1、Designation: C759 10Standard Test Methods forChemical, Mass Spectrometric, Spectrochemical, Nuclear,and Radiochemical Analysis of Nuclear-Grade PlutoniumNitrate Solutions1This standard is issued under the fixed designation C759; the number immediately following the designation indicates the year ofo
2、riginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 These test methods cover procedures for the chemical,mass sp
3、ectrometric, spectrochemical, nuclear, and radiochemi-cal analysis of nuclear-grade plutonium nitrate solutions todetermine compliance with specifications.1.2 The analytical procedures appear in the following order:SectionsPlutonium by Controlled-Potential Coulometry2Plutonium by Amperometric Titrat
4、ion with Iron(II)2Plutonium by Diode Array SpectrophotometryFree Acid by Titration in an Oxalate Solution 8 to 15Free Acid by Iodate Precipitation-Potentiometric TitrationTest Method16 to 22Uranium by Arsenazo I Spectrophotometric Test Method 23 to 33Thorium by Thorin Spectrophotometric Test Method
5、34 to 42Iron by 1,10-Phenanthroline Spectrophotometric Test Method 43 to 50Impurities by ICP-AESChloride by Thiocyanate Spectrophotometric Test Method 51 to 58Fluoride by Distillation-Spectrophotometric Test Method 59 to 66Sulfate by Barium Sulfate Turbidimetric Test Method 67 to 74Isotopic Composit
6、ion by Mass Spectrometry 75 to 76Plutonium 238 Isotopic Abundance by Alpha SpectrometryAmericium-241 by Extraction and Gamma Counting 77 to 85Americium-241 by Gamma Counting 86 to 94Gamma-Emitting Fission Products, Uranium, and Thorium byGamma-Ray Spectroscopy94 to 102Rare Earths by Copper Spark Spe
7、ctrochemical Test Method 103 to 105Tungsten, Niobium (Columbium), and Tantalum by Spectrochemical Test Method106 to 114Sample Preparation for Spectrographic Analysis for GeneralImpurities115 to 1181.3 The values stated in SI units are to be regarded asstandard. The values given in parentheses are fo
8、r informationonly.1.4 This standard 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 u
9、se. For specificsafeguard and safety hazard statements, see Section 6.2. Referenced Documents2.1 ASTM Standards:3C697 Test Methods for Chemical, Mass Spectrometric, andSpectrochemical Analysis of Nuclear-Grade PlutoniumDioxide Powders and PelletsC852 Guide for Design Criteria for Plutonium Gloveboxe
10、sC1009 Guide for Establishing a QualityAssurance Programfor Analytical Chemistry Laboratories Within the NuclearIndustryC1068 Guide for Qualification of Measurement Methods bya Laboratory Within the Nuclear IndustryC1108 Test Method for Plutonium by Controlled-PotentialCoulometryC1128 Guide for Prep
11、aration of Working Reference Mate-rials for Use in Analysis of Nuclear Fuel Cycle MaterialsC1156 Guide for Establishing Calibration for a Measure-ment Method Used to Analyze Nuclear Fuel Cycle Mate-rialsC1165 Test Method for Determining Plutonium byControlled-Potential Coulometry in H2SO4at a Platin
12、umWorking ElectrodeC1206 Test Method for Plutonium by Iron (II)/Chromium(VI) Amperometric TitrationC1210 Guide for Establishing a Measurement System Qual-ity Control Program forAnalytical Chemistry LaboratoriesWithin the Nuclear IndustryC1235 Test Method for Plutonium by Titanium(III)/Cerium(IV) Tit
13、ration4C1268 Test Method for Quantitative Determination of Am-ericium 241 in Plutonium by Gamma-Ray SpectrometryC1297 Guide for Qualification of Laboratory Analysts forthe Analysis of Nuclear Fuel Cycle Materials1These test methods are under the jurisdiction of ASTM Committee C26 onNuclear Fuel Cycl
14、e and are the direct responsibility of Subcommittee C26.05 onMethods of Test.Current edition approved June 1, 2010. Published July 2010. Originally approvedin 1973. Last previous edition approved in 2004 as C759 04. DOI: 10.1520/C0759-10.2Discontinued as of November 15, 1992.3For referenced ASTM sta
15、ndards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandardsvolume information, refer to the standards Document Summary page onthe ASTM website4Withdrawn. The last approved version of this historical standard is referencedon www.a
16、stm.org.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.C1307 Test Method for PlutoniumAssay by Plutonium (III)Diode Array SpectrophotometryC1415 Test Method for238Pu IsotopicAbundance ByAlphaSpectrometryC1432 Test Method for Determi
17、nation of Impurities inPlutonium: Acid Dissolution, Ion Exchange Matrix Sepa-ration, and Inductively Coupled Plasma-Atomic EmissionSpectroscopic (ICP/AES) AnalysisD1193 Specification for Reagent WaterE50 Practices for Apparatus, Reagents, and Safety Consid-erations for Chemical Analysis of Metals, O
18、res, andRelated MaterialsE115 Practice for Photographic Processing in Optical Emis-sion Spectrographic Analysis4E116 Practice for Photographic Photometry in Spectro-chemical Analysis43. Significance and Use3.1 These test methods are designed to show whether agiven material meets the purchasers speci
19、fications.3.1.1 An assay is performed to determine whether thematerial has the specified plutonium content.3.1.2 Determination of the isotopic content of the plutoniumin the plutonium-nitrate solution is made to establish whetherthe effective fissile content is in compliance with the purchas-ers spe
20、cifications.3.1.3 Impurity content is determined by a variety of meth-ods to ensure that the maximum concentration limit of speci-fied impurities is not exceeded. Determination of impurities isalso required for calculation of the equivalent boron content(EBC).4. Committee C26 Safeguards Statement54.
21、1 The material (plutonium nitrate) to which these testmethods apply is subject to nuclear safeguards regulationsgoverning its possession and use. The following analyticalprocedures in these test methods have been designated astechnically acceptable for generating safeguards accountabilitymeasurement
22、 data: Plutonium by Controlled-Potential Cou-lometry; Plutonium by Amperometric Titration with Iron(II);Plutonium by Diode Array Spectrophotometry and IsotopicComposition by Mass Spectrometry.4.2 When used in conjunction with appropriate CertifiedReference Materials (CRMs), these procedures can demo
23、n-strate traceability to the national measurement base. However,adherence to these procedures does not automatically guaran-tee regulatory acceptance of the resulting safeguards measure-ments. It remains the sole responsibility of the user of these testmethods to assure that their application to saf
24、eguards has theapproval of the proper regulatory authorities.5. Reagents and Materials5.1 Purity of ReagentsReagent grade chemicals shall beused in all test methods. Unless otherwise indicated, it isintended that all reagents shall conform to the specifications ofthe Committee onAnalytical Reagents
25、of theAmerican Chemi-cal Society, where such specifications are available.6Othergrades may be used, provided it is first ascertained that thereagent is of sufficiently high purity to permit its use withoutlessening the accuracy of the determination.5.2 Purity of WaterUnless otherwise indicated, refe
26、renceto water shall be understood to mean reagent water conformingto Specification D1193.6. Safety Hazards6.1 Since plutonium bearing materials are radioactive andtoxic, adequate laboratory facilities, gloved boxes, fume hoods,etc., along with safe techniques, must be used in handlingsamples contain
27、ing these materials.Adetailed discussion of allthe precautions necessary is beyond the scope of these testmethods; however, personnel who handle these materialsshould be familiar with such safe handling practices as aregiven in Guide C852 and in Refs (1) through (3).76.2 Adequate laboratory faciliti
28、es, such as fume hoods andcontrolled ventilation, along with safe techniques, must be usedin this procedure. Extreme care should be exercised in usinghydrofluoric and other hot, concentrated acids. Use of propergloves is recommended. Refer to the laboratorys chemicalhygiene plan and other applicable
29、 guidance for handlingchemical and radioactive materials and for the management ofradioactive, mixed, and hazardous waste.6.3 Hydrofluoric acid is a highly corrosive acid that canseverely burn skin, eyes, and mucous membranes. Hydrofluo-ric acid is similar to other acids in that the initial extent o
30、f aburn depends on the concentration, the temperature, and theduration of contact with the acid. Hydrofluoric acid differsfrom other acids because the fluoride ion readily penetrates theskin, causing destruction of deep tissue layers. Unlike otheracids that are rapidly neutralized, hydrofluoric acid
31、 reactionswith tissue may continue for days if left untreated. Due to theserious consequence of hydrofluoric acid burns, prevention ofexposure or injury of personnel is the primary goal. Utilizationof appropriate laboratory controls (hoods) and wearing ad-equate personal protective equipment to prot
32、ect from skin andeye contact is essential.7. Sampling7.1 A sample representative of the lot shall be taken fromeach lot into a container or multiple containers that are of suchcomposition that corrosion, chemical change, radiolytic de-composition products, and method of loading or sealing willnot di
33、sturb the chemical or physical properties of the sample.(A flame-sealed quartz vial that is suitable for accommodatingpressure resulting from radiolytic decomposition is generallyconsidered to be an acceptable sample container.)5Based upon Committee C26 Safeguards Matrix (C1009, C1068, C1128, C1156,
34、C1210, C1297.).6Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, 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 St
35、ates Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.7The boldface numbers in parentheses refer to the list of references at the end ofthese test methods.C759 1027.2 Sample size shall be sufficient to perform the following:7.2.1 Assay and acceptance tests
36、 at the sellers plant,7.2.2 Assay and acceptance tests at the purchasers plant,and7.2.3 Referee tests in the event they become necessary.7.3 All samples shall be identified clearly, including thesellers lot number.7.3.1 A lot is defined as any quantity of aqueous plutoniumnitrate solution that is un
37、iform in isotopic, chemical, andphysical characteristics by virtue of having been mixed in sucha manner as to be thoroughly homogeneous.7.3.2 All containers used for a lot shall be identifiedpositively as containing material from a particular homoge-neous solution.PLUTONIUM BY CONTROLLED-POTENTIALCO
38、ULOMETRY(This test method was discontinued in 1992 and replaced byTest Method C1165.)PLUTONIUM BY CONTROLLED-POTENTIALCOULOMETRY(With appropriate sample preparation, controlled-potentialcoulometric measurement as described in Test Method C1108may be used for plutonium determination.)PLUTONIUM BY AMP
39、EROMETRIC TITRATIONWITH IRON(II)(This test method was discontinued in 1992 and replaced byTest Method C1206.)TEST METHOD FOR PLUTONIUM ASSAY BYPLUTONIUM(III) DIODE ARRAYSPECTROPHOTOMETRY(With appropriate sample preparation, the measurementdescribed in Test Method C1307 may be used for plutoniumdeter
40、mination.)FREE ACID BY TITRATION IN AN OXALATESOLUTION8. Scope8.1 This test method covers the determination of free acid inplutonium nitrate solutions (4, 5).9. Summary of Test Method9.1 Free acid is determined by titrating an aliquot of sample,which contains an excess of ammonium oxalate added toco
41、mplex the plutonium, back to the original pH of theammonium oxalate solution with standard sodium hydroxidesolution. Micropipets and microburets are required to measurethe small volume of sample and titrant used.10. Interferences10.1 Any metal ions not complexed by oxalate which formprecipitates at
42、the pH of the end point of the titration will causeinterference in this test method.NOTE 1A “rule of thumb” is that 1 mL of saturated ammoniumoxalate solution will complex 6.4 mg of plutonium.11. Apparatus11.1 Magnetic Stirrer.11.2 Microburet.11.3 Micropipets.11.4 pH Meter.12. Reagents and Materials
43、12.1 Ammonium Oxalate Solution, saturated.12.2 Nitric Acid (3.50 N)Prepare solution by dilutingconcentrated nitric acid (HNO3, sp gr 1.42) with water.Standardize by titrating 0.500-mLaliquots with 0.100 N NaOHsolution.12.3 Sodium Hydroxide Solution (0.100 N)Prepare andstandardize in accordance with
44、Practices E50.13. Procedure13.1 Transfer 1.0 mL of saturated ammonium oxalate solu-tion to a small vial and dilute to about 2 mL with water.13.2 Add a stirring bar and insert the electrodes and startstirrer. When the pH value becomes stable, record the value asthe pH of reagent.NOTE 2Normally, the p
45、H value for the saturated solution is approxi-mately 6.4.13.3 Add 20 L of sample to the vial, rinse the pipetthoroughly with water, and stir the solution for 1 min.13.4 Titrate with 0.100 N NaOH solution to within one pHunit of the end point; then, by adding successively smallerincrements, titrate t
46、o the pH of the ammonium oxalate reagentand record the volume of titrant.NOTE 3Allow time for the pH reading to stabilize between additionsof titrant as the end point is approached.13.5 Make a daily check of the system by adding 20 L of3.50 N HNO3to a sample that has already been titrated to theend
47、point and titrate with standard 0.100 N NaOH solutionback to the same pH.14. Calculation14.1 Calculate the free acid (H+, N) as follows:H1, N 5 A 3 N!/V (1)where:A = microlitres of standard NaOH solution required totitrate sample,N = normality of NaOH standard solution, andV = volume of sample, L.15
48、. Precision and Bias15.1 PrecisionOf individual results, 65 % at the 95 %confidence level.15.2 Bias99.4 %.FREE ACID BY IODATE PRECIPITATION-POTENTIOMETRIC TITRATION TEST METHOD16. Scope16.1 This test method covers the determination of free acidin strong acid solutions of plutonium nitrate.C759 10317
49、. Summary of Test Method17.1 Free acid is determined by potentiometric titration withstandard sodium hydroxide solution after precipitation andsubsequent removal of plutonium (up to 50 mg) as plutoniumiodate.18. Interferences18.1 Any hydrolyzable ions that are not precipitated withiodate will interfere.19. Reagents and Materials19.1 Hydrochloric Acid (sp gr 1.19)Concentrated hydro-chloric acid (HCl).19.2 Nitric Acid (1 + 14)Dilute 14 volumes of water with1 volume of concentrated nitric acid (HNO3, sp gr 1.42).19.3 Potassium Iodate (0.3 M)Dissolve 64.2 g of p
