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Designation: E 54 – 80 (Reapproved 1996)

Standard Test Methods for


Chemical Analysis of Special Brasses and Bronzes1
This standard is issued under the fixed designation E 54; 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 Sections
1.1 These test methods cover procedures for the chemical Copper, or Copper and Lead Simultaneously, by the Electro- 2a

analysis2 of the commercial alloys known as copper-base alloy lytic


ingots for sand castings, forging rods, bars, and shapes; Method
Lead:
aluminum brass; manganese bronze; phosphor bronze; copper- Electrolytic Method 2c

silicon alloys; and similar alloys having chemical compositions Sulfate Method 2b
2b
within the following limits.2 Tin by the Iodimetric Titration Method
Silicon:
Element Concentration Range, % Sulfuric Acid Dehydration Method 18 to 19
Copper, % 50 and over Perchloric Acid Dehydration Method 20 to 22
Lead, % 0.0 to 27 Aluminum by the Gravimetric Method 23 to 26
Tin, % 0.0 to 20 Nickel by the Dimethylglyoxime Method 2a

Silicon, % 0.0 to 5 Iron by the Dichromate Method 30 to 33


Aluminum, % 0.0 to 12 Manganese:
Nickel, % 0.0 to 5 Bismuthate Method 2b

Iron, % 0.0 to 5 Persulfate Method 2b

Manganese, % 0.0 to 6 Bromate Method 2d

Sulfur, % 0.0 to 0.1 Phosphorus by the Alkalimetric Method 2b

Phosphorus, % 0.0 to 1.0 Arsenic by the Distillation-Bromate (Moffat) Method 46 to 49


Arsenic, % 0.0 to 1.0 Arsenic and Antimony by the Distillation - Iodometric Method 2d

Antimony, % 0.0 to 1.0 Antimony and Tin by the Manganese Coprecipitation Method 2d

ZincA 0.0 to 50 Sulfur:


_______________ Direct Combustion - Iodate Method 56 to 59
A Evolution Method 60 to 63
In the case of copper-base alloys containing 5.0 % and over of zinc, the zinc
Tin by the Hypophosphite Reduction (Volumetric) Method 64 to 71
is usually calculated by difference. 2a
Zinc by the Ethylenediamine Tetraacetate (Titrimetric) Method
Whenever possible the technique and procedures for analy- Lead by the Disodium (Ethylenedinitrilo) Tetraacetate 2b

sis should be checked against a National Institute of Standards Titrimetric Method


and Technology standard sample having a composition com- 1.3 This standard does not purport to address all of the
parable to the material being analyzed. safety concerns, if any, associated with its use. It is the
1.2 The test methods appear in the following order: responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. For precautions to
1
These test methods are under the jurisdiction of ASTM Committee E-1 on
be observed in these methods, refer to Practices E 50.
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct
responsibility of Subcommittee E01.07 on Cu and Cu Alloys. 2. Referenced Documents
Current edition approved May 30, 1980. Published July 1980. Originally 2.1 ASTM Standards:
published as E 54–46, replacing former B 27, B 28, B 45, and B 46. Last previous
edition E 54–79a.
E 50 Practices for Apparatus, Reagents, and Safety Precau-
2
For procedures for sampling wrought products, see ASTM Practice E 55, tions for Chemical Analysis of Metals3
Sampling Wrought Nonferrous Metals and Alloys for Determination of Chemical
Composition (Annual Book of ASTM Standards, Vol 03.05). For procedures for 3. Significance and Use
sampling cast products, see ASTM Practice E 88, Sampling Nonferrous Metals and
Alloys in Cast Form for Determination of Chemical Composition (Annual Book of 3.1 These test methods for the chemical analysis of metals
ASTM Standards, Vol 03.05). For procedures for the chemical analysis of other and alloys are primarily intended to test such materials for
brasses, see ASTM Method E 36, for Chemical Analysis of Brasses (Discontinued; compliance with compositional specifications. It is assumed
Replaced by Methods E 478, Annual Book of ASTM Standards, Vol 03.05). For
photometric procedures applicable to special brasses and bronzes, see ASTM
that all who use these test methods will be trained analysts
Method E 62, Photometric Methods for Chemical Analysis of Copper and Copper capable of performing common laboratory procedures skill-
Alloys (Annual Book of ASTM Standards, Vol 03.05). fully and safely. It is expected that work will be performed in
2a
Discontinued as of June 30, 1975. a properly equipped laboratory.
2b
Discontinued as of Aug. 27, 1976.
2c
Discontinued as of April 27, 1979.
2d
Discontinued as of May 30, 1980.
3
Annual Book of ASTM Standards, Vol 03.05.

Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.

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4. Apparatus and Reagents with Na 2CO3 and a crystal of NaNO3 or KNO3. Dissolve the melt in water
and H2SO4 and continue in accordance with 18.3. Combine the filtrate
4.1 Apparatus and reagents required for each determination with the original filtrate from 18.3, and complete the determination in
are listed in separate sections preceding the procedure. The accordance with 18.4 to 18.8.
apparatus, standard solutions, and certain other reagents used
18.4 Return the filtrate to the casserole and treat in accor-
in more than one procedure are referred to by number and shall
dance with 18.3.
conform to the requirements prescribed in Practices E 50.
18.5 Transfer the two papers and residues to a platinum
COPPER, OR COPPER AND LEAD crucible. Ignite at a low temperature until the paper has been
SIMULTANEOUSLY, BY THE ELECTROLYTIC TEST consumed, and then at 1100 to 1150°C to constant weight (see
METHOD Note 1). Cool in a desiccator and weigh.
18.6 Add 1 or 2 drops of H2SO4(1 + 1) and sufficient HF (2
(This test method, which consisted of Sections 5 through 8
to 5 mL) to dissolve the residue, and evaporate the solution
of this standard, was discontinued in 1975.)
slowly to dense white fumes. Continue to heat the crucible
LEAD BY THE ELECTROLYTIC TEST METHOD until all of the free H2SO4 has been expelled, and then ignite at
1000°C for 5 min. Cool in a desiccator and weigh. The loss in
(This test method, which consisted of Sections 9 and 10 of
weight represents SiO 2.
this standard, was discontinued in 1979.)
18.7 Blank—Make a blank determination, following the
LEAD BY THE SULFATE TEST METHOD same procedure and using the same amounts of all reagents.
18.8 Calculation—Calculate the percentage of silicon as
(This test method, which consisted of Sections 11 and 12 of
follows:4
this standard was discontinued in 1976.)
Silicon, % 5 @~~A 2 B! 3 0.4675!/ C# 3 100
TIN BY THE IODIMETRIC TITRATION TEST
METHOD where:
A 5 grams of SiO2,
(This test method, which consisted of Sections 13 through B 5 correction for blank, g, and
15, was discontinued in 1976.) C 5 grams of sample used.
19. Precision and Bias
ZINC BY THE OXIDE OR FERROCYANIDE TEST 19.1 This test method was originally approved for publica-
METHOD tion before the inclusion of precision and accuracy statements
(This test method, which consisted of Sections 16 and 17 of within standards was mandated. The original interlaboratory
this standard, was discontinued in 1975.) test data is no longer available. The user is cautioned to verify
by the use of reference materials, if available, that the precision
SILICON BY THE SULFURIC ACID and accuracy of this test method is adequate for the contem-
DEHYDRATION TEST METHOD plated use.
18. Procedure
18.1 Solution of Samples Containing Under 1.0 % of SILICON BY THE PERCHLORIC ACID
Silicon—Transfer 5.0 g of the sample to a 340-mL porcelain DEHYDRATION TEST METHOD
casserole, cover, and dissolve in 10 mL of HCl and 20 mL of 20. Reagents
HNO3. When solution of the sample is complete, add 30 mL of 20.1 Hydrogen Peroxide (3 %).
H2SO 4. 21. Procedure
18.2 Solution of Samples Containing 1.0 to 5.0 % of 21.1 Solution of Samples Containing Under 1.0 % of
Silicon—Transfer 1.00 g of the sample to a 340-mL porcelain Silicon—Transfer 5.0 g of the sample to a 340-mL porcelain
casserole, cover, and dissolve in 5 mL of HCl and 10 mL of casserole, cover, and dissolve in 10 mL of HCl and 20 mL of
HNO3. When solution of the sample is complete, add 15 mL of HNO3. When solution of the sample is complete, add 40 mL of
H2SO 4. HClO4.
18.3 Place the casserole on a hot plate and, with a cover glass 21.2 Solution of Samples Containing 1.0 to 5.0 % of
placed slightly to one side, evaporate until the HCl and HNO3 Silicon—Transfer 1.00 g of the sample to a 340-mL porcelain
have been expelled. Then, with the casserole well covered, heat casserole, cover, and dissolve in 5 mL of HCl and 10 mL of
strongly for several minutes while dense white fumes are being HNO3. When solution of the sample is complete, add 25 mL of
driven off. Allow to cool, add carefully 100 mL of HCl (1 + 5), HClO4.
and bring to a boil. If lead is present in the alloy, add 5 g of 21.3 If appreciable amounts of tin or antimony, or both, are
NH4Cl and continue the boiling until all PbSO4 is in solution. present, add, while stirring, 15 to 30 mL of HBr to volatilize
Filter the solution immediately through an 11-cm close-texture, these constituents. Place the casserole on a hot plate and
ashless paper, scrubbing the casserole with a policeman and evaporate to white fumes. Heat the covered casserole strongly
washing with HCl (1 + 99) to completely transfer the residue to
the paper. Wash the paper and residue (Note 1) thoroughly with
HCl (1 + 99) and reserve. 4
For the recommended procedure for rounding calculated values, see 3.4 and 3.5
of ASTM Recommended Practice E 29, Indicating Which Places of Figures Are to
NOTE 1—If black silicides, such as those of manganese or iron, are Be Considered Significant in Specified Limiting Values, Annual Book of ASTM
present in the residue, ignite in accordance with 18.3. Fuse the residue Standards, Vol 14.02.

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for 15 min while copious white fumes are being driven off. 25.2 For samples containing 0.1 to 1.0 % of aluminum,
Allow to cool, but not to become cold, add 100 to 150 mL of transfer 5.00 g of the sample to a 400-mL beaker and
hot water, stir well, and heat until the salts are dissolved. If decompose with 5 mL of HCl and 20 mL of HNO3, adding
manganese dioxide is present, bring it into solution with a few more HCl if necessary. Continue in accordance with 25.4, 25.5,
drops of H2O 2(3 %). Filter the solution immediately through or 25.6.
an 11-cm, close-texture, ashless paper, scrubbing the casserole 25.3 For samples containing 1.0 % and over of aluminum,
with a policeman and washing with HCl (1 + 99) to completely transfer 1.000 g of the sample to a 250-mL beaker and
transfer the residue to the paper. Wash the paper and residue decompose with 5 mL of HCl and 5 mL of HNO3. Continue in
(see Note 1) thoroughly with HCl (1 + 99) and reserve. accordance with 25.4, 25.5, or 25.6.
21.4 Return the filtrate to the casserole and treat in accor- 25.4 If an appreciable amount of silicon is present, add 5 to
dance with 21.3. 15 mL of H2SO4 and evaporate until the HCl and HNO3 have
21.5 Complete the determination of silicon as described in been expelled. Heat strongly for several minutes while dense
21.5–21.8. white fumes are being driven off. Allow to cool and dissolve
22. Precision and Bias soluble salts in a small amount of water. Transfer to a platinum
22.1 This test method was originally approved for publica- dish, add sufficient HF to volatilize the silicon, and heat slowly
tion before the inclusion of precision and accuracy statements to dense white fumes. Cool and transfer the contents of the dish
within standards was mandated. The original interlaboratory to the original beaker and dilute to 50 mL with H2SO 4 (1 + 19).
test data is no longer available. The user is cautioned to verify Heat to boiling, allow to settle, and filter if a precipitate is
by the use of reference materials, if available, that the precision present. Filter through an 11-cm fine paper, wash, and discard
and accuracy of this test method is adequate for the contem- any residue. Continue in accordance with 25.7 if 5 g of the
plated use. sample were used, or electrolyze in accordance with 25.8 if 1
g of the sample was used.
ALUMINUM BY THE GRAVIMETRIC TEST 25.5 In the absence of an appreciable amount of silicon and
METHOD in the presence of an appreciable amount of lead, add 5 to 10
(Aluminum Content 0.10 % and Over) mL of H2SO4 and evaporate to dense white fumes. Cool and
23. Apparatus dilute to 150 mL. Filter off the PbSO4. Continue in accordance
23.1 Mercury Cathode Cell—Apparatus No. 10B. with 25.7 if 5 g of the sample were used, or electrolyze in
23.2 Filtering Crucible—A 35-mL fritted-glass crucible of accordance with 25.8 if 1 g of the sample was used.
fine porosity (Apparatus No. 2). 25.6 In the absence of appreciable amounts of silicon and
24. Reagents lead, add 20 mL of water and heat gently until brown fumes
24.1 Ferric Chloride Solution (100 g/L)—Dissolve 100 g of have been expelled. Wash down the cover glass and sides of the
FeCl3·6H 2O in water and dilute to 1 L. beaker and dilute to approximately 150 mL. Continue in
24.2 Methyl Red Indicator Solution (0.2 g/L)—Dissolve 0.02 accordance with 25.7 if 5 g of the sample were used, or
g of methyl red indicator in 100 mL of hot water, cool, and electrolyze in accordance with 25.8 if 1 g of the sample was
filter. used.
24.3 Bromcresol Purple Indicator Solution (0.4 g/L)— 25.7 If there is insufficient iron in the alloy to gather the
Dissolve 0.04 g of bromcresol purple indicator in 100 mL of aluminum, add 2 mL of FeCl3 solution (100 g/L). Add NH4OH
hot water, cool, and filter. until the solution is slightly but distinctly ammoniacal, and
24.4 8-Hydroxyquinoline Solution (25 g/L)—Add 50 mL of bring to a boil. Allow the precipitate to settle on the steam bath
acetic acid to 25 g of 8-hydroxyquinoline and warm gently to for 5 min, filter on a loose-texture paper, and wash the beaker
effect solution. Pour the resulting solution into 900 mL of water and precipitate with hot NH4Cl solution (10 g/L) until most of
at 60°C. Cool, filter if necessary, and dilute to 1 L. the blue copper salts have been washed out. Place the paper
25. Procedure and precipitate in the original beaker, and add 5 mL of H2SO
25.1 For samples containing 0.5 % and over of aluminum, 4 and 20 mL of HNO3. Heat until all organic matter is
the electrolyte reserved from the determination of copper on a destroyed, adding small quantities of HNO3 as required.
2-g sample may be used, or a separate sample may be taken. If Evaporate to dense white fumes. Cool, wash down the cover
the electrolyte is used, continue in accordance with 25.10. If a glass and sides of the beaker with water, and evaporate to dense
separate sample (Note 2) is taken, proceed in accordance with white fumes again to remove the last traces of HNO3. Continue
25.2 or 25.3. in accordance with 25.10.
NOTE 2—The preliminary separation of aluminum from interfering
25.8 Add 2 mL of HNO3, and remove the copper by
elements avoids too great contamination of mercury during the subsequent electrolysis. Reserve the electrolyte.
electrolysis. In certain cases, this may not be objectionable if the sample 25.9 To the electrolyte or a suitable aliquot of it, reserved in
is not larger than 1 g, and a direct separation may be carried out in the accordance with 25.8, add sufficient H2SO4 to bring the total
mercury cathode cell as follows: Dissolve 1.000 g of the sample as content of H2SO4 to 5 mL and evaporate to dense white fumes.
described in 25.3. Continue as described in 25.4, 25.5, or 25.6 except that
Allow the solution to cool, wash down the sides of the beaker
before dilution the sample shall twice be taken to dense white fumes to
remove the last traces of HNO 3, and the final volume shall be kept below with water, and evaporate again to dense white fumes to
75 mL. Transfer the solution to the mercury cell and electrolyze in remove the last traces of HNO 3.
accordance with 25.10. Continue in accordance with 25.11–25.14. 25.10 Cool the solution obtained in accordance with 25.7 or

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25.9, and dilute to 25 mL with water. If any PbSO4 is present, within standards was mandated. The original interlaboratory
filter and wash thoroughly with H2SO4 (1 + 19). Transfer the test data is no longer available. The user is cautioned to verify
solution to the mercury cathode cell, keeping the volume below by the use of reference materials, if available, that the precision
100 mL; if slight hydrolysis takes place, disregard it. Electro- and accuracy of this test method is adequate for the contem-
lyze at a current of 3 to 5 A, while vigorously stirring the plated use.
electrolyte and mercury, or electrolyze overnight at a current of
1 to 1.5 A. When electrolysis is complete, separate the mercury NICKEL BY THE DIMETHYLGLYOXIME TEST
from the electrolyte while at least part of the current is kept on; METHOD
if the electrolyte contains floating particles of loose amalgam (This test method, which consisted of Sections 27 through 29
after this separation, filter the electrolyte and discard the of this standard, was discontinued in 1975.)
amalgam.
IRON BY THE DICHROMATE TEST METHOD
25.11 In the absence of beryllium and phosphorus, adjust the
volume of the solution obtained in accordance with 25.10 to 30. Reagents
200 mL. Add 5 mL of HCl and a little paper pulp. Heat the 30.1 Stannous Chloride Solution (50 g/L)—Dissolve 12.5 g
solution to boiling, add 2 drops of methyl red indicator of SnCl2·2H 2O in 25 mL of HCl, and dilute to 250 mL. Keep
solutions, and then add NH4OH until nearly neutral. Add the solution in a well-stoppered bottle.
NH4OH (1 + 3) until a pure yellow color is obtained, boil the 30.2 Mercuric Chloride Solution (saturated)—Add 60 to 100
solution gently for 1 min, adding more NH4OH (1 + 3) if the g of HgCl2 to 400 mL of hot water, shake, and cool to room
solution changes in color to an orange shade. Filter at once on temperature. More water may be added from time to time as
a medium-texture, ashless paper and wash with hot NH4Cl long as crystals remain undissolved.
solution (10 g/L). Transfer paper and precipitate to a weighed 30.3 Sodium Diphenylamine Sulfonate Indicator Solution (2
platinum crucible, dry, and ignite slowly until the paper is g/L).
burned; then ignite at a temperature of approximately 1100°C 30.4 Standard Potassium Dichromate Solution (0.05 N)—
for 10 to 15 min. Cover the crucible with a tight-fitting Reagent No. 10.
platinum cover to prevent absorption of moisture by the ignited 31. Procedure for Alloys Containing Under 0.05 % of
Al2O3, cool in a desiccator, and weigh. Repeat the ignition at Tin, Under 0.01 % of Arsenic, and Under 0.01 % of
1100°C to constant weight. Antimony
25.12 Calculation—Calculate the percentage of aluminum as 31.1 If the iron content is under 0.25 %, transfer 5.0 g of the
follows:4 sample, from which adventitious iron has been removed, to a
400-mL beaker and dissolve in 50 mL of HNO3 (1 + 1). If the
Aluminum, % 5 @~A 3 0.5291!/B# 3 100
iron content is 0.25 % or over, transfer 1.00 to 2.00 g of the
where: sample, from which adventitious iron has been removed, to a
A 5 grams of Al2O3, and 250-mL beaker and dissolve in 25 mL of HNO3 (1 + 1).
B 5 grams of sample used. 31.2 If silicon is present, add a few drops of HF to
25.13 If beryllium or phosphorus is present, adjust the volume decompose any iron silicide. Add 5 to 10 mL of H2SO4 and
of the solution obtained in accordance with 25.10 to 200 mL. evaporate to dense white fumes. Allow to cool, dilute some-
Add 10 mL of HCl, 15 mL of ammonium acetate solution (400 what with water, and filter if necessary. Add 2 to 3 mL of
g/L), and 8 to 10 drops of bromcresol purple indicator solution HNO3, and boil for 5 min.
(0.4 g/L). Add NH4OH (1 + 1) until the indicator becomes a 31.3 Dilute the solution to 150 mL. Add NH4OH until
distinct purple. While stirring, add slowly from a buret slightly but distinctly alkaline, and boil gently for a few
8-hydroxyquinoline solution (25 g/L), using 15 to 20 % in minutes. Remove the beaker from the hot plate, allow the
excess of the amount necessary to precipitate the aluminum. precipitate to settle for a few minutes, and filter while hot,
Heat the solution and precipitate to boiling, while stirring using a medium-texture paper. Wash the beaker and precipitate
occasionally, boil gently for 1 min, and allow to cool to 60°C. a few times, alternately with NH4Cl solution (20 g/L) and hot
Filter off the precipitate, using a 35-mL fritted-glass crucible of water, to remove most of the soluble salts.
fine porosity, and using moderate suction. Wash the precipitate 31.4 Dissolve the precipitate through the paper with 20 mL
with 100 mL of cool water, dry for 3 h at 135°C, cool in a of hot HCl (1 + 1) and wash thoroughly with hot water to
desiccator, and weigh. remove the last traces of iron, collecting the solution and
25.14 Calculation—Calculate the percentage of aluminum as washings in the original beaker. Proceed as described in 31.3.
follows:4 Dissolve the precipitate through the paper with 20 mL of hot
HCl (1 + 1) and wash thoroughly with hot water, collecting the
Aluminum, % 5 @~A 3 0.0587!/B# 3 100
solution and washings in the original beaker.
31.5 Evaporate the solution to 15 to 20 mL and wash down
where: the sides of the beaker. Heat to boiling, and add SnCl2·2H2O
A 5 grams of aluminum oxyquinolate, and solution (50 g/L) drop by drop, while swirling the beaker over
B 5 grams of sample used. a white background, until the yellow color of the FeCl3
26. Precision and Bias disappears. Add 1 drop of SnCl 2 solution in excess, but no
26.1 This test method was originally approved for publica- more.
tion before the inclusion of precision and accuracy statements 31.6 Dilute the reduced solution to 50 mL, cool to room

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temperature, stir, and add at one stroke 10 mL of a saturated 33.1 This test method was originally approved for publica-
solution of HgCl2. The resultant precipitate should be pure tion before the inclusion of precision and accuracy statements
white in color, and in amount should be preferably not more within standards was mandated. The original interlaboratory
than enough to give a pearly opalescence. If the precipitate is test data is no longer available. The user is cautioned to verify
gray or dark, too large an excess of SnCl2 has been used and it by the use of reference materials, if available, that the precision
will be necessary to discard the solution and start anew. To the and accuracy of this test method is adequate for the contem-
properly reduced solution, add 10 mL of H3PO4(1 + 3) and 4 plated use.
drops of sodium diphenylamine sulfonate indicator (2 g/L).
31.7 The volume of the solution to be titrated should not MANGANESE BY THE BISMUTHATE TEST
exceed 100 mL. Titrate slowly with 0.05 N K2Cr 2O7 solution, METHOD
while stirring constantly, until the color of the solution changes (This test method, which consisted of Sections 34 through
from green to a gray-green. Continue the titration, drop by 36, was discontinued in 1976.)
drop, until the first tinge of purple or violet-blue appears.
31.8 Blank—Make a blank determination, following the MANGANESE BY THE PERSULFATE TEST METHOD
same procedure and using the same amounts of all reagents. (This test method, which consisted of Sections 37 and 38,
was discontinued in 1976.)
NOTE 3—Ferric iron must be present in the solution in order to obtain
the purple or violet-blue endpoint color. If the color fails to form, the blank MANGANESE BY THE BROMATE TEST METHOD
is less than the equivalent of 1 drop of 0.02 N FeSO 4 solution, as this
contains sufficient iron to yield an end point. (This test method, which consisted of Sections 39 and 40 of
this standard, was discontinued in 1980.)
31.9 Calculation—Calculate the percentage of iron as fol-
lows:4 PHOSPHORUS BY THE ALKALIMETRIC TEST
Iron, % 5 @~~A 2 B!C3 0.0559!/D# 3 100 METHOD
(This test method, which consisted of Sections 41 through
where:
45, was discontinued in 1976.)
A 5 millilitres of K2Cr2O7 solution required to titrate the
sample, ARSENIC BY THE DISTILLATION-BROMATE
B 5 millilitres of K2Cr2O7 solution required to titrate the (MOFFAT) TEST METHOD
blank,
C 5 normality of the K2Cr2O7 solution, and 46. Apparatus
D 5 grams of sample used. 46.1 Apparatus for Determination of Arsenic by
32. Procedure for Alloys Containing 0.05 % and Over of Distillation—Apparatus No. 66.
Tin, With or Without Arsenic and Antimony 47. Reagents
32.1 It is desirable to remove the tin to facilitate later 47.1 Hydrazine Sulfate.
handling. Arsenic and antimony, if present, must be removed, 47.2 Standard Potassium Bromate Solutions—(0.01 and 0.05
since they interfere in the titration. N)—Reagent No. 9.
32.2 Transfer 5.0 g of the sample, from which adventitious 47.3 Methyl Orange Indicator Solution—Dissolve 0.1 g of
iron has been removed, to a 250-mL beaker. Add 50 mL of methyl orange in 100 mL of water and filter off any residue.
HNO3 (1 + 1), and heat to expel brown fumes. If silicon is 48. Procedure
present, add a few drops of HF to decompose any iron silicide. 48.1 Transfer 2.0 to 3.0 g of the sample (the amount
Dilute the solution to 100 mL with hot water, and digest the depending on the arsenic content) to a 500-mL Erlenmeyer
metastannic acid on a steam bath for 1 h. Filter through double, flask. Add 10 to 15 mL of HNO 3, cover, and heat gently until
close-texture papers into a 400-mL beaker, wash with hot decomposition is complete. Add 10 g of KHSO4 and 30 mL of
HNO3(1 + 99), and reserve the filtrate (Note 4). If HF has been H2SO4. Heat over a flame with constant swirling until dense
used, add 5 to 10 mL of H2SO4 and evaporate to dense white white fumes are evolved. Cool and add about 0.2 g of
fumes. Cool, dilute, and filter if necessary. hydrazine sulfate. Wash down the walls of the flask with about
15 mL of water, and again evaporate to dense white fumes.
NOTE 4—If desired, the alkaline sulfide separation of tin, arsenic, and 48.2 Cool the residue and add 20 mL of water. Shake to
antimony, may be used instead of the HBr treatment. dissolve the soluble salts and cool to room temperature or
32.3 Transfer the paper and contents to the original beaker. below. Add 0.2 g of FeSO 4·7H2O, 50 mL of HCl, and 8 to 10
Add 15 mL of HNO3 and then 10 mL of HClO4. Heat gently g of NaCl. Connect the flask to the distillation apparatus and
until white fumes appear, cool, and wash down the sides of the place 200 mL of water in the receiving beaker. Heat the
beaker. Cover, and add 10 mL of HBr. Remove the cover glass contents of the distilling flask to boiling (a hot plate with a
and boil gently until white fumes appear. Repeat the HBr surface temperature of 275 to 300°C is satisfactory) and
treatment to expel the last traces of tin and antimony. Add 15 continue until the temperature of the vapor in the flask reaches
mL of water and heat to dissolve soluble salts. If SiO2 is 105°C. (The distillate need not be kept cold.) Unstopper the
present, filter the solution, and combine with the filtrate distilling flask, and remove from the hot plate.
reserved in accordance with 32.2. Complete the determination 48.3 Rinse off the delivery tube into the distillate. Heat to
of iron in accordance with 31.3–31.9. boiling and boil gently for 10 min. Titrate at 80 to 90°C with
33. Precision and Bias 0.01 N or 0.05 N KBrO3 solution, using methyl orange as

5
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indicator, which should preferably be added near the end of the 58. Procedure
titration. 58.1 Adjust the furnace temperature to 1150°C, which is the
48.4 Blank—Make a blank determination, following the temperature of combustion.
same procedure and using the same amounts of all reagents. 58.2 Add sufficient HCl (3 + 197) to the absorption vessel to
48.5 Calculation—Calculate the percentage of arsenic as cover the tube outlet 1 to 2 in. and then add 2 mL of starch
follows:4 solution. Pass oxygen6 through the system and add a small
Arsenic, % 5 @~~A 2 B!C3 0.0375!/D# 3 100 amount of KIO3 solution until the intensity of the blue color is
that which is to be taken as the end point in the final titration.
where: Read the buret and record as the initial reading. Turn off the
A 5 millilitres of KBrO3 solution required to titrate the oxygen.
sample, 58.3 Transfer 0.5 to 1.0 g of the finely divided sample to a
B 5 millilitres of KBrO3 solution required to titrate the preignited combustion boat, spreading the chips evenly. Place
blank, the boat in the combustion tube, preheating slightly, and then
C 5 normality of the KBrO3 solution, and into the hottest part of the tube. Burn the sample at 1150°C,
D 5 grams of sample used. passing oxygen through the tube at the rate of 500 mL/min.
49. Precision and Bias 58.4 As the oxygen begins to bubble through the absorption
49.1 This test method was originally approved for publica- solution, the blue color will fade. Titrate continuously with
tion before the inclusion of precision and accuracy statements KIO3 solution at such a rate as to maintain, as nearly as
within standards was mandated. The original interlaboratory possible, the initial intensity of the blue color. Near the end of
test data is no longer available. The user is cautioned to verify the combustion period (8 to 10 min), cautiously add KIO3
by the use of reference materials, if available, that the precision solution until the intensity of the blue color is that taken
and accuracy of this test method is adequate for the contem- initially (58.2). Read the buret and record the reading. Subtract
plated use. the initial reading (58.2). The difference is the millilitres of
KIO3 solution required for the titration of the sample.
ARSENIC AND ANTIMONY BY THE DISTILLATION-
58.5 Make a blank determination, following the same
IODOMETRIC TEST METHOD
procedure and using the same amounts of all reagents.
(This test method, which consisted of Sections 50 through 52 58.6 Calculation—Calculate the percentage of sulfur as
of this standard, was discontinued in 1980.) follows:
ANTIMONY AND TIN BY THE MANGANESE Sulfur, % 5 @~~A 2 B! 3 0.00016/C# 3 100
COPRECIPITATION TEST METHOD
where:
(This test method, which consisted of Sections 53 through 55 A 5 millilitres of KIO3 solution required to titrate the
of this standard, was discontinued in 1980.) sample.
B 5 millilitres of KIO3 solution required to titrate the
SULFUR BY THE DIRECT COMBUSTION-IODATE blank, and
TEST METHOD C 5 grams of sample used.
56. Apparatus 59. Precision and Bias
56.1 Apparatus for Determination of Sulfur by Direct 59.1 This test method was originally approved for publica-
Combustion—Apparatus No. 13, except that a furnace, tubes, tion before the inclusion of precision and accuracy statements
and boats capable of operation up to 1200°C can be used. Place within standards was mandated. The original interlaboratory
about a 1⁄2-in. (12.7-mm) plug of asbestos, previously ignited at test data is no longer available. The user is cautioned to verify
1200°C, in the exit end of the tube. (Note 5) One tower by the use of reference materials, if available, that the precision
containing an absorbent such as a 20 to 30-mesh inert base and accuracy of this test method is adequate for the contem-
impregnated with NaOH5 and one tower containing anhydrous plated use.
Mg(ClO 4)2(Anhydrone) are recommended for drying the
oxygen. SULFUR BY THE EVOLUTION TEST METHOD
60. Apparatus
NOTE 5—The asbestos plug is to prevent metallic oxides from condens-
60.1 Apparatus for Determination of Sulfur by Evolution—
ing in the delivery tube. It is necessary to have the plug in a region of not
less than 1100°C to ensure complete dissociation to SO2. The asbestos Apparatus No. 4A, except that the stem of the thistle tube shall
plug should be renewed frequently. contain a ground-glass stopcock and the funnel a connection to
permit the passage of nitrogen through the assembly. The
57. Reagents
digestion flask shall be of 500-mL capacity. The absorption
57.1 Standard Potassium Iodate Solution (0.010 N)
beaker shall be of 400-mL capacity, and preferably of tall form.
—Reagent No. 12. One millilitre of 0.010 N KIO3 solution is
61. Reagents
equivalent to 0.00016 g of sulfur.
61.1 Ammoniacal Cadmium Chloride Solution (8 g Cd
57.2 Starch Solution (10 g/L)—Reagent No. 110, using
Cl2/L)—Dissolve 10 g of CdCl2·21⁄2 H2O in 400 mL of water
soluble starch prepared “according to Lintner.”
and add 600 mL of NH4OH.

5 6
Ascarite and Caroxite have been found satisfactory for this purpose. The regular commercial tank oxygen is satisfactory for this purpose.

6
E 54
61.2 Antimony Chloride Solution (20 g SbCl 3/L)—Dissolve 66. Interferences
2 g of SbCl3 in 50 mL of HCl, and dilute to 100 mL with water. 66.1 Copper is reduced to the cuprous state and prevented
61.3 Starch Solution (10 g/L)—Reagent No. 110, using from interfering by the addition of ammonium thiocyanate.
soluble starch prepared “according to Lintner.” Arsenic, if present in large amounts, may interfere due to the
61.4 Standard Potassium Iodate Solution (0.010 N)— formation of a black precipitate which obscures the end point.
Reagent No. 12. One millilitre of 0.010 N KIO3 solution is Other elements ordinarily present in copper-base alloys do not
equivalent to 0.00016 g of sulfur. interfere.
62. Procedure 67. Apparatus
62.1 Transfer 5.00 g of the sample, (Note 6) to the digestion 67.1 Apparatus for Reduction of Tin—Apparatus No. 7A.
flask and assemble the apparatus. Place 60 mL of ammoniacal 68. Reagents
CdCl2 solution (Note 7 and Note 8) and 150 mL of water in the 68.1 Ammonium Thiocyanate Solution (250 g/L)—Dissolve
absorption beaker. Dissolve a crystal of SnCl2 (Note 9) in 75 250 g of ammonium thiocyanate (NH 4CNS) in water and
mL of HBr and add it to the digestion flask through the funnel. dilute to 1 L.
Pass nitrogen through the system at the rate of 500 to 1000 68.2 Hypophosphorous Acid (30 %) (H 3PO2).
mL/min. Heat the flask and its contents gently until the 68.3 Mercuric Chloride Solution (5 g/L)— Dissolve 5 g of
dissolution of the sample is complete; then boil the solution for mercuric chloride (HgCl2) in water and dilute to 1 L.
about 30 s. If the sample dissolves with difficulty, the addition 68.4 Potassium Iodate, Standard Solution (1 mL 5 0.005 g
of 2 mL of SbCl3 solution to the HBr will facilitate dissolution. Sn)—Dissolve 2.95 g of potassium iodate (KIO3), 40 g of
NOTE 6—If the expected sulfur content is under 0.01 %, the addition of potassium iodide (KI), and 0.35 g of sodium carbonate
a “starter” is necessary. This may be in the form of a weighed amount of (Na2CO3) in water. Transfer to a 1-L volumetric flask, dilute to
a National Institute of Standards and Technology standard sample con- the mark, and mix. Standardize by carrying appropriate stan-
taining sulfur. The equivalent of about 0.02 % of sulfur should be added. dard copper-base alloy samples through the entire procedure,
NOTE 7—Direct sunlight must be avoided; otherwise low results are see Section 69.
obtained.
68.5 Potassium Iodate, Standard Solution (1 mL 5 0.005 g
NOTE 8—It is advisable to add 1 drop of phenolphthalein indicator
solution (10 g/L) (Reagent No. 117) to the CdCl2 solution in order to make Sn)—Transfer 200 mL of standard potassium iodate solution (1
certain of a constant alkalinity. mL 5 0.005 g Sn) to a 1-L volumetric flask, dilute to the mark,
NOTE 9—Stannous chloride is added to prevent oxidation of sulfur due and mix. Standardize as described in 68.4.
to the presence of bromine in the HBr. 68.6 Potassium Iodide (granular).
62.2 Disconnect the absorption flask, add 3 mL of starch 68.7 Sodium Bicarbonate Solution (saturated).
solution, and then 100 mL of HCl (1 + 1), and titrate immedi- 68.8 Starch Solution (10 g/L)—Reagent No. 110.
ately with KIO 3 solution to a persistent blue color. 69. Procedure
62.3 Calculation—Calculate the percentage of sulfur as 69.1 Transfer a 1-g portion of the finely divided sample,
follows: weighed to the nearest 1 mg, to a 500-mL Erlenmeyer flask.
Sulfur, % 5 @~A 3 0.00016!/B# 3 100
Add 60 mL of HCl (1 + 1) and 7 mL of H2O2 (30 %), and warm
gently until dissolution is complete. Boil for 1 min to remove
where: most of the excess oxidant.
A 5 millilitres of KIO3 solution required to titrate the 69.2 Add 10 mL of HgCl2 solution and 10 mL of H3PO 2
sample, and solution, stopper as described in Apparatus 7A, mix, and boil
B 5 grams of sample used. for 5 min. Remove the flask from the hot plate, immerse the
63. Precision and Bias outlet tube in a saturated solution of NaHCO3, and cool the
63.1 This test method was originally approved for publica- flask and its contents below 10°C.
tion before the inclusion of precision and accuracy statements
NOTE 10—It is imperative in this method that the solution be cooled
within standards was mandated. The original interlaboratory
below 10°C before titrating in order to minimize any reaction between
test data is no longer available. The user is cautioned to verify excess H3PO2 and the KIO3 titrating solution.
by the use of reference materials, if available, that the precision
and accuracy of this test method is adequate for the contem- 69.3 Remove the siphon, add 20 mL of NH4CNS solution
plated use. and a small crystal of solid KI to the flask, and mix. Add 5 mL
of starch solution and titrate immediately with the appropriate
TIN BY THE HYPOPHOSPHITE standard KIO3 solution to a lavender end point that persists for
REDUCTION (VOLUMETRIC) TEST METHOD 10 s.
69.4 Blank—Make a blank determination, using a tin-free
64. Scope
copper alloy following the same procedure and using the same
64.1 This test method covers the determination of tin in
amount of all reagents.
copper-base alloys when present in alloying amounts (0.5 to
70. Calculation
20 %).
65. Summary of Test Method 70.1 Calculate the percentage of tin as follows:
65.1 After dissolution of the sample in hydrochloric acid and Tin, % 5 @~A 2 B!C/D# 3 100
hydrogen peroxide, tin is reduced with hypophosphite and
titrated with iodate solution. where:

7
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A 5 millilitres of KIO3 solution required for titration of the and accuracy of this test method is adequate for the contem-
sample, plated use.
B 5 millilitres of KIO3 solution required for titration of the
blank, ZINC BY THE ETHYLENEDIAMINE
C 5 tin equivalent of the KIO3 solution, g/mL, and TETRAACETATE (TITRIMETRIC) TEST METHOD
D 5 grams of sample used. (This test method, which consisted of Sections 72 through 79
71. Precision and Bias of this standard, was discontinued in 1975.)
71.1 This test method was originally approved for publica-
tion before the inclusion of precision and accuracy statements LEAD BY THE DISODIUM (ETHYLENEDINITRILO)
within standards was mandated. The original interlaboratory TETRAACETATE TITRIMETRIC TEST METHOD
test data is no longer available. The user is cautioned to verify (This test method, which consisted of Sections 80 through
by the use of reference materials, if available, that the precision 87, was discontinued in 1976.)

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