1、Designation: C 799 99 (Reapproved 2005)Standard Test Methods forChemical, Mass Spectrometric, Spectrochemical, Nuclear,and Radiochemical Analysis of Nuclear-Grade Uranyl NitrateSolutions1This standard is issued under the fixed designation C 799; the number immediately following the designation indic
2、ates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 These test methods cover procedures for th
3、e chemical,mass spectrometric, spectrochemical, nuclear, and radiochemi-cal analysis of nuclear-grade uranyl nitrate solution to deter-mine compliance with specifications.1.2 The analytical procedures appear in the following order:SectionsDetermination of Uranium 7Specific Gravity by Pycnometry 15-2
4、0Free Acid by Oxalate Complexation 21-27Determination of Thorium 28Determination of Chromium 29Determination of Molybdenum 30Halogens Separation by Steam Distillation 31-35Fluoride by Specific Ion Electrode 36-42Halogen Distillate Analysis: Chloride, Bromide, and Iodide byAmperometric Microtitrimetr
5、y43Determination of Chloride and Bromide 44Determination of Sulfur by X-Ray Fluorescence 45Sulfate Sulfur by (Photometric) Turbidimetry 46Phosphorus by the Molybdenum Blue (Photometric) Method 54-61Silicon by the Molybdenum Blue (Photometric) Method 62-69Carbon by Persulfate Oxidation-Acid Titrimetr
6、y 70Conversion to U3O871-74Boron by Emission Spectrography 75-81Impurity Elements by Spark Source Mass Spectrography 82Isotopic Composition by Thermal Ionization Mass Spectrometry 83Uranium-232 by Alpha Spectrometry 84-90Total Alpha Activity by Direct Alpha Counting 91-97Fission Product Activity by
7、Beta Counting 98-104Entrained Organic Matter by Infrared Spectrophotometry 105Fission Product Activity by Gamma Counting 106Determination of Arsenic 107Determination of Impurities for the EBC Calculation 108Determination of Technetium 99 109Determination of Plutonium and Neptunium 1101.3 This standa
8、rd does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. Specific precau-tionary state
9、ments are given in Section 5.2. Referenced Documents2.1 ASTM Standards:2C 696 Test Methods for Chemical, Mass Spectrometric, andSpectrochemical Analysis of Nuclear-Grade Uranium Di-oxide Powders and PelletsC 761 Test Methods for Chemical, Mass Spectrometric,Spectrochemical, Nuclear, and Radiochemica
10、l Analysis ofUranium HexafluorideC 788 Specification for Nuclear-Grade Uranyl Nitrate So-lutionC 1219 Test Methods for Arsenic In Uranium HexafluorideC 1233 Practice for Determining Equivalent Boron Con-tents of Nuclear MaterialsC 1254 Test Method for the Determination of Uranium InMineral Acids By
11、X-Ray FluorescenceC 1267 Test Method for Uranium By Iron (II) Reduction inPhosphoric Acid Followed By Chromium (VI) Titration inthe Presence of VanadiumC 1287 Test Method for Determination of Impurities inUranium Dioxide By Inductively Coupled Plasma MassSpectrometryC 1295 Test Method for Gamma Ener
12、gy Emission fromFission Products in Uranium Hexafluoride and UranylNitrate SolutionC 1296 Test Method for the Determination of Sulfur inUranium Oxides and Uranyl Nitrate Solutions By X-RayFluorescence (XRF)C 1380 Test Method for Determination of Uranium Contentand Isotopic Composition By Isotope Dil
13、ution Mass Spec-trometryC 1413 Test Method for Isotopic Analysis of HydrolysedUranium Hexafluoride and Uranyl Nitrate Solutions ByThermal Ionization Mass SpectrometryD 1193 Specification for Reagent WaterE12 Terminology Relating to Density and Specific Gravity1These test methods are under the jurisd
14、iction of ASTM Committee C26 onNuclear Fuel Cycle and are the direct responsibility of Subcommittee C26.05 onMethods of Test.Current edition approved June 1, 2005. Published October 2005. Originallyapproved in 1975. Last previous edition approved in 1999 as C 799 99e1.2For referenced ASTM standards,
15、 visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 194
16、28-2959, United States.of Solids, Liquids, and GasesE60 Practice for Photometric and SpectrophotometricMethods for Chemical Analysis of Metals2.2 American Chemical Society Specification:Reagent Chemicals32.3 Other Documents:ISO 7097 Determination of Uranium in Uranium ProductSolutions and Solids wit
17、h Cerium IV Oxidation Titrimet-ric Method43. Significance and Use3.1 Uranyl nitrate solution is used as a feed material forconversion to the hexafluoride as well as for direct conversionto the oxide. In order to be suitable for this purpose, thematerial must meet certain criteria for uranium content
18、, isoto-pic composition, acidity, radioactivity, and impurity content.These methods are designed to show whether a given materialmeets the specifications for these items described in Specifi-cation C 788.3.1.1 An assay is performed to determine whether thematerial has the specified uranium content.3
19、.1.2 Determination of the isotopic content of the uraniumis made to establish whether the effective fissile content is inaccordance with the purchasers specifications.3.1.3 Acidity, organic content, and alpha, beta, and gammaactivity are measured to establish that they do not exceed theirmaximum lim
20、its.3.1.4 Impurity content is determined to ensure that themaximum concentration limit of certain impurity elements isnot exceeded. Impurity concentrations are also required forcalculation of the equivalent boron content (EBC), and the totalequivalent boron content (TEBC).4. Reagents4.1 Purity of Re
21、agentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.3Other grades may beused, provide
22、d it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.4.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water conformingto Specification D 1193.5. Safety Precau
23、tions5.1 Use of this standard does not relieve the user of theobligation to be aware of and to conform to all health andsafety requirements.5.2 The user should also be cognizant of and adhere to allfederal, state, and local regulations for processing, shipping, orin any way using uranyl nitrate solu
24、tions.6. Sampling6.1 Criteria for sampling this material are given in Specifi-cation C 788.DETERMINATION OF URANIUM7. Scope7.1 Uranium can be determined using iron (II) reduction anddichromate titration. Test Method C 1267 can be used.7.2 Uranium can also be determined using cerium (IV)oxidation tit
25、rimetry. ISO 7097 Test Method can be used.7.3 Uranium can also be determined by X-Ray Fluorescenceusing Test Method C 1254.7.4 Previous sections have been deleted.URANIUM BY IGNITION GRAVIMETRY8. Scope8.1 This test method covers the determination of uranium innuclear-grade uranyl nitrate solution. A
26、ppropriate size samplealiquots are chosen to obtain 5 to 10 g of U3O8.9. Summary of Test Method9.1 The uranyl nitrate solution is evaporated to dryness,ignited to U3O8, and weighed. Corrections are made for anyimpurities present (1, 2).10. Interferences10.1 The weight of U3O8is corrected for the non
27、volatileimpurities present as determined by spectrographic analysis.10.2 Volatile anions that are difficult to decompose requirean extended ignition period.11. Apparatus11.1 Heat Lamp, infrared.11.2 Hot Plate.11.3 Muffle Furnace.12. Procedure12.1 Transfer a weighed portion of uranyl nitrate solution
28、containing 5 to 10 g of uranium into a preweighed platinumdish and add 2 drops of HF (48 %).12.2 Position the dish under the heat lamp and evaporate thesolution to dryness.12.3 Place the dish on a hot plate with a surface temperatureof about 300C and heat until most of the nitrate has decom-posed.12
29、.4 Transfer the dish to a muffle furnace and ignite for 2 hat 900C.12.5 Remove the dish to a desiccator and allow to cool toroom temperature.12.6 Weigh the dish; then repeat 12.4-12.6 until a constantweight is obtained.3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical So
30、ciety, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
31、MD.4Available from American National Standards Institute, 11 W. 42nd St., 13thFloor, New York, NY 10036.C 799 99 (2005)213. Calculation13.1 Calculate the uranium content as follows:Uranium, g/g 5 B 2 C!/A! D (1)where:A = sample, g,B =U3O8obtained, g,C = impurity-element oxides, g, andD = gravimetric
32、 factor, grams of uranium/grams ofU3O8(varies according to uranium enrichment).14. Precision14.1 The limit of error at the 95 % confidence level for asingle determination is 60.03 %.SPECIFIC GRAVITY BY PYCNOMETRY15. Scope15.1 This test method covers the determination of thespecific gravity of a solu
33、tion of uranyl nitrate to 60.0004.16. Summary of Test Method16.1 A known volume of the solution adjusted at a con-trolled temperature is weighed and compared to the weight ofwater measured in the same container (Terminology E12).17. Apparatus17.1 Volumetric Flasks, 50-mL, Class A.17.2 Water Bath, te
34、mperature controlled to 60.1C at atemperature slightly above normal room temperature, andprovided with clips for holding volumetric flasks.18. Procedure18.1 Weigh the clean, dry volumetric flask and its stopper tothe nearest 0.1 mg.18.2 Fill the volumetric flask with the uranyl nitrate solutionto a
35、point close to the volume mark, using a thinstemmedfunnel and a glass dropper.18.3 Place the stoppered volumetric flask in the water bathfor 30 min.18.4 Use a finely drawn glass dropper to adjust the liquidvolume to the mark.18.5 Leave the flask in the water bath an additional 10 minto make sure tha
36、t the bath temperature has been reached.18.6 Dry and weigh the flask to the nearest 0.1 mg.18.7 Repeat 18.2-18.6 using boiled and cooled distilledwater instead of the uranyl nitrate solution.19. Calculation19.1 Very accurate determinations of specific gravity re-quire that vacuo corrections be made,
37、 but if a median correc-tion figure in terms of grams per grams of sample is applied tothe solution weights in all cases the resulting error will notexceed 0.05 %.Sp gr 5B 2 A 1 0.0007 B 2 A!C 2 A 1 0.0010 C 2 A!(2)where:B = sample plus flask in air, g,A = flask in air, g,C = water plus flask in air
38、, g,0.0007 g/g = correction factor applicable for densities of1.3 to 1.5, and0.0010 g/g = correction factor for water.20. Precision20.1 The limit of error at the 95 % level for a singledetermination is 60.03 %.FREE ACID BY OXALATE COMPLEXATION21. Scope21.1 This test method covers the determination o
39、f the freeacid content of uranyl nitrate solutions that may contain a ratioof up to 5 moles of acid to 1 mole of uranium.22. Summary of Test Method22.1 To a diluted solution of uranyl nitrate, solid, pulverizedpotassium oxalate is added until a pH of about 4.7 is reached.The solution is then titrate
40、d with standard NaOH solution bythe delta pH method to obtain the inflection point (3).23. Apparatus23.1 pH Meter, with glass and calomel electrodes.23.2 Buret, Class A, 50-mL.24. Reagents24.1 Nitric Acid (2.0 N)Dilute 130 mL of HNO3(sp gr1.42) to 1 L with water. Standardize with sodium hydroxidesol
41、ution (see 24.3).24.2 Potassium Oxalate (K2C2O4H2O), crystals.24.3 Sodium Hydroxide Solution (0.3 N)Dissolve 12.0 gof NaOH in 1 L of water. Standardize with acid potassiumphthalate.525. Procedure25.1 Transfer a 5-mL sample aliquot into a 250-mL beaker.25.2 Add 100 mL of distilled water or such volum
42、e that theuranium concentration will be between 7 and 50 g/L.25.3 Add a spike of sufficient 2.0 N standard HNO3to makethe sample definitely acid if the sample is neutral or aciddeficient.25.4 Add pulverized K2C2O4H2O slowly and with constantstirring until a pH of 4.7 to 4.9 is reached.25.5 Immerse t
43、he titration beaker in an ice bath. (Titrationsmade at room temperature are possible but are less sharp.)25.6 Titrate with 0.3 N NaOH using 0.20-mL incrementsand determine the inflection point by the delta pH or “analyti-cal” method.NOTE 1This test method of locating the end point depends on the fac
44、tthat the second derivative D2pH/Dvol2is zero at the point where the slopeDpH/Dvol is a maximum.26. Calculation26.1 Calculate the free acid normality, N, as follows:N 5 A 3 NB2 C 3 NA!/5 (3)5NBS SRM 84h.C 799 99 (2005)3where:A = NaOH solution used in the titration, mLNB= normality of the NaOH soluti
45、on,C = HNO3solution used in the spike, mL, andNA= normality of HNO3solution.NOTE 2Negative values of free acid indicate an acid deficiency.27. Precision27.1 The limit of error at the 95 % confidence level for asingle determination is 63%.DETERMINATION OF THORIUM28. Scope28.1 The determination of tho
46、rium by the arsenazo (III)(photometric) method has been discontinued, (see C 799-93).28.2 As an alternative, thorium can be determined usingInductively Coupled Plasma Mass Spectrometry (ICP-MS).See Test Method C 1287.28.3 Previous sections have been deleted.DETERMINATION OF CHROMIUM29. Scope29.1 The
47、 determination of chromium by the diphenyl car-bazide method has been discontinued, (see C 799-93).29.2 As an alternative, chromium can be determined usinginductively coupled plasma atomic emission spectrometry(ICP-AES). Test Method C 761 can be used providing atransformation to U3O8so described her
48、eafter in sections117120 A direct conversion to the amonium fluoride plusnitric acid solution can also be used, (see C 761).29.3 As an alternative, chromium can be determined usingatomic absorption spectroscopy. Test Method C 761 can beused.29.4 As an alternative, chromium can be determined usingICP
49、-MS. Test Method C 1287 can be used.29.5 Previous sections have been deleted.DETERMINATION OF MOLYBDENUM30. Scope30.1 The determination of molybdenum by the thiocyanate(photometric) method has been discontinued, (See C 799-93).30.2 As an alternative, molybdenum can be determinedusing ICP-MS. Test Method C 1287 can be used.30.3 As an alternative, molybdenum can be determinedusing ICP-AES.Test Method C 761, sections 251 to 271 can beused providing a tranformation to U3O8as described hereafterin sections 71-74. A direct conversion to the amonium fluorideplus nitric a
