Nuclear energy - Nuclear fuel technology - Determination of plutonium in nitric acid solutions by spectrophotometry (ISO 9463:2019)

This document specifies an analytical method by spectrophotometry, for determining the plutonium concentration in nitric acid solutions, with spectrophotometer implemented in hot cell and glove box allowing the analysis of high activity solutions. Commonly, the method is applicable, without interference, even in the presence of numerous cations, for a plutonium concentration higher than 0,5 mg·l−1 in the original sample with a standard uncertainty, with coverage factor k = 1, less than 5 %.
The method is intended for process controls at the different steps of the process in a nuclear fuel reprocessing plant or in other nuclear facilities.

Kernenergie - Kernbrennstofftechnologie - Spektrophotometrische Plutoniumbestimmung in Salpetersäurelösungen (ISO 9463:2019)

Énergie nucléaire - Technologie du combustible nucléaire - Détermination du plutonium dans les solutions d'acide nitrique par spectrophotométrie (ISO 9463:2019)

Le présent document spécifie une méthode d'analyse par spectrophotométrie, destinée à déterminer la concentration en plutonium dans des solutions d'acide nitrique, le spectrophotomètre étant mis en œuvre dans des chaînes blindées et des boîtes à gants permettant l'analyse de solutions de hautes activités. La méthode est habituellement applicable, sans interférence, même en présence de nombreux cations, pour une concentration en plutonium supérieure à 0,5 mg·l−1 dans l'échantillon d'origine avec une incertitude, avec un facteur d'élargissement k = 1, de moins de 5 %.
La méthode est destinée aux contrôles à différents stades du processus dans une usine de retraitement de combustible nucléaire ou dans d'autres installations nucléaires.

Jedrska energija - Tehnologija jedrskih goriv - Določevanje plutonija v raztopinah dušikove kisline s spektrofotometrijo (ISO 9463:2019)

General Information

Status
Published
Public Enquiry End Date
30-Nov-2020
Publication Date
21-Feb-2021
Technical Committee
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
18-Feb-2021
Due Date
25-Apr-2021
Completion Date
22-Feb-2021

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SLOVENSKI STANDARD
SIST EN ISO 9463:2021
01-april-2021

Jedrska energija - Tehnologija jedrskih goriv - Določevanje plutonija v raztopinah

dušikove kisline s spektrofotometrijo (ISO 9463:2019)

Nuclear energy - Nuclear fuel technology - Determination of plutonium in nitric acid

solutions by spectrophotometry (ISO 9463:2019)

Énergie nucléaire - Technologie du combustible nucléaire - Détermination du plutonium

dans les solutions d'acide nitrique par spectrophotométrie (ISO 9463:2019)
Ta slovenski standard je istoveten z: EN ISO 9463:2021
ICS:
27.120.30 Cepljivi materiali in jedrska Fissile materials and nuclear
gorivna tehnologija fuel technology
SIST EN ISO 9463:2021 en,fr,de

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST EN ISO 9463:2021
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SIST EN ISO 9463:2021
EN ISO 9463
EUROPEAN STANDARD
NORME EUROPÉENNE
February 2021
EUROPÄISCHE NORM
ICS 27.120.30
English Version
Nuclear energy - Nuclear fuel technology - Determination
of plutonium in nitric acid solutions by spectrophotometry
(ISO 9463:2019)
Énergie nucléaire - Technologie du combustible
nucléaire - Détermination du plutonium dans les
solutions d'acide nitrique par spectrophotométrie (ISO
9463:2019)
This European Standard was approved by CEN on 18 January 2021.

CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this

European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references

concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN

member.

This European Standard exists in three official versions (English, French, German). A version in any other language made by

translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management

Centre has the same status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,

Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway,

Poland, Portugal, Republic of North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and

United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels

© 2021 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 9463:2021 E

worldwide for CEN national Members.
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SIST EN ISO 9463:2021
EN ISO 9463:2021 (E)
Contents Page

European foreword ....................................................................................................................................................... 3

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SIST EN ISO 9463:2021
EN ISO 9463:2021 (E)
European foreword

The text of ISO 9463:2019 has been prepared by Technical Committee ISO/TC 85 "Nuclear energy,

nuclear technologies, and radiological protection” of the International Organization for Standardization

(ISO) and has been taken over as EN ISO 9463:2021 by Technical Committee CEN/TC 430 “Nuclear

energy, nuclear technologies, and radiological protection” the secretariat of which is held by AFNOR.

This European Standard shall be given the status of a national standard, either by publication of an

identical text or by endorsement, at the latest by August 2021, and conflicting national standards shall

be withdrawn at the latest by August 2021.

Attention is drawn to the possibility that some of the elements of this document may be the subject of

patent rights. CEN shall not be held responsible for identifying any or all such patent rights.

According to the CEN-CENELEC Internal Regulations, the national standards organizations of the

following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria,

Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland,

Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Republic of

North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the

United Kingdom.
Endorsement notice

The text of ISO 9463:2019 has been approved by CEN as EN ISO 9463:2021 without any modification.

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SIST EN ISO 9463:2021
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SIST EN ISO 9463:2021
INTERNATIONAL ISO
STANDARD 9463
Third edition
2019-01
Nuclear energy — Nuclear fuel
technology — Determination of
plutonium in nitric acid solutions by
spectrophotometry
Énergie nucléaire — Technologie du combustible nucléaire —
Détermination du plutonium dans les solutions d'acide nitrique par
spectrophotométrie
Reference number
ISO 9463:2019(E)
ISO 2019
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SIST EN ISO 9463:2021
ISO 9463:2019(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2019

All rights reserved. Unless otherwise specified, or required in the context of its implementation, no part of this publication may

be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, 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 ISO’s member body in the country of the requester.
ISO copyright office
CP 401 • Ch. de Blandonnet 8
CH-1214 Vernier, Geneva
Phone: +41 22 749 01 11
Fax: +41 22 749 09 47
Email: copyright@iso.org
Website: www.iso.org
Published in Switzerland
ii © ISO 2019 – All rights reserved
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SIST EN ISO 9463:2021
ISO 9463:2019(E)
Contents Page

Foreword ........................................................................................................................................................................................................................................iv

1 Scope ................................................................................................................................................................................................................................. 1

2 Normative references ...................................................................................................................................................................................... 1

3 Terms and definitions ..................................................................................................................................................................................... 1

4 Principle ........................................................................................................................................................................................................................ 1

5 Chemical conditions .......................................................................................................................................................................................... 1

5.1 Stability of Pu(VI) ................................................................................................................................................................................. 1

5.2 Rate of oxidation of Pu(IV) to Pu(VI) ................................................................................................................................... 2

5.3 Destruction of the excess oxidant ........................................................................................................................................... 2

5.4 Comparison of Ce(IV) and Ag(II) ............................................................................................................................................. 2

5.5 Molar extinction coefficient of Pu(VI) ................................................................................................................................. 2

6 Reagents ........................................................................................................................................................................................................................ 3

6.1 General ........................................................................................................................................................................................................... 3

6.2 Common reagents for methods using silver oxide or cerium as oxidant ............................................. 3

6.3 Reagents for method using silver oxide as oxidant ................................................................................................. 3

6.4 Reagents for method using Ce(IV) as oxidant .............................................................................................................. 3

7 Apparatus ..................................................................................................................................................................................................................... 4

8 Test procedure ........................................................................................................................................................................................................ 4

8.1 Preparation of the different solutions................................................................................................................................. 4

8.1.1 Plutonium calibration solution ............................................................................................................................ 4

8.1.2 Sample solutions .............................................................................................................................................................. 5

8.2 Spectrophotometer setup .............................................................................................................................................................. 6

8.3 Measurements ......................................................................................................................................................................................... 6

8.3.1 Background measurement ...................................................................................................................................... 6

8.3.2 Measurements on the calibration solution ............................................................................................... 7

8.3.3 Measurements on the sample solution ......................................................................................................... 7

9 Expression of the result................................................................................................................................................................................. 7

9.1 Calculation of the concentration of plutonium in the sample ........................................................................ 7

9.2 Reproducibility ....................................................................................................................................................................................... 8

9.3 Detection limit ......................................................................................................................................................................................... 8

10 Interferences ............................................................................................................................................................................................................ 8

10.1 Anions ............................................................................................................................................................................................................. 8

10.2 Cations ............................................................................................................................................................................................................ 9

Annex A (informative) Preparation of silver (II) oxide (AgO) .................................................................................................11

Bibliography .............................................................................................................................................................................................................................12

© ISO 2019 – All rights reserved iii
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SIST EN ISO 9463:2021
ISO 9463:2019(E)
Foreword

ISO (the 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

committee 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

electrotechnical 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 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. Details 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 endorsement.

For an explanation of the voluntary nature of standards, the meaning of ISO specific terms and

expressions related to conformity assessment, as well as information about ISO's adherence to the

World Trade Organization (WTO) principles in the Technical Barriers to Trade (TBT) see www .iso

.org/iso/foreword .html.

This document was prepared by Technical Committee ISO/TC 85, Nuclear energy, nuclear technologies,

and radiological protection, Subcommittee SC 5, Nuclear installations, processes and technologies.

This third edition cancels and replaces the second edition (ISO 9463:2009), which has been technically

revised. The main change compared to the previous edition is the use of silver (II) oxide powder for the

plutonium valence adjustment.

Any feedback or questions on this document should be directed to the user’s national standards body. A

complete listing of these bodies can be found at www .iso .org/members .html.
iv © ISO 2019 – All rights reserved
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SIST EN ISO 9463:2021
INTERNATIONAL STANDARD ISO 9463:2019(E)
Nuclear energy — Nuclear fuel technology —
Determination of plutonium in nitric acid solutions by
spectrophotometry
1 Scope

This document specifies an analytical method by spectrophotometry, for determining the plutonium

concentration in nitric acid solutions, with spectrophotometer implemented in hot cell and glove

box allowing the analysis of high activity solutions. Commonly, the method is applicable, without

interference, even in the presence of numerous cations, for a plutonium concentration higher than

0,5 mg·l in the original sample with a standard uncertainty, with coverage factor k = 1, less than 5 %.

The method is intended for process controls at the different steps of the process in a nuclear fuel

reprocessing plant or in other nuclear facilities.
2 Normative references

The following documents are referred to in the text in such a way that some or all of their content

constitutes requirements of this document. For dated references, only the edition cited applies. For

undated references, the latest edition of the referenced document (including any amendments) applies.

ISO 1042, Laboratory glassware — One-mark volumetric flasks
3 Terms and definitions
No terms and definitions are listed in this document.

ISO and IEC maintain terminological databases for use in standardization at the following addresses:

— ISO Online browsing platform: available at https: //www .iso .org/obp
— IEC Electropedia: available at http: //www .electropedia .org/
4 Principle

Plutonium is quantitatively oxidized to the hexavalent state either with cerium (IV) or with silver

oxide. The excess of silver oxide is destroyed by the addition of sulfamic acid. The optical density

of the plutonium (VI) (PuO ) absorption peak at the wavelength of 831 nm is then measured on a

spectrophotometer. The result is obtained by comparison to a calibration performed under similar

conditions (with the same nitrate content).
5 Chemical conditions
5.1 Stability of Pu(VI)

Pu(VI) is very stable under the operating conditions of the method over the range

−1 + −1
2 mol·l < c(H ) < 5 mol·l .
© ISO 2019 – All rights reserved 1
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SIST EN ISO 9463:2021
ISO 9463:2019(E)
5.2 Rate of oxidation of Pu(IV) to Pu(VI)

The rate of oxidation by Ce(IV) decreases as the acidity increases. With the reagent quantities stated in

−1 −1

the method, the oxidation is complete in 2 min or more in 2 mol·l or 3 mol·l nitric acid.

As an example, the oxidation of Pu(IV) in 4 mol·l nitric acid is complete in between 10 min and 15 min

[2]
when the Ce/Pu initial ratio is higher than 20 .
With silver oxide, the oxidation is very fast, much faster than with Ce(IV).
2+ + 4+ 3+

In addition, the Ag /Ag redox potential is higher than that of Ce /Ce and is better adapted to cope

with the presence of organic traces in solution.

On the other hand, cerium presents the advantage to be stable in sulfuric acid so that it can be added as

a precise quantity in solution.
5.3 Destruction of the excess oxidant

With cerium the excess reagent and product Ce(III), does not interfere (no absorption above 450 nm)

[2]
and does not need to be destroyed .

With silver oxide as oxidant, the excess reagent shall be destroyed by reaction with a small excess of

[2]
sulfamic acid or rise of temperature .
5.4 Comparison of Ce(IV) and Ag(II)

As regards Pu(IV) oxidation into Pu(VI), the reactivity and use of Ce(IV) and Ag(II) are compared in

Table 1, in order to guide the analyst in the selection of the best reactant for oxidation.

Table 1 — Comparison of Ce(IV) and Ag(II)
Oxidizer Ag(II) Ce(IV)
Introduction of reactants − +
Spectral interferences − +
Oxidizing power ++ +
Oxidation kinetics ++ −
Oxidizer excess destruction Sulfamic acid or rise of temperature Not necessary
Operating temperature Room temperature
5.5 Molar extinction coefficient of Pu(VI)

The nominal molar extinction coefficient i.e. the molar attenuation coefficient of Pu(VI) in nitric acid

−1 −1 −1 −1[3]

solution varies between 400 l·mol ·cm and 500 l·mol ·cm , with a very narrow full width at half

maximum (FWHM) of about 4 nm.

The molar extinction coefficient and therefore absorbance depends upon a number of parameters, for

example:

— The nitrate ion concentration. The decrease in molar extinction coefficient becomes more

−1 −1

pronounced at higher nitrate levels. At about 3 mol·l nitrate, an increase of 0,1 mol·l in the total

nitrate content causes a decrease of about 0,7 % in the molar extinction coefficient.

— The acidity. This change is generally less than 0,1 % for a free acid change of 0,1 mol·l . Thus the

influence of free acidity is an order of magnitude less than that of the nitrate content.

1) The molar extinction coefficient is the absorbance of light by a chemical species at a given wavelength and for

a 1 cm light path. It is an intrinsic property of the species. The SI unit of molar attenuation coefficient is the square

2 −1 −1 −2 −1 −1

metre per mole (m ·mol ), but in practice, it is usually taken as the mol ⋅cm or the l.mol ⋅cm .

2 © ISO 2019 – All rights reserved
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SIST EN ISO 9463:2021
ISO 9463:2019(E)

— The temperature. The decrease in molar extinction coefficient is about 0,5 % per degree Celsius.

6 Reagents
6.1 General
All reagents shall be of analytical grade.

This procedure requires that measurements are made in nitric acid medium as this permits either

Ce(IV) or silver oxide to be used as oxidant and is convenient for most applications. Commonly the

sample is diluted into
...

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