution, mg, and
through a 3.0-µm membrane filter into a 250-mL beaker. Wash B = sample represented in the test solution taken for
any residue with hot water and reserve the filtrate. Transfer the analysis, mg.
membrane filter and residue to a platinum crucible. Moisten the
25
E34 – 11
323. Precision and Bias23 329.3 Lithium Standard Solution A (1 mL = 1.00 mg Li)—
323.1 Precision—Eight laboratories cooperated in testing Dry a quantity of lithium carbonate (Li2CO3) (purity: 99.5 %
this test method by analyzing each of the samples on three min), for 12 h at 140°C. Weigh 5.324 g into a beaker and cover
separate days. Repeatability (R1) and reproducibility (R2) were with 20 mL of water. Dissolve by adding HCl (1+1), dropwise.
calculated by analysis of variance (Practice E173) using M Add an additional 10 mL of HCl (1+1) and heat gently to
= 1. The data obtained are summarized in Table 19. remove CO2. Cool, transfer to a 1-L volumetric flask, dilute to
volume, and mix. Store in a polyethylene bottle.
TABLE 19 Statistical Information 329.4 Lithium Standard Solution B (1 mL = 0.040 mg
Repeatabil- Reproduci- Li)—Pipet 10 mL of Lithium Standard Solution A into a
Test Specimen
Gallium ity (R1, bility (R2, 250-mL volumetric flask, dilute to volume, and mix. Prepare
Found, % E173E173, E173E173,
M = 1) M = 1)
fresh as needed.
Alcoa Standard GA-2-A, 1075 Alloy 0.0053 0.00049 0.00050 329.5 Lithium Standard Solution C (1 mL = 0.020 mg
(0.005 % Ga) Li)—Pipet 10 mL of Lithium Standard Solution A into a
NBS 85b 2024 Alloy (0.019 % Ga) 0.0204 0.00108 0.00258
500-mL volumetric flask, dilute to volume, and mix. Prepare
fresh as needed.
323.2 Bias—No information of the accuracy of this test 329.6 Lithium Standard Solution D (1 mL = 0.008 mg
method is available. The accuracy may be judged, however, by Li)—Pipet 20 mL of Lithium Standard Solution B into a
comparing the accepted reference values with the correspond- 100-mL volumetric flask, dilute to volume, and mix. Prepare
ing arithmetic average obtained by interlaboratory testing. fresh as needed.
LITHIUM BY THE ATOMIC ABSORPTION TEST 330. Calibration

METHOD 330.1 Calibration Solutions:
324. Scope 330.1.1 0.002 to 0.02 % Li—Using pipets, transfer 0, 5, 10,
324.1 This test method covers the determination of lithium 15, 20, and 25 mL of Lithium Standard Solution D to 100-mL
in concentrations from 0.001 to 4 %. volumetric flasks containing 5 mL of HCl (1+1). Add 20 mL of
325. Summary of Test Method Aluminum Solution A to each flask, cool, dilute to volume, and
325.1 An acid solution of the sample is aspirated into the mix.
air-acetylene flame of an atomic absorption spectrophotometer. 330.1.2 0.02 to 0.5 % Li—Using pipets, transfer 0, 5, 10, 15,
The absorption of the lithium resonance line at 670.8 nm is 20, and 25 mL of Lithium Standard Solution C to 100-mL
measured and compared with the absorption of matched matrix volumetric flasks containing 8.5 mL of HCl (1+1). Add 2 mL
calibration solutions containing known amounts of lithium. of Aluminum Solution A to each flask, dilute to volume, and
326. Concentration Range mix.
326.1 If the optimum concentration range is not known, 330.1.3 0.5 to 4 % Li—Using pipets, transfer 0, 5, 10, 15, 20,
determine it in accordance with Guide E1024. A sensitivity of and 25 mL of Lithium Standard Solution B to 200-mL
0.035 µg/mL for 0.0044 absorbance is widely obtained. volumetric flasks containing 17 mL of HCl (1+1). Add 5 mL of
327. Interferences Aluminum Solution B to each flask, dilute to volume, and mix.
327.1 Elements normally present do not interfere when their 330.2 Reference Solution—The zero lithium addition cali-
concentrations are less than the maximum limits shown in 1.1. bration solution is used for the reference solution for each
328. Apparatus range of calibration.
328.1 Atomic Absorption Spectrophotometer—Determine 330.3 Since sensitivity may vary among instruments, deter-
that the instrument is suitable for use in accordance with Guide mine the suitability of the selected concentration range and
E1024. The percent variability for the highest calibration apparatus in accordance with Guide E1024. Scale expansion
solution (Vc) should not exceed 1 %. may be required to meet the minimum response criteria for
329. Reagents some ranges. Sample and calibration solutions must always
329.1 Aluminum Solution A (1 mL = 50 mg Al)—Transfer 25 contain approximately the same quantity of aluminum per
g of aluminum (purity: 99.99 % min) to a 1-L beaker. Add 100 millilitre.
mL of water and a small drop of mercury. Add 275 mL of HCl 331. Procedure
in small increments, heating moderately to accelerate dissolu- 331.1 Test Solution:
tion. When dissolution is complete, add 2 mL of H2O2(30 %) 331.1.1 Transfer a 1.000-g sample, weighed to the nearest 1
and boil gently for 5 min. Cool, transfer to a 500-mL mg, to a 400-mL beaker. Add 20 mL of water and cover with
volumetric flask, dilute to volume, and mix. Store in a a ribbed cover glass. Add 27 mL of HCl (1+1) in small
polyethylene bottle. increments. Warm, if necessary, to complete dissolution. When
329.2 Aluminum Solution B (1 mL = 5.0 mg Al)—Pipet 10 the reaction subsides, add 2 mL of H2O2 (30 %) and boil for 5
mL of Aluminum Solution A into a 100-mL volumetric flask. min.
Dilute to volume, and mix. Store in a polyethylene bottle. 331.1.2 Filter through a medium-porosity paper into a
100-mL volumetric flask. Wash the filter with hot water, but be
23
Supporting data are available from ASTM Headquarters. Request RR:E01- careful not to exceed about 85 mL total filtrate. Reserve the
1050. filtrate.
26
E34 – 11
331.1.3 When a visible residue is present, transfer the filter A
Lithium, % 5 B 3 100 (18)
paper and residue to a platinum crucible, dry, and ignite at
600°C. Cool, add 5 mL of HF, and then add HNO3 dropwise
where:
until a clear solution is obtained. Evaporate carefully to
A = lithium in the final test solution, mg, and
dryness, cool, and dissolve the residue in 5 drops of HCl (1+1) B = sample represented in the test solution taken for
and a minimum amount of water. Heat to dissolve the salts, and analysis, mg.
add this solution to the filtrate reserved in 331.1.2.
331.1.4 Cool the solution from 331.1.2 or the combined 334. Precision and Bias
solutions from 331.1.3. Dilute to volume and mix. 334.1 Precision—Eight laboratories cooperated in testing
331.1.5 For lithium concentrations less than 0.02 %, aspirate this test method by analyzing each of the samples on three
the solution from 331.1.4. Use calibration solutions prepared in separate days. Repeatability (R1) and reproducibility (R2) were
accordance with 330.1.1. calculated by analysis of variance (Practice E173) using M
331.1.6 For lithium concentrations between 0.02 and 0.5 %, = 1. The data obtained are summarized in Table 20.
pipet 10 mL of the solution obtained in 331.1.4 into a 100-mL 334.2 Bias—No certified reference materials suitable for
volumetric flask containing 8 mL of HCl (1+1), cool, dilute to testing this test method were available when the interlaboratory
volume, and mix. Use calibration solutions prepared in accor- testing program was conducted. The user of this test method is
dance with 330.1.2. encouraged to employ accepted reference materials, if avail-
331.1.7 For lithium concentrations between 0.5 and 4.0 %, able, to determine the accuracy of this test method as applied
prepare a solution as described in 331.1.6. Pipet 25 mL into a in a specific laboratory.
200-mL volumetric flask containing 15 mL of HCl (1+1), cool, 335. Keywords
dilute to volume, and mix. Use calibration solutions prepared 335.1 aluminum and aluminum alloys; analysis; chemical
in accordance with 330.1.3. analysis
332. Measurements
332.1 Optimize the instrument response and take prelimi- TABLE 20 Statistical Information
nary readings; then complete the analysis and determine the Repeatability Reproducibility
Lithium
lithium concentration using the graphical or ratio procedure in Test Specimen
Found, %
(R1, E173, (R2, E173,
M = 1) M = 1)
accordance with Guide E1024. The graphical procedure is
preferred above 0.02 % lithium. 1075 Alloy 0.00627 0.000563 0.000673
2020 Alloy 0.9567 0.02615 0.05251
333. Calculation 1.5 Cu, 1.1 Mg, 3.5 Li Alloy 3.457 0.0431 0.1340
333.1 Calculate the percentage of lithium as follows:
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What are the different methods described for analyzing the chemical composition of aluminum and aluminum alloys?

What composition ranges does this standard cover for the different elements in aluminum alloys?

Designation: E34 – 11

Standard Test Methods for

1. Scope Procedure Sections

7. Sampling CHROMIUM BY THE PERSULFATE OXIDATION

148.1.2 Add 25 mL of NaOH Solution A, cover, and, if

188. Scope 194. Calibration

249.2 Reference Solution—The 0 calibration solution is used where:

270. Preparation of Calibration Curve

282. Precision and Bias18 287.3 Beryllium, Standard Solution A (1 mL = 0.1 mg

Add 50 mL of aluminum solution to each flask, dilute to TABLE 16 Statistical Information

LITHIUM BY THE ATOMIC ABSORPTION TEST 330. Calibration

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