ASTM D283-84(1999)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation:D283–84(Reapproved1999)
Standard Test Methods for
Chemical Analysis of Cuprous Oxide and Copper Pigments
This standard is issued under the fixed designation D283; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the Department of Defense.
1. Scope 3. Significance and Use
1.1 These test methods cover procedures for the chemical 3.1 This collection of test methods is used by pigment
analysis of cuprous oxide and copper pigments. producersandpaint manufacturersforprocesscontrol,product
1.2 Theanalyticalproceduresappearinthefollowingorder: acceptance, and research and development.
Sections
4. Treatment of Sample
Total Copper 7
Total Reducing Power as Cuprous Oxide 8 and 9
4.1 Grind dry pigments, if lumpy or not finely ground, to a
Metallic Copper 10 and 11
fine powder and thoroughly mix (Note 1). Large samples may
Cuprous Oxide 12
Cupric Oxide 13
be thoroughly mixed and a representative portion taken and
Metals Other than Copper 14-16
powderediflumpyornotfinelyground.Inallcasesthoroughly
Chlorides and Sulfates 17 and 18
mixthesamplebeforetakingportionsforanalysis.Preserveall
Acetone-Soluble Matter 19
Water 20
samples in dry, dark, airtight and completely filled bottles or
Stability 21
containers to prevent oxidation. Some commercial copper
Coarse Particles 22
oxides appear to segregate or oxidize rather easily. Therefore,
Coarse Particles Insoluble in Nitric Acid 23
the thorough mixing of the sample to ensure homogeneity and
1.3 This standard does not purport to address all of the
therapidhandlingofthesample,whenexposedtolightandair,
safety concerns , if any, associated with its use. It is the
are extremely important factors in obtaining accurate results.
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- NOTE 1—It is very important that the sample be thoroughly mixed.
Somesamplesofcuprousoxidearenothomogeneoussoarelikelytogive
bility of regulatory limitations prior to use. Specific hazard
trouble when an attempt is made to obtain concordant results. By placing
statements are given in Section 6.
afewgramsofasampleonasheetofwhitepaperanddrawingitoutwith
a spatula, it is frequently found that the sample contains coarse particles
2. Referenced Documents
of black scale, along with small balls of bright red cuprous oxide. Thus,
2.1 ASTM Standards:
it may be necessary to pass the pigment through a No. 60 (250-µm) sieve,
D185 Test Methods for Coarse Particles in Pigments,
break up any lumps of ground pigment by gentle pressure, and grind any
coarse particles failing to pass through the sieve. Since oxidation of slight
Pastes, and Paints
or even considerable magnitude may take place, these operations should
D1193 Specification for Reagent Water
be performed quickly, avoiding prolonged grinding and exposure to light
D1208 Test Methods for Common Properties of Certain
and air.
Pigments
5. Reagents
5.1 Purity of Reagents—Reagent grade chemicals shall be
ThesetestmethodsareunderthejurisdictionofASTMCommitteeD-1onPaint
and Related Coatings, Materials, and Applications and are the direct responsibility used in all tests. Unless otherwise indicated, it is intended that
of Subcommittee D01.31 on Pigment Specifications.
all reagents shall conform to the specifications of the Commit-
Current edition approved Oct. 26, 1984. Published January 1984. Originally
tee onAnalytical Reagents of theAmerican Chemical Society,
e2
published as D283–28. Last previous edition D283–52(1978) .
Annual Book of ASTM Standards, Vol 06.03.
Annual Book of ASTM Standards, Vol 11.01.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D283–84 (1999)
where such specifications are available. Other grades may be of sulfuric acid (H SO ) (1+1). Dissolve the salt and acid in
2 4
used, provided it is first ascertained that the reagent is of water,cooltoroomtemperature,anddiluteto1L.Standardize
sufficiently high purity to permit its use without lessening the this solution against analyzed bright copper foil that has been
accuracy of the determination. freed from all oxide coating.
5.2 Purity of Water—Unlessotherwiseindicated,references
8.2 Ferric Chloride Solution—Dissolve 75 g of ferric chlo-
towatershallbeunderstoodtomeanreagentwaterconforming ride (FeCl ·6 H O) in a mixture of 150 mL of hydrochloric
3 2
to Type II of Specification D1193.
acid (HCl) (sp gr 1.19) and 400 mL of distilled water. Add 5
5.3 Ammonium Sulfate—((NH ) SO ). mL of hydrogen peroxide (H O ) (30%) and boil to remove
4 2 4 2 2
5.4 Nitric Acid (sp gr 1.42)—Concentration nitric acid
the excess.
(HNO ). 8.3 Ferrous Ammonium Sulfate, Standard Solution (0.03
5.5 Perchloric Acid (70%)—Concentrated perchloric acid
N)—Dissolve 12 g of ferrous ammonium sulfate
(HClO ). (Fe(NH) (SO ) ·6 H O) in 200 to 300 mL of water and add
2 4 2 2
40 mL of H SO (sp gr 1.84), while stirring constantly. Dilute
2 4
6. Hazards
to 1 L in a volumetric flask.Afew pieces of mossy aluminum
6.1 Warning—Concentrated mineral acids cause burns of
may be added to stabilize the solution. The solution should be
the skin and eyes. Concentrated bases are also hazardous.
restandardized frequently against 0.1 N ceric ammonium ni-
Avoidcontactwithskinoreyes.Incaseofcontactimmediately
trate solution.
flush skin or eyes with plenty of water. See appropriate MCA
8.4 Orthophenanthroline Indicator Solution (0.5 % in
Safety Data Sheets for further information before handling
water)—Orthophenanthroline ferrous complex (ferroin) shall
dangerous chemicals.
be used as the indicator.
6.2 Chemicals that have been declared toxic should be
disposed of as hazardous chemicals and not discharged into a
9. Procedure
sink.
9.1 Weigh accurately (Note 2) 0.15 g of the sample and
place in a 250-mL, vented, glass-stoppered Erlenmeyer flask
TOTAL COPPER
previously filled with carbon dioxide (CO ) or other inert gas.
7. Procedure
Addafewsmallglassbeadsand10mLofFeCl solution.Heat
gently for 15 min, stirring occasionally and maintaining at all
7.1 Weigh accurately 1.0 g of the sample and transfer to a
times an atmosphere of CO or other inert gas.
300-mL electrolytic beaker. Add 10 mL of concentrated nitric 2
acid (HNO ) and boil several minutes. Add 10 mL of HClO
3 4
NOTE 2—The use of a 0.4-mLmicro beaker for weighing the specimen
(70%) and fume for 5 min. Cool, dilute to a volume of
is advised. The beaker is weighed first and the sample introduced into the
approximately 150 mL, and add 1 mL of HNO and1gof beaker, the correct weight obtained, and the entire beaker and its contents
dropped into the flask. This eliminates errors in weighing caused by
(NH) SO .
2 4
brushing the sample from glass balance pans.
7.2 Carefully weigh the platinum electrode to 0.1 mg.
Electroplate the copper on a rotating platinum electrode at a
9.2 After the specimen has been dissolved, cool, add 50 mL
current of 2 A for 2 h. Dilute with water and continue the
of distilled water, and titrate at once with 0.1 N ceric ammo-
electrolysis for 15 min. When the deposition is complete,
nium nitrate solution until near the end point. Add 2 drops of
remove the electrode, wash with water and acetone, dry, and
orthophenanthroline indicator solution and complete the titra-
weigh to 0.1 mg. Save the electrolyte for the determination of
tion. A sharp, distinct color change from orange to pale green
metals other than copper (Section 15).
occurs at the end point. Back-titrate with 0.03 N ferrous
7.3 Calculate the percent of total copper, Cu.
ammonium sulfate solution to the orange color.
9.3 Calculation—Calculate the percent of total reducing
TOTAL REDUCING POWER AS CUPROUS OXIDE
power, A, as cuprous oxide (Cu O) as follows:
8. Reagents
V N – V N 30.07154
1 1 2 2
A 5 3100 (1)
S
8.1 Ceric Ammonium Nitrate, Standard Solution (0.1 N)— 1
Mix 54.826 g of ceric ammonium nitrate (Ce(NH ) (NO ) )
4 2 3 6
where:
(either reagent grade or reference standard purity) with 56 mL
V = Ce(NH ) (No3) solutionrequiredtotitratethe
1 4 2 6
specimen, mL,
N = normality of the Ce(NH ) (No3) solution,
1 4 2 6
Reagent Chemicals, American Chemical Society Specifications, American
V = Fe(NH ) (SO ) solutionrequiredfortheback-
Chemical Society, Washington, DC. For suggestions on the testing of reagents not 2 4 2 4 2
listed by the American Chemical Society, see Analar Standards for Laboratory
titration, mL,
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
N = normality of the Fe(NH ) (SO ) solution,
2 4 2 4 2
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
S = specimen weight, g, and
MD.
D283–84 (1999)
a 25-mm diameter, beveled-edge, perforated porcelain filter disk in a 60°,
0.07154 = equivalent weight of Cu O/1000.
75-mmdiameterglassfunnel.Usingsuction,prepareanasbestosfilterpad
on the porcelain disk of sufficient thickness and retentiveness to hold the
METALLIC COPPER
finelydividedresidue.Washtheasbestospadseveraltimeswithdenatured
alcoholtoremoveallwaterfromthepad.Filterthemetalliccopper-cupric
10. Reagents
oxide residue on this asbestos pad with the suction on at the start of the
10.1 CericAmmoniumNitrate,StandardSolution (0.1N)— filtration. Keep the solution cold by the addition of dry ice and proceed
with washing the residue, transferring it to the original extraction flask,
See 8.1.
and the subsequent titration as directed in Section 11.
10.2 Denatured Alcohol (Formula No. 2B)
10.3 Extraction Solution—Add 40 mL of HCl (sp gr 1.19)
11.5 Transfertheentireresidue,filterpaper,andbeadstothe
to 1 L of denatured alcohol. Mix thoroughly. Add 40 g of
original extraction flask and dissolve the residue in 25 mL of
stannous chloride (SnCl ·2H O) and stir until completely
FeCl solution, keeping an atmosphere of CO above the
2 2 3 2
dissolved.
samplebyadditionofdryice.Heatonasteambathtodissolve
10.4 Ferric Chloride Solution—See 8.2.
the copper. Add 50 mL of distilled water and 3 drops of
10.5 Orthophenanthroline Indicator— See 5.4.
orthophenanthroline indicator solution.Titrate with 0.1 N ceric
ammoniumnitratesolutionuntilthecolorchangesfromorange
11. Procedure
to pale green.
11.1 Add approximately 20 mL of 4-mm diameter glass 11.6 Calculation—Calculate the percent of metallic copper
content, B, as follows:
beads to a 250-mL Phillips beaker (assay flask). Weigh
accurately 0.15 g of sample on a tared, glazed paper approxi-
V C
1 B 5 3100 (2)
mately ⁄2 in. (13 mm) square or a small watch glass that will
S
fitintothePhillipsbeaker,andtransferthespecimenandpaper
where:
or watch glass to the beaker.
V = ceric ammonium nitrate solution required for titra-
11.2 Add 25 mL of denatured alcohol and swirl vigorously 3
tion of the sample, mL,
for approximately 1 min to remove any surface coating and
C = copper equivalent of the ceric ammonium nitrate
break up lumps. While swirling the flask, slowly add 100 mL
solution, g/mL, and
of the extraction solution.
S = specimen weight, g.
11.3 After the addition of the extraction solution, swirl the
flask vigorously for 5 min, adding lumps of dry ice (solid
CUPROUS OXIDE
carbondioxide)(Note3)continuouslyduringthistimetolower
the temperature of the solution to approximately −10°C. Break
12. Calculation
up any lumps in the solution with a glass rod or policeman.
12.1 Calculate the percent of cuprous oxide (Cu O), D,as
11.4 Filter off the metallic copper-cupric oxide residue 2
follows:
usinga125-mmclose-texturepaper,afilterconetosupportthe
paper,andsuction(Note4).Continuetheadditionofdryiceto
D 5 A 22.252B (3)
the flask and filter paper during the filtration to keep the
where:
solution cold. Wash the flask and filter paper with 150 to 200
A = total reducing power as cuprous oxide (Section 9), %,
mL of denatured alcohol, continuing the use of suction.
and
NOTE 3—Duringthe5-minswirlingperiodapproximately25to30gof
B = metallic copper (Section 11), %.
dryiceisaddedinapproximately5-gportions.Theinitiallumpsofdryice
volatilizerapidlyduetothetemperatureofthesolution.Approximately15
CUPRIC OXIDE
g of dry ice is added in the first 2 min with a subsequent temperature drop
to 0°C. The remaining 15 g volatilizes more slowly and gradually lowers
13. Calculation
the temperature to the vicinity of −10°C. These directions are not critical,
but merely serve as a guide. The solution must be kept very cold in order
13.1 Calculate the percent of cupric oxide (CuO), E,as
to obtain correct and reproducible results. During the filtration period,
follows:
additions of dry ice to the flask should be continued to keep the solution
E 51.252~F 2 B! 21.112D (4)
cold until all of the extraction solution has been filtered.
NOTE 4—In the great majority of cases, the metallic copper-cupric
where:
oxide residue is completely retained by the use of a suitable close-texture
F = total copper (Section 7), %,
filter paper. The filtration is rapid and can be readily completed in 5 min
B = metallic copper (Section 11), %, and
with proper suction. The filtrate should be carefully examined for the
D = cuprous oxide (Section 12),% .
presence of finely divided particles of copper. In the event that extremely
finely divided particles of copper are present and pass through the filter
paper,asevidencedbythepresenceinthefiltrateofareddishcolor,which
METALS OTHER THAN COPPER
may be transient, the following method of filtration should be used: Place
14. Reagents
14.1 CericAmmoniumNitrate,StandardSolution (0.1N)—
This test method is based on the procedure described by Irvin Baker and R.
See 8.1.
Stevens Gibbs, “Determination of Metallic Copper in Cuprous Oxide—Cupric
14.2 Diphenylamine Indicator—Dissolve1gof dipheny-
OxideMixtures,” Industrial and Engineering Chemistry,AnalyticalEdition,Vol13,
February 15, 1946, p. 124. lamine in 100 mL of H SO (sp gr 1.84).
2 4
D283–84 (1999)
14.3 Potassium Ferricyanide Solution(50g/L)—Dissolve5 CHLORIDES AND SULFATES
g of potassium ferricyanide (K Fe(CN) ), in 100 mL of
3 6
17. Reagents
distilled water. Keep tightly stoppered in a dark bottle.
14.4 Potassium Ferrocyanide, Standard Solution (1
17.1 Barium Chloride Solution (100 g/L)—Dissolve 117 g
mL=0.001 g Zn)—Dissolve 5.0 g of potassium ferrocyanide
of BaCl ·2H O in water and dilute to 1 L.
2 2
(KFe(CN) ·3H O) in distilled water and dilute to 1 L.
17.2 Silver Nitrate Solution—Dissolve5gof silver nitrate
6 2
Standardize with analyzed
...