1、BSI Standards PublicationBS ISO 21613:2015(U, Pu)O2 Powdersand sintered pellets Determination of chlorine andfluorineBS ISO 21613:2015 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of ISO 21613:2015.The UK participation in its preparation was entrusted to TechnicalC
2、ommittee NCE/9, Nuclear fuel cycle technology.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standar
3、ds Institution 2015. Published by BSI StandardsLimited 2015ISBN 978 0 580 76904 7ICS 27.120.20Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 31 July 2015.Amendmen
4、ts issued since publicationDate Text affectedBS ISO 21613:2015 ISO 2015(U, Pu)O2 Powders and sintered pellets Determination of chlorine and fluorinePoudres et pastilles frittes (U,Pu)O2 Dtermination du chlore et du fluorINTERNATIONAL STANDARDISO21613First edition2015-06-15Reference numberISO 21613:2
5、015(E)BS ISO 21613:2015ISO 21613:2015(E)ii ISO 2015 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2015, Published in SwitzerlandAll rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form or by any means, electronic or mechan
6、ical, including photocopying, or posting on the internet or an intranet, without prior written permission. Permission can be requested from either ISO at the address below or ISOs member body in the country of the requester.ISO copyright officeCh. de Blandonnet 8 CP 401CH-1214 Vernier, Geneva, Switz
7、erlandTel. +41 22 749 01 11Fax +41 22 749 09 47copyrightiso.orgwww.iso.orgBS ISO 21613:2015ISO 21613:2015(E)Foreword iv1 Scope . 12 Normative references 13 Principle 14 Reagents 15 Equipment . 45.1 Standard laboratory equipment. 45.5 Ion analysis measuring with selective electrode equipment 55.6 Ion
8、-exchange chromatography system 55.7 Mortar . 56 Operating procedure 66.1 Sample pyrohydrolysis . 66.1.1 Blank test 66.1.2 (U,Pu)O2powder sample 66.1.3 (U,Pu)O2pellet sample . 66.1.4 Pyrohydrolysis . 66.2 Measurement of pyrohydrolysis solutions 86.2.1 Measurement by selective electrode 86.2.2 Measur
9、ement by ionic chromatography . 96.3 Expression of results 96.3.1 Calculation . 96.3.2 Validation limits .106.3.3 Determination limits .106.3.4 Determination uncertainty 117 Test report 11Bibliography .12 ISO 2015 All rights reserved iiiContents PageBS ISO 21613:2015ISO 21613:2015(E)ForewordISO (the
10、 International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committe
11、e has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechni
12、cal standardization.The procedures used to develop this document and those intended for its further maintenance are described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the different types of ISO documents should be noted. This document was drafted in
13、 accordance with the editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. D
14、etails of any patent rights identified during the development of the document will be in the Introduction and/or on the ISO list of patent declarations received (see www.iso.org/patents).Any trade name used in this document is information given for the convenience of users and does not constitute an
15、 endorsement.For an explanation on the meaning of ISO specific terms and expressions related to conformity assessment, as well as information about ISOs adherence to the WTO principles in the Technical Barriers to Trade (TBT) see the following URL: Foreword - Supplementary informationThe committee r
16、esponsible for this document is ISO/TC 85, Nuclear energy, nuclear technologies, and radiological protection, Subcommittee SC 5, Nuclear fuel cycle.iv ISO 2015 All rights reservedBS ISO 21613:2015INTERNATIONAL STANDARD ISO 21613:2015(E)(U, Pu)O2 Powders and sintered pellets Determination of chlorine
17、 and fluorine1 ScopeThis International Standard describes a method for determining chlorine and fluorine in mixed (U,Pu)O2powders and sintered pellets. It is applicable for the analysis of samples containing 5 g.g1to 50 g.g1of chlorine and 2 g.g1to 50 g.g1of fluorine.For UO2powder and sintered pelle
18、ts, refer to ISO 22875.2 Normative referencesThe following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced documen
19、t (including any amendments) applies.ISO 3696, Water for analytical laboratory use Specification and test methodsISO 22875, Nuclear energy Determination of chlorine and fluorine in uranium dioxide powder and sintered pelletsISO 9892, Uranium metal, uranium dioxide powder and pellets, and uranyl nitr
20、ate solutions Determination of fluorine content Fluoride ion selective electrode method3 PrincipleThe samples are pyrohydrolyzed at 850 C 1 000 C in a tubular furnace with steam or moist oxygen. Chlorine and fluorine are trapped as halogenated acids and entrained in an aqueous solution. Chloride and
21、 fluoride ions are measured using selective electrodes or another appropriate method, for instance, ionic chromatography.4 ReagentsUse only reagents of recognized analytical grade.4.1 Demineralised water, complying with at least grade 1 in accordance with ISO 3696 is recommended.4.2 Anhydrous sodium
22、 chloride (NaCl), analytical grade.4.3 Anhydrous sodium fluoride (NaF), analytical grade.4.4 Concentrated sodium hydroxide solution, w(NaOH) = 32 %, relative density approximately 1,35 g.ml1.Concentrated sodium hydroxide solution (4.4) is used to prepare sodium hydroxide solutions (4.4.1, 4.4.2, and
23、 4.4.3). Concentrations of solutions (4.4.1, 4.4.2, and 4.4.3) are examples of reference solutions that are acceptable for use.4.4.1 Sodium hydroxide solution, c(NaOH) = 5 mol.l1.This reagent can also be prepared by using solid sodium hydroxide in various ways. ISO 2015 All rights reserved 1BS ISO 2
24、1613:2015ISO 21613:2015(E)For example, the procedure can be as follows.Pour 460 ml of concentrated sodium hydroxide solution (4.4) into 1 000 ml volumetric flask, dilute to the mark using demineralised water (4.1), and mix.This reagent can also be prepared by dissolving solid sodium hydroxide (4.5)
25、in solution using demineralised water (4.1).4.4.2 Sodium hydroxide solution, c(NaOH) = 0,5 mol.l1.Pour 46 ml of concentrated sodium hydroxide solution (4.4) into 1 000 ml volumetric flask, dilute to the mark using demineralised water (4.1), and mix.4.4.3 Sodium hydroxide solution, c(NaOH) = 0,05 mol
26、.l1.Pour 100 ml of 0,5 mol/l1sodium hydroxide (4.4.2) into 1 000 ml volumetric flask, dilute to the mark using demineralised water (4.1), and mix.4.4.4 Sodium hydroxide solution, c(NaOH) = 104mol.l1(or pH 10).The concentration of solution (4.4.4) is an example of a receiver solution that can be used
27、 for a measurement by chromatography.4.5 Anhydrous sodium hydroxide (NaOH), granules.4.6 Glacial acetic acid, (CH3COOH), relative density approximately 1,06 g.ml1.4.7 Sodium acetate, (CH3COONa) analytical grade.4.8 Buffer solution.Using the following buffer solution is recommended in order to ensure
28、 that the absorbing solution remains alkaline. An example of the procedure to prepare the buffer solution is as follows.Pour 15 ml of acetic acid (4.6) into 1 000 ml polyethylene volumetric flask and dissolve 50 g of sodium acetate (4.7). Adjust the solution volume to about 900 ml with demineralised
29、 water (4.1). Adjust the pH to 5,3 with the 5 mol.l1sodium hydroxide solution (4.4.1), for example, then dilute to the mark using demineralised water (4.1) and mix.pH adjustment can be performed with a different sodium hydroxide solution concentration.Another reagent such as NaOH solution with pheno
30、lphthalein can also be used.4.9 Chloride reference solution.4.9.1 Primary chloride reference solution, c(Cl-) = 0,5 g.l1.Dissolve 166 mg of dry anhydrous sodium chloride (4.2) in demineralised water (4.1). Pour into a 200 ml volumetric flask, then dilute to the mark using demineralised water (4.1) a
31、nd mix.Primary chloride reference solution (4.9.1) is used to prepare chloride reference solutions (4.9.2, 4.9.3, 4.9.4, 4.9.5, and 4.9.6). Concentrations of solutions (4.9.2, 4.9.3, 4.9.4, and 4.9.5) are examples of reference solutions that can be used for calibration of selective electrodes. Exact
32、 concentrations of calibration solutions should be determined by the user based upon the expected concentration of analyte in the NaOH buffer solution.2 ISO 2015 All rights reservedBS ISO 21613:2015ISO 21613:2015(E)4.9.2 Chloride reference solution, c(Cl-) = 35 mg.l1.Pipette 70 ml of the primary ref
33、erence solution (4.9.1) into 1 000 ml flask. Dilute to the mark with the 0,05 mol.l1sodium hydroxide solution (4.4.3) and mix.4.9.3 Chloride reference solution, c(Cl-) = 8 mg.l1.Pipette 16 ml of the primary reference solution (4.9.1) into 1 000 ml flask. Dilute to the mark with the 0,05 mol.l1sodium
34、 hydroxide solution (4.4.3) and mix.4.9.4 Chloride reference solution, c(Cl-) = 2,5 mg.l1.Pipette 5 ml of the primary reference solution (4.9.1) into 1 000 ml flask. Dilute to the mark with the 0,05 mol.l1sodium hydroxide solution (4.4.3) and mix.4.9.5 Chloride reference solution, c(Cl-) = 2 mg.l1.P
35、ipette 25 ml of the reference solution (4.9.3) into a 100 ml flask. Dilute to the mark with the 0,05 mol.l1sodium hydroxide solution (4.4.3) and mix.4.9.6 Chloride reference solution, c(Cl-) = X mg.l1.Other chloride reference solution concentrations may be used. For example, a reference solution can
36、 be prepared by diluting the reference solution of 4.9.1 with the 0,05 mol.l1sodium hydroxide solution (4.4.3) to obtain the reference solution (4.9.6).4.10 Fluoride reference solution.4.10.1 Primary fluoride reference solution, c(F-) = 0,5 g.l1.Dissolve 221 mg of dry anhydrous sodium fluoride (4.3)
37、 in demineralised water (4.1). Pour into a 200 ml volumetric flask, dilute to the mark using demineralised water (4.1), and mix.Primary fluoride reference solution (4.10.1) is used to prepare fluoride reference solutions (4.10.2, 4.10.3, 4.10.4, 4.10.5, and 4.10.6). Concentrations of solutions (4.10
38、.2, 4.10.3, 4.10.4, and 4.10.5) are examples of reference solutions that can be used for calibration of selective electrodes. Exact concentrations of calibration solutions should be determined by the user based upon the expected concentration of analyte in the NaOH buffer solution.4.10.2 Fluoride re
39、ference solution, c(F-) = 5 mg.l1.Pipette 10 ml of the primary reference solution (4.10.1) into 1 000 ml flask. Dilute to the mark with the 0,05 mol.l1sodium hydroxide solution (4.4.3) and mix.4.10.3 Fluoride reference solution, c(F-) = 2,5 mg.l1.Pipette 25 ml of the reference solution (4.10.2) into
40、 a 50 ml flask. Dilute to the mark with the 0,05 mol.l1sodium hydroxide solution (4.4.3) and mix.4.10.4 Fluoride reference solution, c(F-) = 1 mg.l1.Pipette 10 ml of the reference solution (4.10.2) into a 50 ml flask. Dilute to the mark with the 0,05 mol.l1sodium hydroxide solution (4.4.3) and mix.4
41、.10.5 Fluoride reference solution, c(F-) = 0,5 mg.l1.Pipette 10 ml of the reference solution (4.10.2) into a 100 ml flask. Dilute to the mark with the 0,05 mol.l1sodium hydroxide solution (4.4.3) and mix. ISO 2015 All rights reserved 3BS ISO 21613:2015ISO 21613:2015(E)4.10.6 Fluoride reference solut
42、ion, c(F-) = X mg.l1.Other fluoride reference solution concentrations may be used. For example, a reference solution can be prepared by diluting reference solution of 4.10.1 with the 0,05 mol.l1sodium hydroxide solution (4.4.3) to obtain the reference solution (4.10.6).4.11 U308or anhydrous tungsten
43、 acid.Application of halogen free U3O8powder or anhydrous tungsten acid can be used in order to accelerate the pyrohydrolysis reaction.4.12 Concentrated eluent solution for chromatography, 4-hydroxybenzoic acid c(HOC6H4COOH) = 10 mmol.l1and N,N-Diethylethanolamine, c(C2H5)2NCH2CH2CH2OH) = 11 mmol.l1
44、.For example, the procedure to prepare concentrated eluent solution can be as follows.Dissolve 1,38g of 4-hydroxybenzoic acid with 700 ml demineralised water (4.1).Transfer 1,48 ml aliquot of N,N-Diethylethanolamine into 1 000 ml volumetric flask. Add all dissolved 4-hydroxybenzoic acid and dilute t
45、o 1 000 ml with demineralised water (4.1). Homogenize.Prepared solution should be stored in a polyethylene bottle and kept in a refrigerator.Other concentrated eluent solution such as KOH, NaOH, or NaHC03/Na2CO3can also be used.4.13 Standard eluent solutions for chromatography.For example, the proce
46、dure to prepare standard eluent solutions can be as follows.Transfer 50 ml aliquot of concentrated eluent solution (4.12) into a 500 ml volumetric flask and dilute to 500 ml with demineralised water (4.1) (heated to the room temperature before use). Homogenize.The make-up of the standard eluent solu
47、tion is 4-hydroxybenzoic acid, c(HOC6H4COOH) = 1,0 mmol.l1and N,N-Diethylethanolamine, c(C2H5)2NCH2CH2CH2OH) = 1,1 mmol.l1(approximately pH 7,9).Filtration of the solution to remove fine particles before use is recommended.Other standard eluent solutions such as KOH, NaOH, or NaHC03/Na2CO3with diffe
48、rent concentrations can also be used.4.14 Flow gas, pure air or oxygen.5 Equipment5.1 Standard laboratory equipment5.2 Pyrohydrolysis equipment, refer to Figure 1.5.2.1 Tubular furnace, equipped with a calibrated temperature regulator.4 ISO 2015 All rights reservedBS ISO 21613:2015ISO 21613:2015(E)5
49、.2.2 Tube with condenser, Inconel1), platinum, or quartz.5.2.3 Steam generator, consisting of a reservoir for water (4.1) and provisions for heating and temperature regulation to adjust the flow rate of the steam.5.2.4 Combustion boats, of Inconel1), platinum, ceramic, or quartz.5.3 Volumetric flasks or test tube, 10, 50, 100, and 1 000 ml. Flasks of any material can be used after verification of acceptable blank levels of fluoride and chloride.5.4 Balance, capable of reading the nearest 1 mg
