ASTM E581-76(1996)
(Test Method)Standard Test Methods for Chemical Analysis of Manganese-Copper Alloys
Standard Test Methods for Chemical Analysis of Manganese-Copper Alloys
SCOPE
1.1 These test methods cover the chemical analysis of manganese-copper alloys having chemical compositions within the following limits: Element Concentration Range, % Copper 68.0 to 72.0 Manganese 28.0 to 32.0 Carbon 0.03 max Iron 0.01 max Phosphorus 0.01 max Silicon 0.05 max Sulfur 0.01 max
1.2 The test methods appear in the following order: Sections Iron by the 1,10-Phenanthroline Photo- metric Method 8 to 17 Manganese by the (Ethylenedinitrilo) Tet- raacetic Acid (EDTA--Back-Titrimet- ric Method 18 to 24 Phosphorus by the Molybdivanadophos- phoric Acid Extraction Photometric Method 25 to 35
1.3 This standard does not purport to address all of the safety problems, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For precaution to be observed in the use of certain reagents, refer to Practices E50. A specific precautionary statement is given in Note 2.
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An American National Standard
Designation: E 581 – 76 (Reapproved 1996)
Standard Test Methods for
Chemical Analysis of Manganese-Copper Alloys
This standard is issued under the fixed designation E 581; 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 (e) indicates an editorial change since the last revision or reapproval.
1. Scope E 88 Practice for Sampling Nonferrous Metals and Alloys
in Cast Form for Determination of Chemical Composition
1.1 These test methods cover the chemical analysis of
E 173 Practice for Conducting Interlaboratory Studies of
manganese-copper alloys having chemical compositions
Methods for Chemical Analysis of Metals
within the following limits:
Element Concentration Range, %
3. Significance and Use
Copper 68.0 to 72.0
Manganese 28.0 to 32.0
3.1 These test methods for the chemical analysis of metals
Carbon 0.03 max
and alloys are primarily intended to test such materials for
Iron 0.01 max
compliance with compositional specifications. It is assumed
Phosphorus 0.01 max
Silicon 0.05 max
that all who use these test methods will be trained analysts
Sulfur 0.01 max
capable of performing common laboratory procedures skill-
1.2 The test methods appear in the following order: fully and safely. It is expected that work will be performed in
a properly equipped laboratory.
Sections
Iron by the 1,10-Phenanthroline Photometric Method 8-17
Manganese by the (Ethylenedinitrilo) Tetraacetic Acid (EDTA—
4. Apparatus, Reagents, and Photometric Practice
Back-Titrimetric Method 18-24
4.1 Apparatus and reagents required for each determination
Phosphorus by the Molybdivanadophosphoric Acid Extraction Pho-
tometric Method 25-35
are listed in separate sections of each test method. The
apparatus, standard solutions, and certain other reagents used
1.3 This standard does not purport to address all of the
in more than one procedure are referred to by number and shall
safety concerns, if any, associated with its use. It is the
conform to the requirements prescribed in Practices E 50,
responsibility of the user of this standard to establish appro-
except that photometers shall conform to the requirements
priate safety and health practices and determine the applica-
prescribed in Practice E 60.
bility of regulatory limitations prior to use. For precaution to
be observed in the use of certain reagents, refer to Practices
5. Sampling
E 50. A specific precautionary statement is given in Note 2.
5.1 For procedures for sampling the material, refer to
2. Referenced Documents Practices E 55 and E 88.
2.1 ASTM Standards:
6. Rounding Calculated Values
E 29 Practice for Using Significant Digits in Test Data to
6.1 Calculated values shall be rounded to the desired num-
Determine Conformance with Specifications
ber of places as directed in 3.4 to 3.6 of Practice E 29.
E 50 Practices for Apparatus, Reagents, and Safety Precau-
tions for Chemical Analysis of Metals
7. Interlaboratory Studies
E 55 Practice for Sampling Wrought Nonferrous Metals and
7.1 These test methods have been evaluated in accordance
Alloys for Determination of Chemical Composition
with Practice E 173, unless otherwise noted in the precision
E 60 Practice for Photometric and Spectrophotometric
section.
Methods for Chemical Analysis of Metals
IRON BY THE 1,10-PHENANTHROLINE
1 PHOTOMETRIC METHOD
These methods are under the jurisdiction of ASTM Committee E-1 on
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct
8. Scope
responsibility of Subcommittee E01.05 on Cu, Pb, Zn, Cd, Sn, Be, their Alloys and
Related Metals.
8.1 This test method covers the determination of iron in
Current edition approved Aug. 27, 1976. Published October 1976.
2 concentrations from 0.003 to 0.02 %.
Annual Book of ASTM Standards, Vol 14.02.
Annual Book of ASTM Standards, Vol 03.05.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
E 581 – 76 (1996)
9. Summary of Test Method 14.4 Photometry:
14.4.1 Multiple-Cell Photometer—Measure the cell correc-
9.1 The sample is dissolved in hydrochloric acid and hy-
drogen peroxide, and the excess oxidant removed by evapora- tion using absorption cells with a 2-cm light path and a light
tion. The iron is extracted with methyl isobutyl ketone-benzene band centered at approximately 510 nm. Using the test cell,
mixture. The iron is extracted from the organic phase into a take the photometric readings of the calibration solutions.
hydroxylamine hydrochloride solution and the red-colored
14.4.2 Single-Cell Photometer—Transfer a suitable portion
1,10-phenanthroline complex is formed. Photometric measure-
of the reference solution to an absorption cell with a 2-cm light
ment is made at approximately 510 nm.
path and adjust the photometer to the initial setting, using a
light band centered at approximately 510 nm. While maintain-
10. Concentration Range
ing this adjustment, take the photometric readings of the
10.1 The recommended concentration range is from 0.005
calibration solutions.
to 0.125 mg of iron per 50 mL of solution using a 2-cm cell.
14.5 Calibration Curve—Plot the net photometric readings
NOTE 1—This test method has been written for cells having a 2-cm
of the calibration solutions against milligrams of iron per 50
light path. Cells having other dimensions may be used, provided suitable
mL of solution.
adjustments can be made in the amounts of sample and reagents used.
15. Procedure
11. Stability of Color
15.1 Test Solution:
11.1 The color develops within 5 min and is stable for at
least 4 h.
15.1.1 Transfer a 2.0-g sample, weighed to the nearest 10
mg, to a 400-mL beaker.
12. Interferences
15.1.2 Carry a reagent blank through the entire procedure,
12.1 Elements ordinarily present do not interfere if their
using the same amounts of all reagents but with the sample
concentrations are under the maximum limits shown in 1.1.
omitted.
15.1.3 Add 25 mL of HCl (7 + 3) and then H O as needed
2 2
13. Reagents
to dissolve the alloy completely. When dissolution is complete,
13.1 Hydroxylamine Hydrochloride Solution (10 g/L)—
add 20 mL of HCl and heat carefully to decompose excess
Prepare a solution as directed for Reagent No. 131, but dilute
peroxide. Cool to room temperature, transfer to a 125-mL
to 500 mL.
conical separatory funnel. Add HCl (1 + 1), as required, to
13.2 Iron, Standard Solution A (1 mL = 0.125 mg Fe)—
adjust the volume to 50 mL.
Prepare a solution as directed for Reagent No. 4, but use
15.1.4 Add 20 mL of MIBK - benzene mixture to the
0.1250 g instead of the specified weight.
separatory funnel and shake 1 min. Allow the phases to
13.3 Iron, Standard Solution B (1 mL = 0.00625 mg Fe)—
separate, discard the aqueous phase, wash the organic phase 3
Using a pipet, transfer 50 mL of iron solution A (1 mL = 0.125
times with 3 to 5-mL portions of HCl (1 + 1) to remove copper,
mg Fe) to a 1-L volumetric flask, dilute to volume with HCl
and discard the washings. Extract the iron from the organic
(1 + 49), and mix.
phase by shaking vigorously 30 s with 10 mL of NH OH·HCl
13.4 Methyl Isobutyl Ketone-Benzene Mixture—Mix 200 2
solution. Transfer the aqueous phase to a 50-mL volumetric
mL of methyl isobutyl ketone (MIBK) and 100 mL of benzene.
flask. Repeat the extraction with a second 10-mL portion of
13.5 1,10-Phenanthroline-Ammonium Acetate Buffer
NH OH·HCl solution, and transfer the extract to the 50-mL
Solution—Dissolve 1.0 g of 1,10-phenanthroline monohydrate 2
flask. Dilute to 40 mL and proceed as directed in 15.3.
in 5 mL of HCl in a 600-mL beaker. Add 215 mL of
CH COOH, and, while cooling, carefully add 265 mL of
15.2 Reference Solution—Use the reagent blank solution
NH OH. Cool to room temperature. Using a pH meter, check
prepared as directed in 15.1.2.
the pH; if it is not between 6.0 and 6.5, adjust it to that range
15.3 Color Development—Proceed as directed in 14.3.
by adding acetic acid or NH OH as required. Dilute to 500 mL.
15.4 Photometry—Proceed as directed in 14.4.
14. Preparation of Calibration Curve
16. Calculation
14.1 Calibration Solutions:
16.1 Convert the net photometric reading of the test solution
14.1.1 Using pipets, transfer 1, 2, 5, 10, 15, and 20 mL of
to milligrams of iron by means of the calibration curve.
iron solution B (1 mL = 0.00625 mg Fe) to 50-mL volumetric
Calculate the percentage of iron as follows:
flasks. Dilute to 20 mL.
14.1.2 Add 20 mL of NH OH·HCl solution, mix, and allow
Iron, % 5 A/ B 3 10 (1)
2 ~ !
to stand 1 min. Proceed as directed in 14.3.
14.2 Reference Solution—Transfer 20 mL of water to a
where:
50-mL volumetric flask and proceed as directed in 14.1.2.
A = milligrams of iron found in 50 mL of the final test
14.3 Color Development—Add 5 mL of 1,10-
solution, and
phenanthroline-ammonium acetate buffer solution, dilute to
B = grams of sample represented in 50 mL of the final test
volume, and mix. Allow to stand at least 5 min but not more
solution.
than 4 h.
E 581 – 76 (1996)
17. Precision and Bias 21.2 Copper Solution (25 g/L)—Transfer 2.50 g of copper
(purity: 99.9 % min) to a 250-mL beaker. Add 20 mL of
17.1 Seven laboratories cooperated in testing this test
HNO (1 + 1). When dissolution is complete, boil to expel
method and obtained the data shown in Table 1. Although 3
oxides of nitrogen. Cool, dilute to 100 mL, and mix.
samples covered by this test method with iron concentrations
21.3 Disodium (Ethylenedinitrilo)tetraacetic Acid Dihy-
near the lower limit of the scope were not available for testing,
drate (EDTA), Standard Solution (0.05 M)—Prepare a solu-
the precision data obtained should apply. The reproducibility
tion as directed for Reagent No. 22, but use 18.6127 g instead
(R ) and repeatability (R ) are not tabulated because the
1 2
of the specified weight. Standardize the solution as follows:
required number of data were not obtained paired.
Using a pipet, transfer 25 mL of zinc solution (0.0500 M)toa
17.2 The accuracy of this test method could not be evalu-
400-mL beaker. Add 25 mL of buffer solution and dilute to
ated because adequate certified standard reference materials
about 250 mL. Add 4 to 6 drops of eriochrome black-T
were unavailable at the time of testing. The user is cautioned to
indicator solution and titrate with EDTA standard solution to
verify by the use of certified reference materials, if available,
the color change from magenta to blue. Calculate the molarity
that the accuracy of this test method is adequate for the
of the EDTA solution as follows:
contemplated use.
1.25
Molarity of EDTA solution, A 5 (2)
MANGANESE BY THE B
(ETHYLENEDINITRILO)TETRAACETIC ACID
(EDTA)—BACK-TITRIMETRIC METHOD
where:
A = molarity of EDTA solution, and
18. Scope
B = millilitres of EDTA solution required to titrate 25 mL
18.1 This test method covers the determination of manga-
of zinc standard solution (0.05 M).
nese in concentrations from 28.0 to 32.0 %.
21.4 Eriochrome Black-T Indicator Solution (8 g/L)—
Reagent No. 44.
19. Summary of Test Method
21.5 Hydroxylamine Hydrochloride Solution (100 g/L)—
Reagent No. 131.
19.1 The sample is dissolved in nitric acid. Manganese is
21.6 Manganese, Standard Solution (0.05 M)—Prepare a
chelated with disodium (ethylenedinitrilo) tetraacetate
solution as directed for Reagent No. 24, Method A, but use
(EDTA), which is added in excess. The pH of the solution is
2.7470 g instead of the specified weight. Standardize as
adjusted to 10 and sodium cyanide is added to complex copper.
follows: Using a pipet, transfer 25 mL of the manganese
The manganese is then determined by back-titration with
solution to a 400-mL beaker. Add 10 mL of copper solution.
standard manganese solution.
Proceed as directed in 22.2. Calculate the EDTA equivalent of
the solution as follows:
20. Interferences
EDTA equivalent, mL EDTA/mLMn 5 30.00/~25.00 3 C! (3)
20.1 The elements ordinarily present do not interfere if their
concentrations are under the maximum limits shown in 1.1.
where:
21. Reagents
C = millilitres of manganese solution required for titration
21.1 Buffer Solution (pH 10)—Transfer 54 g of ammonium
of excess EDTA solution.
chloride (NH Cl) to a 1-L beaker, dissolve in 500 mL of water,
21.7 Sodium Cyanide Solution (200 g/L)—Dissolve 200 g
add 350 mL of NH OH, dilute to 1 L, and mix. Store in a
of sodium cyanide (NaCN) in water, and dilute to 1 L. Store in
polyethylene bottle.
a plastic bottle.
NOTE 2—Caution: The preparation, storage, and use of NaCN solu-
tions require care and attention. Avoid inhalation of fumes and exposure
of the skin to the chemical or its solutions. Work in a well-ventilated hood.
Refer to Section 6 of Practices E 50.
Supporting data are available from ASTM Headquarters. Request RR: E03-
1006.
21.8 Sodium Tartrate Solution (250 g/L)—Dissolve 250 g of
sodium tartrate in water, and dilute to 1 L. Store in a plastic
TABLE 1 Tabulation of Interlaboratory Data of Iron by the 1, 10-
bottle.
Phenanthroline Photometric Method
21.9 Zinc, Standard Solution (0.050 M)—Transfer 3.2690 g
Iron, %
of zinc (purity: 99.9 % min) to a 400-mL beaker, and cover.
Laboratory
1st Day 2nd Day Add 25 mL of HNO (1 + 1) and warm gently until the zinc is
dissolved. Boil to expel oxides of nitrogen. Cool, transfer to a
1 0.0136 0.0134
2 0.0140 0.0124
1-L volumetric flask, dilute to volume, and mix.
3 0.0144 0.0142
4 0.0144 0.0144
22. Procedure
5 0.0120 0.0120
6 0.0133 0.0138
22.1 Transfer a 5.0-g sample, weighed to the nearest 1 mg,
7 0.0149 0.0149
to a 400-mL beaker, and cover. Cautiously, add 40 mL of
¯ ¯
Xi = 0.01380 Yi = 0.01359
HNO (1 + 1) and warm gently until dissolution is complete.
E 581 – 76 (1996)
Boil to expel oxides of nitrogen. Cool, transfer to a 500-mL 27. Concentration Range
volumetric flask, dilute to volume, and mix. Using a pipet,
27.1 The recommended concentration range is from 0.0035
transfer 25 mL of the test solution to a 400-mL beaker.
to 0.07 mg of phosphorus per 15 mL of solution, using a 2-cm
22.2 Add 10 mL of NH OH·HCl solution. Using a pipet,
cell.
add 30 mL of EDTA solution, and mix. Add 5 mL of sodium
NOTE 3—This test method has been written for cells having a 2-cm
tartrate solution, 25 mL of buffer solution, and 10 mL of NaCN
light path. Cells having other dimensions may be used, provided suitable
solution, mixing after each addition. Adjust the volume to
adjustments can be made in the amounts of sample and reagents used.
about 200 mL. Add 4 to 6 drops of eriochrome black-T
indicator solution. Using a 10-mL buret, titrate the exce
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