ASTM E362-99

Standard Test Methods for the Determination of Arsenic and Lead in Silicomanganese and Ferrosilicon Manganese (Withdrawn 2005)

SCOPE
1.1 These test methods cover the chemical analysis of silicomanganese and ferrosilicon manganese having chemical compositions within the following limits: ElementConcentration, %Arsenic0.10 maxCarbon3.0 maxChromium0.50 maxLead0.030 maxManganese50.0 to 68.0Molybdenum0.10 maxNickel0.20 maxPhosphorus0.20 maxSilicon35.0 maxSulfur0.04 maxTin0.010 max
1.2 The test methods in this standard are contained in the sections indicated below: SectionsArsenic by the Molybdenum Blue Photometric Method (0.002to 0.06 %) Lead by the Dithizone Photometric Method (0.02 to 0.05 %)
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Specific hazards statements are given in Section 5 and in special warning paragraphs throughout these test methods.
WITHDRAWN RATIONALE
These test methods cover the chemical analysis of silicomanganese and ferrosilicon manganese having chemical compositions within the following limits: ElementConcentration, %Arsenic0.10 maxCarbon3.0 maxChromium0.50 maxLead0.030 maxManganese50.0 to 68.0Molybdenum0.10 maxNickel0.20 maxPhosphorus0.20 maxSilicon35.0 maxSulfur0.04 maxTin0.010 max
Formerly under the jurisdiction of Committee E01 on Analytical Chemistry for Metals, Ores, and Related Materials, these test methods were withdrawn in May 2005. This standard is being withdrawn without replacement because it does not have ILS supporting data and most laboratories are using instrumental techniques for analysis rather than the old wet chemical methods.

General Information

• Status: Withdrawn
• Publication Date: 09-Dec-1999
• Withdrawal Date: 17-May-2005
• ICS: 77.040.30 - Chemical analysis of metals
• Technical Committee: E01 - Analytical Chemistry for Metals, Ores, and Related Materials
• Drafting Committee: E01.01 - Iron, Steel, and Ferroalloys

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation:E362–99
Standard Test Methods for
the Determination of Arsenic and Lead in Silicomanganese
and Ferrosilicon Manganese
This standard is issued under the fixed designation E 362; 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 32 PracticesforSamplingFerroalloysandSteelAdditives
for Determination of Chemical Composition
1.1 These test methods cover the chemical analysis of
E 50 Practices for Apparatus, Reagents, and Safety Precau-
silicomanganese and ferrosilicon manganese having chemical
tions for Chemical Analysis of Metals
compositions within the following limits:
E 60 Practice for Photometric and Spectrophotometric
Element Concentration, %
Methods for Chemical Analysis of Metals
Arsenic 0.10 max
E 173 Practice for Conducting Interlaboratory Studies of
Carbon 3.0 max
Methods for Chemical Analysis of Metals
Chromium 0.50 max
E 882 Guide for Accountability and Quality Control in the
Lead 0.030 max
Manganese 50.0 to 68.0
Chemical Analysis Laboratory
Molybdenum 0.10 max
Nickel 0.20 max
3. Significance and Use
Phosphorus 0.20 max
Silicon 35.0 max
3.1 These test methods for the chemical analysis of metals
Sulfur 0.04 max
and alloys are primarily intended as referee methods to test
Tin 0.010 max
such materials for compliance with compositional specifica-
1.2 The test methods in this standard are contained in the
tions, particularly those under the jurisdiction of ASTM Com-
sections indicated below:
mittee A–1 on Steel, Stainless Steel, and Related Alloys,
Sections
specifically Specification A 483.
3.2 It is assumed that all who use these test methods will be
Arsenic by the Molybdenum Blue Photometric Method (0.002
to 0.06 %) 9-19 trained analysts capable of performing common laboratory
Lead by the Dithizone Photometric Method (0.02 to 0.05 %) 20-30
proceduresskillfullyandsafely.Itisexpectedthatworkwillbe
performed in a properly equipped laboratory under appropriate
1.3 This standard does not purport to address all of the
quality control practices such as those described in Guide
safety concerns, if any, associated with its use. It is the
E 882.
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
4. Reagents and Photometric Practice
bility of regulatory limitations prior to use. Specific hazards
4.1 Reagents:
statements are given in Section 5 and in special warning
4.1.1 Purity of Reagents—Unless otherwise indicated, all
paragraphs throughout these test methods.
reagents used in these test methods shall conform to the
2. Referenced Documents
“Reagent Grade” Specifications of the American Chemical
Society. Other chemicals may be used, provided it is first
2.1 ASTM Standards:
ascertained that they are of sufficiently high purity to permit
A 483 Specification for Silicomanganese
their use without adversely affecting the expected performance
D 1193 Specification for Reagent Water
of the determination, as indicated in the Precision and Bias
E 29 Practice for Using Significant Digits in Test Data to
section.
Determine Conformance with Specifications
1 5
These test methods are under the jurisdiction of ASTM Committee E-1 on Annual Book of ASTM Standards, Vol 03.05.
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct Annual Book of ASTM Standards, Vol 03.06.
responsibility of Subcommittee E01.01 on Iron, Steel, and Ferroalloys. Reagent Chemicals, American Chemical Society Specifications, American
Current edition approved Dec. 10, 1999. Published February 2000. Originally Chemical Society, Washington, DC. For suggestions on the testing of reagents not
published as E 362 – 70 T. Last previous edition E 362 – 90 (1995)e1 listed by the American Chemical Society, see Analar Standards for Laboratory
Annual Book of ASTM Standards, Vol 01.02. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Annual Book of ASTM Standards, Vol 11.01. and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
Annual Book of ASTM Standards, Vol 14.02. MD.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
E362
4.1.2 Purity of Water—Unless otherwise indicated, refer- procedure should give satisfactory results at lower and higher
ences to water shall be understood to mean reagent water as concentrations, this test method’s Calibration and Procedure
defined by Type II of Specification D 1193. sections cover the range from 0.001 to 0.1 %.
4.2 Photometric Practice—Shall conform to Practice E 60. 9.2.1 Users of this test method are cautioned that its use on
samplesoutsideofthe0.02to0.06 %rangeisnotsupportedby
5. Hazards
interlaboratory testing.
5.1 For precautions to be observed in the use of certain
10. Summary of Test Method
reagentsandequipmentinthesetestmethods,refertoPractices
10.1 The sample is fused with sodium peroxide and sodium
E 50.
carbonate and the melt is dissolved in acid. Arsenic, iron, and
6. Sampling
other elements are precipitated with ammonium hydroxide.
The filtered precipitate is dissolved in acid. Ammonium bro-
6.1 For procedures for sampling the material, and for
particle size of the sample for chemical analysis, refer to mide and hydrazine sulfate are added and the arsenic is
distilled as arsenic tribromide. The distillate is evaporated to
Practices E 32.
dryness and reacted with ammonium molybdate and hydrazine
7. Rounding Calculated Values
sulfate to form the molybdenum blue complex. Photometric
7.1 Calculated values shall be rounded to the desired num- measurement is made at 850 nm.
ber of places as directed in 3.4 to 3.6 of Practice E 29.
11. Concentration Range
8. Interlaboratory Studies
11.1 The recommended concentration range is from 0.005
to 0.15 mg of arsenic per 50 mL of solution using a 1-cm cell.
8.1 These test methods have been evaluated in accordance
with Practice E 173, unless otherwise noted in the Precision
NOTE 1—This test method has been written for cells having a 1-cm
and Bias section.
light path. Cells having other dimensions may be used, provided suitable
adjustments can be made in the amount of sample and reagents used.
ARSENIC BY THE MOLYBDENUM BLUE
12. Stability of Color
PHOTOMETRIC METHOD
12.1 The color is stable for at least 2 h.
9. Scope
13. Interferences
9.1 This test method covers the determination of arsenic in
silicomanganese and ferrosilicon manganese in concentrations
13.1 The elements ordinarily present do not interfere if their
from 0.02 to 0.06 %.
concentrations are under the maximum limits shown in 1.1.
9.2 The limits of the scope have been set at 0.02 to 0.06 %
14. Apparatus
because test materials containing other arsenic concentrations
were unavailable for testing. However, recognizing that the 14.1 Distillation Apparatus, Fig. 1.
FIG. 1 Arsenic Distillation Apparatus
E362
14.2 Zirconium Crucibles, 30-mL capacity. 17. Procedure
17.1 Test Solution:
15. Reagents
17.1.1 Select and weigh a sample to the nearest 0.2 mg in
15.1 Ammonium Bromide (NH Br).
accordance with the following:
15.2 Ammonium Molybdate Solution (10 g/L)—Dissolve
Arsenic, % Sample Weight, g
2.5 g of ammonium heptamolybdate tetrahydrate
0.001 to 0.015 0.500
((NH ) Mo O ·4H O) in 40 mL of warm water. Add 128 mL
4 6 7 24 2
0.01 to 0.04 0.250
of H SO (1+3), dilute to 250 mL, and mix.
2 4
0.035 to 0.10 0.125
15.3 Ammonium Molybdate-Hydrazine Sulfate Solution—
Transfer the sample to a 30-mL zirconium crucible contain-
Dilute 100 mL of Ammonium Molybdate solution to 900 mL,
ing8gofNa O and2gofNa CO .
add 10 mL of Hydrazine Sulfate Solution, dilute to 1 L, and 2 2 2 3
17.1.2 Mix (Note 2) thoroughly with a metal spatula. Fuse
mix. Do not use a solution that has stood more than 1 h.
carefully over a free flame by holding the crucible with a pair
15.4 Arsenic Standard Solution A (1 mL 5 0.10 mg As)—
of tongs and slowly revolving it around the outer edge of the
Transfer 0.1320 g of arsenic trioxide (As O)toa1-L
2 3
flame until the contents have melted down quietly; raise the
volumetric flask, dissolve in 100 mL of HCl, cool, dilute to
temperature gradually to avoid spattering (Note 3). When the
volume, and mix.
contents are molten, give the crucible a rotary motion to stir up
15.5 Arsenic Standard Solution B (1 mL 5 0.01 mg As)—
any unattacked particles of the alloy adhering to the bottom or
Using a pipet, transfer 100 mLofArsenic Standard SolutionA
sides. Finally, increase the temperature until the crucible is
(1 mL 5 0.10 mg As) to a 1-L volumetric flask, dilute to
bright red for 1 min. Cool the crucible to room temperature.
volume, and mix.
Transfer the crucible to an 800-mLbeaker containing 60 mLof
15.6 Hydrazine Sulfate—((NH ) ·H SO ).
2 2 2 4
H SO (1 + 1)and200mLofwater.Dissolvethemelt;remove
2 4
15.7 Hydrazine Sulfate Solution (1.5 g/L)—Dissolve 1.5 g
and rinse the crucible.
of hydrazine sulfate ((NH ) ·H SO ) in water, dilute to 1 L,
2 2 2 4
and mix. Do not use a solution that has stood more than 1 day.
NOTE 2—Warning: Use proper safety practices and equipment when
15.8 Sodium Carbonate (Na CO ).
performing sodium peroxide fusions.
2 3
15.9 Sodium Peroxide (Na O )—35 mesh or finer. NOTE 3—If the reaction proceeds violently with spattering because of
2 2
too rapid heating, the use of insufficient Na CO , or the lack of thorough
2 3
16. Preparation of Calibration Curve
mixing, appreciable loss may occur and the work should be repeated.
16.1 Calibration Solutions: 17.1.3 Add H SO dropwise until the solution clears.
2 3
16.1.1 Using pipets, transfer 1, 2, 5, 10, and 15 mL of 17.1.4 Heat to boiling, and cool. While stirring vigorously,
Arsenic Standard Solution B (1 mL 5 0.01 mgAs) to 125-mL add NH OH until the solution is alkaline to litmus, and then
Erlenmeyer flasks. add 3 to 5 mLin excess. Heat to boiling, remove from the heat,
16.1.2 Add 10 mL of HNO and evaporate the solution to and allow the precipitate to settle. Filter on a coarse filter paper
dryness on a hot plate. Bake for 30 min at 150 to 180°C. and wash five times with hot water. Discard the filtrate.
Remove from the hot plate. Add 45 mL of Ammonium Remove the filter paper, carefully open it, and place it on the
Molybdate-Hydrazine Sulfate Solution to each flask, warm inside wall of the original 800-mLbeaker.Wash the precipitate
gently to dissolve the residue, and transfer the solution to a from the paper using a fine stream of water. Pass 25 mL of
50-mL volumetric flask. Proceed as directed in 16.3. HNO (1 + 1) over the paper, and wash well with water but do
16.2 Reference Solution—Transfer 10 mL of water to a not exceed a total volume of 40 mL. Discard the paper. Warm
125-mL Erlenmeyer flask and proceed as directed in 16.1.2. gently until the precipitate dissolves.
16.3 Color Development—Heat the flask in a boiling water 17.1.5 Transfer the solution to the distillation flask, add 1 g
bath for 15 min. Remove the flask, cool to room temperature, ofNH Brand0.75gofhydrazinesulfate.Add20mLofHNO
4 3
dilute to volume with Ammonium Molybdate-Hydrazine Sul- (1 + 1) to the receiving flask, and place the flask in an 800-mL
fate Solution and mix. beaker containing cold water.Assemble the apparatus (Fig. 1),
16.4 Photometry: heat the distillation flask, and distill into the receiving flask.
16.4.1 Multiple-Cell Photometer—Measure the cell correc- 17.1.6 Distill until the volume is reduced to 10 mL or until
tion using the reference solution (16.2) in absorption cells with oxides of nitrogen are noted in the distillation flask. Remove
a 1-cm light path and a light band centered at approximately the distillation flask from the heat source. Place the receiving
850 nm. Using the test cell, take the photometric readings of flask on a hot plate and evaporate the solution to dryness. Bake
the calibration solutions versus the reference solution. for 30 min at 150 to 180°C. Add 45 mL of Ammonium
16.4.2 Single-Cell Photometer—Transfer a suitable portion Molybdate-Hydrazine Sulfate solution to the flask, warm
of the Reference Solution to an absorption cell with a 1-cm gently to dissolve the residue, and transfer the solution to a
light path and adjust the photometer to the initial setting, using 50-mL volumetric flask. Proceed as directed in 17.3.
a light band centered at approximately 850 nm. While main- 17.2 Reference Solution—Carry a reagent blank through the
taining this adjustment, take the photometric readings of the entire procedure using the same amounts of all reagents with
calibration solutions. the sample omitted, for use as a reference solution.
16.5 Calibration Curve—Plot the net photometric readings 17.3 Color Development—Proceed as directed in 16.3.
of the calibration solutions against milligrams of arsenic per 50 17.4 Photometry—Take the photometric reading of the test
mL of solution. solution as directed in 16.4
E362
NOTE 4—This test method has been written for cells having a 1-cm
18. Calibration
light path. Cells having other dimensions may be used, provided suitable
18.1 Convertthenetphotometricreadingofthetestsolution
adjustments can be made in the amounts of sample and reagents used.
to milligrams of arsenic by means of the calibration curve.
Calculate the percentage of arsenic as follows: 23. Stability of Color
Arsenic, % 5 A/~B 3 10! (1) 23.1 The color is quite stable if the solution is protected
againstevaporationanddecompositionofchloroform.Because
where:
of the volatility of the solvent, it is advisable to make all
A 5 arsenic found in 50 mL of final test solution, mg, and
readings promptly. The color develops almost immediately.
B 5 sample represented in 50 mL of final test solution, g.
24. Interferences
24.1 The elements ordinarily present do not interfere if their
19. Precision and Bias
concentrations are under the maximum limits shown in 1.1. If
19.1 Precision—Nine laboratories cooperated in testing this
more than 0.005 % bismuth is present, it must be removed as
test method and obtained the data summarized in Table 1.
directed in Note 8 in order to avoid high results for lead.
Samples with arsenic concentrations near the upper limit of the
scope were not available for testing. The user is cautioned to
25. Apparatus
verify by the use of reference materials, if available, that the
25.1 Glassware—Useonlyborosilicatebeakers,covers,and
precision and bias of this test method is adequate for the
funnels.Wash all glassware with hot HNO (1 + 1) and reserve
cont
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