ASTM E352-23

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: E352 − 23
Standard Test Methods for
Chemical Analysis of Tool Steels and Other Similar Medium-
and High-Alloy Steels
This standard is issued under the fixed designation E352; 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.
1. Scope
Sections
Copper by the Sulfide Precipitation-
1.1 These test methods cover the chemical analysis of tool
Electrodeposition Gravimetric Method (0.01 % to 2.0 %) 70–77
steels and other similar medium- and high-alloy steels having Lead by the Ion-Exchange—Atomic
Absorption Spectrometry Method (0.001 % to 0.01 %) 99–108
chemical compositions within the following limits:
Manganese by the Periodate
Element Composition Range, % Spectrophotometric Method (0.10 % to 5.00 %) 9–18
Aluminum 0.005 to 1.5
Molybdenum by the Ion Exchange–
Boron 0.001 to 0.10 8-Hydroxyquinoline Gravimetric Method 203–210
Carbon 0.03 to 2.50 Molybdenum by the Thiocyanate
Chromium 0.10 to 14.0 Spectrophotometric Method (0.01 % to 1.50 %) 162–173
Cobalt 0.10 to 14.0 Nickel by the Dimethylglyoxime
Copper 0.01 to 2.0 Gravimetric Method (0.1 % to 4.0 %) 144–151
Lead 0.001 to 0.01 Phosphorus by the Alkalimetric Method (0.01 % to 0.05 %) 136–143
Manganese 0.10 to 15.00 Phosphorus by the Molybdenum Blue
Molybdenum 0.01 to 10.00 Spectrophotometric Method (0.002 % to 0.05 %) 19–29
Nickel 0.02 to 4.00 Silicon by the Gravimetric Method (0.10 % to 2.50 %) 45–51
Nitrogen 0.001 to 0.20 Sulfur by the Gravimetric
Method—Discontinued 1988 29–35
Phosphorus 0.002 to 0.05
Silicon 0.10 to 2.50 Sulfur by the Combustion-Iodate
Titration Method—Discontinued 2012 36–44
Sulfur 0.002 to 0.40
Tungsten 0.01 to 21.00 Sulfur by the Chromatographic
Vanadium 0.02 to 5.50 Gravimetric Method—Discontinued 1980 109–116
Tin by the Solvent Extraction—
1.2 The test methods in this standard are contained in the
Atomic Absorption Spectrometry Method (0.002 % to 0.10 %) 152–161
sections indicated below: Vanadium by the Atomic
Absorption Spectrometry Method (0.006 % to 0.15 %) 193–202
Sections
Carbon, Total, by the Combustion— 1.3 Test methods for the determination of carbon and sulfur
Thermal Conductivity Method—
not included in this standard can be found in Test Methods
Discontinued 1986 125–135
E1019.
Carbon, Total, by the Combustion Gravimetric
Method—Discontinued 2012 78–88
1.4 Some of the composition ranges given in 1.1 are too
Chromium by the Atomic Absorption
broad to be covered by a single test method and therefore this
Spectrometry Method (0.006 % to 1.00 %) 174–183
Chromium by the Peroxydisulfate
standard contains multiple test methods for some elements.
Oxidation—Titration Method (0.10 % to 14.00 %) 184–192
The user must select the proper test method by matching the
Chromium by the Peroxydisulfate-Oxidation
Titrimetric Method—Discontinued 1980 117–124 information given in the Scope and Interference sections of
Cobalt by the Ion-Exchange—
each test method with the composition of the alloy to be
Potentiometric Titration Method (2 % to 14 %) 52–59
analyzed.
Cobalt by the Nitroso-R-Salt
Spectrophotometric Method (0.10 % to 5.0 %) 60–69
1.5 The values stated in SI units are to be regarded as
Copper by the Neocuproine
standard.
Spectrophotometric Method (0.01 % to 2.00 %) 89–98
1.6 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
These test methods are under the jurisdiction of the ASTM Committee E01 on
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct
priate safety, health, and environmental practices and deter-
responsibility of Subcommittee E01.01 on Iron, Steel, and Ferroalloys.
mine the applicability of regulatory limitations prior to use.
Current edition approved Nov. 15, 2023. Published December 2023. Originally
ɛ1 Specific hazards statements are given in Section 6 and in
approved in 1968. Last previous edition approved in 2018 as E352 – 18 . DOI:
10.1520/E0352-23. special “Warning” paragraphs throughout these test methods.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E352 − 23
1.7 This international standard was developed in accor- 3. Terminology
dance with internationally recognized principles on standard-
3.1 For definitions of terms used in these test methods, refer
ization established in the Decision on Principles for the
to Terminology E135.
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
4. Significance and Use
Barriers to Trade (TBT) Committee.
4.1 These test methods for the chemical analysis of metals
and alloys are primarily intended as referee methods to test
2. Referenced Documents
such materials for compliance with compositional specifica-
2.1 ASTM Standards:
tions particularly those under the jurisdiction of ASTM Com-
D1193 Specification for Reagent Water
mittee A01 on Steel, Stainless Steel, and Related Alloys. It is
E29 Practice for Using Significant Digits in Test Data to
assumed that all who use these test methods will be trained
Determine Conformance with Specifications
analysts capable of performing common laboratory procedures
E50 Practices for Apparatus, Reagents, and Safety Consid-
skillfully and safely. It is expected that work will be performed
erations for Chemical Analysis of Metals, Ores, and
in a properly equipped laboratory under appropriate quality
Related Materials
control practices such as those described in Guide E882.
E60 Practice for Analysis of Metals, Ores, and Related
5. Apparatus, Reagents, and Instrumental Practices
Materials by Spectrophotometry
E135 Terminology Relating to Analytical Chemistry for
5.1 Apparatus—Specialized apparatus requirements are
Metals, Ores, and Related Materials
listed in the “Apparatus” Section in each method.
E173 Practice for Conducting Interlaboratory Studies of
5.1.1 In the methods specifying spectrophotometric testing,
Methods for Chemical Analysis of Metals (Withdrawn
the cells utilized to contain the reference material solutions and
1997)
sample solutions in spectrophotometers are referred to as
E350 Test Methods for Chemical Analysis of Carbon Steel,
“absorption cells”. Please note that the radiant energy passed
Low-Alloy Steel, Silicon Electrical Steel, Ingot Iron, and
through the cells can be measured as absorbance or transmit-
Wrought Iron
tance. These methods refer to absorbance measurements. Refer
E351 Test Methods for Chemical Analysis of Cast Iron—All
to Practices E60 for details.
Types
5.2 Reagents:
E353 Test Methods for Chemical Analysis of Stainless,
5.2.1 Purity of Reagents—Reagent grade chemicals shall be
Heat-Resisting, Maraging, and Other Similar Chromium-
used in all tests. Unless otherwise indicated, all reagents shall
Nickel-Iron Alloys
conform to the Specifications of the Committee on Analytical
E354 Test Methods for Chemical Analysis of High-
Reagents of the American Chemical Society where such
Temperature, Electrical, Magnetic, and Other Similar Iron,
specifications are available. Other chemicals may be used,
Nickel, and Cobalt Alloys
provided it is first ascertained that they are of sufficiently high
E882 Guide for Accountability and Quality Control in the
purity to permit their use without adversely affecting the
Chemical Analysis Laboratory
expected performance of the determination, as indicated in the
E1019 Test Methods for Determination of Carbon, Sulfur,
section on “Precision and Bias.”
Nitrogen, and Oxygen in Steel, Iron, Nickel, and Cobalt
5.2.2 Purity of Water—Unless otherwise indicated, refer-
Alloys by Various Combustion and Inert Gas Fusion
ences to water shall mean reagent water conforming to Type I
Techniques
or Type II of Specification D1193. Type III or IV may be used
E1024 Guide for Chemical Analysis of Metals and Metal
if they effect no measurable change in the blank or sample.
Bearing Ores by Flame Atomic Absorption Spectropho-
tometry (Withdrawn 2004) 5.3 Spectrophotometric Practice—Spectrophotometric
practice prescribed in these test methods shall conform to
E1601 Practice for Conducting an Interlaboratory Study to
Evaluate the Performance of an Analytical Method Practice E60.
E1806 Practice for Sampling Steel and Iron for Determina-
6. Hazards
tion of Chemical Composition
6.1 For precautions to be observed in the use of certain
2.2 Other Document:
reagents and equipment in these methods, refer to Practices
ISO 5725 Precision of Test Methods—Determination of
E50.
Repeatability and Reproducibility for Inter-Laboratory
Tests
7. Sampling
7.1 For procedures to sample the material, refer to Practice
E1806.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. “Reagent Chemicals, American Chemical Society Specifications,” American
The last approved version of this historical standard is referenced on Chemical Society, Washington, DC, www.acs.org. For suggestions on the testing of
www.astm.org. Reagents not listed by the American Chemical Society, see the United States
Available from American National Standards Institute (ANSI), 25 W. 43rd St., Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc.
4th Floor, New York, NY 10036, http://www.ansi.org. (USPC), Rockville, MD, www.usp.org.
E352 − 23
8. Interlaboratory Studies and Rounding Calculated 13.2 The spectral transmittance curve of permanganate ions
Values exhibits two useful minima, one at approximately 526 nm, and
the other at 545 nm. The latter is recommended when a
8.1 These test methods have been evaluated in accordance
“narrow-band” spectrophotometer is used.
with Practice E173 (withdrawn 1997) or ISO 5725. Practice
E173 has been replaced by Practice E1601. The 13.3 Tungsten, when present in amounts of more than 0.5 %
Reproducibility, R2, of E173 corresponds to the Reproducibil- interferes by producing a turbidity in the final solution. A
ity Index, R, of E1601. The Repeatability, R1, of E173 special procedure is provided for use with samples containing
corresponds to the Repeatability Index, r, of E1601. more than 0.5 % tungsten which eliminates the problem by
preventing the precipitation of the tungsten.
8.2 Rounding of test results obtained using these test meth-
ods shall be performed as directed in ASTM E29, Rounding
14. Reagents
Method, unless an alternative rounding method is specified by
14.1 Manganese, Standard Solution (1 mL = 0.032 mg
the customer or applicable material specification.
Mn)—Transfer the equivalent of 0.4000 g of assayed, high-
purity manganese (purity: 99.99 % minimum), to a 500-mL
MANGANESE BY THE METAPERIODATE
volumetric flask and dissolve in 20 mL of HNO by heating.
SPECTROPHOTOMETRIC METHOD
Cool, dilute to volume, and mix. Using a pipet, transfer 20 mL
to a 500-mL volumetric flask, dilute to volume, and mix.
9. Scope
14.2 Nitric-Phosphoric Acid Mixture—Cautiously, while
9.1 This method covers the determination of manganese
stirring, add 100 mL of HNO and 400 mL of H PO to 400
3 3 4
from 0.10 % to 5.00 %.
mL of water. Cool, dilute to 1 L, and mix. Prepare fresh as
needed.
10. Summary of Method
14.3 Potassium Metaperiodate Solution (7.5 g/L)—Dissolve
10.1 Manganous ions are oxidized to permanganate ions by
7.5 g of potassium metaperiodate (KIO ) in 200 mL of hot
treatment with periodate. Tungsten when present at composi-
HNO (1 + 1), add 400 mL of H PO , cool, dilute to 1 L, and
3 3 4
tions greater than 0.5 % is kept in solution with phosphoric
mix.
acid. Solutions of the samples are fumed with HClO so that
14.4 Water, Pretreated with Metaperiodate—Add 20 mL of
the effect of periodate is limited to the oxidation of manganese.
Spectrophotometric absorbance measurement is made at 545 KIO solution to 1 L of water, mix, heat at not less than 90 °C
for 20 min to 30 min, and cool. Use this water to dilute
nm.
solutions to volume that have been treated with KIO solution
11. Concentration Range
to oxidize manganese, and thus avoid reduction of permangan-
ate ions by any reducing agents in the untreated water.
11.1 The recommended concentration range is 0.15 mg to
(Caution—Avoid the use of this water for other purposes.)
0.8 mg of manganese per 50 mL of solution, using a 1-cm cell
(Note 1) and a spectrophotometer with a band width of 10 nm
15. Preparation of Calibration Curve
or less.
15.1 Calibration Solutions—Using pipets, transfer 5 mL, 10
NOTE 1—This method has been written for cells having a 1-cm light
mL, 15 mL, 20 mL, and 25 mL of manganese standard solution
path and a “narrow-band” instrument. The concentration range depends
(1 mL = 0.032 mg Mn) to 50-mL borosilicate glass volumetric
upon band width and spectral region used as well as cell optical path
length. Cells having other dimensions may be used, provided suitable
flasks, and, if necessary, dilute to approximately 25 mL.
adjustments can be made in the amounts of sample and reagents used.
Proceed as directed in 15.3.
15.2 Reference Solution—Transfer approximately 25 mL of
12. Stability of Color
water to a 50-mL borosilicate glass volumetric flask. Proceed
12.1 The color is stable for at least 24 h.
as directed in 15.3.
13. Interferences 15.3 Color Development—Add 10 mL of KIO solution,
and heat the solutions at not less than 90 °C for 20 min to 30
13.1 HClO treatment, which is used in the procedure,
min (Note 2). Cool, dilute to volume with pretreated water, and
yields solutions which can be highly colored due to the
mix.
presence of Cr (VI) ions. Although these ions and other colored
ions in the sample solution undergo no further change in color
NOTE 2—Immersing the flasks in a boiling water bath is a preferred
means of heating them for the specified period to ensure complete color
quality upon treatment with metaperiodate ion, the following
development.
precautions must be observed when filter spectrophotometers
are used: Select a filter with maximum transmittance between 15.4 Spectrophotometry:
545 nm and 565 nm. The filter must transmit not more than 5 % 15.4.1 Multiple-Cell Spectrophotometer—Measure the cell
of its maximum at a wavelength shorter than 530 nm. The band correction using the Reference Solution (15.2) in absorption
width of the filter should be less than 30 nm when measured at cells with a 1-cm light path and using a light band centered at
50 % of its maximum transmittance. Similar restrictions apply 545 nm. Using the test cell, take the spectrophotometric
with respect to the wavelength region employed when other absorbance readings of the calibration solutions versus the
“wide-band” instruments are used. Reference Solution (15.2)
E352 − 23
15.4.2 Single-Cell Spectrophotometer—Transfer a suitable chromium is oxidized and the HCl is expelled, but avoid
portion of the Reference Solution (15.2) to an absorption cell heating to fumes of SO . Cool, add 50 mL of water, digest, if
with a 1-cm light path and adjust the spectrophotometer to the necessary, to dissolve the salts, cool, and transfer the solution
initial setting, using a light band centered at 545 nm. While to either a 100-mL or 500-mL volumetric flask as directed in
maintaining this adjustment, take the spectrophotometric ab- 16.1. Proceed to 16.1.3.
sorbance readings of the calibration solutions. 16.1.3 Cool the solution to room temperature, dilute to
volume, and mix. Allow insoluble matter to settle, or dry-filter
15.5 Calibration Curve—Follow the instrument manufac-
through a coarse paper and discard the first 15 mL to 20 mL of
turer’s instructions for generating the calibration curve. Plot
the filtrate, before taking aliquots.
the net spectrophotometric absorbance readings of the calibra-
16.1.4 Using a pipet, transfer 10 mL to 20 mL aliquots, as
tion solutions against the milligrams of manganese per 50 mL
specified in 16.1 to two 50-mL borosilicate glass volumetric
of solution.
flasks. Treat one portion as directed in 16.3. Treat the other
16. Procedure portion as directed in 16.4.1.
16.1 Test Solutions—Select and weigh a sample as follows: 16.2 Reagent Blank Solution—Carry a reagent blank
through the entire procedure using the same amounts of all
Tolerance in Dilu- Aliquot
Sample Sample tion, Volume, reagents with the sample omitted.
Manganese, % Mass, g Mass, mg mL mL
16.3 Color Development—Proceed as directed in 15.3.
0.10 to 0.5 0.80 0.5 100 20
16.4 Reference Solutions:
0.45 to 1.0 0.35 0.3 100 20
0.85 to 2.0 0.80 0.5 500 20
16.4.1 Background Color Solution—To one of the sample
0.95 to 5.0 0.80 0.5 500 10
aliquots in a 50-mL volumetric flask, add 10 mL of nitric-
Transfer it to a 300-mL Erlenmeyer flask.
phosphoric acid mixture, and heat the solution at not less than
16.1.1 For Samples Containing Not More Than 0.5 %
90 °C for 20 min to 30 min (Note 2). Cool, dilute to volume
Tungsten:
(with untreated water), and mix.
16.1.1.1 To dissolve samples that do not require HF, add 8
16.4.2 Reagent Blank Reference Solution—Transfer the re-
mL to 10 mL of HCl (1 + 1), and heat. Add HNO as needed
3 agent blank solution (16.2) to the same size volumetric flask as
to hasten dissolution, and then add 3 mL to 4 mL in excess.
used for the test solutions and transfer the same size aliquots as
When dissolution is complete, cool, then add 10 mL of HClO ;
4 used for the test solutions to two 50-mL volumetric flasks.
evaporate to fumes to oxidize chromium, if present, and to
Treat one portion as directed in 16.3 and use as reference
expel HCl. Continue fuming until salts begin to separate. Cool,
solution for test samples. Treat the other as directed in 16.4.1
add 50 mL of water, and digest if necessary to dissolve the
and use as reference solution for Background Color Solutions.
salts. Cool and transfer the solution to either a 100-mL or
16.5 Spectrophotometry—Establish the cell corrections with
500-mL volumetric flask as indicated in 16.1. Proceed to
the Reagent Blank Reference solution to be used as a reference
16.1.3.
solution for Background Color solutions. Take the spectropho-
16.1.1.2 For samples whose dissolution is hastened by HF,
tometric absorbance readings of the Background Color Solu-
add 8 mL to 10 mL of HCl (1 + 1), and heat. Add HNO and
tions and the test solutions versus the respective Reagent Blank
a few drops of HF as needed to hasten dissolution, and then add
Reference Solutions as directed in 15.4.
3 mL to 4 mL of HNO . When dissolution is complete, cool,
then add 10 mL of HClO , evaporate to fumes to oxidize
17. Calculation
chromium, if present, and to expel HCl. Continue fuming until
17.1 Convert the net spectrophotometric absorbance reading
salts begin to separate. Cool, add 50 mL of water, digest if
of the test solution and of the background color solution to
necessary to dissolve the salts, cool, and transfer the solution to
either a 100-mL or 500-mL volumetric flask as indicated in
16.1. Proceed to 16.1.3.
TABLE 1 Statistical Information—Manganese by the
16.1.2 For Samples Containing More Than 0.5 % Tungsten: Metaperiodate Spectrophotometric Method
16.1.2.1 To dissolve samples that do not require HF, add 8
Man- Repeata- Repro-
ganese bility ducibil-
mL to 10 mL of H PO , 10 mL of HClO , 5 mL to 6 mL of
3 4 4 Test Specimen
Found, (R , ity (R ,
1 2
H SO , and 3 mL to 4 mL of HNO . Heat moderately until the
2 4 3
% E173) E173)
sample is decomposed, and then heat to copious white fumes
1. Special W high-speed tool 0.160 0.012 0.035
for 10 min to 12 min or until the chromium is oxidized and the
steel (NIST 440, 0.15
Mn)
HCl is expelled, but avoid heating to fumes of SO . Cool, add
2. Tool steel (NIST 153a, 0.183 0.005 0.010
50 mL of water, and digest, if necessary, to dissolve the salts.
0.192 Mn)
Transfer the solution to either a 100-mL or 500-mL volumetric
3. W high-speed tool steel 0.268 0.010 0.034
(NIST 441, 0.27 Mn)
flask as directed in 16.1. Proceed to 16.1.3.
4. Alloy Steel (NIST, 159, 0.819 0.010 0.034
16.1.2.2 For samples whose dissolution is hastened by HF,
a, 0.807 Mn)
add 8 mL to 10 mL of H PO , 10 mL of HClO , 5 mL to 6 mL 5. Low Alloy Steel (NIST 1.91 0.02 0.04
3 4 4
100b, 1.89 Mn)
of H SO , 3 mL to 4 mL of HNO , and a few drops of HF. Heat
2 4 3
6. Stainless Steel (NIST 444, 4.60 0.04 0.13
moderately until the sample is decomposed, and then heat to
4.62 Mn)
copious white fumes for 10 min to 12 min or until the
E352 − 23
milligrams of manganese by means of the calibration curve. 24. Apparatus
Calculate the percentage of manganese as follows:
24.1 Glassware must be phosphorus- and arsenic-free. Boil
Manganese, % 5 A 2 B / C × 10 (1) the glassware with HCl and rinse with water before use. It is
~ ! ~ !
recommended that the glassware used for this determination be
where:
reserved for this use only. Many detergents contain phosphorus
A = manganese, mg, found in 50 mL of the final test
and must not be used for cleaning purposes.
solution,
B = apparent manganese, mg, found in 50 mL of the final
25. Reagents
background color solution, and
25.1 Ammonium Molybdate Solution (20 g/L)—Cautiously,
C = sample mass, g, represented in 50 mL of the final test
while stirring and cooling, add 300 mL of H SO to 500 mL of
2 4
solution.
water and cool. Add 20 g of ammonium heptamolybdate
((NH ) Mo O ·4H O), cautiously dilute to 1 L, and mix.
4 6 7 24 2
18. Precision and Bias
25.2 Ammonium Molybdate-Hydrazine Sulfate Solution—
18.1 Precision—Nine laboratories cooperated in testing this
Dilute 250 mL of the ammonium molybdate solution to 600
method and obtained the data summarized in Table 1.
mL, add 100 mL of the hydrazine sulfate solution, dilute to 1
18.2 Bias—The accuracy of this test method has been
L, and mix. Do not use a solution that has stood for more than
deemed satisfactory based upon the data for the certified
1 h.
reference materials in Table 1. Users are encouraged to use
25.3 Hydrazine Sulfate Solution (1.5 g/L)—Dissolve 1.5 g
these or similar reference materials to verify that the test
of hydrazine sulfate ((NH ) ·H SO ) in water, dilute to 1 L,
2 2 2 4
method is performing accurately in their laboratories.
and mix. Discard any unused solution after 24 h.
25.4 Phosphorus Standard Solution A (1 mL = 1.0 mg
PHOSPHORUS BY THE MOLYBDENUM BLUE
P)—Transfer 2.292 g of anhydrous disodium hydrogen phos-
SPECTROPHOTOMETRIC METHOD
phate (Na HPO ), previously dried to constant mass at 105 °C,
2 4
to a 500-mL volumetric flask; dissolve in about 100 mL of
19. Scope
water, dilute to volume, and mix.
19.1 This test method covers the determination of phospho-
25.5 Phosphorus Standard Solution B (1 mL = 0.01 mg
rus from 0.002 % to 0.05 %.
P)—Using a pipet, transfer 10 mL of Solution A (1 mL = 1.0
mg P) to a 1-L volumetric flask, add 50 mL of HClO (1 + 5),
20. Summary of Method
dilute to volume, and mix.
20.1 The sample is dissolved in mixed acids and the
25.6 Phosphorus Standard Solution C (1 mL = 0.10 mg
solution is fumed with HClO . Ammonium molybdate is added
P)—Using a pipet, transfer 50 mL of Solution A (1 mL = 1.0
to react with the phosphorus to form the heteropoly phospho-
mg P) to a 500-mL volumetric flask, add 50 mL of HClO (1
molybdate. This species is then reduced with hydrazine sulfate
+ 5), dilute to volume, and mix.
to form the molybdenum blue complex. Spectrophotometric
absorbance measurement is made at 650 nm or 825 nm, 25.7 Sodium Sulfite Solution (100 g/L)—Dissolve 100 g of
depending upon the concentration. sodium sulfite (Na SO ) in water, dilute to 1 L, and mix.
2 3
26. Preparation of Calibration Curve for Concentrations
21. Concentration Range
from 0.005 mg/100 mL to 0.05 mg/100 mL
21.1 The recommended concentration range is from 0.005
26.1 Calibration Solutions—Using pipets, transfer 5 mL, 10
mg to 0.05 mg of phosphorus per 100 mL of solution when
mL, 15 mL, 25 mL, and 50 mL of Phosphorus Standard
measured at 825 nm and from 0.05 mg to 0.3 mg of phosphorus
Solution B (1 mL = 0.01 mg P) to 100-mL volumetric flasks.
per 100 mL of solution when measured at 650 nm, using a
Add 20 mL of HClO , dilute to volume, and mix. Using a pipet,
1-cm cell. 4
transfer 10 mL of each solution to a 100-mL borosilicate glass
NOTE 3—This test method has been written for cells having a 1-cm light
path. Cells having other dimensions may be used, provided suitable
volumetric flask. Proceed as directed in 26.3.
adjustments can be made in the amounts of sample and reagents used.
26.2 Reagent Blank—Transfer 12 mL of HClO (1 + 5) to a
100-mL borosilicate glass volumetric flask.
22. Stability of Color
26.3 Color Development:
22.1 The molybdenum blue complex is stable for at least 2
26.3.1 Add 15 mL of Na SO solution, boil gently for 30 s,
2 3
h.
and add 50 mL of ammonium molybdate-hydrazine sulfate
solution that has been prepared within the hour.
23. Interferences
26.3.2 Heat the solutions at not less than 90 °C for 20 min,
23.1 None of the elements usually present interfere except
quickly cool, dilute to volume, and mix.
arsenic which is removed by volatilization as the bromide. The
NOTE 4—Immersing the flasks in a boiling water bath is the preferred
interference of tungsten at compositions greater than 0.5 % is
means of heating them for complete color development.
avoided by proceeding directly with a small sample mass rather
than an aliquot portion of a larger sample. 26.4 Reference Solution—Water.
E352 − 23
26.5 Spectrophotometry: 27.2.1 Test Solution:
26.5.1 Multiple-Cell Spectrophotometer—Measure the re- 27.2.1.1 Transfer 0.100-g samples, weighed to the nearest
agent blank (which includes the cell correction) versus the 0.1 mg, to two 100-mL Erlenmeyer flasks.
reference solution (26.4) using absorption cells with a 1-cm 27.2.1.2 Add 5 mL of a mixture of 1 volume of HNO and
light path and using a light band centered at 825 nm. Using the 3 volumes of HCl. When the reaction has ceased, add 2.5 mL
test cell, take the spectrophotometric absorbance readings of of HClO and 5 mL of HBr (1 + 4). Evaporate the solutions to
the calibration solutions versus the reference solution. copious white fumes; then, without delay, fume strongly
26.5.2 Single-Cell Spectrophotometer—Transfer a suitable enough to cause the white fumes to clear the neck of the flasks,
portion of the reference solution (26.4) to an absorption cell and continue at this rate for 1 min.
with a 1-cm light path and adjust the spectrophotometer to the 27.2.1.3 Cool the solutions, and add 10 mL of water. Filter
initial setting using a light band centered at 825 nm. While through a 9-cm fine paper collecting the filtrate in a 100-mL
maintaining this adjustment, take the spectrophotometric ab- borosilicate glass volumetric flask. Wash the paper and in-
sorbance readings of the reagent blank solution and of the soluble matter 5 times with 3-mL portions of water. Treat one
calibration solutions. solution as directed in 27.2.3 and the other as directed in
27.2.4.
26.6 Calibration Curve—Follow the instrument manufac-
27.2.2 Reagent Blank Solution—Proceed as directed in
turer’s instructions for generating the calibration curve. Plot
27.2.1.2 and 27.2.1.3.
the net spectrophotometric absorbance readings of the calibra-
27.2.3 Color Development—Proceed as directed in 26.3.
tion solutions against the milligrams of phosphorus per 100 mL
27.2.4 Reference Solutions:
of solution.
27.2.4.1 Water—Use this as the reference solution for the
reagent blank solution.
27. Procedure
27.2.4.2 Background Color Reference Solution—Add 15
27.1 For Samples Containing Less Than 0.5 % Tungsten:
mL of Na SO solution to the second 10-mL portion obtained
2 3
27.1.1 Test Solution:
in 27.2.1.3. Boil gently for 30 s, add 50 mL of H SO (3 + 37),
2 4
27.1.1.1 Transfer a 1.0-g sample, weighed to the nearest 0.5
cool, dilute to volume, and mix. Use this as the reference
mg, to a 250-mL Erlenmeyer flask.
solution for the test solution.
27.1.1.2 Add 15 mL of a freshly prepared mixture of 1
27.2.5 Spectrophotometry—Proceed as directed in 27.1.5.
volume of HNO and 3 volumes of HCl, slowly and in small
portions. When the reaction has ceased, add 10 mL of HClO
28. Calculation
and evaporate to fumes. Remove the flask immediately to
28.1 Convert the net spectrophotometric absorbance reading
avoid undue loss of HClO , cool, and add 20 mL of HBr (1 +
of the test solution and of the reagent blank solution to
4). Evaporate the solution to copious white fumes and then,
milligrams of phosphorus by means of the appropriate calibra-
without delay, fume strongly enough to cause the white fumes
tion curve. Calculate the percent of phosphorus as follows:
to clear the neck of the flask, and continue at this rate for 1 min.
Phosphorus,% 5 ~A 2 B!⁄~C × 10! (2)
27.1.1.3 Cool the solution, add 60 mL of HClO (1 + 5), and
swirl to dissolve the salts. Transfer to a 100-mL volumetric
where:
flask, cool, dilute to volume, and mix. Allow insoluble matter
A = phosphorus found in 100 mL of the final test solution,
to settle or dry filter the solution. Using a pipet, transfer 10-mL
mg,
portions to two 100-mL borosilicate glass volumetric flasks;
B = phosphorus found in 100 mL of the final reagent blank
treat one as directed in 27.1.3 and the other as directed in
solution, mg, and
27.1.4.2.
C = sample represented in 100 mL of the final test solution,
27.1.2 Reagent Blank Solution—Carry a reagent blank
g.
through the entire procedure using the same amount of all
reagents with the sample omitted.
29. Precision and Bias
27.1.3 Color Development—Proceed with one of the 10-mL
29.1 Precision—Eight laboratories cooperated in testing this
portions obtained in 27.1.1.3, as directed in 26.3.
method and obtained the data summarized in Table 2.
27.1.4 Reference Solutions:
27.1.4.1 Water—Use this as the reference solution for the
reagent blank solution. TABLE 2 Statistical Information—Phosphorus – Molybdenum
Blue – Spectrophotometric Method
27.1.4.2 Background Color Reference Solution—Add 15
Phos- Repeata- Repro-
mL of Na SO solution to the second 10-mL portion obtained
2 3
phorus bility ducibil-
in 27.1.1.3. Boil gently for 30 s, add 50 mL of H SO (3 + 37), Test Specimen
2 4
Found, (R , ity (R ,
1 2
cool, dilute to volume, and mix. Use this as the reference
% E173) E173)
solution for the test solution.
1. Tool steel 5Mo-6W-4Cr-2V 0.029 0.011 0.008
(NIST 132a, 0.029 P)
27.1.5 Spectrophotometry—Take the spectrophotometric
2. Tool steel 8Co-9Mo-2W- 0.023 0.008 0.007
absorbance readings of the reagent blank solution and of the
4Cr-2V (NIST 153a,
test solution (using the respective reference solutions) as
0.023 P)
3. Tool steel 18W-4Cr-1V 0.022 0.005 0.007
directed in 26.5.
(NIST 50c, 0.022 P)
27.2 For Samples Containing More Than 0.5 % Tungsten:
E352 − 23
29.2 Bias—The accuracy of this test method has been to the papers, and scrub the beakers thoroughly with a
deemed satisfactory based upon the data for the certified rubber-tipped rod. Wash the papers and precipitates alternately
reference materials in Table 2. Users are encouraged to use with 3 mL to 5 mL portions of hot HCl (1 + 19) and hot water,
these or similar reference materials to verify that the test for a total of 6 times. Finally wash the papers twice with H SO
2 4
method is performing accurately in their laboratories. (1 + 49). Transfer the papers to platinum crucibles.
48.2.4 Dry the papers and heat at 600 °C until the carbon is
removed. Finally ignite at 1100 °C to 1150 °C to constant mass
SULFUR BY THE GRAVIMETRIC METHOD
(at least 30 min). Cool in a desiccator and weigh.
48.2.5 Add enough H SO (1 + 1) to moisten the SiO , and
2 4 2
(This method, which consisted of Sections 29 through 35 of
add 3 mL to 5 mL of HF. Evaporate to dryness and then heat
this standard, was discontinued in 1988.)
at a gradually increasing rate until H SO is removed. Ignite
2 4
SULFUR BY THE COMBUSTION-IODATE
for 15 min at 1100 °C to 1150 °C, cool in a desiccator, and
TITRATION METHOD weigh.
48.2.6 Calculate the percent of silicon as follows:
(This method, which consisted of Sections 36 through 44 of
Silicon,% 5 @~A 2 B! 2 ~C 2 D!# × 0.4674⁄E × 100 (3)
this standard, was discontinued in 2012.)
where:
A = initial mass of crucible plus impure SiO when 65 mL of
SILICON BY THE GRAVIMETRIC METHOD
HClO was taken, g,
45. Scope B = final mass of crucible plus impurities when 65 mL of
HClO was taken, g,
45.1 This method covers the determination of silicon from
C = initial mass of crucible plus impure SiO when 15 mL of
0.10 % to 2.50 %.
HClO was taken, g,
D = final mass of crucible plus impurities when 15 mL of
46. Summary of Method
HClO was taken, g, and
46.1 After dissolution of the sample, silicic acid is dehy-
E = nominal mass (80 g) of 50 mL of HClO .
drated by fuming with H SO or HClO . The solution is
2 4 4
48.3 Sodium Silicate Solution—Transfer 11.0 g of sodium
filtered, and the impure silica is ignited and weighed. The silica
silicate (Na SiO ·9H O) to a 400-mL beaker. Add 150 mL of
is then volatilized with HF. The residue is ignited and weighed; 2 3 2
water and dissolve the salt. Filter through a medium paper,
the loss in mass represents silica.
collecting the filtrate in a 1-L volumetric flask, dilute to
47. Interferences
volume, and mix. Store in a polyethylene bottle. Use this
solution to determine the suitability of the HClO .
47.1 The elements normally present do not interfere if their
compositions are under the maximum limits shown in 1.1.
48.4 Tartaric Acid Solution (20.6 g/L)—Dissolve 20.6 g of
tartaric acid (C H O ) in water, dilute to 1 L, and filter.
4 6 6
48. Reagents
48.5 Water—Use freshly prepared Type II water known to
48.1 The analyst should ensure by analyzing blanks and
be free of silicon. Water distilled from glass, demineralized in
other checks that possible silicon contamination of reagents
columns containing silicon compounds, or stored for extended
will not significantly bias the results.
periods in glass, or combination thereof, has been known to
48.2 Perchloric Acid (HClO ):
absorb silicon.
48.2.1 Select a lot of HClO that contains not more than
49. Procedure
0.0002 % silicon for the analysis of samples containing silicon
in the range from 0.02 % to 0.10 % and not more than 0.0004
49.1 Select and weigh a sample as follows:
% silicon for samples containing more than 0.10 % by
Dehydrating Acid, mL
determining duplicate values for silicon as directed in 48.2.2 – Tolerance in
Sample Sample H SO
2 4
48.2.6.
Silicon, % Mass, g Mass, mg (1 + 4) HClO
48.2.2 Transfer 15 mL of HClO (Note 5) to each of two
4 0.1 to 0.1 4.0 4 150 60
400-mL beakers. To one of the beakers transfer an additional 1.0 to 1.75 3.0 3 100 50
1.75 to 2.50 2.0 2 100 40
50 mL of HClO . Using a pipet, transfer 20 mL of Na SiO
4 2 3
Transfer it to a 400-mL beaker or a 300-mL porcelain
solution (1 mL = 1.00 mg Si) to each of the beakers. Evaporate
casserole. Proceed as directed in 49.2 if tungsten is greater than
the solutions to fumes and heat for 15 min to 20 min at such a
0.5% or if tungsten is less than 0.5%, proceed as directed in
rate that HClO refluxes on the sides of the beakers. Cool
49.2 or 49.3.
sufficiently, and add 100 mL of water (40 °C to 50 °C).
49.2 Sulfuric Acid Dehydration (H SO ):
2 4
NOTE 5—The 15-mL addition of HClO can be from the same lot as the
49.2.1 Add amounts of HCl or HNO , or mixtures and
one to be tested. Once a lot has been established as having less than 0.0002
% silicon, it should preferably be used for the 15-mL addition in all
dilutions of these acids, that are sufficient to dissolve the
subsequent tests of other lots of acid.
sample; and then add the H SO (1 + 4) as specified in 49.1,
2 4
48.2.3 Add paper pulp and filter immediately, using low-ash and cover. Heat until dissolution is complete. Remove and
11-cm medium-porosity filter papers. Transfer the precipitates rinse the cover glass; substitute a ribbed cover glass.
E352 − 23
49.2.2 Evaporate until salts begin to separate; at this point 50. Calculation
evaporate the solution rapidly to the first appearance of fumes
50.1 Calculate the percent of silicon as follows:
and fume strongly for 2 min to 3 min. Cool sufficiently, and add
Silicon,% 5 @ A 2 B × 0.4674 ⁄C# × 100 (4)
~~ ! !
100 mL of water (40 °C to 50 °C). Stir to dissolve the salts and
heat, if necessary, but do not boil. Proceed immediately as
where:
directed in 49.4.
A = initial mass of crucible and impure SiO , g,
B = final mass of crucible and residue, g, and
49.3 Perchloric Acid (HClO ) Dehydration:
C = sample used, g.
49.3.1 Add amounts of HCl or HNO , or mixtures and
dilutions of these acids, which are sufficient to dissolve the
51. Precision and Bias
sample, and cover. Heat until dissolution is complete. Add
51.1 Precision—Eleven laboratories cooperated in testing
HNO to provide a total of 35 mL to 40 mL, followed by
this method and obtained the data summarized in Table 3.
HClO as specified in the table in 49.1. Remove and rinse the
Samples with tungsten below 0.5 % were not available for
cover glass; substitute a ribbed cover glass.
testing the HClO dehydration procedure; neither were samples
49.3.2 Evaporate the solution to fumes and heat for 15 min 4
available with tungsten greater than 0.5 % for testing the
to 20 min at such a rate that the HClO refluxes on the sides of
H SO dehydration procedure near the upper limit of the scope.
the container. Cool sufficiently and add 100 mL of water (40 °C 2 4
to 50 °C). Stir to dissolve the salts and heat to boiling. If the
51.2 Bias—Either this method has no bias, or this method is
sample solution contains more than 100 mg of chromium, add,
subject to bias under certain sample conditions. Only one
while stirring, 1 mL of tartaric acid solution for each 25 mg of
certified reference material was available for testing during the
chromium.
interlaboratory study, see Table 3. The user of this method is
encouraged to utilize accepted reference materials, if available,
49.4 Add paper pulp and filter immediately, on a low-ash
to determine the presence or absence of bias.
11-cm medium-porosity filter paper. Collect the filtrate in a
600-mL beaker. Transfer the precipitate to the paper, and scrub
the container thoroughly with a rubber-tipped rod. Wash the
COBALT BY THE ION-EXCHANGE—
paper and precipitate alternately with 3 mL to 5 mL portions of
POTENTIOMETRIC TITRATION METHOD
hot HCl (1 + 19) and hot water until iron salts are removed but
for not more than a total of ten washings. If the HClO
52. Scope
dehydration method was followed, wash the paper twice more
52.1 This method covers the determination of cobalt from
with H SO (1 + 49), but do not collect these washings in the
2 4
2 % to 14 %.
filtrate; discard the washings. Transfer the paper to a platinum
crucible and reserve.
53. Summary of Method
49.5 Add 15 mL of HNO to the filtrate, stir, and evaporate
3 53.1 Cobalt is separated from interfering elements by selec-
in accordance with either 49.2 or 49.3, depending upon the
tive elution from an anion-exchange column using HCl. The
dehydrating acid used. Filter immediately, using a low-ash,
cobalt is oxidized to the trivalent state with ferricyanide, and
9-cm 100-porosity filter paper, and wash as directed in 49.4.
the excess ferricyanide is titrated potentiometrically with
cobalt solution.
49.6 Transfer the paper and precipitate to the reserved
platinum crucible. Dry the papers and then heat the crucible at
54. Interferences
600 °C until the carbon is removed. Finally ignite at 1100 °C
54.1 The elements normally present do not interfere if their
to 1150 °C to constant mass (at least 30 min). Cool in a
compositions are under the maximum limits shown in 1.1.
desiccator and weigh.
49.7 Add enough H SO (1 + 1) to moisten the impure
2 4 55. Apparatus
SiO , and add 3 mL to 5 mL of HF. Evaporate to dryness and
55.1 Ion-Exchange Column, approximately 25 mm in diam-
then heat at a gradually increasing rate until H SO is removed.
2 4
eter and 300 mm in length, tapered at one end, and provided
Ignite at 1100 °C to 1150 °C for 15 min, cool in a desiccator,
with a stopcock to control the flow rate, and a second, lower
and weigh. If the sample contains more than 0.5 % tungsten,
stopcock to stop the flow. A Jones Reductor (Fig. 1) may be
ignite at 750 °C instead of 1100 °C to 1150 °C after
adapted to this method. A reservoir for the eluants may be
volatilization of SiO .
added at the top of the column.
55.2 pH meter, with a platinum and a saturated calomel
electrode.
TABLE 3 Statistical Information—Silicon – Gravimetric Method
56. Reagents
Silicon
Repeatability Reproducibility
Test Specimen Found,
56.1 Ammonium Citrate Solution (200 g/l)—Dissolve 200 g
(R , E173) (R , E173)
1 2
%
of di–ammonium hydrogen citrate in water and dilute to 1 L.
H SO Dehydration
2 4
1. Tool steel 5Mo-6W-4Cr-2V 0.193 0.019 0.031
56.2 Bromine
(NIST 132a, 0.19 Si)
56.3 Cobalt, Standard Solution (1mL = 1.5 mg of Co):
E352 − 23
FIG. 1 Jones Reductor
56.3.1 Preparation—Dry a weighing bottle in an oven at retained on the screen, periodically, if necessary, to avoid
130 °C for 1 h, cool in a desiccator, and weigh. Transfer 3.945 undue clogging of the openings. When the bulk of the collected
g of cobalt sulfate (CoSO ) that has been heated at 550 °C for resin has settled, decant the water and transfer approximately
1 h to the weighing bottle. Dry the bottle and contents at 130 100 mL of resin to a 400-mL beaker. Add 200 mL of HCl (1 +
°C for 1 h, cool in desiccator, stopper the bottle, and weigh. 19), stir vigorously, allow the resin to settle for 4 min to 6 min,
The difference in mass is the amount of CoSO taken. Transfer decant 150 mL to 175 mL of the suspension, and discard.
the weighed CoSO to a 400-mL beaker, rinse the weighing Repeat the treatment with HCl (1 + 19) twice more, and reserve
bottle with water, and transfer the rinsings to the beaker. Add the coarser resin for the column preparation.
150 mL of water and 20 mL of HNO , and heat to dissolve the
56.4.2 Prepare the column as follows: Place a 10-mm to
salts. Cool, transfer to a 1-L volumetric flask, dilute to volume,
20-mm layer of glass wool or polyvinyl chloride plastic fiber in
and mix.
the bottom of the column, and add a sufficient amount of the
56.3.2 Standardization—Calculate the cobalt concentration
prepared resin to fill the column to a height of approximately
as follows:
140 mm. Place a 20-mm layer of glass wool or polyvinyl
chloride plastic fiber at the top of the resin bed to protect it
Cobalt, mg⁄mL 5 mass of CoSO , g × 0.38026 (5)
from being carried into suspension when the solutions are
56.4 Ion-Exchange Resin:
added. While passing a minimum of 35 mL of HCl (7 + 5)
56.4.1 Use an anion exchange resin of the alkyl quaternary
through the column, with the hydrostatic head 100 mm above
ammonium type (chloride form) consisting of spherical beads
the top of the resin bed, adjust the flow rate to not more than
having a nominal crosslinkage of 8 %, and 0.075-mm to
3.0 mL per min. Drain to 10 mm to 20 mm above the top of the
0.037-mm (200-nominal to 400-nominal mesh) size. To re-
resin bed and then close the lower stopcock.
move those beads greater than about 180-μm in diameter as
well as the excessively fine beads, treat the resin as follows: NOTE 6—The maximum limits of 0.125 g of cobalt and 0.500 g in the
sample solution take into account the exchange capacity of the resin, the
Transfer a supply of the resin to a beaker, cover with water, and
physical dimensions of the column, and the volume of eluants.
allow sufficient time (at least 30 min) for the beads to undergo
maximum swelling. Place a 180-μm (No. 80) screen, 150 mm 56.5 Potassium Ferricyanide, Standard Solution (1 mL =
in diameter over a 2-L beaker. Prepare a thin slurry of the resin
3.0 mg of Co):
and pour it onto the screen. Wash the fine beads through the
56.5.1 Dissolve 16.68 g of potassium ferricyanide
screen, using a small stream of water. Discard the beads
(K Fe(CN) ) in water and dilute to 1 L. Store the solut
...