ASTM E35-88(1997)
(Test Method)Standard Test Methods for Chemical Analysis of Magnesium and Magnesium Alloys
Standard Test Methods for Chemical Analysis of Magnesium and Magnesium Alloys
SCOPE
1.1 These test methods cover the chemical analysis of magnesium and magnesium alloys having chemical compositions within the following limits: Aluminum, % 0.5 to 12 Copper, % 0.005 to 0.1 Iron, % 0.002 to 0.1 Lead, % 0.001 to 0.5 Manganese, % 0.01 to 2.0 Nickel, % 0.0005 to 0.5 Rare earth elements, % 0.2 to 10 Silicon, % 0.01 to 0.8 Thorium, % 0.2 to 25 Tin, % 0.5 to 10 Zinc, % 0.3 to 20 Zirconium, % 0.03 to 1.0 Magnesium, % remainder
1.2 The analytical procedures appear in the following order: Section Aluminum: Benzoate-Oxinate (Gravimetric) Method 8 to 15 Sodium Hydroxide (Potentiometric) Method (Op- tional Routine Method) 16 to 23 Copper: Neocuproine (Photometric) Method 24 to 33 Hydrobromic Acid-Phosphoric Acid (Photometric) Method 34 to 43 Iron by the 1,10-Phenanthroline (Photometric) Method 44 to 53 Lead by the Dithizone (Photometric) Method 54 to 63 Magnesium---Analysis for Manganese and Zinc by Direct Current Plasma Spectroscopy (Proposal) 2 Manganese by the Periodate (Photometric) Method 64 to 73 Nickel: Dimethylglyoxime Extraction (Photometric) Method 74 to 83 Dimethylglyoxime (Gravimetric) Method 84 to 91 Rare Earth Elements by the Sebacate-Oxalate (Gravi- metric) Method 92 to 98 Silicon: Perchloric Acid (Gravimetric) Method 99 to 104 Molybdosilicic Acid (Photometric) Method 105 to 114 Thorium by the Benzoate-Oxalate (Gravimetric) Method 115 to 121 Tin by the Iodine (Volumetric) Method 122 to 129 Zinc: Ethylenediamine Tetraacetate (Volumetric) Method 130 to 137 Potassium Ferrocyanide (Volumetric) Method 138 to 144 Zirconium by the Alizarin Red (Photometric) Method 145 to 154
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 to determine the applicability of regulatory limitations prior to use. Specific precautions are given in Section 5.
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Standards Content (Sample)
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Designation:E35–88 (Reapproved 1997)
Standard Test Methods for
Chemical Analysis of Magnesium and Magnesium Alloys
ThisstandardisissuedunderthefixeddesignationE 35;thenumberimmediatelyfollowingthedesignationindicatestheyearoforiginal
adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.Asuperscript
epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope
Zinc:
Ethylenediamine Tetraacetate (Volumetric)
1.1 These test methods cover the chemical analysis of
Method 130-137
magnesium and magnesium alloys having chemical composi-
Potassium Ferrocyanide (Volumetric)
Method 138-144
tions within the following limits:
Zirconium by theAlizarin Red (Photometric)
Aluminum,% 0.5 to 12
Method 145-154
Copper,% 0.005 to 0.1
Iron,% 0.002 to 0.1
1.3 This standard does not purport to address all of the
Lead,% 0.001 to 0.5
safety concerns, if any, associated with its use. It is the
Manganese,% 0.01 to 2.0
responsibility of the user of this standard to establish appro-
Nickel,% 0.0005 to 0.5
Rare earth elements,% 0.2 to 10
priate safety and health practices and determine the applica-
Silicon,% 0.01 to 0.8
bility of regulatory limitations prior to use. Specific precau-
Thorium,% 0.2 to 25
tions are given in Section 5.
Tin,% 0.5 to 10
Zinc,% 0.3 to 20
Zirconium,% 0.03 to 1.0
2. Referenced Documents
Magnesium,% remainder
2.1 ASTM Standards:
1.2 The analytical procedures appear in the following order:
E29 Practice for Using Significant Digits in Test Data to
Section
Determine Conformance With Specifications
Aluminum:
E30 Test Methods for Chemical Analysis of Steel, Cast
Benzoate-Oxinate (Gravimetric) Method 8-15
Iron, Open-Hearth Iron, and Wrought Iron
Sodium Hydroxide (Potentiometric) Method
(Optional Routine Method) 16-23
E50 Practices for Apparatus, Reagents, and Safety Precau-
Copper: 4
tions for Chemical Analysis of Metals
Neocuproine (Photometric) Method 24-33
E55 Practice for SamplingWrought Nonferrous Metals and
HydrobromicAcid-PhosphoricAcid
(Photometric) Method 34-43
Alloys for Determination of Chemical Composition
Iron by the 1,10-Phenanthroline (Photometric)
E60 Practice for Photometric and Spectrophotometric
Methods for Chemical Analysis of Metals
Method 44-53
Lead by the Dithizone (Photometric) Method 54-63
E88 Practice for Sampling Nonferrous Metals and Alloys
Magnesium—Analysis for Manganese
in Cast Form for Determination of Chemical Composition
an Zinc by Direct Current Plasma
Spectroscopy (Proposal)
3. Significance and Use
Manganese by the Periodate (Photometric)
Method 64-73
3.1 These test methods for the chemical analysis of metals
Nickel:
and alloys are primarily intended to test such materials for
Dimethylglyoxime Extraction (Photometric)
Method 74-83
compliance with compositional specifications. It is assumed
Dimethylglyoxime (Gravimetric) Method 84-91
that all who use these test methods will be trained analysts
Rare Earth Elements by the Seba-
cate- Oxalate (Gravimetric) Method 92-98 capable of performing common laboratory procedures skill-
Silicon:
fully and safely. It is expected that work will be performed in
PerchloricAcid (Gravimetric) Method 99-104
a properly equipped laboratory.
MolybdosilicicAcid (Photometric) Method 105-114
Thorium by the Benzoate-Oxalate
4. Apparatus, Reagents, and Photometric Practice
(Gravimetric) Method 115-121
Tin by the Iodine (Volumetric) Method 122-129
4.1 Apparatus and reagents required for each determination
are listed in separate sections preceding the procedure. The
apparatus, standard solutions, and certain other reagents used
These test methods are under the jurisdiction of ASTM Committee E-1 on
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct
responsibility of Subcommittee E01.04 on Aluminum and Magnesium. Appears in the gray pages of the Annual Book of ASTM Standards, Vol 03.05.
Current edition approved Jan. 29, 1988. Published March 1988. Originally Annual Book of ASTM Standards, Vol 14.02.
published as E35 – 42. Last previous edition E35 – 63 (1980). Annual Book of ASTM Standards, Vol 03.05.
Copyright ©ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA19428-2959, United States.
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Please contact ASTM International (www.astm.org) for the latest information.
E35–88 (1997)
in more than one procedure are referred to by number and shall 12. Reagents
conform to the requirements prescribed in Practices E 50E50,
12.1 Ammonium Benzoate Solution (100 g/L)—Dissolve
except that photometers shall conform to the requirements
100 g of ammonium benzoate in 1 L of warm water and add 1
prescribed in Practice E 60E60.
mg of thymol as a preservative.
4.2 The photometric practice prescribed in these test meth-
12.2 Ammonium Tartrate Solution (30 g/L)—Dissolve 30 g
ods shall conform to Practice E 60E60.
of ammonium tartrate in 500 mL of water, add 120 mL of
NH OH, and dilute to 1 L.
5. Safety Precautions
12.3 Benzoate Wash Solution—To 100 mL of the ammo-
5.1 For precautions to be observed in the use of certain nium benzoate solution, add 900 mLof warm water and 20 mL
reagents in these test methods, reference shall be made to of glacial acetic acid.
Practices E 50E50. 12.4 8–Quinolinol (Oxine) Solution (50 g/L)—Dissolve 50
5.2 Because of the reactivity of magnesium with mineral g of 8-quinolinol in 120 mL of glacial acetic acid and dilute to
acids, it is recommended that concentrated acids should not be 1 L. Filter and store in a dark bottle.
added directly to the alloy, especially in the case of finely
divided material. 13. Procedure
13.1 Weigh, to the nearest 1 mg, a portion of the sample
6. Sampling
calculated to contain 0.2 to 0.3 g of aluminum and transfer to
6.1 Wrought products shall be sampled in accordance with a 400-mL beaker containing 50 mL of water. Dissolve the
Practice E 55E55. Cast products shall be sampled in accor- sample by adding, in small portions, a total of 10 mL of HCl
dance with Practice E 88E88. per gram of sample.When dissolved, cool to room temperature
and dilute to 500 mL in a volumetric flask. Any residue of
7. Rounding Calculated Values undissolved silica, which might contain some occluded alumi-
num, should be kept in suspension.
7.1 Calculated values shall be rounded to the desired num-
13.2 Pipet a 50.0-mL aliquot into a 400-mL beaker and
ber of places in accordance with the rounding method of
dilute to 100 mL. Neutralize the solution with NH OH (1 + 1)
Practice E 29E29.
byaddingdropwisewithstirringuntiltheprecipitatethatforms
as each drop strikes finally redissolves only very slowly; that
ALUMINUM BY THE BENZOATE-OXINATE
is, until nearly all of the free acid is neutralized without
(GRAVIMETRIC) TEST METHOD
permanent precipitation of Al(OH) . Add 1 mL of glacial
acetic acid, about1gofNH Cl, and 20 mL of ammonium
8. Scope
benzoate solution. Heat the mixture to boiling while stirring,
8.1 This test method covers the determination of aluminum
keep at gentle boiling for 5 min, and then filter on a medium
in concentrations from 0.5 to 12 %. Since this test method is
paper.Wash the precipitate eight to ten times with hot benzoate
capable of giving very accurate results, it is recommended for
wash solution, making no effort to transfer all of the precipitate
referee analysis.
to the filter paper.
13.3 Dissolve the precipitate with five 10-mL portions of
9. Summary of Test Method
hot ammonium tartrate solution, washing with hot water after
9.1 Aluminum is precipitated first as the benzoate and then
each portion is added. Collect the solution in the original
as the oxinate. The latter is dried and weighed.
beaker and dilute to 150 to 200 mL. Heat the solution to 70 to
90°C, add 20 mL of 8-quinolinol solution, and digest for 15
10. Interferences
min without boiling. Filter the solution through a tared,
10.1 No appreciable interference is caused by the ordinary fritted-glass crucible, and wash eight times with hot water,
transferring all of the precipitate.
quantities of zinc, manganese, tin, or silicon found in magne-
sium alloys. Copper will remain largely insoluble in hydro- 13.4 Dry the precipitate for2hat120to 130°C, cool, and
weigh as aluminum oxinate (Al(C H ON) ).
chloric acid, the amount going into solution being too small to
9 6 3
cause serious interference. Zirconium and thorium would
14. Calculation
interfere if present, but are not usually encountered in
magnesium-aluminum alloys. Zirconium and aluminum are
14.1 Calculate the percentage of aluminum as follows:
incompatible. Iron can be removed by precipitation from the
Aluminum, % 5 [~A 3 0.0587!/B] 3 100 (1)
ammoniacal tartrate solution with hydrogen sulfide just before
the precipitation with 8-quinolinol. Interference due to minor
where:
quantities of iron and cerium can be eliminated by the addition
A = aluminum oxinate, g, and
of hydroxylamine hydrochloride prior to the precipitation of B = sample in aliquot used, g.
the aluminum as the benzoate.
15. Precision and Bias
11. Apparatus
15.1 This test method was originally approved for publica-
11.1 Filtering Crucible—A 15-mL fritted-glass crucible of tion before the inclusion of precision and bias statements
medium porosity. Apparatus No. 2. within standards was mandated. The original interlaboratory
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Please contact ASTM International (www.astm.org) for the latest information.
E35–88 (1997)
test data is no longer available. The user is cautioned to verify 21.2 When the dissolution is complete, cool to room tem-
bytheuseofreferencematerials,ifavailable,thattheprecision perature and add 20 mL of the indicator-buffer solution. Place
and bias of this test method is adequate for the contemplated the beaker in the titration assembly, start the stirrer, and titrate
use. the excess acid with dropwise additions of NH OH (1 + 2)
until the potentiometer shows a rapid increase in deflection.
ALUMINUM BY THE SODIUM HYDROXIDE
Continue titrating with 1 N NaOH solution, using two-drop
(POTENTIOMETRIC) TEST METHOD
increments, to the first potentiometric break, shown by a
(Optional Rapid Method)
maximum deflection at a potential of 150 to 190 mV and
occurring very nearly at the color change from yellow to blue.
16. Scope
21.3 Heat the solution to 80°C and, while maintaining the
16.1 This test method covers the rapid determination of
temperature of the solution at this level, titrate again with 1 N
aluminum in concentrations from 2 to 12 %. For referee
NaOH solution to a second end point as shown by a maximum
analysis, the method described in Sections 8-15 shall be used.
deflection occurring at a potential of 275 to 300 mV.
NOTE 1—The reaction upon which this titration is based is believed to
17. Summary of Test Method
be as follows:
17.1 The sample is dissolved in hydrochloric acid, the
2 AlCl 1 5 NaOH→ Al ~OH! Cl 1 5 NaCl (2)
3 2 5
excess acid is partially neutralized with ammonium hydroxide
(1 + 2), and the neutralization is completed with 1 N sodium
22. Calculation
hydroxide solution to a final potentiometric end point. Alumi-
22.1 Calculate the percentage of aluminum as follows:
num is then titrated with 1 N sodium hydroxide solution to a
Aluminum, % 5 [~AB 3 0.0108!/C] 3 100 (3)
final potentiometric end point.
where:
18. Interferences
A = NaOH solution required for titration of the sample
18.1 Bismuth interferes with the potential changes of the
from the first to the second potentiometric end point,
antimony electrode and may be removed, if present, by
mm,
precipitation with hydrogen sulfide and explusion of excess
B = normality of the NaOH solution, and
hydrogen sulfide by boiling before titration. Copper and silver
C = sample used, g.
lower the potentials of the end points but do not interfere with
23. Precision and Bias
the deflections. The presence of abnormal amounts of dis-
solved silicic acid and ferric iron cause high results. Ceric
23.1 This test method was originally approved for publica-
cerium, thorium, zirconium, titanium, and tin must be absent.
tion before the inclusion of precision and bias statements
Zinc, cadmium, nickel, and manganese do not interfere.
within standards was mandated. The original interlaboratory
test data is no longer available. The user is cautioned to verify
19. Apparatus
bytheuseofreferencematerials,ifavailable,thattheprecision
19.1 Apparatus for Potentiometric Titration—Apparatus
and bias of this test method is adequate for the contemplated
No. 3B. The titration assembly shall consist of an antimony
use.
electrode and a saturated calomel electrode with a potassium
COPPER BY THE NEOCUPROINE (PHOTOMETRIC)
chloride salt bridge terminating in a porous-glass or porcelain
TEST METHOD
plug. These shall dip into a titration beaker, which shall be
provided with a thermometer and a mechanical stirrer and be
24. Scope
mounted on a support in such a way that the beaker can be
24.1 This test method covers the determination of copper in
heated.
concentrations under 0.05 %.
20. Reagents
25. Summary of Test Method
20.1 Bromophenol Blue Indicator Solution (4 g/L)—Place
25.1 Cuprous copper is separated from other metals by
0.40gofbromophenolblueinamortar,add8.25mLofsodium
extraction of the neocuproine complex with chloroform. Pho-
hydroxide solution (5 g NaOH per litre), and mix until solution
tometric measurement is made at approximately 455 nm.
is complete. Dilute to 100 mL with water and mix.
26. Concentration Range
20.2 Indicator-Buffer Solution—Add 8 mL of bromophenol
26.1 The recommended concentration range is from 0.005
blue indicator solution to 1 L of saturated NH Cl solution.
to 0.05 mg of copper in 50 mL of solution, using a cell depth
20.3 Sodium Hydroxide, Standard Solution (1 N)—See
of 5 cm.
Reagent No. 16.
NOTE 2—This test method has been written for cells having a 5-cm
21. Procedure
light path. Cells having other dimensions may be used, provided suitable
21.1 Weigh, to the nearest 1 mg, a portion of the sample
adjustments can be made in the amounts of sample and reagents used.
calculated to contain approximately 0.15 g of aluminum and
27. Stability of Color
place it in a 250-mLbeaker containing 50 mLof water.Add, in
small portions, 7.5 mL of HCl per gram of sample, and then 1 27.1 The color develops in an aqueous media within 5 min,
mL in excess. and the extracted complex is stable for at least a week.
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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...
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