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.

1
 E 54
4. Apparatus and Reagents
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
in more than one procedure are referred to by number and shall
conform to the requirements prescribed in Practices E 50.
COPPER, OR COPPER AND LEAD
SIMULTANEOUSLY, BY THE ELECTROLYTIC TEST
METHOD
(This test method, which consisted of Sections 5 through 8
of this standard, was discontinued in 1975.)
LEAD BY THE ELECTROLYTIC TEST METHOD
(This test method, which consisted of Sections 9 and 10 of
this standard, was discontinued in 1979.)
LEAD BY THE SULFATE TEST METHOD
(This test method, which consisted of Sections 11 and 12 of
this standard was discontinued in 1976.)
TIN BY THE IODIMETRIC TITRATION TEST
METHOD
(This test method, which consisted of Sections 13 through
15, was discontinued in 1976.)
ZINC BY THE OXIDE OR FERROCYANIDE TEST
METHOD
(This test method, which consisted of Sections 16 and 17 of
this standard, was discontinued in 1975.)
SILICON BY THE SULFURIC ACID
DEHYDRATION TEST METHOD
18. Procedure
18.1 Solution of Samples Containing Under 1.0 % of
Silicon—Transfer 5.0 g of the sample to a 340-mL porcelain
casserole, cover, and dissolve in 10 mL of HCl and 20 mL of
HNO3. When solution of the sample is complete, add 30 mL of
H2SO 4.
18.2 Solution of Samples Containing 1.0 to 5.0 % of
Silicon—Transfer 1.00 g of the sample to a 340-mL porcelain
casserole, cover, and dissolve in 5 mL of HCl and 10 mL of
HNO3. When solution of the sample is complete, add 15 mL of
H2SO 4.
18.3 Place the casserole on a hot plate and, with a cover glass
placed slightly to one side, evaporate until the HCl and HNO3
have been expelled. Then, with the casserole well covered, heat
strongly for several minutes while dense white fumes are being
driven off. Allow to cool, add carefully 100 mL of HCl (1 + 5),
and bring to a boil. If lead is present in the alloy, add 5 g of
NH4Cl and continue the boiling until all PbSO4 is in solution.
Filter the solution immediately through an 11-cm close-texture,
ashless paper, scrubbing the casserole with a policeman and
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.
NOTE 1—If black silicides, such as those of manganese or iron, are
present in the residue, ignite in accordance with 18.3. Fuse the residue
2
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
with the original filtrate from 18.3, and complete the determination in
accordance with 18.4 to 18.8.
18.4 Return the filtrate to the casserole and treat in accor-
dance with 18.3.
18.5 Transfer the two papers and residues to a platinum
crucible. Ignite at a low temperature until the paper has been
consumed, and then at 1100 to 1150°C to constant weight (see
Note 1). Cool in a desiccator and weigh.
18.6 Add 1 or 2 drops of H2SO4(1 + 1) and sufficient HF (2
to 5 mL) to dissolve the residue, and evaporate the solution
slowly to dense white fumes. Continue to heat the crucible
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
weight represents SiO 2.
18.7 Blank—Make a blank determination, following the
same procedure and using the same amounts of all reagents.
18.8 Calculation—Calculate the percentage of silicon as
follows:4
Silicon, % 5 @~~A 2 B! 3 0.4675!/ C# 3 100
where:
A 5 grams of SiO2,
B 5 correction for blank, g, and
C 5 grams of sample used.
19. Precision and Bias
19.1 This test method was originally approved for publica-
tion before the inclusion of precision and accuracy statements
within standards was mandated. The original interlaboratory
test data is no longer available. The user is cautioned to verify
by the use of reference materials, if available, that the precision
and accuracy of this test method is adequate for the contem-
plated use.
SILICON BY THE PERCHLORIC ACID
DEHYDRATION TEST METHOD
20. Reagents
20.1 Hydrogen Peroxide (3 %).
21. Procedure
21.1 Solution of Samples Containing Under 1.0 % of
Silicon—Transfer 5.0 g of the sample to a 340-mL porcelain
casserole, cover, and dissolve in 10 mL of HCl and 20 mL of
HNO3. When solution of the sample is complete, add 40 mL of
HClO4.
21.2 Solution of Samples Containing 1.0 to 5.0 % of
Silicon—Transfer 1.00 g of the sample to a 340-mL porcelain
casserole, cover, and dissolve in 5 mL of HCl and 10 mL of
HNO3. When solution of the sample is complete, add 25 mL of
HClO4.
21.3 If appreciable amounts of tin or antimony, or both, are
present, add, while stirring, 15 to 30 mL of HBr to volatilize
these constituents. Place the casserole on a hot plate and
evaporate to white fumes. Heat the covered casserole strongly
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
Be Considered Significant in Specified Limiting Values, Annual Book of ASTM
Standards, Vol 14.02.
 E 54
for 15 min while copious white fumes are being driven off.
Allow to cool, but not to become cold, add 100 to 150 mL of
hot water, stir well, and heat until the salts are dissolved. If
manganese dioxide is present, bring it into solution with a few
drops of H2O 2(3 %). Filter the solution immediately through
an 11-cm, close-texture, ashless paper, scrubbing the casserole
with a policeman and washing with HCl (1 + 99) to completely
transfer the residue to the paper. Wash the paper and residue
(see Note 1) thoroughly with HCl (1 + 99) and reserve.
21.4 Return the filtrate to the casserole and treat in accor-
dance with 21.3.
21.5 Complete the determination of silicon as described in
21.5–21.8.
22. Precision and Bias
22.1 This test method was originally approved for publica-
tion before the inclusion of precision and accuracy statements
within standards was mandated. The original interlaboratory
test data is no longer available. The user is cautioned to verify
by the use of reference materials, if available, that the precision
and accuracy of this test method is adequate for the contem-
plated use.
ALUMINUM BY THE GRAVIMETRIC TEST
METHOD
(Aluminum Content 0.10 % and Over)
23. Apparatus
23.1 Mercury Cathode Cell—Apparatus No. 10B.
23.2 Filtering Crucible—A 35-mL fritted-glass crucible of
fine porosity (Apparatus No. 2).
24. Reagents
24.1 Ferric Chloride Solution (100 g/L)—Dissolve 100 g of
FeCl3·6H 2O in water and dilute to 1 L.
24.2 Methyl Red Indicator Solution (0.2 g/L)—Dissolve 0.02
g of methyl red indicator in 100 mL of hot water, cool, and
filter.
24.3 Bromcresol Purple Indicator Solution (0.4 g/L)—
Dissolve 0.04 g of bromcresol purple indicator in 100 mL of
hot water, cool, and filter.
24.4 8-Hydroxyquinoline Solution (25 g/L)—Add 50 mL of
acetic acid to 25 g of 8-hydroxyquinoline and warm gently to
effect solution. Pour the resulting solution into 900 mL of water
at 60°C. Cool, filter if necessary, and dilute to 1 L.
25. Procedure
25.1 For samples containing 0.5 % and over of aluminum,
the electrolyte reserved from the determination of copper on a
2-g sample may be used, or a separate sample may be taken. If
the electrolyte is used, continue in accordance with 25.10. If a
separate sample (Note 2) is taken, proceed in accordance with
25.2 or 25.3.
NOTE 2—The preliminary separation of aluminum from interfering
elements avoids too great contamination of mercury during the subsequent
electrolysis. In certain cases, this may not be objectionable if the sample
is not larger than 1 g, and a direct separation may be carried out in the
mercury cathode cell as follows: Dissolve 1.000 g of the sample as
described in 25.3. Continue as described in 25.4, 25.5, or 25.6 except that
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
75 mL. Transfer the solution to the mercury cell and electrolyze in
accordance with 25.10. Continue in accordance with 25.11–25.14.
3
25.2 For samples containing 0.1 to 1.0 % of aluminum,
transfer 5.00 g of the sample to a 400-mL beaker and
decompose with 5 mL of HCl and 20 mL of HNO3, adding
more HCl if necessary. Continue in accordance with 25.4, 25.5,
or 25.6.
25.3 For samples containing 1.0 % and over of aluminum,
transfer 1.000 g of the sample to a 250-mL beaker and
decompose with 5 mL of HCl and 5 mL of HNO3. Continue in
accordance with 25.4, 25.5, or 25.6.
25.4 If an appreciable amount of silicon is present, add 5 to
15 mL of H2SO4 and evaporate until the HCl and HNO3 have
been expelled. Heat strongly for several minutes while dense
white fumes are being driven off. Allow to cool and dissolve
soluble salts in a small amount of water. Transfer to a platinum
dish, add sufficient HF to volatilize the silicon, and heat slowly
to dense white fumes. Cool and transfer the contents of the dish
to the original beaker and dilute to 50 mL with H2SO 4 (1 + 19).
Heat to boiling, allow to settle, and filter if a precipitate is
present. Filter through an 11-cm fine paper, wash, and discard
any residue. Continue in accordance with 25.7 if 5 g of the
sample were used, or electrolyze in accordance with 25.8 if 1
g of the sample was used.
25.5 In the absence of an appreciable amount of silicon and
in the presence of an appreciable amount of lead, add 5 to 10
mL of H2SO4 and evaporate to dense white fumes. Cool and
dilute to 150 mL. Filter off the PbSO4. Continue in accordance
with 25.7 if 5 g of the sample were used, or electrolyze in
accordance with 25.8 if 1 g of the sample was used.
25.6 In the absence of appreciable amounts of silicon and
lead, add 20 mL of water and heat gently until brown fumes
have been expelled. Wash down the cover glass and sides of the
beaker and dilute to approximately 150 mL. Continue in
accordance with 25.7 if 5 g of the sample were used, or
electrolyze in accordance with 25.8 if 1 g of the sample was
used.
25.7 If there is insufficient iron in the alloy to gather the
aluminum, add 2 mL of FeCl3 solution (100 g/L). Add NH4OH
until the solution is slightly but distinctly ammoniacal, and
bring to a boil. Allow the precipitate to settle on the steam bath
for 5 min, filter on a loose-texture paper, and wash the beaker
and precipitate with hot NH4Cl solution (10 g/L) until most of
the blue copper salts have been washed out. Place the paper
and precipitate in the original beaker, and add 5 mL of H2SO
4 and 20 mL of HNO3. Heat until all organic matter is
destroyed, adding small quantities of HNO3 as required.
Evaporate to dense white fumes. Cool, wash down the cover
glass and sides of the beaker with water, and evaporate to dense
white fumes again to remove the last traces of HNO3. Continue
in accordance with 25.10.
25.8 Add 2 mL of HNO3, and remove the copper by
electrolysis. Reserve the electrolyte.
25.9 To the electrolyte or a suitable aliquot of it, reserved in
accordance with 25.8, add sufficient H2SO4 to bring the total
content of H2SO4 to 5 mL and evaporate to dense white fumes.
Allow the solution to cool, wash down the sides of the beaker
with water, and evaporate again to dense white fumes to
remove the last traces of HNO 3.
25.10 Cool the solution obtained in accordance with 25.7 or
 E 54
25.9, and dilute to 25 mL with water. If any PbSO4 is present,
filter and wash thoroughly with H2SO4 (1 + 19). Transfer the
solution to the mercury cathode cell, keeping the volume below
100 mL; if slight hydrolysis takes place, disregard it. Electro-
lyze at a current of 3 to 5 A, while vigorously stirring the
electrolyte and mercury, or electrolyze overnight at a current of
1 to 1.5 A. When electrolysis is complete, separate the mercury
from the electrolyte while at least part of the current is kept on;
if the electrolyte contains floating particles of loose amalgam
after this separation, filter the electrolyte and discard the
amalgam.
25.11 In the absence of beryllium and phosphorus, adjust the
volume of the solution obtained in accordance with 25.10 to
200 mL. Add 5 mL of HCl and a little paper pulp. Heat the
solution to boiling, add 2 drops of methyl red indicator
solutions, and then add NH4OH until nearly neutral. Add
NH4OH (1 + 3) until a pure yellow color is obtained, boil the
solution gently for 1 min, adding more NH4OH (1 + 3) if the
solution changes in color to an orange shade. Filter at once on
a medium-texture, ashless paper and wash with hot NH4Cl
solution (10 g/L). Transfer paper and precipitate to a weighed
platinum crucible, dry, and ignite slowly until the paper is
burned; then ignite at a temperature of approximately 1100°C
for 10 to 15 min. Cover the crucible with a tight-fitting
platinum cover to prevent absorption of moisture by the ignited
Al2O3, cool in a desiccator, and weigh. Repeat the ignition at
1100°C to constant weight.
25.12 Calculation—Calculate the percentage of aluminum as
follows:4
Aluminum, % 5 @~A 3 0.5291!/B# 3 100
where:
A 5 grams of Al2O3, and
B 5 grams of sample used.
25.13 If beryllium or phosphorus is present, adjust the volume
of the solution obtained in accordance with 25.10 to 200 mL.
Add 10 mL of HCl, 15 mL of ammonium acetate solution (400
g/L), and 8 to 10 drops of bromcresol purple indicator solution
(0.4 g/L). Add NH4OH (1 + 1) until the indicator becomes a
distinct purple. While stirring, add slowly from a buret
8-hydroxyquinoline solution (25 g/L), using 15 to 20 % in
excess of the amount necessary to precipitate the aluminum.
Heat the solution and precipitate to boiling, while stirring
occasionally, boil gently for 1 min, and allow to cool to 60°C.
Filter off the precipitate, using a 35-mL fritted-glass crucible of
fine porosity, and using moderate suction. Wash the precipitate
with 100 mL of cool water, dry for 3 h at 135°C, cool in a
desiccator, and weigh.
25.14 Calculation—Calculate the percentage of aluminum as
follows:4
Aluminum, % 5 @~A 3 0.0587!/B# 3 100
where:
A 5 grams of aluminum oxyquinolate, and
B 5 grams of sample used.
26. Precision and Bias
26.1 This test method was originally approved for publica-
tion before the inclusion of precision and accuracy statements
4
within standards was mandated. The original interlaboratory
test data is no longer available. The user is cautioned to verify
by the use of reference materials, if available, that the precision
and accuracy of this test method is adequate for the contem-
plated use.
NICKEL BY THE DIMETHYLGLYOXIME TEST
METHOD
(This test method, which consisted of Sections 27 through 29
of this standard, was discontinued in 1975.)
IRON BY THE DICHROMATE TEST METHOD
30. Reagents
30.1 Stannous Chloride Solution (50 g/L)—Dissolve 12.5 g
of SnCl2·2H 2O in 25 mL of HCl, and dilute to 250 mL. Keep
the solution in a well-stoppered bottle.
30.2 Mercuric Chloride Solution (saturated)—Add 60 to 100
g of HgCl2 to 400 mL of hot water, shake, and cool to room
temperature. More water may be added from time to time as
long as crystals remain undissolved.
30.3 Sodium Diphenylamine Sulfonate Indicator Solution (2
g/L).
30.4 Standard Potassium Dichromate Solution (0.05 N)—
Reagent No. 10.
31. Procedure for Alloys Containing Under 0.05 % of
Tin, Under 0.01 % of Arsenic, and Under 0.01 % of
Antimony
31.1 If the iron content is under 0.25 %, transfer 5.0 g of the
sample, from which adventitious iron has been removed, to a
400-mL beaker and dissolve in 50 mL of HNO3 (1 + 1). If the
iron content is 0.25 % or over, transfer 1.00 to 2.00 g of the
sample, from which adventitious iron has been removed, to a
250-mL beaker and dissolve in 25 mL of HNO3 (1 + 1).
31.2 If silicon is present, add a few drops of HF to
decompose any iron silicide. Add 5 to 10 mL of H2SO4 and
evaporate to dense white fumes. Allow to cool, dilute some-
what with water, and filter if necessary. Add 2 to 3 mL of
HNO3, and boil for 5 min.
31.3 Dilute the solution to 150 mL. Add NH4OH until
slightly but distinctly alkaline, and boil gently for a few
minutes. Remove the beaker from the hot plate, allow the
precipitate to settle for a few minutes, and filter while hot,
using a medium-texture paper. Wash the beaker and precipitate
a few times, alternately with NH4Cl solution (20 g/L) and hot
water, to remove most of the soluble salts.
31.4 Dissolve the precipitate through the paper with 20 mL
of hot HCl (1 + 1) and wash thoroughly with hot water to
remove the last traces of iron, collecting the solution and
washings in the original beaker. Proceed as described in 31.3.
Dissolve the precipitate through the paper with 20 mL of hot
HCl (1 + 1) and wash thoroughly with hot water, collecting the
solution and washings in the original beaker.
31.5 Evaporate the solution to 15 to 20 mL and wash down
the sides of the beaker. Heat to boiling, and add SnCl2·2H2O
solution (50 g/L) drop by drop, while swirling the beaker over
a white background, until the yellow color of the FeCl3
disappears. Add 1 drop of SnCl 2 solution in excess, but no
more.
31.6 Dilute the reduced solution to 50 mL, cool to room
 E 54
temperature, stir, and add at one stroke 10 mL of a saturated
solution of HgCl2. The resultant precipitate should be pure
white in color, and in amount should be preferably not more
than enough to give a pearly opalescence. If the precipitate is
gray or dark, too large an excess of SnCl2 has been used and it
will be necessary to discard the solution and start anew. To the
properly reduced solution, add 10 mL of H3PO4(1 + 3) and 4
drops of sodium diphenylamine sulfonate indicator (2 g/L).
31.7 The volume of the solution to be titrated should not
exceed 100 mL. Titrate slowly with 0.05 N K2Cr 2O7 solution,
while stirring constantly, until the color of the solution changes
from green to a gray-green. Continue the titration, drop by
drop, until the first tinge of purple or violet-blue appears.
31.8 Blank—Make a blank determination, following the
same procedure and using the same amounts of all reagents.
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
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.
31.9 Calculation—Calculate the percentage of iron as fol-
lows:4
Iron, % 5 @~~A 2 B!C3 0.0559!/D# 3 100
where:
A 5 millilitres of K2Cr2O7 solution required to titrate the
sample,
B 5 millilitres of K2Cr2O7 solution required to titrate the
blank,
C 5 normality of the K2Cr2O7 solution, and
D 5 grams of sample used.
32. Procedure for Alloys Containing 0.05 % and Over of
Tin, With or Without Arsenic and Antimony
32.1 It is desirable to remove the tin to facilitate later
handling. Arsenic and antimony, if present, must be removed,
since they interfere in the titration.
32.2 Transfer 5.0 g of the sample, from which adventitious
iron has been removed, to a 250-mL beaker. Add 50 mL of
HNO3 (1 + 1), and heat to expel brown fumes. If silicon is
present, add a few drops of HF to decompose any iron silicide.
Dilute the solution to 100 mL with hot water, and digest the
metastannic acid on a steam bath for 1 h. Filter through double,
close-texture papers into a 400-mL beaker, wash with hot
HNO3(1 + 99), and reserve the filtrate (Note 4). If HF has been
used, add 5 to 10 mL of H2SO4 and evaporate to dense white
fumes. Cool, dilute, and filter if necessary.
NOTE 4—If desired, the alkaline sulfide separation of tin, arsenic, and
antimony, may be used instead of the HBr treatment.
32.3 Transfer the paper and contents to the original beaker.
Add 15 mL of HNO3 and then 10 mL of HClO4. Heat gently
until white fumes appear, cool, and wash down the sides of the
beaker. Cover, and add 10 mL of HBr. Remove the cover glass
and boil gently until white fumes appear. Repeat the HBr
treatment to expel the last traces of tin and antimony. Add 15
mL of water and heat to dissolve soluble salts. If SiO2 is
present, filter the solution, and combine with the filtrate
reserved in accordance with 32.2. Complete the determination
of iron in accordance with 31.3–31.9.
33. Precision and Bias
5
33.1 This test method was originally approved for publica-
tion before the inclusion of precision and accuracy statements
within standards was mandated. The original interlaboratory
test data is no longer available. The user is cautioned to verify
by the use of reference materials, if available, that the precision
and accuracy of this test method is adequate for the contem-
plated use.
MANGANESE BY THE BISMUTHATE TEST
METHOD
(This test method, which consisted of Sections 34 through
36, was discontinued in 1976.)
MANGANESE BY THE PERSULFATE TEST METHOD
(This test method, which consisted of Sections 37 and 38,
was discontinued in 1976.)
MANGANESE BY THE BROMATE TEST METHOD
(This test method, which consisted of Sections 39 and 40 of
this standard, was discontinued in 1980.)
PHOSPHORUS BY THE ALKALIMETRIC TEST
METHOD
(This test method, which consisted of Sections 41 through
45, was discontinued in 1976.)
ARSENIC BY THE DISTILLATION-BROMATE
(MOFFAT) TEST METHOD
46. Apparatus
46.1 Apparatus for Determination of Arsenic by
Distillation—Apparatus No. 66.
47. Reagents
47.1 Hydrazine Sulfate.
47.2 Standard Potassium Bromate Solutions—(0.01 and 0.05
N)—Reagent No. 9.
47.3 Methyl Orange Indicator Solution—Dissolve 0.1 g of
methyl orange in 100 mL of water and filter off any residue.
48. Procedure
48.1 Transfer 2.0 to 3.0 g of the sample (the amount
depending on the arsenic content) to a 500-mL Erlenmeyer
flask. Add 10 to 15 mL of HNO 3, cover, and heat gently until
decomposition is complete. Add 10 g of KHSO4 and 30 mL of
H2SO4. Heat over a flame with constant swirling until dense
white fumes are evolved. Cool and add about 0.2 g of
hydrazine sulfate. Wash down the walls of the flask with about
15 mL of water, and again evaporate to dense white fumes.
48.2 Cool the residue and add 20 mL of water. Shake to
dissolve the soluble salts and cool to room temperature or
below. Add 0.2 g of FeSO 4·7H2O, 50 mL of HCl, and 8 to 10
g of NaCl. Connect the flask to the distillation apparatus and
place 200 mL of water in the receiving beaker. Heat the
contents of the distilling flask to boiling (a hot plate with a
surface temperature of 275 to 300°C is satisfactory) and
continue until the temperature of the vapor in the flask reaches
105°C. (The distillate need not be kept cold.) Unstopper the
distilling flask, and remove from the hot plate.
48.3 Rinse off the delivery tube into the distillate. Heat to
boiling and boil gently for 10 min. Titrate at 80 to 90°C with
0.01 N or 0.05 N KBrO3 solution, using methyl orange as
 E 54
indicator, which should preferably be added near the end of the
titration.
48.4 Blank—Make a blank determination, following the
same procedure and using the same amounts of all reagents.
48.5 Calculation—Calculate the percentage of arsenic as
follows:4
Arsenic, % 5 @~~A 2 B!C3 0.0375!/D# 3 100
where:
A 5 millilitres of KBrO3 solution required to titrate the
sample,
B 5 millilitres of KBrO3 solution required to titrate the
blank,
C 5 normality of the KBrO3 solution, and
D 5 grams of sample used.
49. Precision and Bias
49.1 This test method was originally approved for publica-
tion before the inclusion of precision and accuracy statements
within standards was mandated. The original interlaboratory
test data is no longer available. The user is cautioned to verify
by the use of reference materials, if available, that the precision
and accuracy of this test method is adequate for the contem-
plated use.
ARSENIC AND ANTIMONY BY THE DISTILLATION-
IODOMETRIC TEST METHOD
(This test method, which consisted of Sections 50 through 52
of this standard, was discontinued in 1980.)
ANTIMONY AND TIN BY THE MANGANESE
COPRECIPITATION TEST METHOD
(This test method, which consisted of Sections 53 through 55
of this standard, was discontinued in 1980.)
SULFUR BY THE DIRECT COMBUSTION-IODATE
TEST METHOD
56. Apparatus
56.1 Apparatus for Determination of Sulfur by Direct
Combustion—Apparatus No. 13, except that a furnace, tubes,
and boats capable of operation up to 1200°C can be used. Place
about a 1⁄2-in. (12.7-mm) plug of asbestos, previously ignited at
1200°C, in the exit end of the tube. (Note 5) One tower
containing an absorbent such as a 20 to 30-mesh inert base
impregnated with NaOH5 and one tower containing anhydrous
Mg(ClO 4)2(Anhydrone) are recommended for drying the
oxygen.
NOTE 5—The asbestos plug is to prevent metallic oxides from condens-
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
plug should be renewed frequently.
57. Reagents
57.1 Standard Potassium Iodate Solution (0.010 N)
—Reagent No. 12. One millilitre of 0.010 N KIO3 solution is
equivalent to 0.00016 g of sulfur.
57.2 Starch Solution (10 g/L)—Reagent No. 110, using
soluble starch prepared “according to Lintner.”
5 6
Ascarite and Caroxite have been found satisfactory for this purpose.
6
58. Procedure
58.1 Adjust the furnace temperature to 1150°C, which is the
temperature of combustion.
58.2 Add sufficient HCl (3 + 197) to the absorption vessel to
cover the tube outlet 1 to 2 in. and then add 2 mL of starch
solution. Pass oxygen6 through the system and add a small
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.
Read the buret and record as the initial reading. Turn off the
oxygen.
58.3 Transfer 0.5 to 1.0 g of the finely divided sample to a
preignited combustion boat, spreading the chips evenly. Place
the boat in the combustion tube, preheating slightly, and then
into the hottest part of the tube. Burn the sample at 1150°C,
passing oxygen through the tube at the rate of 500 mL/min.
58.4 As the oxygen begins to bubble through the absorption
solution, the blue color will fade. Titrate continuously with
KIO3 solution at such a rate as to maintain, as nearly as
possible, the initial intensity of the blue color. Near the end of
the combustion period (8 to 10 min), cautiously add KIO3
solution until the intensity of the blue color is that taken
initially (58.2). Read the buret and record the reading. Subtract
the initial reading (58.2). The difference is the millilitres of
KIO3 solution required for the titration of the sample.
58.5 Make a blank determination, following the same
procedure and using the same amounts of all reagents.
58.6 Calculation—Calculate the percentage of sulfur as
follows:
Sulfur, % 5 @~~A 2 B! 3 0.00016/C# 3 100
where:
A 5 millilitres of KIO3 solution required to titrate the
sample.
B 5 millilitres of KIO3 solution required to titrate the
blank, and
C 5 grams of sample used.
59. Precision and Bias
59.1 This test method was originally approved for publica-
tion before the inclusion of precision and accuracy statements
within standards was mandated. The original interlaboratory
test data is no longer available. The user is cautioned to verify
by the use of reference materials, if available, that the precision
and accuracy of this test method is adequate for the contem-
plated use.
SULFUR BY THE EVOLUTION TEST METHOD
60. Apparatus
60.1 Apparatus for Determination of Sulfur by Evolution—
Apparatus No. 4A, except that the stem of the thistle tube shall
contain a ground-glass stopcock and the funnel a connection to
permit the passage of nitrogen through the assembly. The
digestion flask shall be of 500-mL capacity. The absorption
beaker shall be of 400-mL capacity, and preferably of tall form.
61. Reagents
61.1 Ammoniacal Cadmium Chloride Solution (8 g Cd
Cl2/L)—Dissolve 10 g of CdCl2·21⁄2 H2O in 400 mL of water
and add 600 mL of NH4OH.
The regular commercial tank oxygen is satisfactory for this purpose.
 E 54
61.2 Antimony Chloride Solution (20 g SbCl 3/L)—Dissolve
2 g of SbCl3 in 50 mL of HCl, and dilute to 100 mL with water.
61.3 Starch Solution (10 g/L)—Reagent No. 110, using
soluble starch prepared “according to Lintner.”
61.4 Standard Potassium Iodate Solution (0.010 N)—
Reagent No. 12. One millilitre of 0.010 N KIO3 solution is
equivalent to 0.00016 g of sulfur.
62. Procedure
62.1 Transfer 5.00 g of the sample, (Note 6) to the digestion
flask and assemble the apparatus. Place 60 mL of ammoniacal
CdCl2 solution (Note 7 and Note 8) and 150 mL of water in the
absorption beaker. Dissolve a crystal of SnCl2 (Note 9) in 75
mL of HBr and add it to the digestion flask through the funnel.
Pass nitrogen through the system at the rate of 500 to 1000
mL/min. Heat the flask and its contents gently until the
dissolution of the sample is complete; then boil the solution for
about 30 s. If the sample dissolves with difficulty, the addition
of 2 mL of SbCl3 solution to the HBr will facilitate dissolution.
NOTE 6—If the expected sulfur content is under 0.01 %, the addition of
a “starter” is necessary. This may be in the form of a weighed amount of
a National Institute of Standards and Technology standard sample con-
taining sulfur. The equivalent of about 0.02 % of sulfur should be added.
NOTE 7—Direct sunlight must be avoided; otherwise low results are
obtained.
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
certain of a constant alkalinity.
NOTE 9—Stannous chloride is added to prevent oxidation of sulfur due
to the presence of bromine in the HBr.
62.2 Disconnect the absorption flask, add 3 mL of starch
solution, and then 100 mL of HCl (1 + 1), and titrate immedi-
ately with KIO 3 solution to a persistent blue color.
62.3 Calculation—Calculate the percentage of sulfur as
follows:
Sulfur, % 5 @~A 3 0.00016!/B# 3 100
where:
A 5 millilitres of KIO3 solution required to titrate the
sample, and
B 5 grams of sample used.
63. Precision and Bias
63.1 This test method was originally approved for publica-
tion before the inclusion of precision and accuracy statements
within standards was mandated. The original interlaboratory
test data is no longer available. The user is cautioned to verify
by the use of reference materials, if available, that the precision
and accuracy of this test method is adequate for the contem-
plated use.
TIN BY THE HYPOPHOSPHITE
REDUCTION (VOLUMETRIC) TEST METHOD
64. Scope
64.1 This test method covers the determination of tin in
copper-base alloys when present in alloying amounts (0.5 to
20 %).
65. Summary of Test Method
65.1 After dissolution of the sample in hydrochloric acid and
hydrogen peroxide, tin is reduced with hypophosphite and
titrated with iodate solution.
7
66. Interferences
66.1 Copper is reduced to the cuprous state and prevented
from interfering by the addition of ammonium thiocyanate.
Arsenic, if present in large amounts, may interfere due to the
formation of a black precipitate which obscures the end point.
Other elements ordinarily present in copper-base alloys do not
interfere.
67. Apparatus
67.1 Apparatus for Reduction of Tin—Apparatus No. 7A.
68. Reagents
68.1 Ammonium Thiocyanate Solution (250 g/L)—Dissolve
250 g of ammonium thiocyanate (NH 4CNS) in water and
dilute to 1 L.
68.2 Hypophosphorous Acid (30 %) (H 3PO2).
68.3 Mercuric Chloride Solution (5 g/L)— Dissolve 5 g of
mercuric chloride (HgCl2) in water and dilute to 1 L.
68.4 Potassium Iodate, Standard Solution (1 mL 5 0.005 g
Sn)—Dissolve 2.95 g of potassium iodate (KIO3), 40 g of
potassium iodide (KI), and 0.35 g of sodium carbonate
(Na2CO3) in water. Transfer to a 1-L volumetric flask, dilute to
the mark, and mix. Standardize by carrying appropriate stan-
dard copper-base alloy samples through the entire procedure,
see Section 69.
68.5 Potassium Iodate, Standard Solution (1 mL 5 0.005 g
Sn)—Transfer 200 mL of standard potassium iodate solution (1
mL 5 0.005 g Sn) to a 1-L volumetric flask, dilute to the mark,
and mix. Standardize as described in 68.4.
68.6 Potassium Iodide (granular).
68.7 Sodium Bicarbonate Solution (saturated).
68.8 Starch Solution (10 g/L)—Reagent No. 110.
69. Procedure
69.1 Transfer a 1-g portion of the finely divided sample,
weighed to the nearest 1 mg, to a 500-mL Erlenmeyer flask.
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
most of the excess oxidant.
69.2 Add 10 mL of HgCl2 solution and 10 mL of H3PO 2
solution, stopper as described in Apparatus 7A, mix, and boil
for 5 min. Remove the flask from the hot plate, immerse the
outlet tube in a saturated solution of NaHCO3, and cool the
flask and its contents below 10°C.
NOTE 10—It is imperative in this method that the solution be cooled
below 10°C before titrating in order to minimize any reaction between
excess H3PO2 and the KIO3 titrating solution.
69.3 Remove the siphon, add 20 mL of NH4CNS solution
and a small crystal of solid KI to the flask, and mix. Add 5 mL
of starch solution and titrate immediately with the appropriate
standard KIO3 solution to a lavender end point that persists for
10 s.
69.4 Blank—Make a blank determination, using a tin-free
copper alloy following the same procedure and using the same
amount of all reagents.
70. Calculation
70.1 Calculate the percentage of tin as follows:
Tin, % 5 @~A 2 B!C/D# 3 100
where:
 E 54

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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