EN ISO 13032:2012

SLOVENSKI STANDARD
01-maj-2012
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Petroleum products - Determination of low concentration of sulfur in automotive fuels -
Energy-dispersive X-ray fluorescence spectrometric method (ISO 13032:2012)
Mineralölerzeugnisse - Bestimmung niedriger Schwefelgehalte in Kraftstoffen -
Energiedispersives Röntgenfluoreszenzspektrometrieverfahren (ISO 13032:2012)
Produits pétroliers - Détermination de la teneur en soufre en faible concentration dans
les carburants pour automobiles - Méthode spectrométrique de fluorescence de rayons X
dispersive en énergie (ISO 13032:2012)
Ta slovenski standard je istoveten z: EN ISO 13032:2012
ICS:
75.160.20 7HNRþDJRULYD Liquid fuels
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EUROPEAN STANDARD
EN ISO 13032
NORME EUROPÉENNE
EUROPÄISCHE NORM
March 2012
ICS 75.160.20
English Version
Petroleum products - Determination of low concentration of
sulfur in automotive fuels - Energy-dispersive X-ray fluorescence
spectrometric method (ISO 13032:2012)
Produits pétroliers - Détermination de la teneur en soufre Mineralölerzeugnisse - Bestimmung niedriger
en faible concentration dans les carburants pour Schwefelgehalte in Kraftstoffen - Energiedispersives
automobiles - Méthode spectrométrique de fluorescence de Röntgenfluoreszenzspektrometrieverfahren (ISO
rayons X dispersive en énergie (ISO 13032:2012) 13032:2012)
This European Standard was approved by CEN on 29 February 2012.

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, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom.

EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2012 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 13032:2012: E
worldwide for CEN national Members.

Contents Page
Foreword .3
Foreword
This document (EN ISO 13032:2012) has been prepared by Technical Committee CEN/TC 19 “Gaseous and
liquid fuels, lubricants and related products of petroleum, synthetic and biological origin” the secretariat of
which is held by NEN, in collaboration with Technical Committee ISO/TC 28 " Petroleum products and
lubricants".
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 September 2012, and conflicting national standards shall be
withdrawn at the latest by September 2012.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. CEN [and/or CENELEC] 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, Romania, Slovakia, Slovenia, Spain,
Sweden, Switzerland, Turkey and the United Kingdom.
INTERNATIONAL ISO
STANDARD 13032
First edition
2012-03-01
Petroleum products — Determination of
low concentration of sulfur in automotive
fuels — Energy-dispersive X-ray
fluorescence spectrometric method
Produits pétroliers — Détermination de la teneur en soufre en faible
concentration dans les carburants pour automobiles — Méthode
spectrométrique de fluorescence de rayons X dispersive en énergie
Reference number
ISO 13032:2012(E)
©
ISO 2012
ISO 13032:2012(E)
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means,
electronic or mechanical, including photocopying and microfilm, without permission in writing from either ISO at the address below or ISO’s
member body in the country of the requester.
ISO copyright office
Case postale 56 • CH-1211 Geneva 20
Tel. + 41 22 749 01 11
Fax + 41 22 749 09 47
E-mail copyright@iso.org
Web www.iso.org
Published in Switzerland
ii © ISO 2012 – All rights reserved

ISO 13032:2012(E)
Contents Page
Foreword .iv
Introduction . v
1 Scope . 1
2 Normative references . 1
3 Principle . 1
4 Reagents and materials . 1
4.1 Diluent oil . 1
4.2 Sulfur compounds . 2
4.3 Reference materials (CRMs) . 2
4.4 Quality control samples . 2
5 Apparatus . 2
5.1 Energy-dispersive X-ray fluorescence instrument . 2
6 Sampling and sample handling . 3
7 Apparatus preparation . 4
7.1 Analyser . 4
7.2 Sample cups . 4
8 Calibration . 4
8.1 General . 4
8.2 Preparation of primary standards . 4
8.3 Calibration standards . 5
8.4 Calibration procedure . 6
9 Procedure . 7
10 Calculation . 7
11 Expression of results . 7
12 Precision . 8
12.1 General . 8
12.2 Repeatability, r . 8
12.3 Reproducibility, R . 8
13 Test report . 8
Annex A (informative) Matrix effects . 9
Annex B (normative) Guidelines for measuring low sulfur concentrations . 11
Bibliography .12
ISO 13032:2012(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.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
The main task of technical committees is to prepare International Standards. Draft International Standards
adopted by the technical committees are circulated to the member bodies for voting. Publication as an
International Standard requires approval by at least 75 % of the member bodies casting a vote.
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.
ISO 13032 was prepared by the European Committee for Standardization (CEN) Technical Committee
CEN/TC 19, Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological
origin, in collaboration with ISO Technical Committee TC 28, Petroleum products and lubricants, in accordance
with the Agreement on technical cooperation between ISO and CEN (Vienna Agreement).
iv © ISO 2012 – All rights reserved

ISO 13032:2012(E)
Introduction
This International Standard is directed specifically at the lower end of the concentration range covered in
[2]
ISO 20847 . By selecting the instrument type, a better signal-to-background ratio for sulfur K-L emission is
2,3
assured. A knowledge of the general composition of the sample for analysis is advantageous in obtaining the
best test result.
NOTE IUPAC X-ray line notation (S K-L ) is used in this International Standard; the corresponding Siegbahn X-ray
2,3
line notation (S-Ka) is being phased out.
Where matrix matching is not used and where the C:H mass ratio of the test sample is known or can be
determined, accuracy can be improved by the use of Equation (A.1) (see A.2.3) to correct the result to the
C:H mass ratio of the calibration standards, i.e. the reference diluent oil (see 4.1).
Some instruments include the capability for instrument-based matrix correction; notes on the use of this
approach to compensate for matrix effects in the test sample are provided in A.3 for information.
[3]
This International Standard is based on IP test method PM DU developed by the Energy Institute.
INTERNATIONAL STANDARD ISO 13032:2012(E)
Petroleum products — Determination of low concentration
of sulfur in automotive fuels — Energy-dispersive X-ray
fluorescence spectrometric method
WARNING — The use of this International Standard may involve hazardous materials, operations and
equipment. This International Standard does not purport to address all of the safety problems associated
with its use. It is the responsibility of the user of this International Standard to establish appropriate
safety and health practices and determine the applicability of regulatory limitations prior to use.
1 Scope
This International Standard specifies an energy dispersive X-ray fluorescence (EDXRF) test method for the
determination of sulfur content in automotive gasoline containing up to 3,7 % (m/m) oxygen [including those
blended with ethanol up to 10 % (V/V)], and in diesel fuels [including those containing up to about 10 % (V/V)
fatty acid methylester (FAME)] having sulfur contents in the range 8 mg/kg to 50 mg/kg.
Other products can be analysed and other sulfur contents can be determined according to this test method;
however, no precision data for products other than automotive fuels and for results outside the specified range
have been established for this International Standard.
For reasons of spectral overlap, this International Standard is not applicable to leaded automotive gasoline,
gasoline having a content of greater than 8 mg/kg lead replacement or to product and feedstock containing
lead, silicon, phosphorus, calcium, potassium or halides at concentrations greater than one tenth of the
concentration of sulfur measured or more than 10 mg/kg, whichever is the greater.
NOTE For the purposes of this International Standard, the terms “% (m/m)” and “% (V/V)” are used to represent the
mass fraction, m, and the volume fraction, f, of a material respectively.
2 Normative references
The following referenced documents are indispensable for the application 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 3170:2004, Petroleum liquids — Manual sampling
ISO 3171:1988, Petroleum liquids — Automatic pipeline sampling
3 Principle
The test portion, in a cup fitted with an X-ray transparent window, is placed in a beam of exciting radiation from
an X-ray tube. The intensity of the sulfur K-L characteristic X-radiation is measured and the accumulated
2,3
count is compared with a calibration curve constructed from sulfur standards covering the range of sulfur
contents under examination.
NOTE The exciting radiation can be either direct or indirect via a polarizing or secondary target.
4 Reagents and materials
4.1 Diluent oil
The reference diluent oil is white oil (light paraffin oil) of high purity grade, with a maximum sulfur content of
0,5 mg/kg. However, if only one type of matrix is to be analysed (e.g. motor gasoline), the accuracy of results
ISO 13032:2012(E)
may be improved by using a matrix-matched diluent. These should match, approximately, the aromatic and
oxygen contents of the material to be analysed and should consist of high-purity components of less than
0,5 mg/kg sulfur content.
NOTE 1 Suitable components for the matched matrix diluent include n-heptane, 2,2,4-trimethylpentane, toluene,
xylenes, ethanol, methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE) and tertiary amyl methyl ether (TAME).
NOTE 2 For the analysis of diesel fuels containing FAME, the accuracy of results can be improved by use of a matched
matrix diluent oil of the white oil with FAME.
4.2 Sulfur compounds
4.2.1 General
Sulfur compounds of known sulfur content shall be used for the preparation of the primary standards. The
compounds given in 4.2.2 to 4.2.5 are suitable and their nominal sulfur contents are given. Where the purity of
these compounds is less than 99 % (m/m), either the concentrations and nature of all impurities are to be known
or certified reference materials (CRMs) shall be used instead.
4.2.2 Dibenzothiophene (DBT), with a nominal sulfur content of 17,399 % (m/m), or
4.2.3 Dibutylsulfide (DBS), with a nominal sulfur content of 21,915 % (m/m), or
4.2.4 Thionaphthene (Benzothiophene) (TNA), with a nominal sulfur content of 23,890 % (m/m), or
4.2.5 Dibutyldisulfide (DBDS), with a nominal sulfur content of 35,950 % (m/m).
4.3 Reference materials (CRMs)
CRMs from accredited suppliers, containing a range of sulfur concentrations, are suitable alternatives to the
compounds listed in 4.2.2 to 4.2.5 for use as calibration standards.
4.4 Quality control samples
Stable samples representative of the materials being analysed, which have a sulfur content that is known by
this test method over a substantial period of time, or are supplied commercially with a certified value. Ensure,
before use, that the material is within its shelf-life.
5 Apparatus
5.1 Energy-dispersive X-ray fluorescence instrument
5.1.1 Performance characteristics.
For a 10 mg/kg sulfur standard (see 8.3), the instrument shall be capable of meeting the following performance
characteristics:
RR− R ≥ 1,3 (1)
()
sb b
and
CR() < 5% (2)
V s
where
2 © ISO 2012 – All rights reserved

ISO 13032:2012(E)
R is the gross count rate (counts per second) for the sulfur region of interest for a 10 mg/kg sulfur
s
standard;
R is the gross count rate (counts per second) for the same region of interest for a blank sample
b
[diluent oil (4.1)];
C is the coefficient of variation (relative standard deviation) based on 10 individual measurements of
V
the calibration standard.
The 10 mg/kg sulfur standard shall be a CRM (4.3) or shall be prepared from one of the compounds given in
4.2.2 to 4.2.5 following the procedures described in Clause 8.
5.1.2 Source of X-ray excitation, with significant flux at X-ray energies above 2,5 keV.
For X-ray detectors with a resolution greater than 200 eV at 2,3 keV, all characteristic X-ray lines originating
from the X-ray tube anode shall have an energy above 3,3 keV to ensure minimal background variation due to
scatter from the X-ray tube anode lines.
5.1.3 Removable sample cup, providing a sample depth of at least 5 mm and equipped with replaceable
X-ray transparent film.
NOTE The transparent film is normally polyester or polycarbonate film with a thickness of between 2 µm and 6 µm.
Polyester film is the preferred choice as samples of very high aromatic content can dissolve polycarbonate film. There are
possibly trace amounts of silicon, calcium and sulfur in some types of film. However, the effects are normally cancelled
out where samples and standards are analysed using the same batch of film. It is important that samples, standards and
blanks be measured using the same batch of film to avoid bias.
5.1.4 X-ray detector, with a resolution not exceeding 800 eV at 2,3 keV.
5.1.5 Means of discriminating between sulfur K-L characteri
...