1、Designation: C 759 04Standard Test Methods forChemical, Mass Spectrometric, Spectrochemical, Nuclear,and Radiochemical Analysis of Nuclear-Grade PlutoniumNitrate Solutions1This standard is issued under the fixed designation C 759; the number immediately following the designation indicates the year o
2、foriginal 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 the chemical,mass
3、 spectrometric, 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 Tit
4、ration 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 Meth
5、od 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 Compo
6、sition 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
7、Spectrochemical Test Method 103 to 105Tungsten, Niobium (Columbium), and Tantalum by Spectrochemical Test Method106 to 114Sample Preparation for Spectrographic Analysis for GeneralImpurities123 to 1261.3 This standard does not purport to address all of thesafety concerns, if any, associated with its
8、 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. For specificsafeguard and safety hazard statements, see Section 6.2. Referenced Documents2.1 ASTM Standards:3C 697
9、 Test Methods for Chemical, Mass Spectrometric, andSpectrochemical Analysis of Nuclear-Grade PlutoniumDioxide Powders and PelletsC 852 Guide for Design Criteria for Plutonium GloveboxesC 1009 Guide for Establishing a Quality Assurance Pro-gram for Analytical Chemistry Laboratories Within theNuclear
10、IndustryC 1068 Guide for Qualification of Measurement Methodsby a Laboratory Within the Nuclear IndustryC 1108 Test Method for Plutonium by Controlled-PotentialCoulometryC 1128 Guide for Preparation of Working Reference Mate-rials for Use in the Analysis of Nuclear Fuel CycleMaterialsC 1156 Guide fo
11、r Establishing Calibration for a Measure-ment Method Used to Analyze Nuclear Fuel Cycle Mate-rialsC 1165 Test Method for Determining Plutonium by Con-trolled Potential Coulometry in H2SO4at a PlatinumWorking ElectrodeC 1206 Test Method for Plutonium by Iron (II)/Chromium(VI) Amperometric TitrationC
12、1210 Guide for Establishing a Measurement SystemQuality Control Program for Analytical Chemistry Labo-ratories Within the Nuclear IndustryC 1235 Test Method for Plutonium by Titanium(III)/Cerium(IV) TitrationC 1268 Test Method for Quantitative Determination ofAmericium 241 in Plutonium by Gamma-Ray
13、Spectrom-etryC 1297 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 Cycle and are the direct responsibility of Subcommittee C26.05 onMethods of Test.Current edition appro
14、ved Jan. 1, 2004. Published February 2004. Originallyapproved in 1973. Last previous edition approved in 1998 as C 759 98.2Discontinued as of November 15, 1992.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of
15、 ASTMStandardsvolume information, refer to the standards Document Summary page onthe ASTM website1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.C 1307 Test Method for Plutonium Assay by Plutonium(III)Diode Array SpectrophotometryC 1
16、415 Test Method for238Pu Isotopic Abundance by AlphaSpectrometryC 1432 Test Method for Determination of Impurities inPlutonium: Acid Dissolution, Ion Exchange matrix Sepa-ration, and Inductively Coupled Plasma-Atomic EmissionSpectroscopic (ICP/AES) AnalysisD 1193 Specification for Reagent WaterE 50
17、Practices for Apparatus, Reagents, and Safety Precau-tions for Chemical Analysis of MetalsE 115 Practice for Photographic Processing in OpticalEmission Spectrographic AnalysisE 116 Practice for Photographic Photometry in Spectro-chemical Analysis3. Significance and Use3.1 These test methods are desi
18、gned to show whether agiven material meets the purchasers specifications.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 effe
19、ctive fissile content is in compliance with the purchas-ers specifications.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 equival
20、ent boron content(EBC).4. Committee C-26 Safeguards Statement44.1 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 astechnicall
21、y acceptable for generating safeguards accountabilitymeasurement 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 appropriat
22、e CertifiedReference Materials (CRMs), these procedures can demon-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 u
23、ser of these testmethods to assure that their application to safeguards 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 conf
24、orm to the specifications ofthe Committee on Analytical Reagents of the American Chemi-cal Society, where such specifications are available.5Othergrades may be used, provided it is first ascertained that thereagent is of sufficiently high purity to permit its use withoutlessening the accuracy of the
25、 determination.5.2 Purity of WaterUnless otherwise indicated, referenceto water shall be understood to mean reagent water conformingto Specification D 1193.6. Safety Hazards6.1 Since plutonium bearing materials are radioactive andtoxic, adequate laboratory facilities, gloved boxes, fume hoods,etc.,
26、along with safe techniques, must be used in handlingsamples containing these materials. A detailed 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 Gui
27、de C 852 and in Refs (1) through (3).67. 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 distur
28、b 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.)7.2 Sample size shall be sufficient to perform the following:7.2.1 Assay and
29、 acceptance tests 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 so
30、lution that is uniform 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 CONTR
31、OLLED-POTENTIALCOULOMETRY(This test method was discontinued in 1992 and replaced byTest Method C 1165.)PLUTONIUM BY CONTROLLED-POTENTIALCOULOMETRY(With appropriate sample preparation, controlled-potentialcoulometric measurement as described in Test Method C 1108may be used for plutonium determinatio
32、n.)4Based upon Committee C-26 Safeguards Matrix (C 1009, C 1068, C 1128,C 1156, C 1210, C 1297.).5“Reagent Chemicals, American Chemical Society Specifications,” Am. Chemi-cal Soc., Washington, DC. For suggestions on the testing of reagents not listed bythe American Chemical Society, see “Reagent Che
33、micals and Standards,” by JosephRosin, D. Van Nostrand Co., Inc., New York, NY, and the “United StatesPharmacopeia.”6The boldface numbers in parentheses refer to the list of references at the end ofthese test methods.C759042PLUTONIUM BY AMPEROMETRIC TITRATIONWITH IRON(II)(This test method was discon
34、tinued in 1992 and replaced byTest Method C 1206.)TEST METHOD FOR PLUTONIUM ASSAY BYPLUTONIUM(III) DIODE ARRAYSPECTROPHOTOMETRY(With appropriate sample preparation, the measurementdescribed in Test Method C 1307 may be used for plutoniumdetermination.)FREE ACID BY TITRATION IN AN OXALATESOLUTION8. S
35、cope8.1 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 tocomplex the plutonium, back to the original pH of theammoniu
36、m 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 the pH of the end point of the titration will causeinterfe
37、rence 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 Materials12.1 Ammonium Oxalate Solution, saturated.12.2 Nitric Acid
38、 (3.50 N)Prepare solution by dilutingconcentrated nitric acid (HNO3, sp gr 1.42) with water.Standardize by titrating 0.500-mL aliquots with 0.100 N NaOHsolution.12.3 Sodium Hydroxide Solution (0.100 N)Prepare andstandardize in accordance with Practices E 50.13. Procedure13.1 Transfer 1.0 mL of satur
39、ated 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 pH value for the saturated solution is approxi-mately 6.4
40、.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 to the pH of the ammonium oxalate reagentand record the v
41、olume 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 point and titrate with standard 0.100 N NaOH solutionbac
42、k 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. Precision and Bias15.1 PrecisionOf individual results,
43、6 5 % 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.17. Summary of Test Method17.1 Free acid is determined by potentio
44、metric 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
45、)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 potas-sium iodate (KIO3) in 900 mL of water, adjust the pH to 4.3by adding HNO3(1 + 14), and dilute
46、to 1 L with water.19.4 Sodium Hydroxide ( 0.3 M)Prepare and standardizein accordance with Practices E 50 after making the followingalterations: Use 15 mL of the NaOH solution (50 g/50 mL), andin step 42.2, transfer 1.200 g of National Institute for StandardsC759043and Technology (NIST) potassium aci
47、d phthalate SRM 84 h orits replacement to a 250-mL Erlenmeyer flask instead of 0.4000g.20. Procedure20.1 Pipet 50 mL of KIO3(0.3 M) into a beaker and stirwhile adding an aliquot of sample solution containing nogreater than 50 mg of plutonium.20.2 After precipitation is complete, filter the solutiont
48、hrough either a medium porosity glass frit or a fine texturedacid-washed filter paper and collect the filtrate in a beaker.20.3 Wash the precipitate with two 25-mL portions of 0.3 MKIO3solution, and combine the washings with the filtrate fromstep 20.2.20.4 Dissolve the precipitate in HNO3(sp gr 1.42
49、) or HCl(sp gr 1.19) and transfer to a residue bottle.20.5 Transfer the sample from 20.3 to the titration appara-tus, position the electrodes and a magnetic stirring bar in thesolution, and start the stirrer.20.6 Titrate the free acid in the solution by adding the 0.3 MNaOH solution from a 5-mL buret and plot the titration curve(pH versus mL NaOH solution).20.7 Determine the end point of the titration from themidpoint of the inflection on the titration curve and record thevolume of 0.3 M NaOH solutions by the steps given in 20.5through 20.7 of the procedure.21.
