ASTM C697-98

NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
Designation: C 697 – 98
Standard Test Methods for
Chemical, Mass Spectrometric, and Spectrochemical
Analysis of Nuclear-Grade Plutonium Dioxide Powders and
Pellets
This standard is issued under the fixed designation C 697; 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 C 757 Specification for Nuclear-Grade Plutonium Dioxide
Powder, Sinterable
1.1 These test methods cover procedures for the chemical,
C 852 Guide for Design Criteria for Plutonium Glove-
mass spectrometric, and spectrochemical analysis of nuclear-
boxes
grade plutonium dioxide powders and pellets to determine
C 1009 Guide for Establishing a Quality Assurance Pro-
compliance with specifications.
gram for Analytical Chemistry Laboratories Within the
1.2 The analytical procedures appear in the following order:
Nuclear Industry
Sections
C 1068 Guide for Qualification of Measurement Methods
Plutonium Sample Handling 8 to 10
Plutonium by Controlled-Potential Coulometry
by a Laboratory Within the Nuclear Industry
Plutonium by Ceric Sulfate Titration 11 to 18
C 1108 Test Method for Plutonium by Controlled-Potential
Plutonium by Amperometric Titration with Iron(II)
Coulometry
Plutonium by Diode Array Spectrophotometry
Nitrogen by Distillation Spectrophotometry Using Nessler 19 to 26
C 1128 Guide for Preparation of Working Reference Mate-
Reagent
rials for Use in the Analysis of Nuclear Fuel Cycle
Carbon (Total) by Direct Combustion–Thermal Conductivity 27 to 38
Materials
Total Chlorine and Fluorine by Pyrohydrolysis 39 to 46
Sulfur by Distillation Spectrophotometry 47 to 55
C 1156 Guide for Establishing Calibration for a Measure-
Plutonium Isotopic Analysis by Mass Spectrometry
ment Method Used to Analyze Nuclear Fuel Cycle Mate-
Rare Earth Elements by Spectroscopy 56 to 63
Trace Elements by Carrier–Distillation Spectroscopy 64 to 71 rials
Impurity Elements by Spark-Source Mass Spectrography 72 to 78
C 1165 Test Method for Determining Plutonium by
Moisture by the Coulometric Electrolytic Moisture Analyzer 79 to 86
Controlled-Potential Coulometry in H SO at a Platinum
2 4
Total Gas in Reactor-Grade Plutonium Dioxide Pellets 87 to 94
Plutonium-238 Isotopic Abundance by Alpha Spectrometry 95 to 102 Working Electrode
Americium-241 in Plutonium by Gamm-Ray Spectrometry
C 1168 Practice for Preparation and Dissolution of Pluto-
Rare Earths By Copper Spark-Spectroscopy 103 to 112
nium Materials for Analysis
Plutonium Isotopic Analysis by Mass Spectrometry 113 to 121
C 1206 Test Method for Plutonium by Iron (II)/Chromium
Oxygen-To-Metal Atom Ratio by Gravimetry 122 to 130
(VI) Amperometric Titration
1.3 This standard does not purport to address all of the
C 1210 Guide for Establishing a Measurement System
safety concerns, if any, associated with its use. It is the
Quality Control Program for Analytical Chemistry Labo-
responsibility of the user of this standard to establish appro-
ratories Within the Nuclear Industry
priate safety and health practices and determine the applica-
C 1268 Test Method for Quantitative Determination of
bility of regulatory limitations prior to use. For specific
Americium 241 in Plutonium by Gamma-Ray Spectrom-
precautionary statements, see Sections 6, 23, 32, 127, and 60.9
etry
and 117.5.1 .
C 1297 Guide for Qualification of Laboratory Analysts for
the Analysis of Nuclear Fuel Cycle Materials
2. Referenced Documents
C 1307 Test Method for Plutonium Assay by Plutonium(III)
2.1 ASTM Standards:
Diode Array Spectrophotometry
D 1193 Specification for Reagent Water
E 60 Practice for Photometric and Spectrophotometric
These methods are under the jurisdiction of ASTM Committee C-26 on Nuclear
Methods for Chemical Analysis of Metals
Fuel Cycle and are the direct responsibility of Subcommittee C26.05 on Methods of
E 115 Practices for Photographic Processing in Optical
Test.
Current edition approved Feb. 10, 1998. Published May 1998. Originally
published as C 697 – 72. Last previous edition C 697 – 92.
2 5
Discontinued as of November 15, 1992. Annual Book of ASTM Standards, Vol 12.01.
3 6
Discontinued—see 1989 Annual Book of ASTM Standards, Vol 12.01. Annual Book of ASTM Standards, Vol 11.01.
4 7
Discontinued as of May 30, 1980. Annual Book of ASTM Standards, Vol 03.05.
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NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
C 697
7 9
Emission Spectrographic Analysis where such specifications are available. Other grades may be
used, provided it is first ascertained that the reagent is of
E 116 Practice for Photographic Photometry in Spectro-
sufficiently high purity to permit its use without lessening the
chemical Analysis
accuracy of the determination.
E 909 Master Matrix for Development of Standards to
3 5.2 Purity of Water—Unless otherwise indicated, references
Assist in Safeguarding of Nuclear Materials
to water shall be understood to mean reagent water conforming
to Specification D 1193.
3. Significance and Use
3.1 Plutonium dioxide is used in mixtures with uranium
6. Safety Precautions
dioxide as a nuclear-reactor fuel. In order to be suitable for this
6.1 Since plutonium bearing materials are radioactive and
purpose, the material must meet certain criteria for plutonium
toxic, adequate laboratory facilities, gloved boxes, fume hoods,
content, isotopic composition, and impurity content. These test
etc., along with safe techniques, must be used in handling
methods are designed to show whether or not a given material
samples containing these materials. A detailed discussion of all
meets the specifications for these items as described in Speci-
the precautions necessary is beyond the scope of these test
fication C 757.
methods; however, personnel who handle these materials
3.1.1 An assay is performed to determine whether the
should be familiar with such safe handling practices as are
material has the minimum plutonium content specified on a dry
given in Guide 852 and in Refs (1) through (3).
weight basis.
7. Sampling and Dissolution
3.1.2 Determination of the isotopic content of the plutonium
in the plutonium dioxide powder is made to establish whether
7.1 Criteria for sampling this material are given in Specifi-
the effective fissile content is in compliance with the purchas- cation C 757.
er’s specifications.
7.2 Samples can be dissolved using the appropriate disso-
lution technique described in Practice C 1168.
3.1.3 Impurity content is determined to ensure that the
maximum concentration limit of certain impurity elements is
PLUTONIUM SAMPLE HANDLING
not exceeded. Determination of impurities is also required for
calculation of the equivalent boron content (EBC).
8. Scope
8 8.1 This test method covers the conditions necessary to
4. Committee C-26 Safeguards Statement
preserve the integrity of plutonium dioxide samples. Condi-
4.1 The materials (plutonium dioxide powders and pellets)
tions listed here are directed toward the analytical chemist.
to which these test methods apply are subject to nuclear
However, they are just as applicable to any group handling the
safeguards regulations governing their possession and use. The
material.
following analytical procedures in these test methods have
been designated as technically acceptable for generating safe-
9. Summary of Test Method
guards accountability measurement data: Plutonium by
9.1 Plutonium dioxide is very hygroscopic. In a short time it
Controlled-Potential Coulometry; Plutonium by Ceric Sulfate
can sorb sufficient water from an uncontrolled atmosphere to
Titration; Plutonium by Amperometric Titration with Iron (II);
destroy the validity of the most accurate analytical methods.
Plutonium by Diode Array Spectrometry Plutonium-238 Iso-
An atmosphere with a dew point of −23°C has been found
topic Abundance by Alpha Spectrometry; and Plutonium Iso-
adequate to prevent sorption of water, but care must be
topic Analysis by Mass Spectrometry.
exercised to use equipment and sample containers known to be
4.2 When used in conjunction with appropriate Certified
dry.
Reference Materials (CRMs), these procedures can demon-
strate traceability to the national measurement base. However, 10. Sample Handling Conditions
adherence to these procedures does not automatically guaran-
10.1 All sampling and critical weighings are to be per-
tee regulatory acceptance of the resulting safeguards measure-
formed in an atmosphere with a dew point no greater
ments. It remains the sole responsibility of the user of these test
than −23°C.
methods to assure that its application to safeguards has the
10.2 All sampling equipment, including bottles, is to be
approval of the proper regulatory authorities.
dried before use. Plastic bottles are not to be used since they
cannot be adequately dried. Glass bottles and aluminum foil
5. Reagents
are to be dried at 110°C for at least 1 h and kept in a desiccator
until used.
5.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
all reagents shall conform to the specifications of the Commit-
“Reagent Chemicals, American Chemical Society Specifications,” Am. Chemi-
tee on Analytical Reagents of the American Chemical Society,
cal Soc., Washington, DC. For suggestions on the testing of reagents not listed by
the American Chemical Society, see “Reagent Chemicals and Standards,” by Joseph
Rosin, D. Van Nostrand Co., Inc., New York, NY, and the “United States
Pharmacopeia.”
8 10
Based upon Committee C-26 Safeguards Matrix (C 1009, C 1068, C 1128, The boldface numbers in parentheses refer to the list of references at the end
C 1156, C 1210, C 1297). of these test methods.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
C 697
NOTE 1—It has been shown that plutonium dioxide will sorb water
H SO (sp gr 1.84) and 5 parts of water. Dilute to 100 mL and
2 4
from apparently dry aluminum foil. The foil should be dried at 110°C
add 3 drops of 0.01 M osmium tetroxide solution (0.25 g of
before use.
osmium tetroxide in 100 mL of 0.1 N H SO ) and 1 drop of
2 4
10.3 Quantitative methods to correct for moisture absorp-
ferroin indicator. Titrate with 0.1 N ceric sulfate solution until
tion, such as drying, must be avoided. The sample will not be orange-red color changes to pale blue. The equivalent weight
representative under these conditions. It is virtually impossible
of arsenous oxide 5 49.455.
to get equal amounts of moisture in the sample and bulk of the
15.2 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
material at the same time.
chloric acid (HCl).
15.3 Hydrochloric Acid (6 N)—Prepare by diluting 500 mL
PLUTONIUM BY CONTROLLED-
of HCl (sp gr 1.19) to 1 L with water.
POTENTIAL COULOMETRY
15.4 Hydrofluoric Acid (48 %)—Concentrated hydrofluoric
(This test method was discontinued in 1992 and replaced by
acid (HF).
Test Method C 1165.)
15.5 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
(HNO ).
PLUTONIUM BY CONTROLLED-POTENTIAL
15.6 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
COULOMETRY
(H SO ).
2 4
(With appropriate sample preparation, controlled-potential
15.7 Titanous Trichloride Solution—A 20 % solution is
coulometric measurement as described in Test Method C 1108
available commercially. Store TiCl under a nitrogen atmo-
may be used for plutonium determination.)
sphere.
PLUTONIUM BY CERIC SULFATE TITRATION
16. Procedure
11. Scope
16.1 In a humidity-controlled glove box, accurately weigh
11.1 This test method (4) covers the determination of the approximately1gofPuO powder.
plutonium content of nuclear-grade plutonium dioxide pow- 16.2 Dissolve the sample in a platinum crucible with HCl or
ders.
HNO and 150 μL HF.
16.3 Fume the samples with H SO to remove nitrates,
2 4
12. Summary of Test Method
nitrites, and fluoride. Samples dissolved with only HCl do not
12.1 Weighed samples of low-fired (less than 950°C) plu-
require fuming. Add sufficient aluminum chloride to complex
tonium dioxide are dissolved in a mixture of hydrochloric
fluorides.
acid-hydrofluoric acid or nitric acid-hydrofluoric acid. The
16.4 Transfer the solution to a 50-mL flask and dilute to
sample solution is fumed with sulfuric acid to remove nitrates,
volume with 6 N HCl.
nitrites, and fluoride. Plutonium in a sample aliquot is reduced
16.5 Transfer 2.00 mL of the sample solution to a 50-mL
to Pu (III) by the addition of an excess of titanous trichloride.
beaker. Add 10 mL of water and stir the solution. Aliquots may
The excess reductant is oxidized by a standard ceric sulfate
be taken by weight.
solution and the Pu (III) titrated to Pu (IV). The end points are
16.6 Add sufficient TiCl reagent to give a meter reading of
determined potentiometrically.
approximately 1100 mV. The solution should be a blue-purple
color.
13. Interferences
16.7 Titrate the sample and excess TiCl with standard ceric
13.1 Iron, copper, tungsten, uranium, nitrates, nitrites, and
sulfate solution. Record the volume of titrant and the millivolt
those ions which have oxidation potential above
reading after each addition. The end point is the point at which
Pu ~III! → Pu ~IV! 1 e, E° 5 0.97 V (1)
DmV/DmL reaches a maximum. Record the volume of titrant
corresponding to this point. At this point the excess Ti (III) is
or below
oxidized to Ti (IV) and the oxidation of Pu (III) begins.
Ti ~III! 1 H O → TiO ~II! 1 2H 1 e, E° 5 0.0 V (2)
16.8 Continue the titration until a second end point occurs
near 500 mV, which is the point at which the oxidation of Pu
14. Apparatus
(III) to Pu (IV) is complete. Record the volume of titrant at this
14.1 Dry Box—A box with humidity controlled to a dew
point. The difference in volume between these two end points
point of less than −23° C.
is the amount of ceric sulfate solution required to titrate the
14.2 Microburet, 1 to 7-mL capacity.
plutonium.
14.3 Potentiometer, having a range from 0 to 1400 mV.
17. Calculation
15. Reagents
17.1 Calculate the plutonium content (Pu), mass %, as
15.1 Ceric Sulfate Solution (0.1 N)—Dissolve 65 g of ceric
follows:
ammonium sulfate [(NH ) Ce(SO ) ·2 H O] in 600 mL of 1 M
4 4 4 4 2
Pu 5 V ! V ! N! W !/ A! W! 3 100 (3)
H SO and dilute to 1 L with water. Standardize (15) as @~ ~ ~ ~ ~ ~ #
1 2
...