ASTM C759-98
(Test Method)Standard Test Methods for Chemical, Mass Spectrometric, Spectrochemical, Nuclear, and Radiochemical Analysis of Nuclear-Grade Plutonium Nitrate Solutions
Standard Test Methods for Chemical, Mass Spectrometric, Spectrochemical, Nuclear, and Radiochemical Analysis of Nuclear-Grade Plutonium Nitrate Solutions
SCOPE
1.1 These test methods cover procedures for the chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade plutonium nitrate solutions to determine compliance with specifications.
1.2 The analytical procedures appear in the following order: Sections Plutonium by Controlled-Potential Coulometry 2 Plutonium by Amperometric Titration with Iron (II) 2 Free Acid by Titration in an Oxalate Solution 16 to 23 Free Acid by Iodate Precipitation- Potentiometric Titration Test Method 24 to 30 Uranium by Arsenazo I Spectrophotometric Test Method 31 to 41 Thorium by Thorin Spectrophotometric Test Method 42 to 50 Iron by 1,10-Phenanthroline Spectrophotometric Test Method 51 to 58 Chloride by Thiocyanate Spectrophotometric Test Method 59 to 66 Fluoride by Distillation-Spectrophotometric Test Method 67 to 74 Sulfate by Barium Sulfate Turbidimetric Test Method 75 to 82 Isotopic Composition by Mass Spectrometry 83 to 84 Americium-241 by Extraction and Gamma Counting 85 to 93 Americium-241 by Gamma Counting 94 to 102 Gamma-Emitting Fission Products, Uranium, and Thorium by Gamma-Ray Spectroscopy 103 to 110 Rare Earths by Copper Spark Spectrochemical Test Method 111 to 113 Tungsten, Niobium (Columbium), and Tantalum by Spectro-chemical Test Method 114 to 122 Sample Preparation for Spectrographic Analysis for General Impurities 123 to 126
1.3 This standard does not purport to address all of the safety problems, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific safeguard and safety hazard statements, see Section 5.
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Standards Content (Sample)
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Designation: C 759 – 98
Standard Test Methods for
Chemical, Mass Spectrometric, Spectrochemical, Nuclear,
and Radiochemical Analysis of Nuclear-Grade Plutonium
Nitrate Solutions
This standard is issued under the fixed designation C 759; 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 697 Test Methods for Chemical, Mass Spectrometric, and
Spectrochemical Analysis of Nuclear-Grade Plutonium
1.1 These test methods cover procedures for the chemical,
Dioxide Powders and Pellets
mass spectrometric, spectrochemical, nuclear, and radiochemi-
C 852 Guide for Design Criteria for Plutonium Glove-
cal analysis of nuclear-grade plutonium nitrate solutions to
boxes
determine compliance with specifications.
C 1009 Guide for Establishing a Quality Assurance Pro-
1.2 The analytical procedures appear in the following order:
gram for Analytical Chemistry Laboratories Within the
Sections
Nuclear Industry
Plutonium by Controlled-Potential Coulometry
C 1068 Guide for Qualification of Measurement Methods
Plutonium by Amperometric Titration with Iron(II)
by a Laboratory Within the Nuclear Industry
Plutonium by Diode Array Spectrophotometry 4
V 1108 Test Method for Plutonium by Controlled-Potential
Free Acid by Titration in an Oxalate Solution 8 to 15
Free Acid by Iodate Precipitation-Potentiometric Titration 16 to 22
Coulometry
Test Method
C 1128 Guide for Preparation of Working Reference Mate-
Uranium by Arsenazo I Spectrophotometric Test Method 23 to 33
rials for Use in the Analysis of Nuclear Fuel Cycle
Thorium by Thorin Spectrophotometric Test Method 34 to 42
Iron by 1,10-Phenanthroline Spectrophotometric Test Method 43 to 50
Materials
Chloride by Thiocyanate Spectrophotometric Test Method 51 to 58
C 1156 Guide for Establishing Calibration for a Measure-
Fluoride by Distillation-Spectrophotometric Test Method 59 to 66
Sulfate by Barium Sulfate Turbidimetric Test Method 67 to 74 ment Method Used to Analyze Nuclear Fuel Cycle Mate-
Isotopic Composition by Mass Spectrometry 75 to 76
rials
Americium-241 by Extraction and Gamma Counting 77 to 85
C 1165 Test Method for Determining Plutonium by Con-
Americium-241 by Gamma Counting 86 to 94
Gamma-Emitting Fission Products, Uranium, and Thorium by 94 to 102 trolled Potential Coulometry in H SO at a Platinum
2 4
Gamma-Ray Spectroscopy
Working Electrode
Rare Earths by Copper Spark Spectrochemical Test Method 103 to 105
C 1206 Test Method for Plutonium by Iron (II)/Chromium
Tungsten, Niobium (Columbium), and Tantalum by Spectro 106 to 114
chemical Test Method (VI) Amperometric Titration
Sample Preparation for Spectrographic Analysis for General 123 to 126
C 1210 Guide for Establishing a Measurement System
Impurities
Quality Control Program for Analytical Chemistry Labo-
1.3 This standard does not purport to address all of the
ratories Within the Nuclear Industry
safety concerns, if any, associated with its use. It is the
C 1268 Test Method for Quantitative Determination of
responsibility of the user of this standard to establish appro-
Americium 241 in Plutonium by Gamma-Ray Spectrom-
priate safety and health practices and determine the applica-
etry
bility of regulatory limitations prior to use. For specific
C 1297 Guide for Qualification of Laboratory Analysts for
safeguard and safety hazard statements, see Section 6.
the Analysis of Nuclear Fuel Cycle Materials
C 1307 Test Method for Plutonium Assay by Plutonium(III)
2. Referenced Documents
Diode Array Spectrophotometry
2.1 ASTM Standards:
D 1193 Specification for Reagent Water
E 50 Practices for Apparatus, Reagents, and Safety Precau-
tions for Chemical Analysis of Metals
These test methods are under the jurisdiction of ASTM Committee C-26 on
Nuclear Fuel Cycle and are the direct responsibility of Subcommittee C26.05 on
Methods of Test.
Current edition approved Feb. 10, 1998. Published May 1998. Originally Annual Book of ASTM Standards, Vol 12.01.
pub-lished as C 759 – 73. Last previous edition C 759 – 92. Annual Book of ASTM Standards, Vol 11.01.
2 5
Discontinued as of November 15, 1992. Annual Book of ASTM Standards, Vol 03.05.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
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 759
E 115 Practice for Photographic Processing in Optical 6. Safety Hazards
Emission Spectrographic Analysis
6.1 Since plutonium bearing materials are radioactive and
E 116 Practice for Photographic Photometry in Spectro-
toxic, adequate laboratory facilities, gloved boxes, fume hoods,
chemical Analysis
etc., along with safe techniques, must be used in handling
samples containing these materials. A detailed discussion of all
3. Significance and Use
the precautions necessary is beyond the scope of these test
3.1 These test methods are designed to show whether a
methods; however, personnel who handle these materials
given material meets the purchaser’s specifications.
should be familiar with such safe handling practices as are
3.1.1 An assay is performed to determine whether the
given in Guide C 852 and in Refs (1) through (3).
material has the specified plutonium content.
7. Sampling
3.1.2 Determination of the isotopic content of the plutonium
in the plutonium-nitrate solution is made to establish whether
7.1 A sample representative of the lot shall be taken from
the effective fissile content is in compliance with the purchas- each lot into a container or multiple containers that are of such
er’s specifications.
composition that corrosion, chemical change, radiolytic de-
3.1.3 Impurity content is determined by a variety of meth- composition products, and method of loading or sealing will
ods to ensure that the maximum concentration limit of speci-
not disturb the chemical or physical properties of the sample.
fied impurities is not exceeded. Determination of impurities is (A flame-sealed quartz vial that is suitable for accommodating
also required for calculation of the equivalent boron content
pressure resulting from radiolytic decomposition is generally
(EBC).
considered to be an acceptable sample container.)
7.2 Sample size shall be sufficient to perform the following:
4. Committee C-26 Safeguards Statement
7.2.1 Assay and acceptance tests at the seller’s plant,
4.1 The material (plutonium nitrate) to which these test
7.2.2 Assay and acceptance tests at the purchaser’s plant,
methods apply is subject to nuclear safeguards regulations and
governing its possession and use. The following analytical
7.2.3 Referee tests in the event they become necessary.
procedures in these test methods have been designated as 7.3 All samples shall be identified clearly, including the
technically acceptable for generating safeguards accountability
seller’s lot number.
measurement data: Plutonium by Controlled-Potential Cou- 7.3.1 A lot is defined as any quantity of aqueous plutonium
lometry; Plutonium by Amperometric Titration with Iron(II);
nitrate solution that is uniform in isotopic, chemical, and
Plutonium by Diode Array Spectrophotometry and Isotopic physical characteristics by virtue of having been mixed in such
Composition by Mass Spectrometry.
a manner as to be thoroughly homogeneous.
4.2 When used in conjunction with appropriate Certified 7.3.2 All containers used for a lot shall be identified
Reference Materials (CRMs), these procedures can demon- positively as containing material from a particular homoge-
strate traceability to the national measurement base. However, neous solution.
adherence to these procedures does not automatically guaran-
PLUTONIUM BY CONTROLLED-POTENTIAL
tee regulatory acceptance of the resulting safeguards measure-
COULOMETRY
ments. It remains the sole responsibility of the user of these test
(This test method was discontinued in 1992 and replaced by
methods to assure that their application to safeguards has the
Test Method C 1165.)
approval of the proper regulatory authorities.
PLUTONIUM BY CONTROLLED-POTENTIAL
5. Reagents and Materials
COULOMETRY
5.1 Purity of Reagents—Reagent grade chemicals shall be
(With appropriate sample preparation, controlled-potential
used in all test methods. Unless otherwise indicated, it is
coulometric measurement as described in Test Method C 1108
intended that all reagents shall conform to the specifications of
may be used for plutonium determination.)
the Committee on Analytical Reagents of the American Chemi-
cal Society, where such specifications are available. Other
PLUTONIUM BY AMPEROMETRIC TITRATION
grades may be used, provided it is first ascertained that the
WITH IRON(II)
reagent is of sufficiently high purity to permit its use without
(This test method was discontinued in 1992 and replaced by
lessening the accuracy of the determination.
Test Method C 1206.)
5.2 Purity of Water—Unless otherwise indicated, reference
to water shall be understood to mean reagent water conforming
TEST METHOD FOR PLUTONIUM ASSAY BY
to Specification D 1193.
PLUTONIUM(III) DIODE ARRAY
SPECTROPHOTOMETRY
(With appropriate sample preparation, the measurement
Based upon Committee C-26 Safeguards Matrix (C 1009, C 1068, C 1128,
described in Test Method C 1307 may be used for plutonium
C 1156, C 1210, C 1297.).
determination.)
“Reagent Chemicals, American Chemical Society Specifications,” Am. Chemi-
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 The boldface numbers in parentheses refer to the list of references at the end of
Pharmacopeia.” 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 759
FREE ACID BY TITRATION IN AN OXALATE 14. Calculation
+
SOLUTION
14.1 Calculate the free acid (H , N) as follows:
H , N 5 ~A 3 N!/V (1)
8. Scope
8.1 This test method covers the determination of free acid in
where:
plutonium nitrate solutions (4, 5).
A 5 microlitres of standard NaOH solution required to
titrate sample,
9. Summary of Test Method
N 5 normality of NaOH standard solution, and
9.1 Free acid is determined by titrating an aliquot of sample, V 5 volume of sample, μL.
which contains an excess of ammonium oxalate added to
15. Precision and Bias
complex the plutonium, back to the original pH of the
ammonium oxalate solution with standard sodium hydroxide
15.1 Precision—Of individual results,6 5 % at the 95 %
solution. Micropipets and microburets are required to measure
confidence level.
the small volume of sample and titrant used.
15.2 Bias—99.4 %.
10. Interferences
FREE ACID BY IODATE PRECIPITATION-
POTENTIOMETRIC TITRATION TEST METHOD
10.1 Any metal ions not complexed by oxalate which form
precipitates at the pH of the end point of the titration will cause
16. Scope
interference in this test method.
16.1 This test method covers the determination of free acid
NOTE 1—A “rule of thumb” is that 1 mL of saturated ammonium
in strong acid solutions of plutonium nitrate.
oxalate solution will complex 6.4 mg of plutonium.
11. Apparatus 17. Summary of Test Method
11.1 Magnetic Stirrer. 17.1 Free acid is determined by potentiometric titration with
11.2 Microburet. standard sodium hydroxide solution after precipitation and
11.3 Micropipets. subsequent removal of plutonium (up to 50 mg) as plutonium
11.4 pHJ Meter. iodate.
12. Reagents and Materials 18. Interferences
12.1 Ammonium Oxalate Solution, saturated.
18.1 Any hydrolyzable ions that are not precipitated with
12.2 Nitric Acid (3.50 N)—Prepare solution by diluting iodate will interfere.
concentrated nitric acid (HNO , sp gr 1.42) with water.
19. Reagents and Materials
Standardize by titrating 0.500-mL aliquots with 0.100 N NaOH
solution.
19.1 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
12.3 Sodium Hydroxide Solution (0.100 N)—Prepare and
chloric acid (HCl).
standardize in accordance with Practices E 50.
19.2 Nitric Acid (1 + 14)—Dilute 14 volumes of water with
1 volume of concentrated nitric acid (HNO , sp gr 1.42).
13. Procedure
19.3 Potassium Iodate ( 0.3 M)—Dissolve 64.2 g of potas-
13.1 Transfer 1.0 mL of saturated ammonium oxalate solu- sium iodate (KIO ) in 900 mL of water, adjust the pH to 4.3
tion to a small vial and dilute to about 2 mL with water.
by adding HNO (1 + 14), and dilute to 1 L with water.
13.2 Add a stirring bar and insert the electrodes and start
19.4 Sodium Hydroxide ( 0.3 M)—Prepare and standardize
stirrer. When the pH value becomes stable, record the value as
in accordance with Practices E 50 after making the following
the pH of reagent.
alterations: Use 15 mL of the NaOH solution (50 g/50 mL), and
in step 42.2, transfer 1.200 g of National Institute for Standards
NOTE 2—Normally, the pH value for the saturated solution is approxi-
and Technology (NIST) potassium acid phthalate SRM 84 h or
mately 6.4.
its replacement to a 250-mL Erlenmeyer flask instead of 0.4000
13.3 Add 20 μL of sample to the vial, rinse the pipet
g.
thoroughly with water, and stir the solution for 1 min.
13.4 Titrate with 0.100 N NaOH solution to within one pH
20. Procedure
unit of the end point; then, by adding successively smaller
20.1 Pipet 50 mL of KIO (0.3 M) into a beaker and stir
increments, titrate to the pH of the ammonium oxalate reagent
while adding an aliquot of sample solution containing no
and record the volume of titrant.
greater than 50 mg of plutonium.
NOTE 3—Allow time for the pH reading to stabilize between additions
20.2 After precipitation is complete, filter the solution
of titrant as the end point is approached.
through either a medium porosity glass frit or a fine textured
13.5 Make a daily check of the system by adding 20 μL of acid-washed filter paper and collect the filtrate in a beaker.
3.50 N HNO to a sample that has already been titrated to the 20.3 Wash the precipitate with two 25-mL portions of 0.3 M
end point and titrate with standard 0.100 NM NaOH solution KIO solution, and combine the washings with the filtrate from
back to the same pH. step 20.2.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
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