SIST EN IEC 60746-4:2019

SLOVENSKI STANDARD
SIST EN IEC 60746-4:2019
01-julij-2019
Izražanje lastnosti elektrokemičnih analizatorjev - 4. del: Raztopljeni kisik v vodi
merjen z membranskimi amperometričenimi celicami (IEC 60746-4:2018)
Expression of performance of electrochemical analyzers - Part 4: Dissolved oxygen in
water measured by membrane covered amperometric sensors (IEC 60746-4:2018)
Angabe zum Betriebsverhalten von elektrochemischen Analysatoren - Teil 4: Gelöster
Sauerstoff in Wasser mit Hilfe membranbedeckter amperometrischer Messzellen (IEC
60746-4:2018)
Expression des qualités de fonctionnement des analyseurs électrochimiques - Partie 4:
Oxygène dissous dans l'eau mesuré par des capteurs ampérométriques recouverts
d'une membrane (IEC 60746-4:2018)
Ta slovenski standard je istoveten z: EN IEC 60746-4:2019
ICS:
19.080 Električno in elektronsko Electrical and electronic
preskušanje testing
71.040.10 Kemijski laboratoriji. Chemical laboratories.
Laboratorijska oprema Laboratory equipment
SIST EN IEC 60746-4:2019 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST EN IEC 60746-4:2019

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SIST EN IEC 60746-4:2019


EUROPEAN STANDARD EN IEC 60746-4

NORME EUROPÉENNE

EUROPÄISCHE NORM
March 2019
ICS 71.040.40; 19.080

English Version
Expression of performance of electrochemical analyzers - Part 4:
Dissolved oxygen in water measured by membrane-covered
amperometric sensors
(IEC 60746-4:2018)
Expression des qualités de fonctionnement des analyseurs Angabe zum Betriebsverhalten von elektrochemischen
électrochimiques - Partie 4: Oxygène dissous dans l'eau Analysatoren - Teil 4: Gelöster Sauerstoff in Wasser mit
mesuré par des capteurs ampérométriques recouverts Hilfe membranbedeckter amperometrischer Messzellen
d'une membrane (IEC 60746-4:2018)
(IEC 60746-4:2018)
This European Standard was approved by CENELEC on 2019-01-17. CENELEC 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 CENELEC 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 CENELEC member into its own language and notified to the CEN-CENELEC Management Centre has the
same status as the official versions.
CENELEC members are the national electrotechnical committees of Austria, Belgium, Bulgaria, Croatia, Cyprus, the Czech Republic,
Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia,
Lithuania, Luxembourg, Malta, the Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden,
Switzerland, Turkey and the United Kingdom.


European Committee for Electrotechnical Standardization
Comité Européen de Normalisation Electrotechnique
Europäisches Komitee für Elektrotechnische Normung
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2019 CENELEC All rights of exploitation in any form and by any means reserved worldwide for CENELEC Members.
 Ref. No. EN IEC 60746-4:2019 E

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SIST EN IEC 60746-4:2019
EN IEC 60746-4:2019 (E)
European foreword
The text of document 65B/1128/FDIS, future edition 2 of IEC 60746-4, prepared by SC 65B
"Measurement and control devices" of IEC/TC 65 "Industrial-process measurement, control and
automation" was submitted to the IEC-CENELEC parallel vote and approved by CENELEC as
EN IEC 60746-4:2019.
The following dates are fixed:
• latest date by which the document has to be implemented at national (dop) 2019-10-17
level by publication of an identical national standard or by endorsement
• latest date by which the national standards conflicting with the (dow) 2022-01-17
document have to be withdrawn

Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CENELEC shall not be held responsible for identifying any or all such patent rights.

Endorsement notice
The text of the International Standard IEC 60746-4:2018 was approved by CENELEC as a European
Standard without any modification.
In the official version, for Bibliography, the following note has to be added for the standard indicated:
ISO 9001 NOTE Harmonized as EN ISO 9001
ISO 5814:2012 NOTE Harmonized as EN ISO 5814:2012 (not modified)

2

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SIST EN IEC 60746-4:2019
EN IEC 60746-4:2019 (E)
Annex ZA
(normative)

Normative references to international publications
with their corresponding European publications
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.
NOTE 1  Where an International Publication has been modified by common modifications, indicated by (mod), the relevant
EN/HD applies.
NOTE 2  Up-to-date information on the latest versions of the European Standards listed in this annex is available here:
www.cenelec.eu.

Publication Year Title EN/HD Year
IEC 60746-1 2003 Expression of performance of electrochemical EN 60746-1 2003
analyzers - Part 1: General

3

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SIST EN IEC 60746-4:2019



IEC 60746-4

®


Edition 2.0 2018-12




INTERNATIONAL



STANDARD




NORME



INTERNATIONALE











Expression of performance of electrochemical analyzers –

Part 4: Dissolved oxygen in water measured by membrane-covered

amperometric sensors




Expression des qualités de fonctionnement des analyseurs électrochimiques –

Partie 4: Oxygène dissous dans l'eau mesuré par des capteurs ampérométriques


recouverts d'une membrane













INTERNATIONAL

ELECTROTECHNICAL

COMMISSION


COMMISSION

ELECTROTECHNIQUE


INTERNATIONALE




ICS 19.080; 71.040.40 ISBN 978-2-8322-6274-0




Warning! Make sure that you obtained this publication from an authorized distributor.

Attention! Veuillez vous assurer que vous avez obtenu cette publication via un distributeur agréé.

® Registered trademark of the International Electrotechnical Commission
Marque déposée de la Commission Electrotechnique Internationale

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SIST EN IEC 60746-4:2019
– 2 – IEC 60746-4:2018 © IEC 2018
CONTENTS
FOREWORD . 4
1 Scope . 6
2 Normative references . 6
3 Terms and definitions . 6
3.1 Oxygen sensor properties . 7
3.2 Electronics . 7
3.3 Measurement units and solubility of oxygen . 8
3.4 Test media . 9
4 Influence quantities for membrane covered amperometric sensors . 9
4.1 Temperature . 9
4.2 Pressure . 9
4.3 Dissolved substances . 9
4.4 Flow . 9
5 Procedure for specification . 9
5.1 Zero and span drift . 9
5.2 Additional specifications for the sensor unit . 10
5.2.1 Electrode and sensor materials . 10
5.2.2 Dimensions of the sensor . 10
5.2.3 Permitted temperature and pressure range . 10
5.2.4 Temperature measurement and temperature compensation . 10
5.2.5 Pressure compensation . 10
5.2.6 Zero current . 10
5.2.7 Sensor sensitivity . 10
5.2.8 Stabilization time . 10
5.2.9 Oxygen consumption . 10
5.2.10 Flow rate . 10
5.2.11 Method and extent of sensor regeneration . 10
6 Recommended standard values and ranges of influence quantities affecting the
performance of electronic units . 10
7 Verification of values . 11
7.1 General . 11
7.1.1 General aspects of verification of values . 11
7.1.2 Testing procedure for linearity of the electronic unit . 11
7.1.3 Rated reference conditions for testing . 11
7.2 Simulator for testing electronic units . 11
7.3 Calibration solutions . 11
7.4 Testing procedures for complete analyzer (sensor unit connected to
electronic unit) . 11
7.4.1 Intrinsic uncertainty . 11
7.4.2 Linearity uncertainty . 11
7.4.3 Repeatability . 12
7.4.4 Interference uncertainty (whole analyzer) . 12
7.4.5 Zero drift and span drift . 12
7.4.6 Output fluctuation of the analyzer . 12
7.4.7 Delay times T and 90 % rise or fall times T . 13
10 90
7.4.8 Temperature compensation . 13
7.4.9 Operating uncertainty of the whole analyzer . 14

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IEC 60746-4:2018 © IEC 2018 – 3 –
7.4.10 Determination of the sensor unit residual signal . 14
7.4.11 Oxygen consumption . 14
Annex A (informative) Supplementary general information on amperometric oxygen
sensors . 15
A.1 Sensors' performance characteristics . 15
A.2 Precautions . 16
A.3 Sensor calibration techniques . 16
Annex B (informative) Technique for the preparation of batch calibration standards by
the saturation approach [10] . 18
Annex C (informative) Calibration solutions for low levels of oxygen in water
measurement . 19
C.1 System development [10] . 19
C.2 Description and operation of the system . 19
C.3 Further developments . 19
Bibliography . 25

Figure C.1 – Laboratory rig to produce water with a low level of dissolved oxygen . 21
Figure C.2 – Complete system for laboratory testing dissolved oxygen monitor . 22
Figure C.3 – Dimensions of block A . 23
Figure C.4 – Dimensions of block B . 24

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INTERNATIONAL ELECTROTECHNICAL COMMISSION
____________

EXPRESSION OF PERFORMANCE OF
ELECTROCHEMICAL ANALYZERS –

Part 4: Dissolved oxygen in water measured
by membrane-covered amperometric sensors

FOREWORD
1) The International Electrotechnical Commission (IEC) is a worldwide organization for standardization comprising
all national electrotechnical committees (IEC National Committees). The object of IEC is to promote
international co-operation on all questions concerning standardization in the electrical and electronic fields. To
this end and in addition to other activities, IEC publishes International Standards, Technical Specifications,
Technical Reports, Publicly Available Specifications (PAS) and Guides (hereafter referred to as “IEC
Publication(s)”). Their preparation is entrusted to technical committees; any IEC National Committee interested
in the subject dealt with may participate in this preparatory work. International, governmental and non-
governmental organizations liaising with the IEC also participate in this preparation. IEC collaborates closely
with the International Organization for Standardization (ISO) in accordance with conditions determined by
agreement between the two organizations.
2) The formal decisions or agreements of IEC on technical matters express, as nearly as possible, an international
consensus of opinion on the relevant subjects since each technical committee has representation from all
interested IEC National Committees.
3) IEC Publications have the form of recommendations for international use and are accepted by IEC National
Committees in that sense. While all reasonable efforts are made to ensure that the technical content of IEC
Publications is accurate, IEC cannot be held responsible for the way in which they are used or for any
misinterpretation by any end user.
4) In order to promote international uniformity, IEC National Committees undertake to apply IEC Publications
transparently to the maximum extent possible in their national and regional publications. Any divergence
between any IEC Publication and the corresponding national or regional publication shall be clearly indicated in
the latter.
5) IEC itself does not provide any attestation of conformity. Independent certification bodies provide conformity
assessment services and, in some areas, access to IEC marks of conformity. IEC is not responsible for any
services carried out by independent certification bodies.
6) All users should ensure that they have the latest edition of this publication.
7) No liability shall attach to IEC or its directors, employees, servants or agents including individual experts and
members of its technical committees and IEC National Committees for any personal injury, property damage or
other damage of any nature whatsoever, whether direct or indirect, or for costs (including legal fees) and
expenses arising out of the publication, use of, or reliance upon, this IEC Publication or any other IEC
Publications.
8) Attention is drawn to the Normative references cited in this publication. Use of the referenced publications is
indispensable for the correct application of this publication.
9) Attention is drawn to the possibility that some of the elements of this IEC Publication may be the subject of
patent rights. IEC shall not be held responsible for identifying any or all such patent rights.
International Standard IEC 60746-4 has been prepared by subcommittee 65B: Measurement
and control devices, of IEC technical committee 65: Industrial-process measurement, control
and automation.
This second edition cancels and replaces the first edition published in 1992. This edition
constitutes a technical revision.
This edition includes the following significant technical changes with respect to the previous
edition:
a) terms and definitions have been revised to meet the requirements of ISO/IEC Directives
Part 2:2016.
b) ISO 5814:2012 is cited as reference for solubility tables of dissolved oxygen in water with
variable salt content at different pressure and temperature.

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SIST EN IEC 60746-4:2019
IEC 60746-4:2018 © IEC 2018 – 5 –
The text of this International Standard is based on the following documents:
FDIS Report on voting
65B/1128/FDIS 65B/1138/RVD

Full information on the voting for the approval of this International Standard can be found in
the report on voting indicated in the above table.
This document has been drafted in accordance with the ISO/IEC Directives, Part 2.
A list of all parts in the IEC 60746 series, published under the general title Expression of
performance of electrochemical analyzers, can be found on the IEC website.
The committee has decided that the contents of this document will remain unchanged until the
stability date indicated on the IEC website under "http://webstore.iec.ch" in the data related to
the specific document. At this date, the document will be
• reconfirmed,
• withdrawn,
• replaced by a revised edition, or
• amended.

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EXPRESSION OF PERFORMANCE OF
ELECTROCHEMICAL ANALYZERS –

Part 4: Dissolved oxygen in water measured
by membrane-covered amperometric sensors



1 Scope
This part of IEC 60746 is intended:
• to specify terminology, definitions and requirements for statements by manufacturers for
analyzers, sensor units and electronic units used for the determination of dissolved
oxygen partial pressure or concentration;
• to establish performance tests for such analyzers, sensor units and electronic units;
• to provide basic documents to support the applications of quality assurance standards
1
[1] .
This document applies to analyzers using membrane covered amperometric sensors. It
applies to analyzers suitable for use in water containing liquids, ultrapure waters, fresh or
potable water, sea water or other aqueous solutions, industrial or municipal waste water from
water bodies (e.g. lakes, rivers, estuaries), as well as for industrial process streams and
process liquids. Whilst in principle amperometric oxygen-analyzers are applicable in gaseous
phases, the expression of performance in the gas phase is outside the scope of this
document.
This document is applicable to analyzers specified for permanent installation in any location
(indoors or outdoors) using membrane-covered amperometric sensors.
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.
IEC 60746-1:2003, Expression of performance of electrochemical analyzers – Part 1: General
3 Terms and definitions
For the purposes of this document, the terms and definitions given in IEC 60746-1 and the
following apply.
ISO and IEC maintain terminological databases for use in standardization at the following
addresses:
• IEC Electropedia: available at http://www.electropedia.org/
• ISO Online browsing platform: available at http://www.iso.org/obp
___________
1
 Numbers in square brackets refer to the Bibliography.

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IEC 60746-4:2018 © IEC 2018 – 7 –
3.1 Oxygen sensor properties
3.1.1
membrane covered amperometric sensor
sensor with a membrane covered metal cathode, a metal or metal/metal salt anode, optional
auxilliary or reference electrodes and temperature sensors
Note 1 to entry: The electrochemical reduction of molecular oxygen occurs at the membrane-covered cathode.
The metal or metal/metal salt anode provides a well-defined, electrochemically reversible oxidation reaction within
the special filling electrolyte solution of the sensor. A gas-permeable membrane is employed to separate the
electrolyte filling solution from the test medium to avoid contamination and to achieve a stable diffusion potential.
In the case of applications in the gaseous phase the unit, volume fraction (v/v) are used.
Note 2 to entry: The cell can function as an electrochemical two-electrode cell, or as a potentiostatic three-
electrode cell, or either as a galvanic cell. Within potentiostatic three-electrode cells, a high-impedance, current-
free reference electrode is additionally implied to optimize the polarization voltage.
Note 3 to entry: Membrane-covered amperometric sensors are provided with temperature sensors located at the
active sites of the electrode cells being in thermal contact with the media to be measured.
3.1.2
sensor sensitivity
change in electrode current of the amperometric cell caused by the application of a partial
pressure of oxygen
3.1.3
zero current of sensor
current delivered by the sensor when the dissolved oxygen concentration or partial pressure
is zero
Note 1 to entry: The zero current is expressed in µA or in nA.
3.1.4
polarization
voltage to be applied to an amperometric cell during a time period to increase the stability of
the sensor
3.1.5
stabilization time
time period necessary for obtaining a stable measurement after reconnecting the sensor unit
to the electronic unit for polarization purposes (see 3.1.4)
Note 1 to entry: Regeneration of the sensor with a new membrane or an electrolyte change or installation of a
replacement sensor will require a subsequent stabilization time.
3.1.6
oxygen consumption
electrochemical reduction of molecular oxygen at the cathode of amperometric oxygen
sensors
3.2 Electronics
3.2.1
electronic unit
electronic device of an electrochemical two-electrode cell comprises a stabilized DC voltage
source and an electronic circuitry with a low impedance, direct current amplifier and optional
microprocessor circuitries
Note 1 to entry: If the electronic unit of the analyzer comprises a microprocessor device, the detected
amperometric signal will be digitised and evaluated to analyse the oxygen content.
Note 2 to entry: To quantify the amperometric signal of the oxygen reduction, software-based algorithmic routines
or data sets comprising solubility tables of oxygen in water (with consideration of temperature, pressure and
salinity) [2] and a vapour pressure table of water are used.

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3.2.2
auxiliary electronics
electronic devices provided for potentiostatic circuitries and for temperature and pressure
transducers
Note 1 to entry: In electronic devices for three-electrode cells, additional potentiostatic circuitries are
implemented.
3.3 Measurement units and solubility of oxygen
3.3.1
partial pressure
units for the expression of the oxygen partial pressure (pO ):
2
millibar (mbar) or kilopascal (kPa)
Note 1 to entry: In the case of special applications, the units mm Hg (Torr) and inch Hg may be used with known
conversion ratio [2].
Note 2 to entry: In the case of applications in the gaseous phase the unit, volume fraction (v/v) are used.
Volume fraction is the quotient of the volume of a specified component and the sum of the volumes of all
components of a gas mixture before mixing, all volumes referring to the pressure and the temperature of the gas
mixture. Volume fraction will be expressed in %. The volume fraction and volume concentration take the same
value if, at the same state conditions, the sum of the component volumes before mixing and the volume of the
mixture are equal. However, because the mixing of two or more non-ideal gases at the same state conditions is
usually accompanied by a slight contraction (or, less frequently, a slight expansion), this is not generally the case.
[SOURCE: EN 50104:2010, 3.1.5]
3.3.2
concentration
units for expression of the dissolved oxygen concentration (cO ):
2
.
−1
parts per million (ppm) = milligram kg
.
−1
parts per billion (ppb) = µg kg
Note 1 to entry: The mass of the test medium means in this case the mass of the sample water, including salts or
other substances dissolved or suspended in it.
Note 2 to entry: Although ppm (parts per million) units are used in this document, it is sometimes convenient to
.
−3 −3
use the units of milligrams per litre (mg dm ) or of micrograms per litre (µg·dm ).
3.3.3
oxygen saturation index
unit for the expression of the dissolved oxygen in percent (%) to express the relative
saturation of the actual oxygen concentration (parts per million), as fraction of the theoretical
oxygen concentration (parts per million) of the air-saturated solution at the actual conditions
of pressure, temperature and salinity
3.3.4
oxygen solubility
maximal possible dissolved oxygen concentration of the water sample in contact and
equilibrium with air (air-saturated solution) at the actual conditions of pressure, temperature
and salinity
Note 1 to entry: The oxygen solubility in water is dependent on other dissolved organic and inorganic compounds,
dissolved electrolytes, salt-content in seawater (salinity) [2].

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3.4 Test media
3.4.1
test medium
stable mixture of gases (nitrogen, nitrogen + oxygen), saturated with water vapour or
humidifed reference air showing a known concentration or a known partial pressure of oxygen
used for performance tests
Note 1 to entry: The concentration (see 3.3.2) or partial pressure or volume fraction (see 3.3.1) of dissolved
oxygen and its uncertainty range shall be known.
3.4.2
calibration solution
stable mixture of humidified (saturated with water vapour) gases (nitrogen, oxygen) or
humidifed reference air exhibiting a known stable concentration or partial pressure or volume
fraction of oxygen (with tracable uncertainties) used for calibration of the analyzer
3.4.3
zero oxygen solution
solution with dissolved gas (pure nitrogen) or dissolved molecular or ionogenic compounds
(substitutes) used to eliminate the content of free oxygen or a gaseous phase (pure nitrogen)
saturated with water vapourSymbols
4 Influence quantities for membrane covered amperometric sensors
4.1 Temperature
the temperature has
In addition to the temperature dependent solubility-effect of oxygen [2],
an impact on membrane-covered amperometric sensors owing to the temperature-dependent
variation of the diffusion of oxygen molecules at the liquid interfaces of membrane-covered
sensors.
4.2 Pressure
Pressure affects the dissolved oxygen saturation value, or respectively the maximal oxygen
concentration or
...