Designation: E 107 88 (Reapproved 1998)

Standard Test Methods for

Chemical Analysis of Electronic Nickel
1
This standard is issued under the xed designation E 107; 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
1.1 These test methods cover photometric procedures for
the chemical analysis of nickel, intended primarily for use in
electronic devices, having a chemical composition within the
following limits:
Element Concentration Range, %
Nickel 94 to 100
Copper 0.005 to 0.3
Iron 0.0035 to 0.3
Cobalt 0.05 to 1.0
Manganese 0.02 to 0.5
Titanium 0.0005 to 0.5
Silicon 0.001 to 0.3
Aluminum 0.01 to 0.35
Carbon 0.001 to 0.10
Hydrogen 0.0001 to 0.01
Nitrogen 0.0001 to 0.01
Oxygen 0.001 to 0.10
Tungsten 3.0 to 5.0
Magnesium 0.005 to 0.2
1.2 The techniques and procedures covered in these test
methods have been chosen so as to keep the consumption of
sample to a minimum.
1.3 The analytical procedures appear in the following order:
(This standard contains more than one test method for some
elements. In some cases, the use of multiple test methods is
needed to cover the concentration range of the scope of the
standard; in others, multiple test methods are supplied to allow
for variations in availability of instruments and other facilities
among laboratories.)
Sections
Copper by the Hydrobromic Acid (Photometric) Method 8 to 15
Iron by the Thiocyanate (Photometric) Method 16 to 24
Cobalt by the Nitroso-R-Salt (Photometric) Method 25 to 32
Manganese by the Periodate (Photometric) Method 33 to 40
Titanium by the Tiron (Photometric) Method 41 to 48
Silicon by the Molybdenum Blue (Photometric) Method 49 to 56
Aluminum by the Aluminon (Photometric) Method 57 to 64
Carbon by the Low-Pressure Combustion Method 65 to 73
Hydrogen, Nitrogen, and Oxygen by the Vacuum Fusion
Method 74 to 78
Copper by the Neocuproine (Photometric) Method 79 to 87
Tungsten by the Acid Digestion-Cinchonine (Gravimetric)
Method 88 to 92
Magnesium by the 8-Hydroxyquinoline (Photometric)
Method 93 to 102
1.4 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. Specic hazard
statements are given in Section 5.
2. Referenced Documents
2.1 ASTM Standards:
E 29 Practice for Using Signicant Digits in Test Data to
Determine Conformance With Specications
2
E 39 Methods for Chemical Analysis of Nickel
3
E 50 Practices for Apparatus, Reagents, and Safety Precau-
tions for Chemical Analysis of Metals
3
E 55 Practice for Sampling Wrought Nonferrous Metals and
Alloys for Determination of Chemical Composition
3
E 60 Practice for Photometric and Spectrophotometric
Methods for Chemical Analysis of Metals
3
3. Signicance and Use
3.1 These test methods for the chemical analysis of metals
and alloys are primarily intended to test such materials for
compliance with compositional specications. It is assumed
that all who use these test methods will be trained analysts
capable of performing common laboratory procedures skill-
fully and safely. It is expected that work will be performed in
a properly equipped laboratory.
4. Photometric Practice, Apparatus, and Reagents
4.1 Photometers and Photometric PracticePhotometers
and photometric practice prescribed in these test methods shall
conform to Practice E 60.
4.2 Apparatus other than photometers, 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.
5. Hazards
5.1 For precautions to be observed in the use of certain
reagents in these test methods, reference shall be made to
Practices E 50.
1
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 E01.08 on Ni and Co and High Temperature Alloys.
Current edition approved Dec. 30, 1988. Published February 1989. Originally
published as E 107 54 T. Last previous edition E 107 83.
These test methods were developed in cooperation with ASTM Committee F-1
on Electronics.
2
Annual Book of ASTM Standards, Vol 14.02.
3
Annual Book of ASTM Standards, Vol 03.05.
1
AMERICAN SOCIETY FOR TESTING AND MATERIALS
100 Barr Harbor Dr., West Conshohocken, PA 19428
Reprinted from the Annual Book of ASTM Standards. Copyright ASTM
6. Sampling
6.1 The sample shall be selected so as to be representative
of the material to be analyzed.
6.2 For the determination of carbon, hydrogen, nitrogen,
and oxygen, wrought products shall be sampled in accordance
with Practice E 55, with the exception that for the determina-
tion of hydrogen, nitrogen, and oxygen solid pieces are
preferred to millings or drillings, if representative, so as to
minimize the effect of surface area.
7. Rounding Calculated Values
7.1 Calculated values shall be rounded to the desired num-
ber of places in accordance with the rounding method given in
Section 3.4 and 3.5 of Practice E 29.
COPPER BY THE HYDROBROMIC ACID
(PHOTOMETRIC) TEST METHOD
8. Summary of Test Method
8.1 Cupric copper in a mixture of HBr and H
3
PO
4
forms a
red-violet colored complex. Photometric measurement is made
at approximately 600 nm.
NOTE 1By calibrating the system using a light band centered at
approximately 600 nm, this test method can be used to determine higher
concentrations of copper, if necessary. Under these conditions, the range
is from 0.15 to 3.0 mg of copper in 25 mL of solution, using a cell depth
of 2 cm.
9. Concentration Range
9.1 The recommended concentration range is from 0.05 to
0.8 mg of copper per 25 mL of solution, using a cell depth
4
of
2 cm.
10. Stability of Color
10.1 The color develops immediately and is stable for
several days.
11. Interfering Elements
11.1 Gold and the platinum group metals interfere if
present. Provision is made in this test method to eliminate other
interfering elements that might be present in nickel.
12. Reagents
12.1 Copper, Standard Solution (1 mL 5 0.1 mg Cu)
Dissolve 0.1000 g of high-purity copper (99.9 % Cu and over)
in 3 mL of HNO
3
by heating gently in a 125-mL conical ask.
Add 10 mL of HClO
4
and heat to copious fumes to expel
HNO
3
. Cool and add 10 mL of water. Transfer to a 1-L
volumetric ask, dilute to the mark, and mix.
12.2 Hydrobromic Acid - Bromine MixtureAdd 1 volume
of bromine to 16 volumes of HBr and mix.
12.3 Hydrogen Peroxide (3 %)Dilute 1 mL of H
2
O
2
(30 %) to 10 mL with water. Prepare fresh before use.
12.4 Test LeadFinely granulated test lead containing less
than 0.0001 % of copper and less than 0.001 % of iron or
nickel.
13. Preparation of Calibration Curve
13.1 Calibration Solutions:
13.1.1 Transfer 0.5, 1.0, 2.0, 3.0, 4.0, 6.0, and 8.0 mL of
copper solution (1 mL 5 0.1 mg Cu) to 125-mL conical asks.
Add 3 mL of HClO
4
and dilute to 40 mL.
13.1.2 Add 1 g of test lead, cover, and boil at a moderate
rate for 15 min to displace all the copper. Cool somewhat,
remove the solution by decantation, and wash once with water,
decanting thoroughly. Heat the ask gently to remove mois-
ture.
13.1.3 Add 10 mL of HBr Br
2
mixture to the ask, cover,
and heat gently to dissolve the metal. Boil to expel the excess
bromine. Cool to room temperature. Transfer 10 mL of H
3
PO
4
and 1 drop (0.05 mL) of HBr Br
2
mixture to a dry 25-mL
volumetric ask (Note 2). Transfer the sample solution to a
volumetric ask, washing with a few millilitres of HBr. Dilute
to the mark with HBr and mix.
NOTE 2Partial reduction of the copper to the cuprous state may occur
when a bromine-free HBr solution of cupric copper is boiled. For this
reason, it is necessary to add a small amount of bromine to oxidize any
cuprous copper before photometric measurement is made. Bromine in
small amounts does not absorb appreciably at 600 nm.
13.2 Reference SolutionTransfer 40 mL of water and 3
mL of HClO
4
to a 125-mL ask and proceed as directed in
13.1.2 and 13.1.3.
13.3 PhotometryTransfer a suitable portion of the refer-
ence solution to an absorption cell and adjust the photometer to
the initial setting, using a light band centered at approximately
600 nm. While maintaining this photometer adjustment, take
the photometric readings of the calibration solutions.
13.4 Calibration CurvePlot the photometric readings of
the calibration solutions against milligrams of copper per 25
mL of solution.
14. Procedure
14.1 Sample Solution:
14.1.1 Transfer 1.000 g of the sample to a 125-mL conical
ask and add 10 mL of HNO
3
(1 + 1). Cover and warm gently
to dissolve the sample.
14.1.2 When dissolution is as complete as possible, add 6
mL of HClO
4
and heat while swirling over an open ame until
the volume of the solution has been reduced to about 3 mL
(Note 3). Cool, add 10 mL of water plus 2 drops of H
2
O
3
(3 %),
and heat to boiling (Note 4). Dilute to 40 mL with water. If
necessary, lter through a ne paper into a 150-mL ask or
beaker (Note 5). Wash once or twice with water and discard the
paper and precipitate.
NOTE 3It is essential that the fuming operation completely remove
the HNO
3
, yet care should be used to avoid evaporation of too much
HClO
4
, lest an insoluble nickel oxide be formed.
NOTE 4The H
2
O
2
is added to destroy any MnO
2
or HMnO
4
that
might be present.
NOTE 5If more than a small amount of tungsten is present, as
indicated by a colored precipitate at this point, the subsequent method for
the determination of iron should not be used, as the precipitate tends to
hold iron. No apparent difficulties are encountered in the determination of
copper, cobalt, or manganese.
14.1.3 Add 1 g of test lead to the ask or beaker. Cover and
boil gently for 15 min to collect the copper on the lead. Decant
4
These procedures have been written for a cell having a 2-cm light path. Cells
having other dimensions may be used, provided suitable adjustments can be made
in the amount of sample and reagents used.
E 107
2
the ltrate. Quickly wash the container and test lead twice by
decantation with water. Cool the decanted solution and wash
water to room temperature, transfer to a 100-mL volumetric
ask, dilute to the mark, and mix. Reserve this solution for the
determination of cobalt, iron, and manganese (see Note 5).
14.1.4 Add 10 mL of HBr Br
2
mixture to the lead remain-
ing in the ask or beaker, cover, and heat gently to dissolve.
Proceed as directed in 13.1.3.
14.2 Reference SolutionCarry a reagent blank through the
entire procedure, using the same amount of all reagents, for use
as a reference solution.
14.3 PhotometryTake the photometric reading of the
sample solution as described in 13.3.
14.4 CalculationConvert the photometric reading of the
sample solution to milligrams of copper by means of the
calibration curve. Calculate the percentage of copper as fol-
lows:
Copper, % 5 A/~B 3 10! (1)
where:
A 5 copper found, g, and
B 5 sample used, g.
15. Precision and Bias
15.1 This test method was originally approved for publica-
tion before the inclusion of precision and bias statements
within standards was mandated. The original interlaboratory
test data for this test method are no longer available. The user
is cautioned to verify by the use of reference materials, if
available, that the precision and bias of this test method are
adequate for the contemplated use.
IRON BY THE THIOCYANATE (PHOTOMETRIC)
TEST METHOD
16. Summary of Test Method
16.1 Ferric iron forms a red-brown soluble complex with
thiocyanate in acid solution. Photometric measurement is made
at approximately 470 nm.
17. Concentration Range
17.1 The recommended concentration range is from 0.007
to 0.14 mg of iron in 50 mL of solution, using a cell depth
3
of
2 cm.
18. Stability of Color
18.1 The color develops immediately and is reasonably
stable for 30 min in the presence of H
2
O
2
.
19. Interfering Elements
19.1 The elements ordinarily present in electronic nickel do
not interfere with this test method. This test method, however,
is not applicable to alloys containing appreciable amounts of
tungsten (see Note 5).
20. Reagents
20.1 Ammonium Thiocyanate Solution (115 g/L)Dissolve
115 g of NH
4
CNS in 300 mL of water. Filter and dilute to 1 L.
Store in a dark bottle.
20.2 Hydrogen Peroxide Solution (1.5 %)Dilute 1 mL of
H
2
O
2
(30 %) to 20 mL with water. Prepare fresh before use.
20.3 Iron, Standard Solution (1 mL 5 0.025 mg Fe)
Dissolve 0.1756 g of Fe(NH
4
)
2
(SO
4
)
2
6H
2
O in 10 mL of
HNO
3
(1 + 1). Heat to gentle boiling to expel brown fumes.
Cool, dilute to 1 L in a volumetric ask, and mix.
20.4 Nickel Nitrate, Ni(NO
3
)
2
6H
2
O.
21. Preparation of Calibration Curve A
21.1 Calibration Solutions:
21.1.1 Transfer 5.0 g of Ni(NO
3
)
2
6H
2
O to each of two
125-mL conical asks. Add 3 mL of water and warm to
dissolve most of the sample. Add 6 mL of HClO
4
and heat over
an open ame until the volume of the solution has been
reduced to 3 mL. Add 10 mL of water and heat to boiling.
Combine the two solutions, transfer to a 200-mL volumetric
ask, dilute to the mark, and mix.
21.1.2 Transfer 5.0-mL portions of the nickel solution to
seven 50-mL beakers, and add 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, and
6.0 mL of iron solution (1 mL 5 0.025 mg Fe).
21.1.3 Add 5 mL of HNO
3
(1 + 3) to each beaker and boil
for 1 min to expel brown fumes. Cool, transfer to 50-mL
volumetric asks, and dilute to approximately 35 mL. Add 1
mL of H
2
O
2
solution and then add 10 mL of NH
4
CNS solution.
Dilute to the mark and mix.
21.2 Reference SolutionTransfer a 5-mL aliquot of the
nickel solution (21.1.1) to a 50-mL beaker and proceed as
directed in 21.1.3.
21.3 PhotometryTransfer a suitable portion of the refer-
ence solution to an absorption cell and adjust the photometer to
the initial setting, using a light band centered at approximately
470 nm. While maintaining this photometer adjustment, take
the photometric readings of the calibration solutions.
21.4 Calibration CurvePlot the photometric readings of
the calibration solutions against milligrams of iron per 50 mL
of solution.
22. Preparation of Calibration Curve B
22.1 Repeat the preparation of a calibration curve, as
directed in 21.1.2 to 21.4, except to use 20-mL portions of a
nickel solution prepared as directed in 21.1.1.
NOTE 6The presence of varying amounts of nickel affects the ferric
thiocyanate color, and necessitates the preparation of two calibration
curves to cover the analytical range indicated in 1.1.
23. Procedure
23.1 Sample SolutionDepending on the iron content of
the sample, transfer a 5.0 or 20.0-mL aliquot portion of the
solution reserved as directed in 14.1.3 to a 50-mL beaker and
continue as described in 21.1.3.
23.2 Reference SolutionTransfer a corresponding aliquot
of the reagent blank solution reserved from the copper deter-
mination to a beaker and carry through all the steps of the
procedure for use as a reference solution.
23.3 PhotometryTake the photometric reading of the
sample solution as described in 21.3.
23.4 Background ColorTransfer a corresponding aliquot
of the sample solution to a 50-mL beaker, and continue as
directed in 21.1.3 but omit the addition of NH
4
CNS solution.
E 107
3
Take the photometric reading, using a corresponding aliquot of
the reagent blank solution, similarly treated, as the reference
solution.
NOTE 7This background correction may be of considerable magni-
tude and cannot be ignored.
23.5 CalculationsConvert the photometric readings of the
sample solution and the background color solution to milli-
grams of iron by means of the appropriate calibration curve,
based on the size aliquot used. Calculate the percentage of iron
as follows:
Iron, % 5 ~A B!/~C 3 10! (2)
where:
A 5 iron found in the aliquot used, g,
B 5 background color correction, in milligrams of iron,
and
C 5 sample represented in the aliquot used, g.
24. Precision and Bias
24.1 This test method was originally approved for publica-
tion before the inclusion of precision and bias statements
within standards was mandated. The original interlaboratory
test data for this test method are no longer available. The user
is cautioned to verify by the use of reference materials, if
available, that the precision and bias of this test method are
adequate for the contemplated use.
COBALT BY THE NITROSO-R-SALT
(PHOTOMETRIC) TEST METHOD
25. Summary of Test Method
25.1 Cobalt in a hot solution buffered with sodium acetate
forms an orange-colored complex with nitroso-R-salt. The
addition of a controlled amount of HNO
3
destroys interfering
complexes and stabilizes the cobalt complex. Photometric
measurement is made at approximately 515 nm.
26. Concentration Range
26.1 The recommended concentration range is from 0.005
to 0.10 mg of cobalt in 50 mL of solution, using a cell depth
3
of 2 cm.
27. Stability of Color
27.1 The color is stable for more than 2 h.
28. Interfering Elements
28.1 The elements ordinarily present in electronic nickel do
not interfere if their contents are under the maximum limits
shown in Section 1. Excessive amounts of nickel interfere with
full color development, and therefore the recommended aliquot
of the sample solution should not be exceeded.
29. Reagents
29.1 Cobalt, Standard Solution (1 mL 5 0.01 mg Co):
29.1.1 Transfer 0.1000 g of high-purity cobalt (99.9 % Co
and over) to a 1-L volumetric ask. Add 10 mL of
HNO
3
(1 + 1), heat gently until action ceases, and then boil
until free of brown fumes. Cool, dilute to the mark, and mix.
Transfer 100 mL of this solution to a 1-L volumetric ask,
dilute to the mark, and mix.
29.1.2 Alternatively, transfer 0.4770 g of CoSO
4
7H
2
O to a
1-L volumetric ask. Add 75 mL of water and 4 mL of
H
2
SO
4
(1 + 1). Swirl until the salt dissolves, dilute to the mark,
and mix. Standardize the solution as follows: Transfer a
100-mL aliquot to a 400-mL beaker, add 10 mL of HCl, and
dilute to 200 mL. Proceed as described in Methods E 39. For
use, dilute 100 mL of this solution to 1 L in a volumetric ask
and mix.
29.2 Nitroso-R-Salt Solution (7.5 g/L)Dissolve 0.75 g of
nitroso-R-salt in water, lter, and dilute to 100 mL. Do not use
solutions more than 1 week old.
29.3 Sodium Acetate Buffer Solution (500 g/L)Dissolve
500 g of sodium acetate trihydrate in about 600 mL of water,
add 30 mL of acetic acid, lter, and dilute to 1 L.
30. Preparation of Calibration Curve
30.1 Calibration Solutions:
30.1.1 Transfer 0.5, 1.0, 2.0, 4.0, 6.0, 8.0, and 10.0 mL of
cobalt solution (1 mL 5 0.010 mg Co) to seven 50-mL beakers
and dilute to 10 mL.
30.1.2 Add 5 mL of sodium acetate buffer solution, fol-
lowed by 2.0 mL of nitroso-R-salt solution, mixing the solution
after each addition. (The pH of the solutions at this point
should be about 5.5.) Cover the beaker, heat to boiling, and
maintain just under the boiling temperature for 1 to 2 min. Add
5.0 mL of HNO
3
(1 + 2) and boil gently for 1 to 2 min. Cool to
room temperature, transfer to a 50-mL volumetric ask, dilute
to the mark, and mix.
30.2 Reference SolutionTransfer 10 mL of water to a
50-mL beaker and proceed as directed in 30.1.2.
30.3 PhotometryTransfer a suitable portion of the refer-
ence solution to an absorption cell and adjust the photometer to
the initial setting, using a light band centered at approximately
515 nm. While maintaining this photometer adjustment, take
the photometric readings of the calibration solutions.
30.4 Calibration CurvePlot the photometric readings of
the calibration solutions against milligrams of cobalt per 50 mL
of solution.
31. Procedure
31.1 Sample SolutionTransfer 1.0 mL of the sample
solution reserved as directed in 14.1.3 to a 50-mLbeaker, dilute
to 10 mL, and proceed as directed in 30.1.2.
31.2 Reference SolutionTransfer a 1.0-mL aliquot of the
corresponding reagent blank to a 50-mL beaker and proceed as
directed in 30.1.2.
31.3 PhotometryTake the photometric reading of the
sample solution as directed in 30.3.
31.4 CalculationConvert the photometric reading of the
sample solution to milligrams of cobalt by means of the
calibration curve. Calculate the percentage of cobalt as fol-
lows:
Cobalt, % 5 A/~B 3 10! (3)
where:
A 5 cobalt found in the aliquot used, mg, and
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4
B 5 sample represented in the aliquot used, g.
32. Precision and Bias
32.1 This test method was originally approved for publica-
tion before the inclusion of precision and bias statements
within standards was mandated. The original interlaboratory
test data for this test method are no longer available. The user
is cautioned to verify by the use of reference materials, if
available, that the precision and bias of this test method are
adequate for the contemplated use.
MANGANESE BY THE PERIODATE
(PHOTOMETRIC) TEST METHOD
33. Summary of Test Method
33.1 Manganese in acid solution is oxidized to permangan-
ate by means of KIO
4
. Photometric measurement is made at
approximately 540 nm.
34. Concentration Range
34.1 The recommended concentration range is from 0.035
to 0.7 mg of manganese in 50 mL of solution, using a cell
depth
3
of 2 cm.
35. Stability of Color
35.1 The permanganate color is stable indenitely in the
absence of reducing agents.
36. Interfering Elements
36.1 The elements ordinarily present in electronic nickel do
not interfere.
37. Reagents
37.1 Manganese, Standard Solution (1 mL 5 0.05 mg
Mn):
37.1.1 Dissolve 0.500 g of high-purity manganese (contain-
ing not less than 99.5 % Mn) in 10 mL of HNO
3
(1 + 1) and
boil to expel brown fumes. Cool, dilute to 1 L in a volumetric
ask, and mix. Dilute 100 mL of this solution to 1 L in a
volumetric ask and mix.
37.1.2 Alternatively, the solution may be prepared as fol-
lows: Dissolve 1.440 g of KMnO
4
in 200 mL of water, add 20
mL of H
2
SO
4
(1 + 1), and reduce the permanganate by addi-
tions of Na
2
SO
3
or H
2
O
2
. Boil to remove excess SO
2
or H
2
O
2
.
Cool, dilute to 1 L in a volumetric ask, and mix. Dilute 100
mL of this solution to 1 L in a volumetric ask and mix.
37.2 Potassium Periodate Solution (7.5 g/L)Dissolve 7.5
g of KIO
4
in 200 mL of hot HNO
3
(1 + 1), add 400 mL of
H
3
PO
4
, cool, dilute to 1 L, and mix.
37.3 Sodium Nitrite Solution (20 g/L)Dissolve 0.2 g of
NaNO
2
in water and dilute to 10 mL. Do not use solutions
more than 1 day old.
38. Preparation of Calibration Curve
38.1 Transfer 1.0, 2.0, 4.0, 6.0, 8.0, 10.0, 12.0, and 14.0 mL
of manganese solution (1 mL 5 0.05 mg Mn) to 100-mL
beakers. Dilute to 20 mL.
38.1.1 Add 10 mL of KIO
4
solution. Heat to boiling and
digest just below the boiling point until the color develops, and
then an additional 5 min. When color development is complete,
cool, transfer to a 50-mL volumetric ask, dilute to the mark,
and mix.
38.2 Reference SolutionTransfer 20 mL of water to a
100-mL beaker and proceed as directed in 38.1.1
38.3 PhotometryTransfer a suitable portion of the refer-
ence solution to an absorption cell and adjust the photometer to
the initial setting, using a light band centered at approximately
540 nm. While maintaining this photometer adjustment, take
the photometric readings of the calibration solutions.
38.4 Calibration CurvePlot the photometric readings of
the calibration solutions against milligrams of manganese per
50 mL of solution.
39. Procedure
39.1 Sample SolutionTransfer a suitable aliquot, up to 20
mL in volume, of the solution reserved as directed in 14.1.3 to
a 100-mL beaker, dilute to 20 mL, and proceed as directed in
38.1.1.
39.2 Reference SolutionTransfer a suitable amount (ap-
proximately 15 mL) of the sample solution in which the color
has been developed to a clean, dry, 50-mL beaker. Add 1 drop
of NaNO
2
solution and swirl the solution until the permanga-
nate is completely reduced.
39.3 PhotometryTake the photometric reading of the
sample solution as described in 38.3.
39.4 CalculationConvert the photometric reading of the
sample solution to milligrams of manganese by means of the
calibration curve. Calculate the percentage of manganese as
follows:
Manganese, % 5 A/~B 3 10! (4)
where:
A 5 manganese found in the aliquot used, g, and
B 5 sample represented in the aliquot used, g.
40. Precision and Bias
40.1 This test method was originally approved for publica-
tion before the inclusion of precision and bias statements
within standards was mandated. The original interlaboratory
test data for this test method are no longer available. The user
is cautioned to verify by the use of reference materials, if
available, that the precision and bias of this test method are
adequate for the contemplated use.
TITANIUM BY THE TIRON (PHOTOMETRIC)
TEST METHOD
41. Summary of Test Method
41.1 Titanium, in a solution buffered to a pH of approxi-
mately 4.5, forms a yellow complex with tiron (disodium-1,2-
dihydroxybenzene-3,5-disulfonate). Photometric measurement
is made at approximately 400 nm.
42. Concentration Range
42.1 The recommended concentration range is from 0.005
to 0.08 mg of titanium in 50 mL of solution, using a cell depth
3
of 2 cm.
43. Stability of Color
43.1 The colored complex is stable for at least 24 h, but
E 107
5
since there is some instability in the other reagents used, the
measurement should be made as soon as possible after the
colored solutions are prepared.
44. Interfering Elements
44.1 Provision is made in this test method to eliminate
interference by elements ordinarily present in electronic nickel.
45. Reagents
45.1 Ethylenediaminetetraacetic Acid.
45.2 Ferric Nitrate Solution (1 mL 5 approximately 0.1 mg
Fe)Dissolve 0.100 g of Fe (free of titanium) in 20 mL of
HNO
3
. Boil off the fumes, cool, and dilute to 1 L.
45.3 Sodium AcetateAcetic Acid Buffer Solution
Dissolve 270 g of anhydrous sodium acetate in 500 mL of
water, add 240 mL of acetic acid, cool, and dilute to 1 L. Filter
if necessary.
45.4 Sodium DithioniteSodium hydrosulte (Na
2
S
2
O
4
).
45.5 Tiron Solution (40 g/L)Dissolve 4 g of disodium-
1,2-dihydroxybenzene-3,5-disulfonate in water and dilute to
100 mL. When the water-cooled solution becomes pale yellow
on standing for several weeks, it should be discarded.
45.6 Titanium, Standard Solution (1 mL 5 0.001 mg Ti)
Fuse 0.1668 g of TiO
2
with 2 g of KHSO
4
in a platinum
crucible. Dissolve the fusion in 50 mL of H
2
SO
4
and carefully
add 100 mL of water. Cool to room temperature and dilute to
1 L in a volumetric ask. Transfer 100 mL of this solution to
a 1-L volumetric ask and dilute to the mark with
H
2
SO
4
(1 + 19).
46. Preparation of Calibration Curve
46.1 Calibration Solutions:
46.1.1 Transfer 0.5, 1.0, 2.0, 4.0, 6.0, 8.0, and 10.0 mL of
titanium solution (1 mL 5 0.01 mg Ti) to 50-mL volumetric
asks. Add 1 mL of Fe(NO
3
)
3
solution, and dilute to approxi-
mately 20 mL.
46.1.2 Add 1 mL of tiron solution, followed by NH
4
OH
added dropwise until the color changes to a deep red. Cool if
necessary, add 10 mL of buffer solution, dilute to the mark, and
mix. Add a minimum amount (10 to 20 mg) of solid ethylene-
diaminetetraacetic acid and shake well to bleach the iron-tiron
complex. Then add a similar small amount of solid sodium
dithionite and shake to complete the bleaching operation.
NOTE 8The amount of sodium dithionite used should be kept to a
minimum and the photometric readings should be taken as rapidly as
possible, due to the instability of the dithionite and the possible formation
of a turbidity due to the liberation of sulfur.
46.2 Reference SolutionTransfer 1 mL of Fe(NO
3
)
3
solu-
tion to a 50-mL volumetric ask, dilute to approximately 20
mL, and proceed as directed in 47.1.2.
46.3 PhotometryTransfer a suitable portion of the refer-
ence solution to an absorption cell and adjust the photometer to
the initial setting, using a light band centered at 400 nm. While
maintaining this photometer adjustment, take the photometric
readings of the calibration solutions, making the observation as
rapidly as possible after bleaching of the iron complex (see
Note 8).
46.4 Calibration CurvePlot the photometric readings of
the calibration solutions against milligrams of titanium per 50
mL of solution.
47. Procedure
47.1 Sample Solution:
47.1.1 Transfer a 0.500-g portion of the sample to a 150-mL
beaker, cover, and dissolve with 10 mL of HNO
3
(1 + 1). When
dissolution is complete, boil to expel brown fumes, cool, and
dilute to about 50 mL. Add 5.0 mL of Fe(NO
3
)
3
solution and
make ammoniacal in order to precipitate iron and titanium.
Allow the solution to stand on the warm plate until the
precipitate coagulates. Filter and wash with NH
4
OH (1 + 49),
making sure that all blue coloration is washed from the paper.
47.1.2 Transfer the paper and precipitate back into the
original beaker and add 10 mL of HNO
3
and 5 mL of HClO
4
(Warning, see Section 5). Heat gently until the paper is
consumed, and continue heating until copious fumes are
evolved. Cool, dilute somewhat, and lter if necessary. Trans-
fer to a 50-mL volumetric ask, dilute to approximately 20 mL,
and proceed as directed in 46.1.2.
47.2 Reference SolutionCarry a reagent blank through the
entire procedure, using the same amount of all reagents, for use
as a reference solution.
47.3 PhotometryTake the photometric reading of the
sample solution as described in 46.3.
NOTE 9If the titanium content is so high as to make the photometric
reading fall outside the recommended range, an aliquot of the colored
solution may be diluted to 50 mL with water, after adding a further 5 mL
of buffer. It will sometimes be necessary to add a few more milligrams of
dithionite to overcome the reoxidation of the iron. Likewise, the range
may be extended by taking a larger portion of the sample.
47.4 CalculationConvert the photometric readings of the
sample solution to milligrams of titanium by means of the
calibration curve. Calculate the percentage of titanium as
follows:
Titanium, % 5 A/~B 3 10! (5)
where:
A 5 titanium found, mg, and
B 5 sample used, g.
48. Precision and Bias
48.1 This test method was originally approved for publica-
tion before the inclusion of precision and bias statements
within standards was mandated. The original interlaboratory
test data for this test method are no longer available. The user
is cautioned to verify by the use of reference materials, if
available, that the precision and bias of this test method are
adequate for the contemplated use.
SILICON BY THE MOLYBDENUM BLUE
(PHOTOMETRIC) TEST METHOD
49. Summary of Test Method
49.1 After solution in HNO
3
and adjustment of acidity,
ammonium molybdate is added and the resultant molybdisilicic
acid reduced with SnCl
2
. The molybdenum blue color pro-
duced is measured photometrically at 765 nm.
50. Concentration Range
50.1 The recommended concentration range is from 0.0035
E 107
6
to 0.07 mg of silicon in 100 mL of solution, using a cell depth
3
of 2 cm.
51. Stability of Color
51.1 The color develops within 5 min and is stable for at
least an additional 5 min. A uniform time for color develop-
ment should be used for both calibration solutions and samples.
52. Interfering Elements
52.1 Provision is made in this test method for the elimina-
tion of interference from the elements normally present in
electronic nickel.
53. Reagents
NOTE 10Due to the contamination of the reagents, excessive reagent
blank readings may be encountered unless special precautions are taken to
purify the reagents. It is suggested in this case that the distilled water be
redistilled, condensing the steam in a block tin pipe and storing the water
in polyethylene bottles. This water should be used in preparing the
reagents as well as subsequent operations of calibrating and analysis.
Deionizing water from a monobed system is also satisfactory if properly
stored.
Since reagent grade NH
4
OH often exhibits silicon contamination, the
NH
4
OH (2 + 3) (53.1) may be prepared by passing pure gaseous tank
ammonia through a plug of cotton to a piece of polyethylene tubing that
dips into 200 mL of redistilled water contained in a polyethylene bottle
resting in an ice bath. Bubble the gas at a moderate rate for 10 min. Keep
capped with a polyethylene cap when not in use and prepare fresh when
too much ammonia has escaped.
53.1 Ammonium Hydroxide (2 + 3)Prepare NH
4
OH
(2 + 3) free of silicon and store so as to avoid silicon
contamination.
53.2 Ammonium Molybdate Solution (50 g/L)Dissolve 10
g of the larger crystals of (NH
4
)
6
Mo
7
O
24
4H
2
O in water and
dilute to 200 mL. Store in a polyethylene bottle.
53.3 Silicon, Standard Solution (1 mL 5 0.01 mg Si)Fuse
0.107 g of pure anhydrous SiO
2
with 1 g of anhydrous Na
2
CO
3
in a covered platinum crucible. Cool the melt, dissolve
completely in water, and dilute to 500 mL in a volumetric ask.
Transfer at once to a polyethylene bottle. Dilute 50 mL of this
solution to 500 mL in a volumetric ask and transfer at once to
a second polyethylene bottle.
53.4 Stannous Chloride Solution (10 g/L)Transfer 1 g of
the larger crystals of SnCl
2
2H
2
O to a 100-mL volumetric ask
and add 2 mL of HCl. Warm gently until the crystals dissolve
and a clear solution is obtained. Cool, dilute to the mark with
water, and mix. Prepare fresh each day as required.
53.5 Sulfamic Acid Solution (100 g/L)Dissolve 10 g of
sulfamic acid (H
2
NSO
3
H) in water and dilute to 100 mL.
Prepare fresh each day, as required.
54. Preparation of Calibration Curve
54.1 Calibration Solutions:
54.1.1 Transfer 0.5, 1.0, 2.0, 3.0, 5.0, and 7.0 mL of silicon
solution (1 mL 5 0.01 mg Si) to 150-mL beakers. Add 5 mL of
HNO
3
(1 + 1) and then 5 mL of sulfamic acid solution. Dilute to
approximately 45 ml.
54.1.2 Neutralize carefully with NH
4
OH (2 + 3) added
dropwise (preferably from a plastic dropper) until Congo red
paper just turns red (see Note 10). Immediately add 1 mL of
H
2
SO
4
(1 + 3). The total volume of the solutions at this point
should not be more than about 55 mL. Remove the Congo
paper.
54.1.3 Add 10 mL of ammonium molybdate solution, mix,
and allow to stand 5 min. Add 30 mL of H
2
SO
4
(1 + 3) and mix.
Add 1 mL of SnCl
2
solution directly to the solution and mix.
(The SnCl
2
solution must not be allowed to come in contact
with nonacidied ammonium molybdate on the walls of the
beaker; otherwise some reduction of the molybdate will result.)
Transfer the solutions to 100-mL volumetric asks, dilute to
the mark, and mix well by inverting four or ve times.
54.2 Reference SolutionTransfer 5 mL of HNO
3
(1 + 1)
and 5 mL of sulfamic acid solution to a 150-mL beaker and
dilute to approximately 45 mL. Proceed as directed in 54.1.2
and 54.1.3.
54.3 PhotometryTransfer a suitable portion of the refer-
ence solution to an absorption cell and adjust the photometer to
the initial setting, using a light band centered at approximately
765 nm. While maintaining this photometer adjustment, take
the photometric readings of the calibration solutions. The
various operations should be organized in such a way that the
photometric readings are taken about 5 min after the addition
of the SnCl
2
solution.
54.4 Calibration CurvePlot the photometric readings of
the calibration solutions against milligrams of silicon per 100
mL of solution.
55. Procedure
55.1 Sample Solution:
55.1.1 Transfer a portion of the sample (0.200 g for nickel
containing more than 0.005 % of silicon or 0.500 g for nickel
low in silicon) to a 150-mL beaker and add 5 mL of
HNO
3
(1 + 1). Cover and warm gently to dissolve the sample,
avoiding, as much as possible, the loss of HNO
3
by evapora-
tion. When dissolution is complete, heat gently to expel most
of the brown fumes. Cool, wash down the cover, add 5 mL of
sulfamic acid solution, and dilute to approximately 45 mL.
Proceed as directed in 54.1.2 and 54.1.3.
55.1.2 If the sample contains more than 0.025 % of silicon,
cool the solution, following the removal of the brown fumes,
transfer to a 100-mL volumetric ask, and mix. Transfer an
aliquot, preferably containing from 0.02 to 0.05 mg of silicon,
to a 150-mL beaker and add sufficient HNO
3
(1 + 1) to make
the total content 5 mL. Add 5 mL of sulfamic acid solution,
dilute to approximately 45 mL, and proceed as directed in
54.1.2 and 54.1.3.
55.2 Reference SolutionCarry through a reagent blank,
following the same procedure and using the same amount of all
reagents, for use as a reference solution.
55.3 PhotometryTake the photometric reading of the
sample solution as directed in 54.3.
55.4 Background ColorTransfer a similar sample portion
(55.1.1) or a similar aliquot of the sample solution (55.1.2) to
a 150-mL beaker and proceed as described in 55.1.1 or 55.1.2,
omitting the addition of ammonium molybdate solution and
SnCl
2
solution. Take the photometric reading of this solution,
using a similarly treated reagent blank as a reference solution.
55.5 CalculationConvert the photometric reading of the
sample solution and of the background color solution to
E 107
7
milligrams of silicon by means of the calibration curve.
Calculate the percentage of silicon as follows:
Silicon, % 5 ~A B!/~C 3 10! (6)
where:
A 5 silicon found in the sample or aliquot used, mg,
B 5 background color correction, mg of silicon, and
C 5 sample represented in the sample or aliquot used, g.
56. Precision and Bias
56.1 This test method was originally approved for publica-
tion before the inclusion of precision and bias statements
within standards was mandated. The original interlaboratory
test data for this test method are no longer available. The user
is cautioned to verify by the use of reference materials, if
available, that the precision and bias of this test method are
adequate for the contemplated use.
ALUMINUM BY THE ALUMINON
(PHOTOMETRIC) TEST METHOD
57. Summary of Test Method
57.1 After the removal of interfering elements by mercury
cathode separation and cupferron - chloroform extraction, the
aluminum is determined photometrically by the aluminon
method.
58. Concentration Range
58.1 The recommended concentration range is from 0.010
to 0.090 mg of aluminum in 100 mL of solution, using a cell
depth
3
of 2 cm.
59. Stability of Color
59.1 The color is stable for at least 10 min.
60. Interfering Elements
60.1 Provision has been made for the removal of all
commonly encountered interfering elements. This test method
is not suitable for samples that contain beryllium, scandium, or
appreciable amounts of vanadium.
61. Reagents
61.1 AluminonBuffer Composite SolutionAdd 500 g of
ammonium acetate to 1 L of water in a 2-L beaker. Add 80 mL
of acetic acid and stir to dissolve the ammonium acetate. Filter
if necessary. Dissolve 1.000 g of a suitable grade of aluminon
(aurin tricarboxylic acid-ammonium salt) in 50 mL of water
and add to the buffer solution.
5
Dissolve 2 g of benzoic acid in
20 mL of methanol and pour into the buffer solution while
stirring. Dilute the mixture to 2 L in a volumetric ask and mix.
Transfer 10 g of gelatin
5,6
to 250 mL of water in a 400-mL
beaker. Place the beaker in a boiling water bath and allow to
remain, with occasional stirring, until the gelatin has dissolved
completely. Pour the warm gelatin solution into 500 mL of
water while stirring. Cool to room temperature, dilute to 1 L in
a volumetric ask, and mix. Transfer the aluminon and gelatin
solutions to a 4-L, chemically resistant, glass-stoppered bottle,
mix well, and keep in a dark place when not in use.
61.2 Aluminum, Standard Solution (1 mL 5 0.01 mg Al)
Dissolve 0.0200 g of aluminum in 20 mL of HCl by heating
gently. Dilute to 2 L in a volumetric ask.
61.3 Cupferron Solution (10 g/L)Dissolve 1 g of a fresh
supply of cupferron in 100 mL of water. Prepare fresh daily as
needed.
61.4 Meta-Cresol Purple Indicator Solution (1 g/L)
Dissolve 0.1 g of meta-cresol purple in 10 mL of water
containing one pellet of NaOH. Cool and add 90 mL of water.
61.5 Thioglycolic Acid SolutionDilute 10.0 mL of
thioglycolic acid to 250 mL with water in a volumetric ask
and mix well. Keep stoppered when not in use.
62. Preparation of Calibration Curve
62.1 Calibration Solutions:
62.1.1 Transfer 1.0, 2.0, 4.0, 6.0. 8.0, and 10.0 mL of
aluminum solution (1 mL 5 0.01 mg Al) to 100-mL beakers.
Add 1 mL of HClO
4
, and dilute to 50 mL with water.
62.1.2 Add 2.0 mL of thioglycolic acid solution plus 1 drop
of meta-cresol purple indicator solution and neutralize care-
fully with NH
4
OH (using a comparison solution) until a
denite lightening of the pink color results. Do not carry the
neutralization of the orange color of the indicator for fear of
approaching too closely the point where partial hydrolysis of
the aluminum occurs. Transfer the solution to a 100-mL
volumetric ask and add 15.0 mL of aluminonbuffer com-
posite solution. Swirl, place the ask in 300 mL of vigorously
boiling water in a 400-mL beaker, and allow to remain exactly
5 min. Remove to the bench for a minute or so and then place
in a cold-water bath. Cool to room temperature, dilute to the
mark with water, and mix well.
62.2 Reference SolutionTransfer 1 mL of HClO
4
to a
100-mL beaker, dilute to 50 mL with water, and continue as
directed in 62.1.2.
62.3 PhotometryTransfer a suitable portion of the refer-
ence solution to an absorption cell and adjust the photometer to
the initial setting, using a light band centered at approximately
525 nm. While maintaining this photometer adjustment, take
the photometric readings of the calibration solutions, allowing
each to stand 1 or 2 min before making the reading.
62.4 Calibration CurvePlot the photometric readings of
the calibration solutions against milligrams of aluminum per
100 mL of solution.
63. Procedure
63.1 Sample Solution:
63.1.1 Transfer 0.025 to 0.150 g of the milled, sawed, or
rolled sample, preferably containing 0.010 to 0.090 mg of
aluminum, to a 125-mL conical ask. Add 2 mL of
HNO
3
(1 + 1), cover, and warm to dissolve the sample. Ignore
insoluble silicon or tungsten precipitates.
63.1.2 Add 2 mL of HClO
4
, and while swirling without a
cover, heat over a Meker Type ame until the volume is
reduced to 1 mL in order to expel HNO
3
. Cool, add 10 mL of
5
For detailed information of suitable grades of aluminon and gelatin, see Luke,
C. L., and Braun, K. C., Photometric Determination of Aluminum in Manganese
Bronze, Zinc Die-Casting Alloy and Magnesium Alloys, Analytical Chemistry,
ANCHA, Vol 24, 1952, p. 1120.
6
Knox gelatin has been found satisfactory for this purpose.
E 107
8
water, and heat to boiling to expel chlorine. Dilute the sample
to 40 mL with water. Filter, if necessary, through a 9-cm
ne-texture paper and wash well with water. Discard the paper
and precipitate.
63.1.3 Transfer the sample to a 100-mL mercury cathode
beaker containing about 30 mL of mercury. Electrolyze with
stirring and at a current of 4 or 5 Auntil the solution is colorless
and then for 10 or 15 min longer. When the electrolysis is
complete, siphon off the solution while washing the electrodes
and beaker walls with small portions of water.
63.1.4 Transfer the solution to a 150-mL Squibb-type sepa-
ratory funnel, add 2 mL of cupferron solution, swirl, add 15 mL
of chloroform, stopper, and shake vigorously for 1 min. Allow
the layers to separate and then drain off and discard the lower
layer. Wash the solution free of cupferron by repeating the
extraction with a 5-mL portion of chloroform. Transfer the
aqueous solution to a 150 mL beaker and heat to boiling to
expel chloroform. Cool. Proceed as directed in 62.1.1.
63.2 Reference SolutionCarry a reagent blank through the
entire procedure for use as a reference solution.
63.3 PhotometryTake the photometric readings of the
sample solution, using the reagent blank solution as a refer-
ence, as directed in 62.3.
63.4 CalculationBy means of the calibration curve, con-
vert the photometric readings of the sample solution to
milligrams of aluminum. Calculate the percentage of alumi-
num as follows:
Aluminum, % 5 A/~B 3 10! (7)
where:
A 5 aluminum found in sample, mg, and
B 5 sample used, g.
64. Precision and Bias
64.1 This test method was originally approved for publica-
tion before the inclusion of precision and bias statements
within standards was mandated. The original interlaboratory
test data for this test method are no longer available. The user
is cautioned to verify by the use of reference materials, if
available, that the precision and bias of this test method are
adequate for the contemplated use.
CARBON BY THE LOW-PRESSURE
COMBUSTION TEST METHOD
65. Summary of Test Method
65.1 This test method is based on the combustion of the
sample in oxygen at low pressure, freezing the carbon dioxide,
and then measuring it in the gas phase and in a known volume
by means of a McLeod gage.
66. Concentration Range
66.1 The recommended concentration range is from 0.005
to 0.500 mg of carbon in a 0.5-g sample (0.0001 to 0.10 %).
67. Interfering Elements
67.1 The elements ordinarily present in nickel do not
interfere.
68. Apparatus
68.1 The special apparatus required for this determination is
shown schematically in Fig. 1. It shall consist of the following
parts or their equivalents:
68.1.1 Vacuum SourcesA mechanical pump
7
connected at
E, Fig. 1, coupled with a single-stage mercury diffusion pump,
T. (The diffusion pump is shown in detail in Fig. 2.) A
mechanical pump
8
for back vacuum, connected to B and C.
68.2 Induction HeaterVacuum-tube oscillator, 500 Hz, 2
kW output, connected to a heater coil 80 mm in inside diameter
and 75-mm high, designed to efficiently couple the induction
heater with the crucible. The design of the coil will vary with
the make of induction heater but must be adequate to heat the
crucible to at least 1200C.
68.3 Oxygen Purication FurnaceResistance furnace
305-mm (12-in.) long with a 25.4-mm (1-in.) diameter open-
ing, F.
68.4 Furnace AssemblyAspecial glass furnace containing
evacuation port, D, sample storage, Q, and crucible suspension,
P. In an alternative type of furnace construction, preferred by
some users, the crucible is supported on a pedestal from the
bottom. The furnace is heated with an induction heater (68.2)
and cooled by a high-speed blower connected to a glass funnel
at R with a exible fabric hose. The blower should be equipped
with a means of speed variation.
68.5 McLeod Gage, M, with 1-mm tubing, volume of bulb
about 120 mL, range from 0.00002 to 0.7 mm. Calibrate the
gage by weighing before and after lling with mercury and
thus determine the volume of the bulb.
9
68.6 Mercury Wells, W
1
, W
2
, W
3
, and W
4
.
68.7 Stopcocks, vacuum grade. One two-way, 2-mm,
oblique-bore stopcock, S
1
, with mercury seal and evacuated
closed end; one two-way, 15-mm, oblique-bore stopcock, S
7
;
four three-way, 2-mm stopcocks, S
3
to S
6
; one two-way, 4-mm
stopcock, S
2
.
68.8 Adapter, A, for Connection of Apparatus of Oxygen
Pressure RegulatorAll-metal exible tubing having a ared
nut connector on one end and a copper-to-glass seal on the
opposite end.
68.9 Clear Quartz Tube, F
1
, 10 mm in diameter by
400-mm long with three-step seals on each end for sealing to
borosilicate glass.
68.10 Platinum Crucible, with reinforced rim
10
(Fig. 3).
68.11 Ceramic Crucible Liner
11
(Fig. 3).
68.12 Radiation Shield
10
(Fig. 3).
68.13 Optical Pyrometer.
68.14 Palladium-on-Alumina Catalyst.
68.15 Liquid Nitrogen.
68.16 Dewar Flasks, wide-mouth, borosilicate glass.
69. Assembly of Apparatus
69.1 Using suitable support frame, assemble the apparatus
7
Cenco Hypervac No. 25, or its equivalent, has been found satisfactory for this
purpose.
8
Cenco Hyvac, or its equivalent, has been found satisfactory for this purpose.
9
For information on calibration see Dushman, S., Vacuum Technique, John
Wiley & Sons, Inc., 605 Third Ave., New York, NY 10016, 1949, Chapter 6.
10
The Baker and Co., B.T.L., special crucible has been found satisfactory for this
purpose.
11
Coors A1200, high-alumina, or the equivalent, has been found satisfactory for
this purpose.
E 107
9
as shown in Fig. 1 and as described in the following 69.2 to
69.4. All tubing shall be borosilicate glass, with seals carefully
made to ensure freedom from leaks.
69.2 The palladium-alumina catalyst shall be packed into
quartz tube F
1
, and held in place with fragments of quartz
extending to the glass bends at either end. The tube is located
in the furnace, F, Fig. 1.
69.3 The crucible assembly, Fig. 3, shall be suspended from
a glass tripod with 1.27-mm (0.050-in.) platinum wire and this
assembly inserted through the top of the furnace. The length of
the platinum wire shall be so adjusted that the crucible is just
below the sample chute and centrally located within the
furnace. The top of the furnace shall then be resealed with a
torch.
69.4 The mercury cut-offs connected to stopcocks S
3
to S
6
,
Fig. 1, shall be lled with triple-distilled mercury and con-
nected to the system. All stopcocks shall be carefully greased
12
and the system shall then be evacuated and tested for leaks as
described in 72.3. Any leaks shall be repaired before proceed-
ing with the calibration of the measuring volume (Section 70).
70. Calibration of Apparatus
70.1 Calibrate the volume in which the CO
2
is to be
measured as follows: Admit the maximum amount of oxygen
to the system that can be measured by the gage. Record this
differential. With the gas trapped off in the bulb, open the cutoff
K to the pump to remove all of the oxygen external to the bulb.
Raise cutoffs J and K to the calibration lines, just below
atmospheric level, and lower the mercury in the McLeod gage
below the point of cutoff. After the oxygen has expanded in the
volume between the calibrated marks, remeasure the pressure
after pumping out the gas left when the mercury is raised in the
McLeod gage. Calculate the volume as follows:
V
x
5 ~P
b
3 V
b
!/P
x
(8)
where:
V
x
5 unknown volume,
P
x
5 the pressure in volume V
x
, mm Hg,
V
b
5 previously calibrated volume of bulb of McLeod
gage, and
P
b
5 pressure in bulb, mm Hg.
70.2 In a similar manner, an aliquot of CO
2
may be taken
when the initial pressure of gas evolved from a sample is too
high to measure. The amount of gas measured in the aliquot is
then multiplied by the ratio of the volume of the bulb V
6
to the
total volume V
x
between the cutoffs.
71. Preparation of Sample
71.1 Secure the sample in the form of ne millings, nib-
blings, or clippings so as to facilitate complete combustion.
Remove any trace of grease or oil by washing with acetone or
fresh, dry trichloroethylene and store the cleaned samples in
glass protected from dust.
12
Apiezon L or N, or its equivalent, has been found satisfactory for this purpose.
FIG. 1 Diagram of Apparatus for Determining Carbon by the Low-Pressure Method
E 107
10
72. Procedure
72.1 Weigh 0.5 g of the nickel sample and mix with 0.5 g of
silicon steel (carbon less than 0.003 %)
13
to serve as a ux.
Nickel is very difficult to burn completely without the iron. The
heat evolved as a result of the combustion of the steel raises the
temperature sufficiently above the temperature of the crucible
to burn the nickel. Load the sample mixture into the sample
holder by heating and blowing out the end of the tube, Q, Fig.
1, and then inserting the sample. Then reseal the top of the tube
with a torch. Likewise place other samples one in each
side-arm of the tube, Q. As many as 12 to 15 samples may be
loaded into the side-arms at one time. In an alternative
arrangement, the samples are loaded into a tree through a
side-arm tted with a ground glass plug sealed with hard
vacuum wax. In this arrangement 25 to 30 samples can be
loaded at one time without any glass-working.
72.2 Close stopcocks S
1
, S
2
, and S
7
, and turn stopcocks S
3
,
S
4
, S
5
, and S
6
to connect the mercury wells to the rough
vacuum manifold. Turn on the mechanical pumps. Slowly open
stopcock S
7
until the mercury begins to rise in the tubes.
13
National Institute of Standards and Technology standard sample of silicon
steel No. 131 is recommended for this purpose.
FIG. 2 Diffusion Pump
FIG. 3 Crucible Assembly
E 107
11
Counteract this rise by opening stopcock S
2
to the mechanical
pump attached at C, thus keeping the mercury below the level
of cutoff. After the system has been evacuated, close stopcocks
S
3
, S
4
, S
5
, and S
6
. Turn on the heater for the diffusion pump,
and adjust the heater voltage to provide a rapid stream of
mercury vapor through the jet. Turn on the catalyst furnace, F,
and raise the temperature of the catalyst to about 1100C.
Evacuate the entire system for at least 30 min. Then lower the
voltage of the furnace, F, until the temperature of the catalyst
is about 400 to 500C. Raise the mercury in cutoff I by opening
stopcock S
3
to the atmosphere.
72.3 Purify the oxygen by placing Dewar asks containing
liquid nitrogen on traps T
1
, T
2
, and T
3
and slowly admitting
oxygen by means of a diaphragm valve through stopcock S
1
.
After the pressure of oxygen exceeds 160 mm Hg the oxygen
will liquefy in trap T
1
. After about 10 mL of liquid has been
formed, close stopcock S
1
. Partially lower the Dewar ask
from trap T
1
, thus permitting the major portion of oxygen to
distill over the catalyst and recondense in traps T
2
and T
3
. Then
replace the Dewar ask around trap T
1
. Maintain liquid
nitrogen in these asks throughout the day.
72.4 Heat the crucible assembly for an hour or more until a
satisfactory blank (0.0002 % carbon, or less) is obtained by the
following procedure:
72.4.1 Raise the induction coil about the furnace to a point
where the top of the coil is about 3.2 mm (|n! in.) below the top
of the platinum crucible. Turn on the induction heater and
increase the power slowly until the temperature of the crucible
has reached 1150 to 1200C. Measure the crucible temperature
with an optical pyrometer and exercise caution in heating to
avoid melting the crucible rim.
72.4.2 Raise the mercury in the capillary cutoff, K, and the
McLeod gage, M, by opening stopcocks S
6
and S
5
to the
atmosphere. Also open stopcock S
4
to the air until the mercury
reaches a height just below the cutoff, J. Then admit puried
oxygen by lowering the mercury in the capillary cutoff, I, by
turning stopcock S
3
to the vacuum manifold until the oxygen
bubbles through the capillary into the combustion furnace.
Admit oxygen to a pressure of about 160 mm Hg (vapor
pressure of oxygen at liquid nitrogen temperature) as indicated
by the mercury differential on cutoff K. Then raise the mercury
in I by opening stopcock S
3
to the atmosphere. Place a bath
consisting of solid carbon dioxide and ethylene glycol mono-
ethyl ether acetate about trap T
4
and liquid nitrogen about trap
T
5
. Maintain the temperature of the crucible at 1150 to 1200C
for 10 min, then turn off the power. Remove the excess oxygen
by turning stopcock S
6
to the manifold, thus lowering the
mercury sufficiently to allow the oxygen to escape slowly
through the capillary to the pump (Note 11). When the mercury
levels are about equal, open stopcock S
6
to the pump manifold.
This lowers the mercury in cutoff K below all points of cutoff
and permits rapid evacuation. After the system has been
evacuated for 10 min, raise the mercury in cutoff K above the
point of cutoff to the calibrated volume level. Also raise the
mercury in cutoff J above the cutoff to the marked level.
Remove the liquid nitrogen from trap T
5
and allow sufficient
time for the trap to reach room temperature. Then measure the
amount of CO
2
in the calibrated volume, that is, the volume
between calibration lines on cutoffs J and K, by means of the
McLeod gage, M. The value of the blank should not exceed
0.0002 % carbon based on a 0.5-g sample. If the blank is too
high, repeat the above procedure. After obtaining a satisfactory
blank, evacuate the gas through the pump.
NOTE 11The carbon dioxide is frozen out in trap T
5
and the water
vapor and any sulfur compounds are frozen out in trap T
4
.
72.5 In like manner, burn the samples. Remove a sample
from the side-arm with a magnet and allow it to drop into the
crucible. Follow the conditions described for the blank during
the combustion of the sample.
NOTE 12Excess oxygen in the purication train must be removed at
the close of each day. This is accomplished by opening S
1
to B, which is
connected to the Hyvac pump. The oxygen may be removed during the
combustion of the last sample.
72.6 CalculationCalculate the percentage of carbon in the
sample as follows:
Carbon, % 5 @~AB CB 3 0.64593 10
6
3 100!/D# E (9)
where:
A 5 pressure, mm of CO
2
generated from the sample
in volume B,
B (B
x
) 5 volume, mL containing the CO
2
,
C 5 pressure, mm of CO
2
generated from the blank,
D 5 grams of sample used, and
E 5 percentage of carbon added in 0.5 g of silicon
steel ux.
If this work is carried out at some temperature other than
25C (at the McLeod gage), suitable corrections must be
applied to change the volume of gas to 25C.
73. Precision and Bias
73.1 This test method was originally approved for publica-
tion before the inclusion of precision and bias statements
within standards was mandated. The original interlaboratory
test data for this test method are no longer available. The user
is cautioned to verify by the use of reference materials, if
available, that the precision and bias of this test method are
adequate for the contemplated use.
HYDROGEN, NITROGEN, AND OXYGEN BY THE
VACUUM FUSION TEST METHOD
74. Summary of Test Method
74.1 This test method is based on the fusion of the metal in
the presence of carbon in a vacuum. Under these conditions, all
oxides present are reduced to carbon monoxide, and nitrogen
and hydrogen are liberated. The evolved gases are collected
and analyzed by low-pressure techniques. The hydrogen is
oxidized to water and absorbed in anhydrous magnesium
perchlorate. The carbon monoxide is converted to carbon
dioxide and frozen out in liquid nitrogen. The residual gas is
nitrogen.
75. Apparatus and Materials
75.1 Vacuum Fusion ApparatusApparatus No. 16.
76. Preparation of Sample
76.1 The sample is used in chunk form when possible or in
E 107
12
the form submitted for test such as wire, sheet, tubing, rod, or
powder. If the sample is in the form of powder, compress into
pellets, using only sufficient pressure to make the powder
adhere. Do not mill ingot samples, since it is important to
minimize the effect of surface and possible oxide lms. Cut the
sample in the form of a cube or similar shape and to proper size
for loading in the furnace and to avoid sticking in the graphite
funnel. Remove outer heavy scale with abrasive cloth or by
slowly turning on a lathe. Remove any grease or oil present in
a vapor degreaser using clean, dry trichloroethylene or equiva-
lent.
76.2 Remove light scale by immersion in a mixture of 750
mL of acetic acid, 250 mL of HNO
3
, and 15 mL of HCl at 50
to 60C for a limited time, the time being dependent on the
thickness of the scale. Samples that should not be acid-cleaned
or abraded, such as nished cathodes, should be degreased in
a vapor degreaser using trichloroethylene or equivalent, fol-
lowed by a Soxhlet extraction with acetone until no residue can
be detected on a watch glass when the acetone extract is
evaporated to dryness. Do not touch the samples with the
ngers during or after the nal stages of cleaning. Use clean
rubber gloves, or preferably clean tweezers, for handling the
specimens.
77. Procedure
77.1 Place about 38 mm (1
1
2 in.) of graphite powder in the
bottom of the quartz tube. Be very careful not to compact the
graphite. Place the graphite crucible with funnel on top of this
lightly and coaxially to the quartz tube. Place a close-tting
metal cap on top of the funnel and pour graphite powder into
the quartz tube until the top of the funnel is reached. Remove
the cap and blow out any ne graphite that may have fallen into
the graphite crucible with a glass tube connected to a low-
pressure air line. The removal of this graphite is important
because any powder left inside the crucible will outgas
incompletely and will introduce error into the initial samples.
Now hook the special lifting rod (Fig. 22, Practice E 50) into
the two loops in the platinum wire and carefully lift the
crucible assembly into place through the ground joint in the
bottom of the furnace. Make sure the hooks are secure before
removing the lifter. If the crucible does not hang straight,
remove it by lifting out with the other holder shown in Fig. 22,
of Practice E 50, and bend the platinum hooks to correct the
misalignment. Coat the glass plug for the bottom closure with
high-vacuum wax by warming in a soft ame. Also warm the
outer joint with a soft ame, and slip the wax-coated plug into
place and rotate until well seated.
77.2 Weigh 2 g of the sample and insert into the sample
loading arm on the furnace, F, Fig. 18. At any one time at least
ten 2-g samples may be loaded into the sidearm. Close the
sidearm by sealing the cap at the end with high-vacuum wax.
77.3 Set the blower and blower guide in place. Check the
blower to make sure the air ow around the furnace is uniform.
Make sure that all the three-way stopcocks are in a position
such that the mercury bulbs are isolated both from the
atmosphere and from the vacuum manifold. Close the large
right-angle stopcock above the main evacuating pumping
system and close the air release valve on the foreline of the
oil-diffusion pump, DP
3
. Stopcock S
2
on cutoff C
2
may be
opened to the air. Now, turn on the manifold pump. Next, turn
on the forepump. Allow this pump to run until it is operating
quietly (about 2 min). Next, with extreme caution, very slowly
open the large right-angle stopcock, S
13
, located above the
metal diffusion pump, until the mercury begins to rise slowly in
the various tubes. Leave the stopcock in this position. In no
case shall the system be pumped down in less than 5 min; 6 to
10 min is preferable. If the pump-down is too rapid, the ne
graphite in the crucible will uff and may be blown into the
system, thus rendering the apparatus useless until all the
graphite has been removed. The mercury will rise slowly and
uniformly in all the tubes. When a height of about 76 to 102
mm (3 to 4 in.) has been reached, lower the mercury column
carefully by turning the stopcocks momentarily to connect the
mercury-reservoir bulbs with the vacuum manifold. Leave
stopcock S
2
open to the atmosphere at all times. It will be found
that U-tubes C
1
, C
2
, C
4
, C
7
, C
8
, C
9
, C
10
, C
11
, and C
12
will need
no further attention, since the mercury will not now reach the
cutoff. Cutoffs C
3
, C
5
, and C
6
will require attention during
pump-down to keep mercury from rising into the bulbs of the
Toepler pump, T, McLeod gage, M, and into the sidearm of the
gas addition tube, C
6
. The cutoff, C
5
, on the McLeod gage is
the lowest and will require the most attention. Keep manipu-
lating stopcocks S
3
, S
5
, and S
6
in such a fashion that the
mercury does not reach the cutoff in any case. When no further
upward movement is visible in the U-tube C
2
, the main
stopcock may be fully opened. Do this slowly. Next turn on the
main diffusion pump and the transfer and circulating mercury
diffusion pumps. At this point it is good practice to adjust the
height of all the mercury columns (with the exception of C
2
,
which is left all the way up) to a point just below the cutoff.
The special cutoff, C
6
, may be permanently closed and the
mercury sealed off by closing the stopcock in the stem. After
30 to 45 min, the pressure in the system as checked by the
McLeod gage should be so low that the McLeod gage shows no
differential in the heights of the mercury in the two capillary
columns. Pumping for a minimum of 1 h is necessary before
applying heat to the furnace. Fine graphite outgasses very
rapidly when rst heated and may uff out and into the system
if caution is not used.
77.4 Outgas the furnace assembly by heating the graphite
crucible to a temperature of 2400C for at least 2 h by means
of the high-frequency induction heater. Turn on the air blower
at the same time as the induction heater. Raise the temperature
slowly to permit evacuation of the gases evolved and, also, to
avoid displacement of the carbon powder. Measure the tem-
perature of the crucible with an optical pyrometer directed
through the right-angle prism and optical at (Fig. 19, Practice
E 50).
77.5 Make a blank determination by lowering the tempera-
ture of the crucible to 1650C and collecting the gas evolved
during a period of 20 to 30 min. This blank heating period
should correspond to the time the sample is to be heated. Close
all mercury cutoffs. Set the timer for the desired time interval
and open cutoff C
2
. Lower the mercury in the Toepler pump
below the bulb. Maintain the mercury in the McLeod gage
above the sidearm to the expansion bulbs but below the inlet
from the Toepler pump. Gas evolved from the furnace is
E 107
13
pumped through pumps DP
1
and DP
2
into the Toepler pump.
At the end of the collection period, close cutoff C
2
and open
C
1
. Transfer the gas collected in the Toepler pump to the
McLeod gage measuring system by manual operation of the
Toepler pump, until the amount of gas measured in the
McLeod capillary shows no further increase. Measure the
amount of gas collected by reading the mercury level in the
McLeod capillary from which the pressure-volume (PV) prod-
uct is calculated. Analyze the gas for CO, hydrogen, and
nitrogen as described in 77.7. It is possible to obtain a blank
level that will amount to approximately 0.0001 to 0.0002 %
oxygen for a 2-g sample.
77.6 The fusion of the sample is carried out at the same
temperature and length of time as the blank. Turn off the power
to the furnace and allow the furnace to cool 200 to 300C.
Introduce the sample by moving it by means of a magnet until
it drops down the vertical tube into the crucible. Again turn on
the induction heater and continue the fusion for 20 to 30 min
at 1650C. Completeness of removal of gas from the sample is
readily conrmed by successive readings of the PV product
during the collection period. Should an abnormally long time
period be required, a blank correction for a corresponding time
must be made. Collect the gas as in the case of the blank. After
the gas is collected from the sample, raise cutoff C
2
, lower
cutoff C
1
, and allow the furnace to exhaust to the main
evacuation line until the next sample is dropped. Transfer the
gas collected in the Toepler pump to the McLeod gage,
compress into the capillary pipet, and measure the PV product.
If more gas is collected that can be measured in the capillary
pipet, allow it to expand into expansion bulb H
1
or H
2
, or both,
by lowering the mercury in the McLeod gage below the
sidearm level. Since the total volume of the system including
expansion bulbs, McLeod gage, and connecting tubing has
been previously calibrated, the PV product of the gas may be
determined. A total of 3000 mLmm of gas can be measured in
the system shown. The gas is now ready for analysis.
77.7 Condition the reagents prior to an analysis as follows:
First adjust the mercury cutoffs to open all reagents to vacuum.
Use electric furnaces or heating mantles to bake out the
reagents under vacuum, each adjusted by variable autotrans-
formers to the proper temperaturecopper oxide at 325C, and
Mg(ClO
4
)
2
at 240C. Place a Dewar ask containing liquid
nitrogen to cover trap J before the analysis is begun.
77.8 After transferring the gas by means of the Toepler
pump to the McLeod gage and determining the PV product of
the combined CO, hydrogen, and nitrogen, lower the mercury
in the McLeod gage below the cutoff. Open cutoffs C
7
and C
4
to permit the gas to be pumped into the analytical system.
Check the McLeod gage reading after a few minutes to be sure
all gas has been pumped out; then raise the mercury level in the
McLeod gage to just above the cutoff level. Then close cutoff
C
7
. Open cutoff C
11
to permit the gas to circulate through the
copper oxide tube, the Mg(ClO
4
)
2
trap, and the trap cooled
with liquid nitrogen. Circulate the gas for not less than 10 min.
Close cutoff C
4
and lower the mercury in the Toepler pump, C
3
,
to just below the cutoff point. With the cutoffs in these
positions, pump the residual nitrogen into the Toepler bulb.
After ten minutes, transfer this nitrogen into the McLeod gage
in the usual manner and measure the PV product of the
nitrogen. Allow the nitrogen to remain in the McLeod gage.
Lower the mercury level in the Toepler pump below the
sidearm, then remove the liquid nitrogen-lled ask from the
trap, J, releasing CO
2
from the trap. Allow 5 to 10 min for the
CO
2
to collect in the Toepler pump. Transfer the gas into the
McLeod gage as before, and measure the PV product of the
combined CO
2
and nitrogen. The operation is now completed.
The analytical system is exhausted by opening cutoffs C
10
, C
11
,
and C
12
to prepare to run the next sample. The Mg(ClO
4
)
2
can
be kept in a baked-out condition by maintaining at 250C
during overnight periods with the system under vacuum.
Activation or replacement of the copper oxide is required at
intervals. Activation is accomplished by repeated reductions
with hydrogen followed by an oxidation and vacuum bake.
77.9 CalculationsThe difference between the sum of the
PV products for CO
2
and nitrogen and the original PV product
of the combined CO, nitrogen, and hydrogen represents the PV
product of water vapor, which is also equivalent to the PV
product of hydrogen. Measure the gas PV evolved as a result of
the fusion in units of millilitres and millimetres. In each case
correct the amount of gas collected from the sample for the
blank determination on the apparatus. Calculate the percent-
ages of nitrogen, oxygen, and hydrogen as follows:
Nitrogen (measured as N
2
):
Nitrogen, % 5 @~A 3 1.51!/B#3 100 (10)
Oxygen (converted to CO and measured as CO
2
):
Oxygen, % 5 @~A 3 0.86!/B# 3 100 (11)
Hydrogen:
Hydrogen, % 5 @~A 3 0.1084!/B# 3 100 (12)
where:
A 5 pressure-volume (PV) product for the gas in question,
mL and mm at 25C, and
B 5 micrograms of sample used.
78. Precision and Bias
78.1 This test method was originally approved for publica-
tion before the inclusion of precision and bias statements
within standards was mandated. The original interlaboratory
test data for this test method are no longer available. The user
is cautioned to verify by the use of reference materials, if
available, that the precision and bias of this test method are
adequate for the contemplated use.
COPPER BY THE NEOCUPROINE
(PHOTOMETRIC) TEST METHOD
79. Summary of Test Method
79.1 Cuprous copper is reacted with neocuproine. The
colored complex is extracted with chloroform and measured
photometrically at approximately 455 nm.
80. Concentration Range
80.1 The recommended concentration range is from 0.002
to 0.15 mg of copper in 25 mL of solution, using a cell depth
of 1 cm.
81. Stability of Color
81.1 The color is stable for at least 4 days.
E 107
14
82. Interferences
82.1 None of the elements present in electronic nickel
interfere with this test method, as written. Traces of cyanide
and sulde interfere, but 5 mL of H
3
PO
4
can be tolerated.
83. Reagents
83.1 Chloroform.
83.2 Copper, Standard Solution (1 mL 5 0.010 mg Cu)
Transfer 0.1 g of electrolytic copper, weighed to the nearest 0.1
mg, to a 250-mL Erlenmeyer ask. Add 10 mL of
HNO
3
(1 + 1), cover, and heat gently until dissolved. Add 5 mL
of HClO
4
and evaporate to fumes. Fume gently for 5 min and
cool. Add 25 mL of water, heat to boiling, and boil gently for
2 min to evolve chlorine. Cool, transfer to a 1000-mL volu-
metric ask, dilute to the mark, and mix. Transfer 100 mL to a
second 1000-mL volumetric ask, dilute to the mark, and mix.
This nal solution contains 0.010 mg Cu per mL.
83.3 Hydroxylamine Hydrochloride Solution (100 g/L)
Dissolve 10 g of hydroxylamine hydrochloride (NH
2
OH
HCl) in water and dilute to 100 mL.
83.4 Neocuproine Solution (1 g/L)Dissolve 0.1 g of
neocuproine in ethanol (Note 13) and dilute to 100 mL with
ethanol.
NOTE 13Some grades of denatured ethanol form unsuitable turbid
solutions. Absolute methanol may be used, if desired.
83.5 Sodium Citrate Solution (300 g/L)Dissolve 300 g of
sodium citrate in 600 mL of water and dilute to 1 L.
84. Preparation of Calibration Curve
84.1 Calibration Solutions:
84.1.1 Transfer 0.5, 1, 2, 4, 6, 10, 12, and 15 mL of copper
solution (1 mL 5 0.010 mg Cu) to eight 150-mL beakers.
84.1.2 Dilute each solution to 50 mL with water. Add 1 mL
of H
3
PO
4
, 10 mL of sodium citrate solution, and 5 mL of
hydroxylamine hydrochloride solution. Stir well for 30 s and
add 10 mL of neocuproine solution (Note 14). Again stir and,
using a pH meter, adjust the pH of the solution to about 5 with
NH
4
OH (1 + 1) (Note 15).
NOTE 14Use of a magnetic stirrer is recommended for the stirring
operation.
NOTE 15Since the reaction of copper with the reagent is complete
within the pH range of 2.3 to 9.0, this adjustment can be made with pH
paper; however, in highly colored solutions, use of a pH meter is
preferable.
84.1.3 Transfer the solution to a 250-mL pear-shape sepa-
ratory funnel, add 10 mL of chloroform, and shake for 30 s.
After the aqueous and organic layers have separated, transfer
the chloroform layer into a 25-mL volumetric ask containing
4 mL of ethanol. Make a second extraction with 5 mL of
chloroform and separate as before. Dilute to the mark with
ethanol and mix.
84.2 Reference SolutionCarry a reagent blank through all
the steps of 84.1 for use as a reference solution.
84.3 PhotometryTransfer a portion of the reference solu-
tion to the absorption cell and adjust the photometer to the
initial setting, using a light band centered at approximately 455
nm. While maintaining this adjustment, take the photometric
readings of the calibration solutions.
84.4 Calibration CurvePlot the photometric readings of
the calibration solutions against milligrams of copper per 25
mL of solution.
85. Procedure
85.1 Test Solution:
85.1.1 Transfer 0.25 g of the sample, weighed to the nearest
1 mg, to a 250-mL beaker and add 10 mL of HNO
3
and 5 mL
of H
3
PO
4
. Cover, and heat gently until the sample has
dissolved. Wash the cover and sides of the beaker, add 10 mL
of HClO
4
, and evaporate to fumes. Fume gently for 5 min and
cool. Dissolve the salts in 75 mL of water and transfer to a
250-mL volumetric ask. Dilute to the mark and mix.
85.1.2 By means of a pipet, transfer a 25-mL aliquot to a
150-mL beaker. Proceed in accordance with 84.1.2 and 84.1.3.
85.2 Reference SolutionAdd 50 mL of water to a 150-mL
beaker and proceed in accordance with 84.1.2 and 84.1.3.
85.3 PhotometryTake photometric readings of the test
solution as described in 84.3.
86. Calculation
86.1 Convert the photometric reading of the test solution to
milligrams of copper by means of the calibration curve.
Calculate the percentage of copper as follows:
Copper, % 5 A/~B 3 10! (13)
where:
A 5 copper found, mg, and
B 5 sample represented in the aliquot used, g.
87. Precision and Bias
87.1 This test method was originally approved for publica-
tion before the inclusion of precision and bias statements
within standards was mandated. The original interlaboratory
test data for this test method are no longer available. The user
is cautioned to verify by the use of reference materials, if
available, that the precision and bias of this test method are
adequate for the contemplated use.
TUNGSTEN BY THE ACID DIGESTION-
CINCHONINE TEST METHOD
88. Summary of Test Method
88.1 Tungsten is rst separated as tungstic acid after acid
attack and cinchonine digestion. The acid is puried by a
sodium carbonate fusion and reprecipitation, and weighed.
89. Reagents
89.1 Cinchonine Solution (125 g/L)Reagent No. 113.
89.2 Cinchonine Wash SolutionDilute 30 mL of cincho-
nine solution (89.1) to 1 L.
89.3 Sodium Carbonate (Na
2
CO
3
) anhydrous.
90. Procedure
90.1 Transfer 2.0 g of the sample, weighed to the nearest 0.1
mg, to a 400-mL beaker and add 20 mL of HNO
3
. Cover and
heat gently until the sample has dissolved. Add 10 mL of HCl
and evaporate to about 10 mL. Dilute to 150 mL with hot water
and add 5 mL of cinchonine solution and a small amount of
E 107
15
paper pulp. Digest at 90 to 95C for 1 h. Allow to stand at room
temperature overnight.
90.2 Filter through a ne paper and wash with hot cincho-
nine wash solution. Remove the last traces of tungstic acid
from the beaker walls with a small piece of lter paper
moistened with NH
4
OH. Place the precipitate in a platinum
crucible, carefully char the paper at low temperature, and
nally ignite at 750C.
90.3 Fuse the impure tungstic acid with 2 g of anhydrous
Na
2
CO
3
. Leach the melt with hot water, transfer to a 250-mL
beaker, rinse and remove the crucible, and dilute to about 50
mL. Digest for 5 min and lter through a medium paper into a
400-mL beaker. Wash the paper thoroughly with hot water.
Discard the residue.
90.4 Carefully neutralize the ltrate with HCl and add 10
mL in excess. Evaporate to about 10 mL. Dilute to 150 mL
with hot water and add a small amount of lter pulp. Add 5 mL
of cinchonine solution, while stirring, digest at 95C for 20
min, and allow to stand at room temperature overnight.
90.5 Filter through a ne paper and wash with hot cincho-
nine wash solution. Place the precipitate in a tared platinum
crucible, char the paper at low temperature, and nally ignite at
750C.
90.6 Cool and treat the residue with 2 drops of H
2
SO
4
and
1 mL of HF. Evaporate to dryness and ignite again at 750C.
Cool in a desiccator and weigh as tungsten trioxide (WO
3
).
91. Calculation
91.1 Calculate the percentage of tungsten as follows:
Tungsten, % 5 @~A 3 0.793!/B#3 100 (14)
where:
A 5 WO
3
, g, and
B 5 sample used, g.
92. Precision and Bias
92.1 This test method was originally approved for publica-
tion before the inclusion of precision and bias statements
within standards was mandated. The original interlaboratory
test data for this test method are no longer available. The user
is cautioned to verify by the use of reference materials, if
available, that the precision and bias of this test method are
adequate for the contemplated use.
MAGNESIUM BY THE 8-HYDROXY QUINOLINE
(PHOTOMETRIC) TEST METHOD
93. Summary of Test Method
93.1 Magnesium, in a ammoniacal solution, is reacted with
8-hydroxyquinoline. The colored complex is extracted with a
chloroform-ethylene glycol monobutyl ether mixture and mea-
sured photometrically at approximately 400 nm.
94. Concentration Range
94.1 The recommended concentration range is from 0.001
to 0.10 mg of magnesium per 20 mL of chloroform using a cell
depth of 1 cm.
14
95. Stability of Color
95.1 The color is stable for at least 1 h.
96. Interferences
96.1 Calcium, zinc, cadmium, or gallium in amounts greater
than 0.01 mg may interfere; however, these elements are not
likely to be present in sufficiently high concentration in
electronic nickel to cause difficulty.
97. Apparatus
97.1 Separatory Funnels, conical-type 125-mL capacity.
Funnels with TFE-uorocarbon valves, which need no lubri-
cation, are preferred.
98. Reagents
98.1 Ammonium Persulfate Solution (10 g/L)Dissolve 1 g
of ammonium persulfate (NH
4
)
2
S
2
O
8
) in 100 mL of water.
Prepare a fresh solution each day as needed.
98.2 Ethylene Glycol Monobutyl Ether Solution (1 + 1)
Mix 100 mL of ethylene glycol monobutyl ether
15
with 100 mL
of water.
98.3 Ferric Nitrate Solution (10 g/L)Dissolve 2 g of
electrolytic iron wire in 25 mL of HNO
3
(1 + 1), heat to expel
oxides of nitrogen, and cool. Dilute to 200 mL with water and
mix.
98.4 8-Hydroxyquinoline Solution (30 g/L)Transfer 3.00
g of 8-hydroxyquinoline to a dry, 100-mL volumetric ask and
dissolve in 50 mL of chloroform. Dilute to the mark with
chloroform and mix. Prepare a fresh solution just before use.
98.5 Magnesium, Standard Solution (1 mL 5 0.01 mg
Mg)Dissolve 0.0500 g of pure magnesium (not less than
99 % Mg) by warming gently with 5 mL of HNO
3
(1 + 2) in a
covered conical ask. When dissolution is complete, heat to
expel oxides of nitrogen and cool. Transfer to a 500-mL
volumetric ask, dilute to the mark and mix. Dilute 100 mL of
this solution to 1 L in a volumetric ask and mix.
98.6 NickelNickel for use in preparation of the calibration
curve and the reagent blank shall contain not more than
0.001 % of magnesium and a total of not more than 0.005 % of
calcium, zinc, cadmium, and gallium.
98.7 Sodium Cyanide Solution (100 g/L)Transfer 20 g of
sodium cyanide (NaCN) to a 500-mL polyethylene bottle. Add
200 mL of water and swirl to dissolve. Keep stoppered when
not in use.
99. Preparation of Calibration Curve
99.1 Calibration Solutions:
99.1.1 Transfer six 100-mg portions of nickel (98.6) to
125-mL conical asks and dissolve in 2 mL of HNO
3
(1 + 1)
using gentle heat. Keep the asks covered and take care to
14
This test method has been written for a cell having a 1-cm light path. Cells
having other dimensions may be used, provided suitable adjustments can be made
in the amounts of sample and reagents used.
15
Butyl Cellosolve has been found satisfactory for this purpose.
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avoid unnecessary loss of acid. When dissolution is complete,
blow out the brown fumes and cool the solutions.
99.1.2 Add 1.0, 2.0, 4.0, 6.0, 8.0, and 10.0-mL portions of
magnesium solution (1 mL 5 0.01 mg Mg) to the asks and
dilute each to 35 mL.
99.1.3 Add 1 mL of ferric nitrate (Fe(NO
3
)
3
) solution and 1
mL of (NH
4
)
2
S
2
O
8
solution. Add fresh, full-strength NH
4
OH
(Note 4) dropwise while swirling the ask until iron begins to
precipitate; then add 1 mL in excess. Warm the solution to
approximately 65C and lter through a rapid paper into a
125-mL Squibb-type separatory funnel. Lift one corner of the
lter paper to allow the funnel stem to drain, but do not wash
the precipitate.
NOTE 16It is important that the NH
4
OH be full strength and that the
excess be very carefully controlled.
99.1.4 Stopper the separatory funnel and cool under running
water. Rinse the outside surfaces of the separatory funnel,
including the stem bore, with water.
99.2 Reference SolutionTransfer a 100-mg portion of
nickel to a 125-mL conical ask and proceed in accordance
with 99.1.1, 99.1.3, and 99.1.4.
99.3 Color Development:
99.3.1 Add successively to each funnel, mixing between
additions, 10 mL of NH
4
OH, 5 mL of NaCN solution and 5.0
mL of ethylene glycol monobutyl ether. Add 20.0 mL of
8-hydroxyquinoline solution from a pipet. Stopper the separa-
tory funnel, shake the solution momentarily, release the pres-
sure carefully, and then shake vigorously for 1 min.
99.3.2 After the layers have separated, drain 2 or 3 mL of
the chloroform layer through the funnel stem and discard.
Then, drain all but about 2 mL of the remaining chloroform
extract through a dry, rapid lter paper into a dry, 50-mL
conical ask.
99.4 PhotometryTransfer a portion of the reference solu-
tion to an absorption cell and adjust the photometer to the
initial setting using a light band centered at approximately 400
nm. While maintaining this adjustment, take the photometric
readings of the calibration solutions.
99.5 Calibration CurvePlot the photometric readings of
the calibration solutions against milligrams of magnesium per
20 mL of solution.
100. Procedure
100.1 Test SolutionDepending upon the magnesium con-
tent, transfer 10 to 100 mg of the sample to a 125-mL conical
ask. If less than 100 mg of sample is used add sufficient nickel
(98.6) to make a total of 100 mg. Dissolve the sample in 2 mL
of HNO
3
(1 + 1), dilute to 35 mL and proceed in accordance
with 99.1.3 and 99.1.4.
100.2 Reference SolutionTransfer a 100-mg portion of
nickel to a 125-mL conical ask, dissolve in 2 mL of
HNO
3
(1 + 1), and carry through all steps of the procedure for
use as a reference solution.
100.3 Color DevelopmentProceed in accordance with
99.3.1 and 99.3.2.
100.4 PhotometryTake photometric readings of the test
solution as described in 99.4.
101. Calculation
101.1 Convert the photometric reading of the test solution to
milligrams of magnesium by means of the calibration curve.
Calculate the percentage of magnesium of follows:
Magnesium, % 5 A/~B 3 10! (15)
where:
A 5 magnesium in the test solution, mg, and
B 5 sample used, g.
102. Precision and Bias
102.1 This test method was originally approved for publi-
cation before the inclusion of precision and bias statements
within standards was mandated. The original interlaboratory
test data for this test method are no longer available. The user
is cautioned to verify by the use of reference materials, if
available, that the precision and bias of this test method are
adequate for the contemplated use.
103. Keywords
103.1 electronic nickel
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