Standard Test Methods for Chemical, Mass Spectrometric, Spectrochemical, Nuclear, and Radiochemical Analysis of Nuclear-Grade Uranyl Nitrate Solutions

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 Uranium by Ferrous Sulfate Reduction-Potassium 7 to 14 Dichromate Titrimetry Uranium by Ignition Gravimetry 15 to 21 Specific Gravity by Pycnometry 22 to 27 Free Acid by Oxalate Complexation 28 to 34 Thorium by the Arsenazo (III) (Photometric) Method 35 to 42 Chromium by the Diphenylcarbazide (Photometric) Method 43 to 49 Molybdenum by the Thiocyanate (Photometric) Method 50 to 56 Halogens Separation by Steam Distillation 57 to 61 Fluorine by Specific Ion Electrode 62 to 68 Halogen Distillate Analysis: Chloride, Bromide, and Iodide by 69 to 75 Amperometric Microtitrimetry Bromine by the Fluorescein (Photometric) Method 76 to 84 Sulfate Sulfur by (Photometric) Turbidimetry 85 to 92 Phosphorus by the Molybdenum Blue (Photometric) Method 93 to 100 Silicon by the Molybdenum Blue (Photometric) Method 101 to 108 Carbon by Persulfate Oxidation-Acid Titrimetry 109 to 116 Impurities by Emission Spectroscopy 117 to 120 Boron by Emission Spectrography 121 to 127 Impurity Elements by Spark Source Mass Spectrography 128 to 134 Isotopic Composition by Multiple Filament Surface-Ionization 135 to 140 Mass Spectrometry Uranium-232 by Alpha Spectrometry 141 to 147 Total Alpha Activity by Direct Alpha Counting 148 to 154 Fission Product Activity by Beta and Gamma Counting 155 to 161 Entrained Organic Matter by Infrared Spectrophotometry 162 to 174
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.

General Information

Status
Historical
Publication Date
27-Sep-1999
Technical Committee
Drafting Committee
Current Stage
Ref Project

Relations

Buy Standard

Standard
ASTM C799-99e1 - Standard Test Methods for Chemical, Mass Spectrometric, Spectrochemical, Nuclear, and Radiochemical Analysis of Nuclear-Grade Uranyl Nitrate Solutions
English language
14 pages
sale 15% off
Preview
sale 15% off
Preview

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
e1
Designation:C799–99
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 (e) indicates an editorial change since the last revision or reapproval.
e NOTE—Section 1.2 was editorially corrected in September 1999.
1. Scope bility of regulatory limitations prior to use. Specific precau-
tionary statements are given in Section 5.
1.1 These test methods cover procedures for the chemical,
mass spectrometric, spectrochemical, nuclear, and radiochemi-
2. Referenced Documents
cal analysis of nuclear-grade uranyl nitrate solution to deter-
2.1 ASTM Standards:
mine compliance with specifications.
C696 TestMethodsforChemical,MassSpectrometric,and
1.2 Theanalyticalproceduresappearinthefollowingorder:
Spectrochemical Analysis of Nuclear-Grade Uranium Di-
Sections
oxide Powders and Pellets
Determination of Uranium 7
Specific Gravity by Pycnometry 15-20
C761 Test Methods for Chemical, Mass Spectrometric,
Free Acid by Oxalate Complexation 21-27
Spectrochemical, Nuclear, and RadiochemicalAnalysis of
Determination of Thorium 28
Uranium Hexafluoride
Determination of Chromium 29
Determination of Molybdenum 30
C788 Specification for Nuclear-Grade Uranyl Nitrate So-
Halogens Separation by Steam Distillation 31-35 2
lution
Fluoride by Specific Ion Electrode 36-42
C1219 TestMethodsforArsenicInUraniumHexafluoride
Halogen Distillate Analysis: Chloride, Bromide, and Iodide by 43
Amperometric Microtitrimetry
C1233 Practice for Determining Equivalent Boron Con-
Determination of Chloride and Bromide 44
tents of Nuclear Materials
Determination of Sulfur by X-Ray Fluorescence 45
C1254 Test Method for the Determination of Uranium In
Sulfate Sulfur by (Photometric) Turbidimetry 46
Phosphorus by the Molybdenum Blue (Photometric) Method 54-61
Mineral Acids By X-Ray Fluorescence
Silicon by the Molybdenum Blue (Photometric) Method 62-69
C1267 TestMethodforUraniumByIron(II)Reductionin
Carbon by Persulfate Oxidation-Acid Titrimetry 70
PhosphoricAcid Followed By Chromium (VI)Titration in
Conversion to U O 71-74
3 8
Boron by Emission Spectrography 75-81
the Presence of Vanadium
Impurity Elements by Spark Source Mass Spectrography 82
C1287 Test Method for Determination of Impurities in
Isotopic Composition by Thermal Ionization Mass Spectrometry 83
Uranium-232 by Alpha Spectrometry 84-90 Uranium Dioxide By Inductively Coupled Plasma Mass
Total Alpha Activity by Direct Alpha Counting 91-97
Spectrometry
Fission Product Activity by Beta Counting 98-104
C1295 Test Method for Gamma Energy Emission from
Entrained Organic Matter by Infrared Spectrophotometry 105
Fission Products in Uranium Hexafluoride and Uranyl
Fission Product Activity by Gamma Counting 106
Determination of Arsenic 107
Nitrate Solution
Determination of Impurities for the EBC Calculation 108
C1296 Test Method for the Determination of Sulfur in
Determination of Technetium 99 109
Determination of Plutonium and Neptunium 110 Uranium Oxides and Uranyl Nitrate Solutions By X-Ray
Fluorescence (XRF)
1.3 This standard does not purport to address all of the
C1380 TestMethodforDeterminationofUraniumContent
safety concerns, if any, associated with its use. It is the
and Isotopic Composition By Isotope Dilution Mass Spec-
responsibility of the user of this standard to establish appro-
trometry
priate safety and health practices and determine the applica-
C1413 Test Method for Isotopic Analysis of Hydrolysed
Uranium Hexafluoride and Uranyl Nitrate Solutions By
Thermal Ionization Mass Spectrometry
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 Jan. 10, 1999. Published February 1999. Originally
published as C799–75. Last previous edition C799–93. Annual Book of ASTM Standards, Vol 12.01.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
C799
D1193 Specification for Reagent Water 4. Reagents
E12 Terminology Relating to Density and Specific Gravity
4.1 Purity of Reagents—Reagent grade chemicals shall be
of Solids, Liquids, and Gases
used in all tests. Unless otherwise indicated, it is intended that
E50 Practices forApparatus, Reagents, and Safety Precau-
all reagents shall conform to the specifications of the Commit-
tions for Chemical Analysis of Metals
tee onAnalytical Reagents of theAmerican Chemical Society,
E 60 Practice for Photometric and Spectrophotometric
where such specifications are available. Other grades may be
Methods for Chemical Analysis of Metals
used, provided it is first ascertained that the reagent is of
E115 Practice for Photographic Processing in Optical
sufficiently high purity to permit its use without lessening the
Emission Spectrographic Analysis
accuracy of the determination.
E116 Practice for Photographic Photometry in Spectro-
4.2 Purity of Water—Unlessotherwiseindicated,references
chemical Analysis
towatershallbeunderstoodtomeanreagentwaterconforming
E131 Terminology Relating to Molecular Spectroscopy
to Specification D1193.
E168 Practices for General Techniques of Infrared Quanti-
tative Analysis
5. Safety Precautions
E275 Practice for Describing and Measuring Performance
5.1 Use of this standard does not relieve the user of the
of Ultraviolet, Visible, and Near Infrared Spectrophotom-
obligation to be aware of and to conform to all health and
eters
safety requirements.
2.2 American Chemical Society Specification:
5.2 The user should also be cognizant of and adhere to all
Reagent Chemicals
federal,state,andlocalregulationsforprocessing,shipping,or
2.3 Other Documents:
in any way using uranyl nitrate solutions.
ISO 7097 Determination of Uranium in Uranium Product
Solutions and Solids with Cerium IV Oxidation Titrimet- 6. Sampling
ric Method
6.1 Criteria for sampling this material are given in Specifi-
cation C788.
3. Significance and Use
DETERMINATION OF URANIUM
3.1 Uranyl nitrate solution is used as a feed material for
conversion to the hexafluoride as well as for direct conversion
7. Scope
to the oxide. In order to be suitable for this purpose, the
material must meet certain criteria for uranium content, isoto- 7.1 Uraniumcanbedeterminedusingiron(II)reductionand
pic composition, acidity, radioactivity, and impurity content. dichromate titration. Test Method C1267 can be used.
These methods are designed to show whether a given material 7.2 Uranium can also be determined using cerium (IV)
meets the specifications for these items described in Specifi- oxidation titrimetry. ISO 7097 Test Method can be used.
cation C788. 7.3 UraniumcanalsobedeterminedbyX-RayFluorescence
3.1.1 An assay is performed to determine whether the using Test Method C1254.
material has the specified uranium content. 7.4 Previous sections have been deleted.
3.1.2 Determination of the isotopic content of the uranium
URANIUM BY IGNITION GRAVIMETRY
is made to establish whether the effective fissile content is in
accordance with the purchaser’s specifications.
8. Scope
3.1.3 Acidity, organic content, and alpha, beta, and gamma
8.1 Thistestmethodcoversthedeterminationofuraniumin
activity are measured to establish that they do not exceed their
maximum limits. nuclear-grade uranyl nitrate solution. Appropriate size sample
aliquots are chosen to obtain 5 to 10 g of U O .
3.1.4 Impurity content is determined to ensure that the
3 8
maximum concentration limit of certain impurity elements is
9. Summary of Test Method
not exceeded. Impurity concentrations are also required for
calculationoftheequivalentboroncontent(EBC),andthetotal
9.1 The uranyl nitrate solution is evaporated to dryness,
equivalent boron content (TEBC).
ignited to U O , and weighed. Corrections are made for any
3 8
impurities present (1, 2).
10. Interferences
Annual Book of ASTM Standards, Vol 11.01.
4 10.1 The weight of U O is corrected for the nonvolatile
3 8
Annual Book of ASTM Standards, Vol 15.05.
impurities present as determined by spectrographic analysis.
Annual Book of ASTM Standards, Vol 03.05.
Annual Book of ASTM Standards, Vol 14.01.
10.2 Volatile anions that are difficult to decompose require
Reagent Chemicals, American Chemical Society Specifications, American
an extended ignition period.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
11. Apparatus
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
11.1 Heat Lamp, infrared.
MD.
11.2 Hot Plate.
Available from American National Standards Institute, 11 W. 42nd St., 13th
Floor, New York, NY 10036. 11.3 Muffle Furnace.
C799
12. Procedure 18.5 Leave the flask in the water bath an additional 10 min
to make sure that the bath temperature has been reached.
12.1 Transfer a weighed portion of uranyl nitrate solution
18.6 Dry and weigh the flask to the nearest 0.1 mg.
containing 5 to 10 g of uranium into a preweighed platinum
18.7 Repeat 18.2-18.6 using boiled and cooled distilled
dish and add 2 drops of HF (48%).
water instead of the uranyl nitrate solution.
12.2 Positionthedishundertheheatlampandevaporatethe
solution to dryness.
19. Calculation
12.3 Placethedishonahotplatewithasurfacetemperature
19.1 Very accurate determinations of specific gravity re-
of about 300°C and heat until most of the nitrate has decom-
quire that vacuo corrections be made, but if a median correc-
posed.
tion figure in terms of grams per grams of sample is applied to
12.4 Transfer the dish to a muffle furnace and ignite for 2 h
the solution weights in all cases the resulting error will not
at 900°C.
exceed 0.05%.
12.5 Remove the dish to a desiccator and allow to cool to
room temperature. B 2 A 10.0007 ~B 2 A!
Spgr 5 (2)
C 2 A 10.0010 ~C 2 A!
12.6 Weigh the dish; then repeat 12.4-12.6 until a constant
weight is obtained.
where:
B 5 sample plus flask in air, g,
13. Calculation
A 5 flask in air, g,
13.1 Calculate the uranium content as follows:
C 5 water plus flask in air, g,
0.0007 g/g 5 correction factor applicable for densities of
Uranium,g/g 5 ~~B 2 C!/A! D (1)
1.3 to 1.5, and
where:
0.0010 g/g 5 correction factor for water.
A 5 sample, g,
B 5 U O obtained, g,
20. Precision
3 8
C 5 impurity-element oxides, g, and
20.1 The limit of error at the 95% level for a single
D 5 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
SPECIFIC GRAVITY BY PYCNOMETRY of up to 5 moles of acid to 1 mole of uranium.
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
the delta pH method to obtain the inflection point (3).
16. Summary of Test Method
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 9
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.
18.4 Use a finely drawn glass dropper to adjust the liquid
volume to the mark. NBS SRM 84h.
C799
25.3 Addaspikeofsufficient2.0 NstandardHNO tomake DETERMINATION OF MOLYBDENUM
the sample definitely acid if the sample is neutral or acid
30. Scope
deficient.
30.1 The determination of molybdenum by the thiocyanate
25.4 AddpulverizedK C O ·H Oslowlyandwithconstant
2 2 4 2
stirring until a pH of 4.7 to 4.9 is reached. (photometric) method has been discontinued, (See C799-93).
30.2 As an alternative, molybdenum can be determined
25.5 Immerse the titration beaker in an ice bath. (Titrations
using ICP-MS. Test Method C1287 can be used.
made at room temperature are possible but are less sharp.)
30.3 As an alternative, molybdenum can be determined
25.6 Titrate with 0.3 N NaOH using 0.20-mL increments
usingICP-AES.TestMethodC761,sections251to271canbe
and determine the inflection point by the delta pH or “analyti-
used providing a tranformation to U O as described hereafter
3 8
cal” method.
in sections 71-74.Adirect conversion to the amonium fluoride
NOTE 1—Thistestmethodoflocatingtheendpointdependsonthefact
plus nitric acid solution can also be used, (see C761, section
2 2
thatthesecondderivative D pH/Dvol iszeroatthepointwheretheslope
251).
DpH/Dvol is a maximum.
30.4 Previous sections have been deleted.
26. Calculation
HALOGENS SEPARATION BY STEAM
26.1 Calculate the free acid normality, N, as follows: DISTILLATION
N 5 A 3 N 2 C 3 N /5 (3)
~ !
B A
31. Scope
where:
31.1 This test method covers the separation of the halogens
A 5 NaOH solution used in the titration, mL
by means of a steam distillation.
N 5 normality of the NaOH solution,
B
C 5 HNO solution used in the spike, mL, and
32. Summary
...

Questions, Comments and Discussion

Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.