ASTM C799-99(2005)
(Test Method)Standard Test Methods for Chemical, Mass Spectrometric, Spectrochemical, Nuclear, and Radiochemical Analysis of Nuclear-Grade Uranyl Nitrate Solutions
Standard Test Methods for Chemical, Mass Spectrometric, Spectrochemical, Nuclear, and Radiochemical Analysis of Nuclear-Grade Uranyl Nitrate Solutions
SIGNIFICANCE AND USE
Uranyl nitrate solution is used as a feed material for conversion to the hexafluoride as well as for direct conversion to the oxide. In order to be suitable for this purpose, the material must meet certain criteria for uranium content, isotopic composition, acidity, radioactivity, and impurity content. These methods are designed to show whether a given material meets the specifications for these items described in Specification C 788.
3.1.1 An assay is performed to determine whether the material has the specified uranium content.
3.1.2 Determination of the isotopic content of the uranium is made to establish whether the effective fissile content is in accordance with the purchaser’specifications.
3.1.3 Acidity, organic content, and alpha, beta, and gamma activity are measured to establish that they do not exceed their maximum limits.
3.1.4 Impurity content is determined to ensure that the maximum concentration limit of certain impurity elements is not exceeded. Impurity concentrations are also required for calculation of the equivalent boron content (EBC), and the total equivalent boron content (TEBC).
SCOPE
1.1 These test methods cover procedures for the chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solution to determine compliance with specifications.
1.2 The analytical procedures appear in the following order:
Sections Determination of Uranium 7 Specific Gravity by Pycnometry 15-20 Free Acid by Oxalate Complexation 21-27 Determination of Thorium28 Determination of Chromium29 Determination of Molybdenum30 Halogens Separation by Steam Distillation 31-35 Fluoride by Specific Ion Electrode 36-42 Halogen Distillate Analysis: Chloride, Bromide, and Iodide by
Amperometric Microtitrimetry43 Determination of Chloride and Bromide44 Determination of Sulfur by X-Ray Fluorescence45 Sulfate Sulfur by (Photometric) Turbidimetry46 Phosphorus by the Molybdenum Blue (Photometric) Method 54-61 Silicon by the Molybdenum Blue (Photometric) Method62-69 Carbon by Persulfate Oxidation-Acid Titrimetry70 Conversion to U3O871-74 Boron by Emission Spectrography75-81 Impurity Elements by Spark Source Mass Spectrography82 Isotopic Composition by Thermal Ionization Mass Spectrometry83 Uranium-232 by Alpha Spectrometry84-90 Total Alpha Activity by Direct Alpha Counting91-97 Fission Product Activity by Beta Counting98-104 Entrained Organic Matter by Infrared Spectrophotometry105 Fission Product Activity by Gamma Counting106 Determination of Arsenic107 Determination of Impurities for the EBC Calculation108 Determination of Technetium 99109 Determination of Plutonium and Neptunium110
1.3 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 appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Specific precautionary statements are given in Section 5.
7.1 Uranium can be determined using iron (II) reduction and dichromate titration. Test Method C1267 can be used.
7.2 Uranium can also be determined using cerium (IV) oxidation titrimetry. ISO 7097 Test Method can be used.
7.3 Uranium can also be determined by X-Ray Fluorescence using Test Method C1254.
7.4 Previous sections have been deleted.
8.1 This test method covers the determination of uranium in nuclear-grade uranyl nitrate solution. Appropriate size sample aliquots are chosen to obtain 5 to 10 g of U3O8.
15.1 This test method covers the determination of the specific gravity of a solution of uranyl nitrate to ±0.0004.
21.1 This test method covers the determination of the free acid content of uranyl nitrate solutions that may contain a ratio of up to 5 moles of acid to 1 mole of uranium.
28.1 The determination of thorium by the arsenazo (III) (photometric) method has been discontinued, (see C79...
General Information
Relations
Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation:C799–99(Reapproved2005)
Standard Test Methods for
Chemical, Mass Spectrometric, Spectrochemical, Nuclear,
and Radiochemical Analysis of Nuclear-Grade Uranyl Nitrate
Solutions
This standard is issued under the fixed designation C799; 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 (´) indicates an editorial change since the last revision or reapproval.
1. Scope 2. Referenced Documents
1.1 These test methods cover procedures for the chemical, 2.1 ASTM Standards:
mass spectrometric, spectrochemical, nuclear, and radiochemi- C696 Test Methods for Chemical, Mass Spectrometric, and
cal analysis of nuclear-grade uranyl nitrate solution to deter- Spectrochemical Analysis of Nuclear-Grade Uranium Di-
mine compliance with specifications. oxide Powders and Pellets
1.2 Theanalyticalproceduresappearinthefollowingorder: C761 Test Methods for Chemical, Mass Spectrometric,
Spectrochemical, Nuclear, and RadiochemicalAnalysis of
Sections
Determination of Uranium 7
Uranium Hexafluoride
Specific Gravity by Pycnometry 15-20
C788 Specification for Nuclear-Grade Uranyl Nitrate Solu-
Free Acid by Oxalate Complexation 21-27
tion or Crystals
Determination of Thorium 28
Determination of Chromium 29
C1219 Test Methods for Arsenic in Uranium Hexafluoride
Determination of Molybdenum 30
C1233 PracticeforDeterminingEquivalentBoronContents
Halogens Separation by Steam Distillation 31-35
Fluoride by Specific Ion Electrode 36-42 of Nuclear Materials
Halogen Distillate Analysis: Chloride, Bromide, and Iodide by 43
C1254 Test Method for Determination of Uranium in Min-
Amperometric Microtitrimetry
eral Acids by X-Ray Fluorescence
Determination of Chloride and Bromide 44
Determination of Sulfur by X-Ray Fluorescence 45 C1267 Test Method for Uranium by Iron (II) Reduction in
Sulfate Sulfur by (Photometric) Turbidimetry 46
PhosphoricAcid Followed by Chromium (VI) Titration in
Phosphorus by the Molybdenum Blue (Photometric) Method 54-61
the Presence of Vanadium
Silicon by the Molybdenum Blue (Photometric) Method 62-69
Carbon by Persulfate Oxidation-Acid Titrimetry 70 C1287 Test Method for Determination of Impurities in
Conversion to U O 71-74
3 8
Nuclear Grade Uranium Compounds by Inductively
Boron by Emission Spectrography 75-81
Coupled Plasma Mass Spectrometry
Impurity Elements by Spark Source Mass Spectrography 82
Isotopic Composition by Thermal Ionization Mass Spectrometry 83 C1295 Test Method for Gamma Energy Emission from
Uranium-232 by Alpha Spectrometry 84-90
Fission Products in Uranium Hexafluoride and Uranyl
Total Alpha Activity by Direct Alpha Counting 91-97
Nitrate Solution
Fission Product Activity by Beta Counting 98-104
Entrained Organic Matter by Infrared Spectrophotometry 105 C1296 TestMethodforDeterminationofSulfurinUranium
Fission Product Activity by Gamma Counting 106
Oxides and Uranyl Nitrate Solutions by X-Ray Fluores-
Determination of Arsenic 107
cence (XRF)
Determination of Impurities for the EBC Calculation 108
Determination of Technetium 99 109
C1380 Test Method for the Determination of Uranium
Determination of Plutonium and Neptunium 110
Content and Isotopic Composition by Isotope Dilution
Mass Spectrometry
1.3 This standard does not purport to address all of the
C1413 Test Method for Isotopic Analysis of Hydrolyzed
safety concerns, if any, associated with its use. It is the
Uranium Hexafluoride and Uranyl Nitrate Solutions by
responsibility of the user of this standard to establish appro-
Thermal Ionization Mass Spectrometry
priate safety and health practices and determine the applica-
D1193 Specification for Reagent Water
bility of regulatory limitations prior to use. Specific precau-
E12 Terminology Relating to Density and Specific Gravity
tionary statements are given in Section 5.
1 2
These test methods are under the jurisdiction of ASTM Committee C26 on For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Nuclear Fuel Cycle and are the direct responsibility of Subcommittee C26.05 on contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Methods of Test. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved June 1, 2005. Published October 2005. Originally the ASTM website.
e1 3
approved in 1975. Last previous edition approved in 1999 as C799–99 . DOI: Withdrawn. The last approved version of this historical standard is referenced
10.1520/C0799-99R05. on www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
C799–99 (2005)
of Solids, Liquids, and Gases 5.2 The user should also be cognizant of and adhere to all
E60 Practice for Analysis of Metals, Ores, and Related federal,state,andlocalregulationsforprocessing,shipping,or
Materials by Molecular Absorption Spectrometry in any way using uranyl nitrate solutions.
2.2 American Chemical Society Specification:
Reagent Chemicals 6. Sampling
2.3 Other Documents:
6.1 Criteria for sampling this material are given in Specifi-
ISO 7097 Determination of Uranium in Uranium Product
cation C788.
Solutions and Solids with Cerium IV Oxidation Titrimet-
ric Method
DETERMINATION OF URANIUM
3. Significance and Use
7. Scope
3.1 Uranyl nitrate solution is used as a feed material for
7.1 Uraniumcanbedeterminedusingiron(II)reductionand
conversion to the hexafluoride as well as for direct conversion
dichromate titration. Test Method C1267 can be used.
to the oxide. In order to be suitable for this purpose, the
7.2 Uranium can also be determined using cerium (IV)
material must meet certain criteria for uranium content, isoto-
oxidation titrimetry. ISO7097 Test Method can be used.
pic composition, acidity, radioactivity, and impurity content.
7.3 UraniumcanalsobedeterminedbyX-RayFluorescence
These methods are designed to show whether a given material
using Test Method C1254.
meets the specifications for these items described in Specifi-
7.4 Previous sections have been deleted.
cation C788.
3.1.1 An assay is performed to determine whether the
URANIUM BY IGNITION GRAVIMETRY
material has the specified uranium content.
3.1.2 Determination of the isotopic content of the uranium
8. Scope
is made to establish whether the effective fissile content is in
8.1 Thistestmethodcoversthedeterminationofuraniumin
accordance with the purchaser’s specifications.
nuclear-grade uranyl nitrate solution. Appropriate size sample
3.1.3 Acidity, organic content, and alpha, beta, and gamma
aliquots are chosen to obtain 5 to 10 g of U O .
3 8
activity are measured to establish that they do not exceed their
maximum limits.
9. Summary of Test Method
3.1.4 Impurity content is determined to ensure that the
9.1 The uranyl nitrate solution is evaporated to dryness,
maximum concentration limit of certain impurity elements is
not exceeded. Impurity concentrations are also required for ignited to U O , and weighed. Corrections are made for any
3 8
impurities present (1, 2).
calculationoftheequivalentboroncontent(EBC),andthetotal
equivalent boron content (TEBC).
10. Interferences
4. Reagents
10.1 The weight of U O is corrected for the nonvolatile
3 8
4.1 Purity of Reagents—Reagent grade chemicals shall be
impurities present as determined by spectrographic analysis.
used in all tests. Unless otherwise indicated, it is intended that
10.2 Volatile anions that are difficult to decompose require
all reagents shall conform to the specifications of the Commit-
an extended ignition period.
tee onAnalytical Reagents of theAmerican Chemical Society,
where such specifications are available. Other grades may be
11. Apparatus
used, provided it is first ascertained that the reagent is of
11.1 Heat Lamp, infrared.
sufficiently high purity to permit its use without lessening the
11.2 Hot Plate.
accuracy of the determination.
11.3 Muffle Furnace.
4.2 Purity of Water—Unlessotherwiseindicated,references
towatershallbeunderstoodtomeanreagentwaterconforming
12. Procedure
to Specification D1193.
12.1 Transfer a weighed portion of uranyl nitrate solution
containing 5 to 10 g of uranium into a preweighed platinum
5. Safety Precautions
dish and add 2 drops of HF (48%).
5.1 Use of this standard does not relieve the user of the
12.2 Positionthedishundertheheatlampandevaporatethe
obligation to be aware of and to conform to all health and
solution to dryness.
safety requirements.
12.3 Placethedishonahotplatewithasurfacetemperature
of about 300°C and heat until most of the nitrate has decom-
posed.
Reagent Chemicals, American Chemical Society Specifications, American
12.4 Transfer the dish to a muffle furnace and ignite for 2 h
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
at 900°C.
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
12.5 Remove the dish to a desiccator and allow to cool to
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
room temperature.
MD.
12.6 Weigh the dish; then repeat 12.4-12.6 until a constant
Available fromAmerican National Standards Institute (ANSI), 25 W. 43rd St.,
4th Floor, New York, NY 10036, http://www.ansi.org. weight is obtained.
C799–99 (2005)
13. Calculation
A = flask in air, g,
C = water plus flask in air, g,
13.1 Calculate the uranium content as follows:
0.0007 g/g = correction factor applicable for densities of
Uranium,g/g 5 ~~B 2 C!/A! D (1)
1.3 to 1.5, and
0.0010 g/g = correction factor for water.
where:
A = sample, g,
20. Precision
B =U O obtained, g,
3 8
20.1 The limit of error at the 95% level for a single
C = impurity-element oxides, g, and
D = gravimetric factor, grams of uranium/grams of determination is 60.03%.
U O (varies according to uranium enrichment).
3 8
FREE ACID BY OXALATE COMPLEXATION
14. Precision
21. Scope
14.1 The limit of error at the 95% confidence level for a
21.1 This test method covers the determination of the free
single determination is 60.03%.
acidcontentofuranylnitratesolutionsthatmaycontainaratio
of up to 5 moles of acid to 1 mole of uranium.
SPECIFIC GRAVITY BY PYCNOMETRY
22. Summary of Test Method
15. Scope
22.1 Toadilutedsolutionofuranylnitrate,solid,pulverized
15.1 This test method covers the determination of the
potassium oxalate is added until a pH of about 4.7 is reached.
specific gravity of a solution of uranyl nitrate to 60.0004.
The solution is then titrated with standard NaOH solution by
16. Summary of Test Method the delta pH method to obtain the inflection point (3).
16.1 A known volume of the solution adjusted at a con-
23. Apparatus
trolled temperature is weighed and compared to the weight of
23.1 pH Meter, with glass and calomel electrodes.
water measured in the same container (Terminology E12).
23.2 Buret, Class A, 50-mL.
17. Apparatus
24. Reagents
17.1 Volumetric Flasks, 50-mL, Class A.
24.1 Nitric Acid (2.0 N)—Dilute 130 mL of HNO (sp gr
17.2 Water Bath, temperature controlled to 60.1°C at a
1.42) to 1 L with water. Standardize with sodium hydroxide
temperature slightly above normal room temperature, and
solution (see 24.3).
provided with clips for holding volumetric flasks.
24.2 Potassium Oxalate (K C O ·H O), crystals.
2 2 4 2
24.3 Sodium Hydroxide Solution (0.3 N)—Dissolve 12.0 g
18. Procedure
of NaOH in 1 L of water. Standardize with acid potassium
18.1 Weightheclean,dryvolumetricflaskanditsstopperto
phthalate.
the nearest 0.1 mg.
18.2 Fillthevolumetricflaskwiththeuranylnitratesolution
25. Procedure
to a point close to the volume mark, using a thinstemmed
25.1 Transfer a 5-mLsample aliquot into a 250-mLbeaker.
funnel and a glass dropper.
25.2 Add 100 mLof distilled water or such volume that the
18.3 Place the stoppered volumetric flask in the water bath
uranium concentration will be between 7 and 50 g/L.
for 30 min.
25.3 Addaspikeofsufficient2.0 NstandardHNO tomake
18.4 Use a finely drawn glass dropper to adjust the liquid
the sample definitely acid if the sample is neutral or acid
volume to the mark.
deficient.
18.5 Leave the flask in the water bath an additional 10 min
25.4 AddpulverizedK C O ·H Oslowlyandwithconstant
2 2 4 2
to make sure that the bath temperature has been reached.
stirring until a pH of 4.7 to 4.9 is reached.
18.6 Dry and weigh the flask to the nearest 0.1 mg.
25.5 Immerse the titration beaker in an ice bath. (Titrations
18.7 Repeat 18.2-18.6 using boiled and cooled distilled
made at room temperature are possible but are less sharp.)
water instead of the uranyl nitrate solution.
25.6 Titrate with 0.3 N NaOH using 0.20-mL increments
and determine the inflection point by the delta pH or “analyti-
19. Calculation
cal” method.
19.1 Very accurate determinations of specific gravity re-
NOTE 1—Thistestmethodoflocatingtheendpointdependsonthefact
quire that vacuo corrections be made, but if a median correc-
2 2
thatthesecondderivative D pH/Dvol iszeroatthepointwheretheslope
tion figure in terms of grams per grams of sample is applied to
DpH/Dvol is a maximum.
the solution weights in all cases the resulting error will not
exceed 0.05%.
26. Calculation
B 2 A 10.0007 ~B 2 A!
26.1 Calculate the free acid normality, N, as follows:
Spgr 5 (2)
C 2 A 10.0010 C 2 A!
~
N 5 ~A 3 N 2 C 3 N !/5 (3)
B A
where:
B = sample plus flask in air, g,
NBS SRM 84h.
C799–99 (2005)
32. Summary of Test Method
where:
A = NaOH solution used in the titration, mL
32.1 A sample aliquot is mixed with a solution containing
N = normality of the NaOH solution,
B ferrousammoniumsulfate,sulfamicacid,phosphoricacid,and
C = HNO solution used in the spike, mL, and
sulfuric acid. The halogens are then steam distilled at a
N = normality of HNO solution.
A 3
temperature of 140°C.
NOTE 2—Negative values of free acid indicate an acid deficiency.
33. Apparatus
27. Precision
33.1 Steam Distillation Apparatus (see Fig. 1).
27.1 The limit of error at the 95% confidence level for a 33.1.1 Distilling Flask, 200-mL with thermometer well.
33.1.2 Condenser.
single determination is 63%.
33.1.3 Heating Mantle.
DETERMINATION OF THORIUM
33.1.4 Steam Boiler, 500-mL flask.
28. Scope
34. Reagents
28.1 The determination of thorium by the arsenazo (III)
34.1 Absorber Solution (4 M Potassium Hydroxide)—
(photometric) method has been discontinued, (see C799-93).
Dissolve 22.4 g KOH pellets in water and dilute to 100 mL.
28.2 As an alternative, thorium can be determined using
34.2 Acid Mixture—Mix0.2 Mferrousammoniumsul-fate-
Inductively Coupled Plasma Mass Spectrometry (ICP-MS).
0.5 M sulfamic acid (s
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.